Polyolefin Compositions and Articles Made Therefrom and Methods of Manufacture Related Patent (2023)

The invention provides compositions comprising: a) at least one olefin multiblock interpolymer; b) at least one functionalized olefin-based polymer; and optionally c) at least one thermoplastic polyurethane.

Polyolefins as a class of materials have relatively poor adhesion and compatibility with more polar polymeric materials. In most cases, a separate adhesive is required to bond polyolefins to polar substrates such as polyesters, polyamides, polyurethanes, and the like. Also, a third component compatibilizer must normally be used to produce satisfactory melt blends of polyolefins with other more polar thermoplastics. However, significant amounts of compatibilizers are usually required to maintain intimate mixing of the polyolefin and polyurethane.

In North America, approximately 25 million pounds of flexible polyvinyl chloride (f-PVC) is used in thermoformed sheets for automotive applications such as instrument panels and doors. These panels are grained and color matched to other interior parts. Films for automotive applications must meet a number of end-user requirements. Key end use requirements include low gloss, high scratch/surface scratch resistance, high heat resistance and good low temperature impact resistance. In addition, the laminate must have good adhesion to any intermediate layer of polyurethane (PU) foam, for example a foam layer used to add a cushioning or softening effect to an automobile dashboard.

Polymeric films or skins should be low gloss or low gloss, especially when the film is placed under a window, such as in the instrument panel (IP) under the windshield of an automobile. In addition, the gloss of the material must remain low throughout the life of the vehicle. A material's gloss is usually determined by measuring light reflected at specific angles, and a typical test reading is taken at 60 degrees. Reflectance measurements are converted to gloss values, and these values are typically less than or equal to 2 for automotive applications. Flexible or plasticized polyvinyl chloride typically has high gloss values. To reduce the gloss of flexible polyvinyl chloride to acceptable levels for automotive applications, a topcoat of liquid polyurethane is typically applied.

Thermoplastic polyolefin (TPO) films can also be used in automotive applications. Thermoplastic polyolefin films or coatings generally have lower gloss values compared to flexible polyvinyl chloride but also have a polyurethane top coat primarily to improve the scratch/marking properties of the surface and with the secondary benefit of reducing the brightness value. However, new surface grain technologies are emerging (e.g., micrograins transferred from the surface of a grain roller to the extruded sheet during an extrusion) that allow for consistent gloss control across a variety of grain patterns. Predictably, these new technologies can eliminate the need for polyolefin PU surfaces that have just the right level of scratch/stain resistance to meet application needs. Examples of such new technologies are in US Patent No. 5,902,854, which is incorporated herein by reference.

Another end-use requirement is that the sheet (f-PVC or TPO) must withstand the higher service temperatures encountered in automotive interiors, particularly in the summer heat. The current criterion is that the leaves can withstand a temperature. of 120 °C. Oven aged 500 hours while retaining 50% of the original elongation (ISO 188/ASTM E 145, Type IIA, 500 hours at 120°C) without melting, deforming, becoming sticky or showing other physical changes . Parallel to this requirement is the need for the panels to have good impact properties at low temperatures, such as -40°C. This property is particularly important when such panels are used to form seamless airbags (occupant safety during winter airbag deployment is important). of utmost importance; the criterion is no flying debris). The glass transition temperature (Tg) of plasticized polyvinyl chloride is typically -20°C to -30°C and therefore this polymer has degraded low temperature impact properties at temperatures below its Tg. However, thermoplastic polyolefins typically have lower glass transition temperatures compared to polyvinyl chloride and therefore have better cold temperature impact properties. Thermoplastic polyolefins are often the material of choice for seamless airbags and other safety devices that deploy in a vehicle crash, particularly in cold weather.

Thermoplastic polyolefins also have better long-term stability compared to flexible polyvinyl chloride, as evidenced by a small change in rheological and/or mechanical properties after thermal aging at 120°C. At 120°C, polyvinyl chloride generally loses plasticizer and therefore loses elongation (elasticity), becomes brittle and tends to crack.

Thermoplastic olefin (TPO) sheet is increasingly being used for instrument panels and door top panels. The typical assembly process requires the bonding of a thermoformed flexible thermoplastic polyolefin sheet and a hard surface substrate in a molding process, forming a polyurethane foam between the two layers. The hard surface substrate is typically made of a thermoplastic polyolefin, a blend of acrylonitrile butadiene styrene (ABS) or a blend of acrylonitrile butadiene styrene/polycarbonate (ABS/PC). In panel applications, ABS and ABS/PC substrates are being replaced by rigid TPO, typically reinforced with a filler. A polyurethane precursor mixture (a liquid isocyanate, a liquid polyol and a catalyst) is injected between the TPO skin and the hard surface and then reacts to form a foam interlayer.

Unfortunately, due to their non-polar nature, thermoplastic polyolefins generally lack adhesion to polar materials such as polyurethanes. Therefore, a flexible thermoplastic olefin film is conventionally surface treated with a primer solution containing one or more polar compounds to improve adhesion to a polyurethane surface. Typical primer solutions contain a chlorinated maleated polyolefin. Such surface treatment requires a large ventilation area equipped for handling sheets by gravure application; a priming mechanism such as a dip tank; and a drying medium for evaporating water and other solvent carriers. In addition, the flexible thermoplastic olefin skin must adhere to the polyurethane foam without voids or other visible defects. The polyurethane foam must adhere to the thermoplastic polyolefin surface without interfacial delamination (or adhesive failure). Discontinuous application of a primer solution can result in voids forming between the thermoplastic olefin film and the polyurethane foam in unprimed areas. Surface imperfections are a costly problem for auto parts manufacturers because parts that have surface imperfections cannot be used in the assembly of an automobile and instead become scratched.

International Publication No. WO 00/63293 describes a thermoplastic polyurethane/olefin graft polymer blend with an optional compatibilizing polymer. The compatibilizing polymer is a modified polyolefin selected from block and grafted olefin polymers or ionomers having an unsaturated organic compound in the main or side chain.

European Application No. 0347794A1 describes a compatible thermoplastic blend composition comprising: (A) 15 to 60% by weight of a polyolefin, (B) 30 to 70% by weight of a thermoplastic polyurethane and (C) 10 to 35% by weight of at least one modified polyolefin defined as random , Block or grafted olefin copolymer having in its main chain or side chain a functional group selected from carboxylic acid, carboxylate ester, carboxylic acid anhydride, carboxylate, amide, epoxy, hydroxy or acyloxy salts.

US Patent No. US 6,251,982 describes a rubber composite composition comprising: (a) a polydiene diol based hydrogenated polyurethane having a hard segment content of 10% or more; (b) a non-polar extender oil in an amount from 10 to 400 phr; and/or (c) one or more thermoplastic resins in an amount of 5 to 100 phr.

US Patent No. US-A-5,578,680 discloses a vibration absorbing elastomeric composite material comprising: (A) 10-60% by weight of at least one thermoplastic resin selected from the group consisting of olefinic polymers, ethylenic ester unsaturated copolymers and natural rubber, and (B) 90-40% by weight of a polyurethane resin prepared by reacting a polyisocyanate with a polyol in situ in molten thermoplastic resin (A). Polyurethane (B) has a nitrogen atom content of at least 3% by weight and has a solubility parameter at least 2.5 greater than that of the thermoplastic resin and the compound has a tan δ of at least minus 1.0 at 20° C has .°C

U.S. Patent No. US-A-4,883,837 describes a compatible thermoplastic blend composition comprising from about 15 to about 60% by weight of a polyolefin, from about 30 to about 70% by weight of a thermoplastic polyurethane, and from about 10 to about 35 % by weight of at least one modified polyolefin defined as a random, block or graft olefin copolymer having in its main chain or side chain a functional group selected from carboxylic acid, carboxylate ester, acid anhydride, carboxyl, carboxylate, amide, epoxy, hydroxy and acyloxy salts.

US Patent No. 4,198,327 describes a composition for adhesion to polar materials comprising the following: a) 99 to 70 parts by weight of a modified crystalline polyolefin grafted with a monomer selected from unsaturated carboxylic acids and their anhydrides, esters, amides, imides and salts of metals, and wherein the crystalline polyolefin has a degree of crystallinity, measured by X-ray analysis, of at least 25% and contains the grafting monomer in an amount of from 0.0001 to 3% by weight based on the total amount of crystalline polyolefin and grafting monomer; and b) 1 to 30 parts by weight of a hydrocarbon elastomer.

The US patent at the. US-A-5,705,565 describes a thermoplastic polymer blend comprising one or more thermoplastic polymers and a substantially linear ethylene polymer grafted with at least about 0.01% by weight of an unsaturated organic compound having at least one ethylenic establishment site and at least one Carbonyl contains group. The thermoplastic polymer can be selected from polyurethane, polycarbonate, polystyrene, polyester, epoxy, polyamide, a polyolefin containing polar groups, acrylonitrile butadiene styrene copolymer and mixtures thereof.

European Patent Application No. 0657502A1 describes a thermoplastic composition which is a blend of (a) a block copolyetherester, a block copolyetheramide and/or a polyurethane, (b) a thermoplastic homoco- or terpolymer which is incompatible with (a) and (c) ) contains a compatibilizer . The compatibilizer is chosen according to the nature of component (b). It will have a backbone compatible and preferably identical to component (b) and a reactive group compatible or interacting with component (a). The reactive group can be grafted onto this backbone using a grafting monomer with at least one alpha or beta ethylenically unsaturated carboxylic acid and anhydrides and derivatives thereof.

US Patent No. US 6,414,081 describes a compatibilized blend comprising the following: a) an apolar thermoplastic elastomer comprising a thermoplastic polyolefin homopolymer or copolymer and an olefinic rubber which is fully or partially crosslinked; and b) a polar thermoplastic polymer selected from thermoplastic polyurethane (TPU), chlorine-containing polymers, fluorine-containing polymers, polyesters, acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, polyacetal, polycarbonate or polyphenylene oxide ; and c) a compatibilizer selected from i) a condensation copolymer formed from 10 to 90 weight percent of a functionalized olefin polymer and 90 to 10 weight percent of a polyamide, based on the total weight of the functionalized polymer and the polyamide, or ii) a blend of a functionalized olefin polymer and a polyamide, or iii) a blend of (i) and (ii).

US Patent No. US 6,469,099 describes a blend of a polymeric hydrocarbon and a thermoplastic polyurethane compatibilized with a polymeric hydrocarbon containing low levels of isocyanate-reactive groups. The compatibilizer can be prepared by reacting a modified polymer having pendant or built-in reactive amine groups with a hydroxylamine, diamine, or polyether monoamine. The compatibilized blend may further contain a non-TPU engineering thermoplastic to form compatible blends of the polymeric hydrocarbon and the non-TPU engineering thermoplastic.

International Publication No. WO 00/63293 describes a polymer composition comprising a thermoplastic polyurethane and a first olefin graft polymer, the graft polymer comprising at least a first graft moiety and at least a second graft moiety, the first graft moiety being a silane moiety. which promotes crosslinking of the grafted elastomer in the presence of moisture, wherein the second grafted portion is an unsaturated organic compound containing, prior to grafting, at least one ethylenic unsaturation and a polar functionality that promotes olefin and thermoplastic urethane compatibilization.

US Patent No. US-A-5,902,854 describes compositions comprising ethylene interpolymers such as a linear or substantially linear ethylene interpolymer and polydimethylsiloxane. The compositions may further comprise an ethylene homopolymer or interpolymer grafted with maleic anhydride or succinic anhydride groups. The compositions have good abrasion resistance without sacrificing the coefficient of friction.

US Patent No. US-A-4,397,916 describes a laminated multilayer structure consisting of (A) a layer of a graft-modified ethylene resin grafted with an unsaturated carboxylic acid or a functional derivative thereof and (B) a layer of polar resin , containing oxygen or nitrogen or a metal layer in contact with layer (A). Layer (A) is characterized in part by consisting of (i) 1 to 100% by weight of the graft-modified ethylene resin derived from an ethylene polymer containing 0 to 15% by weight of at least one alpha-olefin having 3 bis 30 carbon atoms as a comonomer; and (ii) from 99 to 0 weight percent of an unmodified ethylene polymer containing from 0 to 50 mole percent of at least one alpha-olefin having from 3 to 30 carbon atoms as a comonomer.

International Publication No. WO 96/27622 describes a process for preparing amine-functionalized nucleophilic polyolefins by reacting a polymer having an electrophilic functional group with a diamine having terminal amine groups of different reactivity. The amine functionalized nucleophilic polyolefin has the composition: Polyolefin-X-R1-NHR2 where X is selected from the group consisting of imide, amide, sulfonamide or amine, R1 is a divalent organic radical, R2 is H or an alkyl group. Nucleophilic amine functionalized polyolefin finds uses as a compatibilizer, adhesive, colorable material, and colorable reinforcer.

International Publication No. WO 93/02113 describes graft polymers containing reactive amine functionality which are prepared by: a) providing a thermoplastic polymer containing at least one electrophilic functionality sufficient to react with primary amine groups; and b) reacting in the molten state with a chemical compound comprising a primary amine and a secondary amine, wherein the secondary amine has a reactivity about equal to or less than that of the primary amine. Crosslinking is largely avoided by using selected diamine-containing chemicals. The use of the grafted polymer as a modifier and compatibilizer of polymer compositions is described.

International Publication No. WO 03/008681 describes fibers having improved moisture resistance at elevated temperatures and comprising at least two elastic polymers, one thermoset polymer and the other heat resistant polymer, where the heat resistant polymer makes up at least part of the outer surface of the fiber. Fibers typically have a bicomponent and/or bicomponent core/sheath morphology. Typically, the core comprises a resilient thermoplastic urethane and the shell comprises a homogeneously branched polyolefin, preferably a homogeneously branched, substantially linear ethylene polymer. A fiber component may contain a functionalized polyethylene. (See also WO 03/008680).

Examples of other compositions containing functional ingredients are disclosed in US Patent No. 5,623,019; U.S. Patent No. 6,054,533; U.S. Patent No. 5,578,680; EP1672046; EP0734419B1; EP0657502A1. Additional functionalized polymers and/or compositions are disclosed in International Publication No. WO 99/02603 and US Publication No. 2004/0106744.

There remains a need for low cost polyolefin compositions that can be used as good adhesives to polar substrates such as polyurethane, polycarbonate and polyamide substrates. There is an additional need for such compositions that can be used in overmolding applications and that provide improved adhesion to polar substrates. Some of these needs and others have been met by the next invention.

There also remains a need for low cost polyolefin compositions which may further comprise polyurethanes and/or which comprise low levels, preferably less than 10% by weight, of compatibilizers. It is more advantageous if such compositions can be used as good adhesives to polar substrates such as polyurethane, polycarbonate and polyamide substrates. It is even more advantageous if articles such as sheets and foils can be produced with high surface energies and good adhesive properties. There is an additional need for low cost compatible blends that exhibit improved heat aging performance and are particularly suitable for automotive interior applications exposed to elevated temperatures (up to 120°C). There is an additional need for such compositions that can be used in overmolding applications and provide improved adhesion to polar substrates. Other potentially useful applications include automotive interior applications (thermoformed coatings) and provide one or more of the following properties: a luxurious feel, reduced gloss, and improved grain reproduction needed for vacuum thermoforming processes. Some of these needs and others have been met by the next invention.

There is also a need to develop polyolefin compositions that contain a polyurethane component and that require a minimal amount of compatibilizers or other types of stabilizers to maintain the stability of the polymer phases of the composition and that have high surface energies and good adhesion properties. . Some of these needs and others have been met by the next invention.

There remains a need for improved, low cost polyolefin/polyurethane compositions which contain low levels, preferably less than 10% by weight (based on the total weight of the composition) of compatibilizers and which can be used in articles such as sheets and films and with high surface energies, preferably greater than 30 dynes/cm, and good adhesive properties. There is an additional need for low cost compatible compositions that exhibit improved thermal aging performance and are particularly useful in automotive interior applications exposed to elevated temperatures (up to 120°C). There is an additional need for such compositions that can be used in automotive interior applications (thermoformed coatings) and that provide one or more of the following properties: a luxurious feel, reduced gloss, and improved grain reproduction needed for pressure thermoforming processes.

There is still a need for suitable thermoplastic polyolefin compositions that can be used to form films that do not require a polyurethane topcoat for glare or scratch control and that have good adhesion to polyurethane foams. There is also a need to develop a weather-resistant, low-gloss and/or scratch-resistant film that has good adhesion to PU foams, adhesives and PU coatings. Some of these needs and others have been met by the next invention.

The invention provides a composition comprising:

A) at least one olefinic multiblock interpolymer;

B) at least one functionalized olefin-based polymer; j

C) optionally at least one thermoplastic polyurethane.

COWARD. Figure 1 plots the melting point versus density for various ethylene/α-olefin multiblock interpolymers (polymers of the invention) and comparative polymers (traditional random and Ziegler-Natta).

COWARD. 2 "DSC Tm-Crystaf Tc" plots as a function of heat of fusion for various polymers.

COWARD. Figure 3 shows the effect of density on the elastic recovery of unoriented films made from certain olefin multiblock interpolymers and some traditional random copolymers.

COWARD. Figure 4 shows comonomer content versus TREF elution temperature for various ethylene/1-octene random copolymers and one ethylene/1-octene multiblock copolymer.

COWARD. Figure 5 shows TREF profiles and comonomer content for a multiblock copolymer (Example 5) and a comparative copolymer (Example F*).

COWARD. Figure 6 shows the storage modulus as a function of temperature for various multiblock copolymers (polymers of the invention) and comparative random copolymers.

COWARD. Figure 7 shows TMA data (thermomechanical analysis) versus flexural modulus data for a multiblock copolymer (inventive polymer) and some comparative examples (Versify ™ , ethylene/styrene, Affinity ™ ).

COWARD. 8 is an adhesive test instrumentation scheme.

general description

As discussed above, the invention provides a composition comprising:

A) at least one olefinic multiblock interpolymer;

B) at least one functionalized olefin-based polymer; and optional

C) at least one thermoplastic polyurethane.

In one embodiment, at least one functionalized olefin-based polymer, also referred to as a polyolefin, is formed from a polyolefin and at least one organic compound selected from an "amine-containing compound", a "hydroxyl-containing compound", an "amine-containing compound". imide-containing", an "anhydride-containing compound" or a "carboxylic acid-containing compound".

In another embodiment, the olefin multiblock interpolymer is an ethylene/α-olefin multiblock interpolymer having one or more of the following features:

(1) an average number of blocks greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3; any

(2) at least one molecular fraction that elutes between 40°C and 130°C when fractionated by TREF, characterized in that the fraction has a blocking index of at least 0.5 and up to about 1; any

(3) an Mw/Mn of from about 1.7 to about 3.5, at least a melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, where the numerical values of Tm and d correspond to the relationship :
Tm>-2002,9+4538,5(d)−2422,2(d)²; Ö

(4) a Mw/Mn of from about 1.7 to about 3.5 and characterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius, defined as the temperature difference between the highest DSC peak and the highest CRYSTAF peak, where the numerical values of ΔT and ΔH have the following relationships:
DT>-0,1299(DH)+62.81 paragraph DHgreater than zero and up to 130 J/g,
DT≧48°C for DHbetter than 130 J/g,
where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; any

(5) a percent elastic recovery, Re, at 300% elongation and 1 cycle, measured with a compression molded ethylene/α-olefin interpolymer film, and has a density, d, in grams/cubic centimeter, where the numerical value and the values of Re and d satisfy the following relationship when the ethylene/α-olefin interpolymer is essentially free of a crosslinked phase:
Re>1481-1629(d); Ö

(6) a molecular fraction that elutes between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a molar comonomer content that is at least 5 percent greater than that of an ethylene interpolymer random fraction that eluted between the same temperatures wherein the comparable random ethylene interpolymer has the same comonomers and has a melt index, density and molar comonomer content (on a total polymer basis) within 10 percent of the ethylene/α-olefin interpolymer; any

(7) a 25°C storage modulus G'(25°C) and a 100°C storage modulus G'(100°C), where the ratio of G'(25°C) to G' ( 100°C) ranges from about 1:1 to about 9:1.

In another embodiment, the anhydride containing compound is maleic anhydride.

In another embodiment, at least one functionalized olefin-based polymer is present in an amount less than or equal to 20% by weight based on the total weight of the composition. In another embodiment, at least one functionalized olefin-based polymer is present in an amount less than or equal to 10% by weight based on the total weight of the composition. In another embodiment, at least one functionalized polymer is present in an amount less than or equal to 5% by weight based on the total weight of the composition.

In another embodiment, at least one functionalized olefin-based polymer is present in an amount greater than or equal to 20% by weight based on the total weight of the composition. In another embodiment, at least one functionalized olefin-based polymer is present in an amount greater than or equal to 30% by weight based on the total weight of the composition. In another embodiment, at least one functionalized olefin-based polymer is present in an amount greater than or equal to 40% by weight based on the total weight of the composition.

In another embodiment, the at least one functionalized olefin-based polymer has a density of from about 0.85 g/cc to about 0.91 g/cc. In another embodiment, the at least one functionalized olefin-based polymer has a density of from about 0.84 g/cc to about 0.93 g/cc. In another embodiment, the at least one functionalized olefin-based polymer has a density of from about 0.85 g/cc to about 0.93 g/cc. In another embodiment, the at least one functionalized olefin-based polymer has a density of from about 0.84 g/cc to about 0.90 g/cc.

In another embodiment, the at least one functionalized olefin-based polymer has a melt index (I 2 ) from 0.1 g/10 min to 100 g/10 min. In another embodiment, the at least one functionalized olefin-based polymer has a melt index (I 2 ) from 1 g/10 min to 50 g/10 min. In another embodiment, the at least one functionalized olefin-based polymer has a melt index (I 2 ) from 1 g/10 min to 10 g/10 min the at least one functionalized polyolefin has a melt flow index (I 2 ) of 1 g/10 min to 20 g/10 min.

In another embodiment, at least one functionalized olefin-based polymer is formed from an ethylene-based polymer. In another embodiment, the ethylene-based polymer is an ethylene/α-olefin interpolymer. In another embodiment, the α-olefin is a C3-C20 α-olefin, and preferably a C3-C10 α-olefin. In another embodiment, the α-olefin is selected from the group consisting of 1-propene, 1-butene, 1-hexene and 1-octene, and preferably 1-butene and 1-octene. In another embodiment, the ethylene/alpha-olefin interpolymer used to form the functionalized olefin-based polymer further comprises a diene. In another embodiment, the ethylene/alpha-olefin interpolymer has a density of from 0.85 g/cc to 0.93 g/cc. In another embodiment, the ethylene/α-olefin interpolymer has a melt index (I 2 ) of from 0.01 g/10 min to 1500 g/10 min.

In another embodiment, the ethylene/alpha-olefin interpolymer used to form the functionalized olefin-based polymer is a linear homogeneously branched interpolymer or a substantially linear homogeneously branched interpolymer. In another embodiment, the ethylene/alpha-olefin interpolymer used to form the functionalized olefin-based polymer is a homogeneously branched, substantially linear interpolymer.

In another embodiment, at least one functionalized olefin-based polymer is formed from a propylene-based polymer. In another embodiment, the propylene-based polymer is a propylene/ethylene interpolymer or a propylene/α-olefin interpolymer. In another embodiment, the propylene-based polymer is a propylene/α-olefin interpolymer, wherein the α-olefin is a C4-C20 α-olefin, and preferably a C4-C10 α-olefin. In another embodiment, the α-olefin is selected from the group consisting of 1-butene, 1-hexene and 1-octene. In another embodiment, the propylene/α-olefin interpolymer has a density of from 0.85 g/cc to 0.93 g/cc. In another embodiment, the propylene/α-olefin interpolymer has a melt index (I 2 ) of from 0.01 g/10 min to 1500 g/10 min. In another embodiment, the propylene-based polymer is a propylene/ethylene interpolymer . In another embodiment, the propylene/ethylene interpolymer has a density of 0.85 g/cc to 0.93 g/cc. In another embodiment, the propylene/ethylene interpolymer has a melt index of from 0.01 g/10 min to 1500 g/10 min.

In another embodiment, at least one functionalized polyolefin is formed from a multiblock olefin interpolymer.

In another embodiment, the composition further comprises at least one thermoplastic polyurethane. The at least one thermoplastic polyurethane may comprise chemical moieties derived from (1) a polyester and (2) an aromatic diisocyanate or an aliphatic diisocyanate. In another embodiment, at least one thermoplastic polyurethane comprises chemical entities derived from a polyester and at least one aromatic diisocyanate. In another embodiment, at least one thermoplastic polyurethane comprises chemical entities derived from a polyester and at least one aliphatic diisocyanate. In another embodiment, the at least one thermoplastic polyurethane comprises chemical entities derived from a polyester and a mixture of 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane. In another embodiment, the weight ratio of 1,3-bis(isocyanatomethyl)cyclohexane to 1,4-bis(isocyanatomethyl)cyclohexane is about 1 to 1.

In another embodiment, the polyurethane is formed from a polyester comprising a monomeric unit derived from a diol derived from N-octylpyrrolidone. In another embodiment, the polyurethane is formed from a polyester comprising a monomeric unit derived from polytetramethylene ether glycol. In another embodiment, the polyurethane is formed from a polyester that includes a monomeric unit derived from a polyether. In another embodiment, the thermoplastic polyurethane is a PELLETHANE™ polyurethane.

In another embodiment, the polyester is formed from caprolactone. In another embodiment, the at least one thermoplastic polyurethane has a density of 0.90 g/cc to 1.3 g/cc. In another embodiment, the at least one thermoplastic polyurethane has a melt flow index (I 2 ) of 1 g/10 min to 100 g/10 min. In another embodiment, the at least one thermoplastic polyurethane has a melt flow index (I 2 ) of 1 g/10 min to 10 g/10 min.

In another embodiment, the thermoplastic polyurethane comprises a monomeric unit derived from a diol derivative derived from N-octylpyrrolidone. In another embodiment, the thermoplastic polyurethane comprises a monomer unit derived from polytetramethylene ether glycol. In another embodiment, the thermoplastic polyurethane comprises a monomeric unit derived from a polyether.

In another embodiment, the composition further comprises one or more additives.

In another embodiment, at least one functionalized olefin-based polymer is formed by a method comprising the steps of:

1) grafting onto the backbone of an olefin-based polymer at least one compound comprising at least one "amine-reactive" group to form a grafted olefin-based polymer;
2) reaction of a primary secondary diamine with the grafted olefin-based polymer; j
3) where step 2) occurs after step 1) without isolation of the grafted olefin-based polymer and where both steps occur in a fusion reaction.

In another embodiment, the primary secondary diamine is selected from the group consisting of N-ethylethylenediamine, N-phenylethylenediamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine and N-(2-hydroxyethyl) -ethylenediamine.

In another embodiment, at least one functionalized olefin-based polymer comprises the following functional group covalently bonded to the olefin-based polymer backbone:

onde „NR₁KINDER₂” may be derived from a primary-secondary diamine selected from the group of compounds of structure (I) below:
H₂NR₁—NH—R₂(YO),
wo r₁is a divalent hydrocarbon radical, preferably selected from the group consisting of alkylene, phenylene and particularly preferably -CH2CH2-, -para-phenylene-, -ortho-phenylene- and

R₂is a monovalent hydrocarbon radical containing at least 2 carbon atoms and may be optionally substituted by a heteroatom-containing group, preferably an alkyl or aryl group and more preferably an ethyl or phenyl group.

In another embodiment, at least one functionalized olefin-based polymer is formed by a method comprising the steps of:

1) functionalizing the olefin-based polymer with at least one compound comprising at least one "amine-reactive" group to form a grafted olefin-based polymer;

2) blending the grafted olefin-based polymer in solid, unmolten form with at least one primary secondary diamine;

3) incorporation of the primary secondary diamine into the grafted olefin-based polymer;

4) Reacting the primary secondary diamine with the grafted olefin-based polymer to form an imide-functionalized olefin-based polymer.

In one embodiment, the soaking step occurs at room temperature. In another embodiment, the mixing step takes place at room temperature.

In another embodiment, at least one functionalized olefin-based polymer is formed by a method comprising the steps of:

1) grafting onto the backbone of an olefin-based polymer at least one compound comprising at least one "amine-reactive" group to form a grafted olefin-based polymer;

2) reaction of an alkanolamine with the grafted olefin-based polymer; and wherein step 2) occurs after step 1) without isolation of the grafted olefin-based polymer and wherein both steps 1) and 2) occur in a fusion reaction.

In another embodiment, the alkanolamine is selected from the group consisting of 2-aminoethanol, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 2-(2-aminoethoxy)-ethanol and 2-aminobenzyl alcohol.

In another embodiment, at least one functionalized olefin-based polymer comprises the following functional group covalently bonded to the olefin-based polymer backbone:

onde „NR₁OH" may be derived from an alkanolamine selected from the group of compounds of structure (II) below:
H₂NR₁OH(II),
wo r₁is a divalent hydrocarbon radical, preferably R₁is substituted or unsubstituted alkylene, more preferably R₁is selected from the group consisting of ethylene, propylene, butylene and alkylene substituted by one or more groups selected from the group consisting of alkoxy and phenyl groups, and more preferably R₁safe—CH(OH₂CH₂Yo) CH₂— o y -orthophenylen-CH₂—.

In another embodiment, at least one functionalized olefin-based polymer is formed by a method comprising the steps of:

1) Grafting onto the main chain of an olefin-based polymer in a fusion reaction of at least one compound represented by the following formula (IV) to form a grafted olefin-based polymer:

2) and heat treating the grafted olefin-based polymer to form the imide-functionalized olefin-based polymer and wherein R1 and R2 are independently hydrogen or a C1-C20 hydrocarbyl radical, linear or branched; R3 is hydrogen or a linear or branched C1-C20 hydrocarbyl radical; R4 is a divalent linear or branched hydrocarbon radical; X is OH or NHR₅, where R5 is a linear or branched hydrocarbon radical or a hydroxyethyl group.

In another embodiment, R1 and R2 are independently hydrogen or a C1-C10 hydrocarbyl group. In another embodiment, R3 is hydrogen or a C1-C10 hydrocarbyl radical and R4 is a C1-C20 divalent hydrocarbyl radical.

In another embodiment, at least one functionalized olefin-based polymer comprises the following functional group covalently bonded to the olefin-based polymer backbone:

wherein R1 and R2 are independently hydrogen or a C1-C20 hydrocarbon radical, linear or branched; R4 is a divalent linear or branched hydrocarbon radical; X is OH or NHR₅, where R5 is a linear or branched hydrocarbon radical or a hydroxyethyl group.

In another embodiment, R1 and R2 are independently hydrogen or a C1-C10 hydrocarbyl group. In another embodiment, R4 is a C1-C20 divalent hydrocarbyl radical.

A composition according to the invention may further comprise one or more additives. For example, a composition according to the invention can also contain at least one filler. In another embodiment, the filler is a talc or a talc that has been surface modified with at least one aminosilane. In another embodiment, a composition according to the invention can comprise a polar polymer selected from the group consisting of polyesters, polyamides, polyethers, polyetherimides, polyvinyl alcohols, polycarbonates, polyurethanes, polylactic acids, polyamide esters and combinations thereof.

In another embodiment, the composition has a surface energy greater than or equal to 35 dynes/cm.

A composition according to the invention may comprise a combination of two or more embodiments as described herein.

The invention also provides an article comprising at least one component formed from a composition according to the invention. In another embodiment, the article is a sheet, mat, adhesive, wire wrap, cable, protective clothing, automotive part, shoe component, foam or laminate cover, overmolded article, automotive skin component, awning, canvas, a leather item, a roofing item, steering wheel, powder coating, powder mud lining, consumable, handle, grip, computer component, belt, appliqué, shoe component, conveyor or timing belt, or fabric.

In another embodiment, the article is a tie layer between extruded films, a tie layer between extruded films, a tie layer between extruded profiles, a tie layer between cast films, a tie layer between cast films, a tie layer between cast profiles, or a tie layer between a combination of the above .

The invention also provides a film comprising at least one layer formed from a composition according to the invention. In another embodiment, the invention provides a film comprising at least two layers and having at least one layer formed from a composition of the invention. In another embodiment, a film of the present invention has a moisture vapor transmission rate of at least 7 g/hr/ft.².

The invention also provides an extruded film formed from a composition according to the invention. In another embodiment, the film has a surface energy of greater than or equal to 30 dynes/cm, preferably greater than or equal to 33 dynes/cm, more preferably greater than or equal to 35 dynes/cm. In another embodiment, the film has a thickness of 10 mils to 1000 mils, preferably 15 mils to 500 mils, and most preferably 20 mils to 100 mils. In another embodiment, the film retains at least 50 percent, preferably at least 60 percent, of its original elongation after heat aging at 120°C for 500 hours (ASTM D-882-02).

The invention also provides a coated substrate, the substrate being formed from a composition according to the invention. In one embodiment, the ink comprises at least one additive selected from the group consisting of an acrylic polymer, an alkyl resin, a cellulosic material, a melamine resin, a urethane resin, a carbamate resin, a polyester, a vinyl acetate resin, an epoxy, a polyol and/or a Alcohol. In another embodiment, the ink is a water-based ink. In another embodiment, the ink is an organic solvent based ink.

The invention also relates to a dispersion containing a composition according to the invention. In another embodiment, the dispersion further comprises at least one additive selected from the group consisting of an acrylic polymer, an alkyd resin, a cellulose-based material, a melamine resin, a urethane resin, a carbamate resin, a polyester, a vinyl acetate resin, an epoxy polyol, an alcohol, and combinations thereof. In another embodiment, the dispersion is a water-based dispersion. In another embodiment, the dispersion is an organic solvent-based dispersion.

The invention also provides an injection molded article comprising at least one component formed from a composition of the invention.

The invention also provides an r.f. welded article comprising at least one component formed from a composition according to the invention.

The invention also provides an overmolded article comprising: (a) a substrate formed from a composition comprising a polar polymer, and (b) a molded liner formed from a composition according to the invention. In one embodiment, the polar polymer is a polycarbonate (PC), ABS, PC/ABS, or nylon. The invention also provides an overmolded article comprising: (a) a substrate formed from a composition according to the invention, and (b) a molded liner formed from a composition comprising a polar polymer. In one embodiment, the article is in the form of a handle, strap or belt.

The invention also provides a laminated structure comprising a first layer and a second layer and wherein the first layer is formed from a composition according to the invention and wherein the second layer is formed from a composition comprising a polar polymer. In another embodiment, one of the layers is in the form of a foam. In another embodiment, one of the layers is in the form of a fabric. In another embodiment, the laminated structure is in the form of an awning, a tarpaulin, or a car cover, or a steering wheel. In another embodiment, the second layer is formed from a composition that includes a polycarbonate.

The invention also provides a shaped article comprising a first component and a second component, and wherein the first component is formed from a composition comprising a polar polymer and wherein the second component is formed from a composition according to the invention. In another embodiment, the article is in the form of an automobile cover, applique, shoe component, conveyor belt, timing belt, or consumable.

The invention also provides an article of footwear comprising at least one component formed from a composition of the invention. In another embodiment, the article is selected from the group consisting of a shoe sole, a shoe midsole, a shoe sole, an overmolded article, a natural leather article, a synthetic leather article, an upper, an article laminate, a coated article, a boot, a sandal, galoshes, a plastic shoe and combinations thereof.

The invention also provides a thermoformed sheet comprising at least one layer formed from a composition according to the invention.

The invention also provides an automotive part comprising at least one layer formed from a composition according to the invention. The invention also provides an automotive part, such as an instrument panel or door panel, formed from a composition of the invention.

The invention also provides artificial leather comprising at least one component formed from a composition according to the invention.

The invention also provides artificial turf comprising at least one component formed from a composition according to the invention.

The invention also provides an adhesive comprising at least one component formed from a composition according to the invention. The invention also provides a coated substrate comprising an adhesive of the invention and at least one component made from Kevlar.

The invention also provides an article formed from a composition according to the invention and in which the article has a surface energy of greater than or equal to 35 dynes/cm.

An inventive article may include a combination of two or more embodiments described herein.

The invention also provides a process for preparing a composition according to the invention, which process comprises melt blending components A, B and optionally C. In one embodiment, the desired components are mixed together. In another embodiment, the desired components are sequentially mixed in any order. In another embodiment, the melt blending takes place in an extruder. In another embodiment, the melt blending is done in an "on-line" compounding process.

A method according to the invention may comprise a combination of two or more suitable embodiments as described herein.

A composition according to the invention may comprise a combination of two or more suitable embodiments as described herein.

An article according to the invention may comprise a combination of two or more suitable embodiments as described herein.

Functionalized polymers based on olefins

1. General information

Functionalized olefin-based polymers include, but are not limited to, olefin-based polymers functionalized with carboxylic acid, anhydride, alcohol, amine, epoxy, halogens, isocyanate, and other groups and combinations thereof. The functionalization can occur along the main chain of the olefin-based polymer, at the ends of the chain, as a block segment, and/or as a side chain.

In one embodiment, the functionalized olefin-based polymer is an ethylene-functionalized polymer, and preferably an ethylene/α-olefin-functionalized interpolymer, having a melt index (I₂) greater than or equal to 0.5 g/10 min, preferably greater than or equal to 1 g/10 min, and most preferably greater than or equal to 2 g/10 min, determined using ASTM D-1238 (190 °C, 2.16 kg payload). In another embodiment, the functionalized olefin-based polymer is an ethylene-functionalized polymer, and preferably an ethylene/α-olefin-functionalized interpolymer, having a melt index (I₂) less than or equal to 50 g/10 min, preferably less than or equal to 20 g/10 min and most preferably less than or equal to 10 g/10 min as determined using ASTM D-1238 (190°C, 2, 16 kg payload).

In another embodiment, the functionalized olefin-based polymer is an ethylene-functionalized polymer, and preferably an ethylene/α-olefin-functionalized interpolymer, having a melt index (I₂) from 0.5 g/10 min to 50 g/10 min, preferably from 1 g/10 min to 20 g/10 min and more preferably from 2 g/10 min to 10 g/10 min, determined using ASTM D-1238 (190°C, 2.16 kg load). All individual values and partial ranges from 0.5 g/10 min to 50 g/10 min are recorded and reported here.

In another embodiment, the functionalized olefin-based polymer is a functionalized ethylene-based polymer, and preferably a functionalized ethylene/α-olefin interpolymer, having a density greater than or equal to 0.84 g/cc, preferably greater than or equal to 0.84 g /cc. equal to 0.85 g/cc and more preferably greater than 0.86 g/cc. In another embodiment, the functionalized olefin-based polymer is a functionalized ethylene-based polymer, and preferably a functionalized ethylene/α-olefin interpolymer, having a density less than or equal to 0.91 g/cc, preferably less than or equal to 0.91 g/cc. equal to 0.90 g/cc and more preferably less than or equal to 0.89 g/cc.

In another embodiment, the functionalized olefin-based polymer is an ethylene-functionalized polymer, and preferably an ethylene/α-olefin-functionalized interpolymer, having a density of 0.84 g/cc to 0.91 g/cc. , preferably from 0.85 g/cc to 0.90 g/cc and more preferably from 0.86 g/cc to 0.89 g/cc. All individual values and sub-ranges from 0.84 g/cc to 0.91 g/cc are recorded and shown here.

In another embodiment, the functionalized olefin-based polymer is an amine-functionalized olefin-based polymer, preferably an amine-functionalized ethylene-based polymer, and more preferably an amine-functionalized ethylene/α-olefin interpolymer. In another embodiment, the α-olefin is a C3-C20 α-olefin, preferably a C3-C10 α-olefin, and more preferably propylene, 1-butene, 1-hexene or 1-octene.

In another embodiment, the functionalized olefin-based polymer is a hydroxyl-functionalized olefin-based polymer, preferably a hydroxyl-functionalized ethylene-based polymer, and more preferably a hydroxyl-functionalized ethylene/α-olefin interpolymer. In another embodiment, the α-olefin is a C3-C20 α-olefin, preferably a C3-C10 α-olefin, and more preferably propylene, 1-butene, 1-hexene or 1-octene.

In another embodiment, the functionalized olefin-based polymer is a hydroxyl-functionalized olefin-based polymer, preferably a hydroxyl-functionalized ethylene-based polymer, and more preferably a hydroxyl-functionalized ethylene/α-olefin interpolymer. In another embodiment, the α-olefin is a C3-C10 α-olefin, preferably a C3-C10 α-olefin, and more preferably propylene, 1-butene, 1-hexene or 1-octene.

In one embodiment, the functionalized ethylene-based polymer is an anhydride-functionalized ethylene-based polymer, and preferably an anhydride-functionalized ethylene/α-olefin interpolymer having a melt index (I₂) greater than or equal to 0.1 g/10 min, preferably greater than or equal to 0.5 g/10 min, and most preferably greater than or equal to 1 g/10 min as determined using ASTM D-1238 (190° C, 2.16 kg payload). In another embodiment, the functionalized ethylene-based polymer is an anhydride-functionalized ethylene-based polymer, and preferably an anhydride-functionalized ethylene/α-olefin interpolymer having a melt index (I₂) less than or equal to 50 g/10 min, preferably less than or equal to 20 g/10 min and most preferably less than or equal to 10 g/10 min as determined using ASTM D-1238 (190°C, 2, 16 kg payload).

In another embodiment, the functionalized ethylene-based polymer is an anhydride-functionalized ethylene-based polymer, and preferably an anhydride-functionalized ethylene/α-olefin interpolymer, having a density greater than or equal to 0.84 g/cc, preferably greater than or equal to 0.85 g/cc and most preferably greater than 0.86 g/cc. In another embodiment, the functionalized ethylene-based polymer is an anhydride-functionalized ethylene-based polymer, and preferably an anhydride-functionalized ethylene/α-olefin interpolymer, having a density less than or equal to 0.91 g/cc, preferably less than or equal to 0.90 g/cc and more preferably less than or equal to 0.89 g/cc.

2. Polyolefin polymers used as the base polymer for functionalized olefin-based polymers

Examples of olefin-based polymers include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), linear ethylene/α-olefin interpolymers, ethylene/α-olefin interpolymers. essentially linear or multi-olefinic polymers. interpolymer block.

Suitable base polymers also include polypropylene homopolymers and propylene copolymers and other olefin-based polymers such as those formed from one or more C4-C20 alpha-olefins. Olefin-based polymers may optionally contain copolymerizable conjugated dienes, non-conjugated dienes, and/or vinyl monomers.

i) Ethylene-based polymers for functionalized olefin-based polymers

Preferred maleic anhydride graft polymers include Amplify™ polymers available from The Dow Chemical Company. Additional examples include FUSABOND (available from DuPont), EXXELOR (available from ExxonMobil), and POLYBOND (available from Chemtura).

In one embodiment, the maleic anhydride-grafted polymer comprises from 0.3% to 1.5% by weight of grafted maleic anhydride, based on the total weight of the grafted polymer. In another embodiment, the maleic anhydride-grafted polymer is an ethylene-based maleic anhydride-grafted polymer. In another embodiment, the maleic anhydride-grafted polymer is a maleic anhydride-grafted ethylene/α-olefin interpolymer.

As discussed above, suitable ethylene-based polymers include, for example, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), homogeneously branched linear ethylene polymers, homogeneously branched substantially linear ethylene polymers (i.e., homogeneously branched long chain branched ethylene polymers) and ethylene or olefin multiblock interpolymers.

High density polyethylene (HDPE), useful as the polyolefin resin, typically has a density of from about 0.94 to about 0.97 g/cc. Commercial examples of HDPE are readily available on the market. Other suitable ethylene polymers include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and linear very low density polyethylene (VLDPE). Low density polyethylene (LDPE) is typically manufactured under high pressure using free radical polymerization conditions. Low density polyethylene typically has a density of 0.91 to 0.94 g/cc.

Linear low-density polyethylene (LLDPE) is characterized by little or no long chain branching, unlike traditional LDPE. Processes for making LLDPE are well known in the art and commercial grades of this polyolefin resin are available. LLDPE is generally produced in gas phase fluidized bed reactors or liquid phase solution process reactors using a Ziegler-Natta catalyst system.

Linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), linear homogeneously branched ethylene interpolymers, substantially linear homogeneously branched ethylene interpolymers, or multiblock olefin interpolymers typically have at least one olefin polymerized therein. α-Olefin. As used herein, the term "interpolymer" indicates that the polymer can be a copolymer, a terpolymer, or any polymer having more than one polymerized monomer. Monomers usefully copolymerized with ethylene to prepare the interpolymer include C3-C20 α-olefins, more preferably C3-C10 α-olefins and especially propylene, butene-1, pentene-1, hexene-1, 4-methyl-1-pentene, 1-heptene and 1-octene. Particularly preferred comonomers include propylene, 1-butene, 1-hexene and 1-octene.

In general, suitable ethylene polymers have a melt index of 12, less than or equal to 1500 g/10 min, preferably less than or equal to 1000 g/10 min, most preferably even less than or equal to 500 g/10 min, more preferably less than or equal to 100 g/10 min. 10 min and most preferably less than or equal to 50 g/10 min measured according to ASTM 1238, condition 190°C/2.16 kg.

Commercial examples of suitable ethylene-based interpolymers include ENGAGE™, ATTANE™, AFFINITY™, DOWLEX™, ELITE™, all available from The Dow Chemical Company; EXCEED™ and EXACT™ available from Exxon Chemical Company; and TAFMER™ polymers available from Mitsui Chemical Company.

The terms "homogeneously" and "homogeneously branched" are used in relation to an ethylene/α-olefin interpolymer in which the α-olefin comonomer is randomly distributed within a given polymer molecule and substantially all polymer molecules have the same ethylene ratio to comonomer. Homogeneously branched ethylene interpolymers that can be used in the practice of this invention include linear ethylene interpolymers and substantially linear ethylene interpolymers.

Homogeneously branched linear ethylene interpolymers include ethylene polymers that lack long chain branching but have short chain branching derived from the comonomer polymerized in the interpolymer and are homogeneously distributed both within the same polymer chain and between different polymer chains. That is, homogeneously branched linear ethylene interpolymers lack long chain branching as is the case with linear low density polyethylene polymers or linear high density polyethylene polymers made using branch distribution polymerization processes. Commercial examples of linear branched ethylene/α-olefin interpolymers include TAFMER ™ polymers supplied by Mitsui Chemical Company and EXACT ™ polymers supplied by ExxonMobil Chemical Company.

Substantially linear ethylene interpolymers used in the present invention are described in US Patent Nos. 5,272,236; 5,278,272; 6,054,544; 6,335,410 and 6,723,810; the entire contents of each are incorporated herein by reference. Substantially linear ethylene interpolymers are those in which the comonomer is randomly distributed within a given interpolymer molecule and in which essentially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer. In addition, the substantially linear ethylene interpolymers are homogeneously branched ethylene interpolymers having long chain branching. The long chain branches have the same comonomer distribution as the polymeric backbone and can be about the same length as the length of the polymeric backbone. "Substantially linear" generally refers to a polymer that is replaced by an average of from 0.01 long chain branches per 1000 carbons to 3 long chain branches per 1000 carbons. The length of a long chain branch is greater than the carbon length of a short chain branch formed by incorporation of a comonomer into the polymer backbone.

Some polymers can be replaced from 0.01 long chain branching per 1000 carbons to 1 long chain branching per 1000 carbons, or from 0.05 long chain branching per 1000 carbons to 1 long chain branching per 1000 carbons, or from 0.3 long chain branching branches per 1000 carbons to 1 long chain branching per 1000 carbons. Commercial examples of substantially linear polymers include ENGAGE™ polymers and AFFINITY™ polymers (both available from The Dow Chemical Company).

Substantially linear ethylene interpolymers form a unique class of homogeneously branched ethylene polymers. They differ significantly from the well-known class of conventional homogeneously branched linear ethylene interpolymers taught by Elston in U.S. Patent No. 3,645,992 and, moreover, do not belong to the same class as polymerized linear ethylene polymers. B. ultra-low density polyethylene (ULDPE), linear low density polyethylene (LLDPE) or high density polyethylene (HDPE) prepared, for example, using the methods described by Anderson et al. in U.S. Patent No. 4,076,698); nor do they belong to the same class as radical-initiated, highly branched, low-density polyethylenes such as low-density polyethylene (LDPE), ethylene-acrylic acid copolymers (EAA), and ethylene-vinyl acetate copolymers (EVA). ).

The homogeneously branched, substantially linear ethylene interpolymers useful in the invention have excellent processability while having a relatively narrow molecular weight distribution. Surprisingly, the fluidity ratio (I₁₀/YO₂), according to ASTM D 1238, essentially linear ethylene interpolymers can vary greatly and essentially independently of molecular weight distribution (M_W/METRO_Norteor MWD). This surprising behavior is in complete contrast to that of conventional homogeneously branched linear ethylene interpolymers such as those disclosed by Elston in US Patent No. 3,645,992 and Ziegler-Natta polymerized linear polyethylene interpolymers. for example by Anderson et al. in U.S. Patent No. 4,076,698. In contrast to essentially linear ethylene interpolymers, linear ethylene interpolymers (whether homogeneously or heterogeneously branched) have rheological properties such that as the molecular weight distribution increases, the I₁₀/YO₂the value also increases.

"Long Chain Branching (LCB)" can be determined by standard techniques known in the industry, such as¹³C nuclear magnetic resonance (¹³C NMR spectroscopy), for example using the method of Randall (Rev. Micromole. Chem. Phys., C29 (2&3), pp. 285-297). Two other methods are Gel Permeation Chromatography coupled to a Small Angle Laser Light Scattering Detector (GPC-LALLS) and Gel Permeation Chromatography coupled to a Differential Viscometer Detector (GPC-DV). The use of these techniques to detect long chain branching and the underlying theories are well documented in the literature. See, for example, Zimm, B.H. and Stockmayer, W.H., J. Chem. Soc. Phys., 17, 1301 (1949) and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112.

In contrast to "substantially linear ethylene polymer" "linear ethylene polymer" means that the polymer is free of measurable or detectable long chain branching, i. H. the polymer is replaced with an average of less than 0.01 chain branching. .

Homogeneous branched ethylene polymers useful in the present invention preferably have a single melting peak as measured using differential scanning calorimetry (DSC), in contrast to heterogeneously branched linear ethylene polymers which have two or more melting peaks due to heterogeneous branching. broad branching distribution of the polymer.

Homogeneously branched linear ethylene interpolymers are a well known class of polymers having a linear polymer structure, immeasurable long chain branching and a narrow molecular weight distribution. These polymers are interpolymers of ethylene and at least one alpha-olefin comonomer having from 3 to 20 carbon atoms and are preferably copolymers of ethylene with a C3-C10 alpha-olefin and more preferably copolymers of ethylene with propylene, 1-butene, 1-pentene , 1-hexene, 1-heptene or 1-octene and more preferably propylene, 1-butene, 1-hexene or 1-octene.

This class of polymers is described, for example, by Elston in U.S. Patent No. 3,645,992 and subsequent processes have been developed to prepare such polymers using metallocene catalysts, such as shown in EP 0 129 368, EP 0 260 999, U.S. Patent No. 4,701,432; U.S. Patent No. 4,937,301; U.S. Patent No. 4,935,397; U.S. Patent No. 5,055,438; and WO 90/07526, each incorporated herein by reference. Polymers can be made by conventional polymerization methods (e.g., gas phase, slurry, solution, and high pressure).

In a preferred embodiment of the invention, an ethylene-based interpolymer is used as the base polymer in the grafting reaction. In another embodiment, the ethylene-based interpolymer is an ethylene/α-olefin interpolymer comprising at least one α-olefin. In another embodiment, the interpolymer further comprises at least one diene.

In one embodiment, the ethylene/α-olefin interpolymer has a molecular weight distribution (M_W/METRO_Norte) less than or equal to 10, and preferably less than or equal to 5. More preferably, the ethylene/α-olefin interpolymers have a molecular weight distribution of from 1.1 to 5, and most preferably from about 1.5 to 4 or 1.5 to 3. All individual values and sub-areas approx. 1 to 5 are included here and described here. In another embodiment, the ethylene/α-olefin interpolymer is a homogeneously branched linear ethylene/α-olefin interpolymer or a substantially linear homogeneously branched ethylene/α-olefin interpolymer.

Comonomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene, unconjugated dienes, polyenes. Butadiene, isoprene, pentadiene, hexadiene (e.g. 1,4-hexadiene), octadiene, styrene, halogen-substituted styrene, alkyl-substituted styrene, tetrafluoroethylene, vinylbenzocyclobutene, naphthene, cycloalkene (e.g. cyclopentene, cyclohexene, cyclooctene ) and their mixtures. Typically and preferably, ethylene is copolymerized with a C3-C20 alpha-olefin. Preferred comonomers include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and more preferably include propene, 1-butene, 1-hexene and 1-octene.

Exemplary α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene and 1-decene. The alpha-olefin is desirably a C3-C10 alpha-olefin. Preferably the α-olefin is propylene, 1-butene, 1-hexene or 1-octene. Illustrative interpolymers include ethylene/propylene (EP) copolymers, ethylene/butene (EB) copolymers, ethylene/hexene (EH) copolymers, ethylene/octene (EO) copolymers, ethylene/α-olefin/modified diene interpolymers (EAODM) such as ethylene/propylene/modified diene interpolymers (EPDM) and ethylene/propylene/octene terpolymers. Preferred copolymers include EP, EB, EH and EO polymers.

Suitable comonomers of diene and triene include 7-methyl-1,6-octadiene; 3,7-dimethyl-1,6-octadiene; 5,7-dimethyl-1,6-octadiene; 3,7,11-trimethyl-1,6,10-octatriene; 6-methyl-1,5-heptadiene; 1,3-butadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene; 1,9-decadiene; 1,10 undecads; norbornene; tetracyclododecene; or mixtures thereof and preferably butadiene; hexadienes; and octadienes; and most preferably 1,4-hexadiene; 1,9-decadiene; 4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; dicyclopentadiene; and 5-ethylidene-2-norbornene (ENB).

Additional unsaturated comonomers include 1,3-butadiene, 1,3-pentadiene, norbornadiene and dicyclopentadiene; C8-40 vinyl aromatic compounds including styrene, o-, m- and p-methyl styrene, divinyl benzene, vinyl biphenyl, vinyl naphthalene; and halo-substituted C8-40 vinyl aromatics such as chlorostyrene and fluorostyrene.

In another embodiment, the ethylene/α-olefin interpolymer has a melt index (I₂) from 0.01 g/10 min to 1500 g/10 min, preferably from 0.1 g/10 min to 1000 g/10 min and more preferably from 0.5 g/10 min to 500 g/10 min or from 1 g/10 min to 100 g/10 min determined using ASTM D-1238 (190°C, 2.16 kg load). All individual values and partial ranges from 0.01 g/10 min to 1500 g/10 min are included and described here.

In another embodiment, the ethylene/α-olefin interpolymer has a percent crystallinity of less than or equal to 60 percent, preferably less than or equal to 50 percent, and most preferably less than or equal to 40 percent. measured with DSC. Preferably such polymers have a percent crystallinity of from 2% to 60%, inclusive of all individual values and sub-ranges from 2% to 60%. These individual values and sub-areas are described here.

In another embodiment, the ethylene/α-olefin interpolymer has a density of less than or equal to 0.93 g/cc, preferably less than or equal to 0.92 g/cc, and most preferably less than or equal to 0.91 g/cc. direct current . In another embodiment, the ethylene/α-olefin interpolymer has a density greater than or equal to 0.85 g/cc, preferably greater than or equal to 0.86 g/cc, and most preferably greater than or equal to 0.87 g/cc. DISPLAY.

In another embodiment, the ethylene/α-olefin interpolymer has a density of 0.85 g/cm³a 0,93 g/cm³and preferably 0.86 g/cm³a 0,92 g/cm³and more preferably 0.87 g/cm³a 0,91 g/cm³. All individual values and partial areas of 0.85 g/cm³a 0,93 g/cm³they are included and reported here.

In another embodiment, the ethylene/α-olefin interpolymer has a PRR greater than or equal to 4, preferably greater than or equal to 8, as described below.

The viscosity of the interpolymer is conveniently measured in poise (dyne-second/square centimeter (d-sec/cm²)) at shear rates in the range of 0.1-100 radians per second (rad/sec) and at 190°C, under a nitrogen atmosphere, using a dynamic mechanical spectrometer (such as a RMS-800 or ARES from Rheometrics), under a dynamic sweep performed from 0.1 to 100 rad/sec. The viscosities at 0.1 rad/s and 100 rad/s can each be represented as V_0,1is V₁₀₀, with a ratio between the two denoted as RR and expressed as V_0,1/V₁₀₀.

The PRR value is calculated using the following formula:
PRR=RR+[Interpolymer Mooney Viscosity 3.82 (ML ₁₊₄a 125°C)]x0,3.
The PRR determination is in US Patent No. 6,680,361, incorporated herein by reference in its entirety.

In one embodiment, the ethylene/alpha-olefin interpolymer has a PRR of 1-70 or 4-70. In another embodiment the ethylene/alpha-olefin interpolymer has a PRR of 4-70 or 8-70. In this embodiment the ethylene/α-olefin interpolymer has a PRR of 12 to 60, preferably 15 to 55, and most preferably 18 to 50. Current commercial ethylene/α-olefin interpolymers with normal LCB levels typically have PRR values of less than 3. In another embodiment, the ethylene/α-olefin interpolymer has a PRR of less than 3, and preferably less than 2. In another embodiment, the ethylene/α-olefin interpolymers have a PRR of -1 to 3, preferably 0.5 to 3 , and most preferably 1 to 3. All individual PRR values and sub-ranges from -1 to 70 are included in this document and described herein.

T-type branching is typically obtained by copolymerization of ethylene or other alpha-olefins with unsaturated macromonomers at the chain ends in the presence of a constrained geometry catalyst under appropriate reactor conditions such as those described in WO 00/26268 and equivalents. US Patent No. 6,680,361, which is hereby incorporated by reference in its entirety. As discussed in WO 00/26268, the efficiency or yield of the manufacturing process decreases significantly as the degree of T-type branching increases until it reaches the point where production becomes uneconomical. T-type LCB polymers can be produced by metallocene catalysts with no measurable gels, but with very high levels of T-type LCB. Because the macromonomer that is incorporated into the growing polymer chain has only one reactive site of unsaturation, the result is Polymer only contains side chains of different lengths and at different distances along the polymer main chain.

H-type branching is typically obtained by copolymerization of ethylene or other alpha-olefins with a divalent diene that is reactive with a non-metallocene-type catalyst in the polymerization process. As the name suggests, diene connects one polymer molecule to another polymer molecule via the diene bridge, the resulting polymer molecule looks like an “H” which could be described as a cross-link rather than a long chain branch. H-type branching is typically used when extremely high levels of branching are desired. If too much diene is used, the polymer molecule may become over-branched or cross-linked, causing the polymer molecule to become insoluble in the reaction solvent (in a solution process) and thus causing the polymer molecule to break out, causing the formation of gel particles in the polymer.

In addition, the use of H-type branching agents can deactivate metallocene catalysts and reduce catalyst efficiency. Therefore, when H-type branching agents are used, the catalysts used are generally not metallocene catalysts. The catalysts used to make the H-type branched polymers in US Patent No. 6,372,847 are vanadium-type catalysts.

T-type LCB polymers are disclosed in US Patent No. 5,272,236 wherein the LCB grade is 0.01 LCB/1000 carbons to 3 LCB/1000 carbons and the catalyst is a constrained geometry catalyst. After P. Doerpinghaus and D. Baird, inthe journal of rheology,47(3), pp. 717-736, May/June 2003, "Separating the effects of sparse long-chain branching on rheology from these due to Molecular Weight in Polyethylenes", Free radical processes such as those used to produce polyethylene Density (LDPE) are used. ), produce polymers with extremely high LCB contents. For example, the NA952 resin of Doerpinghaus and Baird, Table I, is an LDPE made by a free radical process and contains 3.9 LCB/1000 carbons according to Table II. Ethylene-alpha-olefins (ethylene-octene copolymers), available from The Dow Chemical Company (Midland, Michigan, USA), which are believed to have intermediate LCB values include Affinity PL1880 and Affinity PL1840 resins in Tables I and II, respectively, and contain 0.018 and 0.057 LCB/1000 carbons.

In one embodiment of the invention, the ethylene/α-olefin component has T-type LCB levels that far exceed commercially available ethylene/α-olefin levels. Table 1A lists the LCB levels of various types of ethylene/α-olefin interpolymers useful in the invention. In another embodiment, the ethylene/α-olefin interpolymers have a PRR greater than or equal to 4.

In another embodiment, the ethylene/α-olefin interpolymers have a PRR greater than or equal to 4, preferably greater than or equal to 8, and a molecular weight distribution (MWD) of 1.1 to 5, preferably 1.5 to 4.5 . more preferably from 1.8 to 3.8 and most preferably from 2.0 to 3.4. All individual values and sub-areas 1.1 to 5 are included here and are reported here. In another embodiment, the ethylene/α-olefin interpolymers have a density less than or equal to 0.93 g/cc, preferably less than or equal to 0.92 g/cc, and most preferably less than or equal to 0.91 g/cc. direct current . In another embodiment, the ethylene/α-olefin interpolymers have a density greater than or equal to 0.86 g/cc, preferably greater than or equal to 0.87 g/cc, and most preferably greater than or equal to 0.88 g/cc. DISPLAY. In another embodiment, the ethylene/alpha-olefin interpolymers have a density of from 0.86 g/cc to 0.93 g/cc and all individual values and sub-ranges from 0.86 g/cc to 0.93 g/cc cc cc are included and described here.

In another embodiment, the ethylene/α-olefin interpolymers have a PRR greater than or equal to 4, preferably greater than or equal to 8, and a melt index of 12, greater than or equal to 0.1 g/10 min, preferably greater or equal to 0.5 g/10 min, or greater than or equal to 1.0 g/10 min. In another embodiment, the ethylene/α-olefin interpolymers have a melt index of 12 less than or equal to 30 g/10 min, preferably less than or equal to 25 g/10 min and most preferably less than or equal to 20 g/10 min. In another embodiment, the ethylene/α-olefin interpolymers have a melt index 12 of from 0.1 g/10 min to 30 g/10 min, preferably from 0.1 g/10 min to 20 g/10 min and more preferably from 0.1 g/10 min to 15 g/10 min All individual values and partial ranges of 0.1 g/10 min to 30 g/10 min are recorded and reported here.

Ethylene/α-olefin interpolymers useful in the invention can be obtained by the method disclosed in US Patent No. 6,680,361 (see also WO 00/26268). A representative list of suitable interpolymers is shown in Table 1A below. EAO-1, EAO-2-1, EAO-8 and EAO-9 were prepared according to the procedure described in WO 00/26268 using a mixed catalyst system described in U.S. Patent No. 6,369,176, fully referenced herein Reference included. EAO-7-1 was prepared in double reactors according to the method described in WO 00/26268. EAO-E-A was prepared as described in U.S. Patent Nos. 5,272,236 and 5,278,272. U.S. Patent Numbers 5,272,236; 5,278,272; 6,680,361; and 6,369,176 are incorporated herein by reference in their entirety.

TABLE 1A

ethylene/α-olefin interpolymers
	mond				% by weight	density
EE. UU.	Goop	MLRA/MV	RRP	Comonômero(s)	ethylene	g/cc

Bouquets T
(low levels)
EAO-A	26.2	0,3	−2,9	buteno
EAO-B	48,6	1.2	−5,5	buteno
T-junctions (low to
trade level)
EAO-C	21.5	0,8	0,6	Octene
EAO-D	34.4	1.2	−0,8	Octene
EAO-E	34.1	1.2	−0,5	Octene
EAO-E-A	32		0	Octene	58	0,86
EAO-F	18.3	0,6	−0,5	buteno
Bouquets T
(hohe Levels)
EAO-1	40.1	3.8	29	buteno	87	0,90
EAO-2	27	2.8	22	buteno
EAO-2-1	26		19	buteno	87	0,90
EAO-3	36,8	2.4	fifteen	buteno
EAO-4	17.8	2.3	12	buteno
EAO-5	15.7	2.0	10	buteno
EAO-6	37.1	7.6	70	Propylene
EAO-7	17.4	3.4	26	69.5 wt% ethylene/	69,5
				30% by weight propylene/
				ENB 0,5%
EAO-7-1	20		21	Propylen/Dien	69,5	0,87
EAO-8	26		45	Propylene	70	0,87
EAO-9	30		17	Octene	70	0,88
Ramos H.
EAO-G	24,5	10.9		76.8 wt% ethylene/
				22.3 wt% propylene/
				ENB 0,9%
EAO-H	27	7.1	72	72 wt% ethylene/
				22 wt% propylene/
				6 % Hexadien
EAO-I	50.4	7.1		71 wt% ethylene/
				23 wt% propylene/
				6 % Hexadien
EAO-J	62,6	8.1	55	71 wt% ethylene/
				23 wt% propylene/
				6 % Hexadien

Mooney Viscosity: ML₁₊₄a 125°C

An ethylene-based polymer may have a combination of two or more suitable embodiments as described herein.

An ethylene/α-olefin interpolymer may have a combination of two or more suitable embodiments as described herein.

ii) Propylene-based polymers for functionalized olefin-based polymers

Suitable propylene-based interpolymers include propylene homopolymers, propylene interpolymers, and reactor grade polypropylene (RCPP) copolymers, which may contain about 1 to about 20 weight percent ethylene or an alpha-olefin comonomer. from 4 to 20 carbon atoms. The propylene interpolymer may be a propylene-based random or block copolymer or a terpolymer.

Suitable comonomers for polymerization with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-unidecene, 1-dodecene, and 4-methyl- 1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, vinylcyclohexane and styrene. Preferred comonomers include ethylene, 1-butene, 1-hexene and 1-octene, and most preferably ethylene.

Optionally, the propylene-based polymer comprises a monomer having at least two double bonds, which are preferably dienes or trienes. Suitable comonomers of diene and triene include 7-methyl-1,6-octadiene; 3,7-dimethyl-1,6-octadiene; 5,7-dimethyl-1,6-octadiene; 3,7,11-trimethyl-1,6,10-octatriene; 6-methyl-1,5-heptadiene; 1,3-butadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene; 1,9-decadiene; 1,10 undecads; norbornene; tetracyclododecene; or mixtures thereof; and preferably butadiene; hexadienes; and octadienes; and most preferably 1,4-hexadiene; 1,9-decadiene; 4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; dicyclopentadiene; and 5-ethylidene-2-norbornene (ENB).

Additional unsaturated comonomers include 1,3-pentadiene, norbornadiene, and dicyclopentadiene; C8-40 vinyl aromatic compounds including styrene, o-, m- and p-methyl styrene, divinyl benzene, vinyl biphenyl, vinyl naphthalene; and halo-substituted C8-40 vinyl aromatics such as chlorostyrene and fluorostyrene.

Propylene interpolymers of particular interest include propylene/ethylene, propylene/1-butene, propylene/1-hexene, propylene/4-methyl-1-pentene, propylene/1-octene, propylene/ethylene/1-butene, propylene/ethylene/ENB , propylene/ethylene/1-hexene, propylene/ethylene/1-octene, propylene/styrene and propylene/ethylene/styrene.

Suitable polypropylenes are formed by means of those skilled in the art, for example using single site catalysts (metallocene or constrained geometry) or Ziegler-Natta catalysts. Propylene and optional comonomers such as ethylene or alpha-olefin monomers are polymerized under conditions known to those skilled in the art, for example as described by Galli et al., Angew. macromole. Chemie, Vol. 120, 73 (1984), or by E.P. Moore et al. in Polypropylene Handbook, Hanser Publishers, New York, 1996, especially pages 11-98. Polypropylene polymers include Shell KF 6100 polypropylene homopolymer; Solvay KS 4005 polypropylene copolymer; Solvay KS 300 polypropylene terpolymer; and INSPIRE™ polymers and VERSIFY™ polymers, both available from The Dow Chemical Company.

Preferably, the propylene-based polymer has a melt flow rate (MFR) in the range of 0.01 to 2000 g/10 min, more preferably in the range of 0.1 to 1000 g/10 min, and most preferably 0.5 to 500 g/min . 10 mins. and more preferably from 1 to 100 g/10 min measured according to ASTM D 1238 at 230°C/2.16 kg.

In another embodiment, the propylene/α-olefin interpolymer has a melt flow rate (MFR) in the range of 0.01 to 300 grams/10 minutes, more preferably in the range of 0.1 to 200 grams/10 minutes, more preferably 0. 5 to 100 grams/10 min or 1 to 50 grams/10 min measured according to ASTM D 1238 at 230°C/2.16 kg. All individual values and sub-ranges from 0.01 to 300 grams/10 min are recorded here and described here.

The propylene-based polymer used in the present invention can have any molecular weight distribution (MWD). Broad or narrow MWD propylene-based polymers are formed by those skilled in the art. Narrow MWD propylene-based polymers can advantageously be provided by visibility slicing or by reactor grade manufacture (no visibility slicing) using single-site catalysis, or by both methods.

The propylene-based polymer can be reactor grade, visbroken, branched or coupled to provide higher nucleation and crystallization rates. The term "coupled" is used herein to refer to propylene-based polymers that are rheologically modified so that they exhibit a change in the flow resistance of the molten polymer during extrusion (e.g., in the extruder just before the annulus). To die). While "visbroken" is in the direction of chain scission, "coupled" is in the direction of crosslinking or lattice. As an example of coupling, a coupling agent (e.g., an azide compound) is added to a polypropylene polymer having a relatively high melt index such that, after extrusion, the resulting polypropylene polymer composition achieves a melt index that is substantially lower than the initial polymer melt. Flow Quotient. Preferably, for coupled or branched polypropylene, the ratio of subsequent MFR to initial MFR is less than or equal to 0.7:1, more preferably less than or equal to 0.2:1.

Branched propylene-based polymers suitable for use in the present invention are commercially available, for example, from Montell North America under the tradenames Profax PF-611 and PF-814. Alternatively, suitable coupled or branched propylene-based polymers can be prepared by means known to those skilled in the art such as peroxide or electron beam treatment, for example as described by DeNicola et al. in U.S. Patent 5,414,027 (the use of high energy (ionizing) radiation in an atmosphere of reduced oxygen content); EP 0 190 889 to Himont (electron beam irradiation of isotactic polypropylene at lower temperatures); U.S. Patent No. 5,464,907 (Akzo Nobel NV); EP 0 754 711 Solvay (peroxide treatment); and U.S. Patent Application Serial No. 09/133,576, filed August 13, 1998 (azide coupling agent). Each of these patents/applications are incorporated herein by reference.

Other suitable propylene-based polymers include VERSIFY™ polymers (The Dow Chemical Company) and VISTAMAXX™ polymers (ExxonMobil Chemical Co.), LICOCENE™ polymers (Clariant), EASTOFLEX™ polymers (Eastman Chemical Co.), REXTAC™ polymers polymers (Hunstman). and VESTOPLAST™ polymers (Degussa). Other suitable polymers include propylene-α-olefin block copolymers and interpolymers and other propylene-based block copolymers and interpolymers known in the art.

In one embodiment, the functionalized propylene-based polymer is formed from a coupled propylene-based polymer and preferably an azide-coupled propylene homopolymer. In another embodiment, the azide-coupled propylene homopolymer has a melt flow rate (MFR) of 1 to 100 g/10 min, preferably 10 to 50 g/10 min, and most preferably 20 to 40 g/10 min. (ASTM D 1238 at 230 °C/2.26kg). In another embodiment, the functionalized propylene-based polymer is a functionalized propylene homopolymer having a melt flow rate (MFR) of 50 to 500 g/10 min, preferably 80 to 450 g/10 min (ASTM D 1238 to 230°C/2.26 kg) .

In a preferred embodiment of the invention, a propylene-based interpolymer is used as the base polymer in the grafting reaction. In another embodiment, the propylene-based interpolymer is a propylene/α-olefin interpolymer comprising at least one α-olefin. In another embodiment, the interpolymer further comprises at least one diene. In another embodiment, the propylene-based interpolymer is a propylene/ethylene interpolymer.

Preferred comonomers include, but are not limited to, ethylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, unconjugated dienes, polyenes B. butadienes, isoprenes, pentadienes, hexadienes (e.g. 1,4-hexadiene), octadienes, styrene, halogen-substituted styrene, alkyl-substituted styrene, tetrafluoroethylene, vinylbenzocyclobutene, naphthenes, cycloalkenes (e.g. cyclopentene, cyclohexene , cyclooctene) and their mixtures. Typically and preferably the comonomer is an ethylene or a C₄-C₂₀α-Olefin. Preferred comonomers include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and more preferably include ethylene, 1-butene, 1-hexene and 1-octene.

In another embodiment, the propylene-based polymer is a propylene/α-olefin interpolymer having a molecular weight distribution less than or equal to 5, and preferably less than or equal to 4, and more preferably less than or equal to 3. More preferably, the propylene/α- Olefin interpolymer has a molecular weight distribution of from 1.1 to 5, more preferably from 1.5 to 4.5, and most preferably from 2 to 4. In another embodiment, the molecular weight distribution is less than 3.5, preferably less than 3.0, more preferably less than 2.8, more preferably less than 2.5, and most preferably less than 2.3. All individual values and sub-ranges from approx. 1 to 5 are included here and described here.

In another embodiment, the propylene/α-olefin interpolymer has a melt flow rate (MFR) of less than or equal to 2000 g/10 min, preferably less than or equal to 1000 g/10 min, and most preferably less than or equal to 500 g/10 min and more preferably less than or equal to 100 g/10 min measured according to ASTM D 1238 at 230°C/2.16 kg. In another embodiment, the propylene/α-olefin interpolymer has a melt flow rate (MFR) greater than or equal to 0.01 g/10 min, preferably greater than or equal to 0.1 g/10 min, most preferably greater than or equal to 0.5 g/10 min or greater than or equal to 1 g/10 min measured according to ASTM D 1238 at 230°C/2.16 kg.

In another embodiment, the propylene/α-olefin interpolymer has a melt flow rate (MFR) in the range of 0.01 to 2000 grams/10 minutes, more preferably in the range of 0.1 to 1000 grams/10 minutes, more preferably 0. 5 to 500 grams/10 min or 1 to 100 grams/10 min measured according to ASTM D 1238 at 230°C/2.16 kg. All individual values and sub-ranges from 0.01 to 2000 grams/10 min are recorded here and described here.

In another embodiment, the propylene/α-olefin interpolymer has a percent crystallinity of less than or equal to 50 percent, preferably less than or equal to 40 percent, and most preferably less than or equal to 35 percent. measured with DSC. Preferably such polymers have a percent crystallinity of from 2% to 50%, inclusive of all individual values and sub-ranges of from 2% to 50%. These individual values and sub-areas are described here.

In another embodiment, the propylene/α-olefin interpolymer has a density of less than or equal to 0.90 g/cc, preferably less than or equal to 0.89 g/cc, and most preferably less than or equal to 0.88 g/cc. direct current . In another embodiment, the propylene/α-olefin interpolymer has a density greater than or equal to 0.83 g/cc, preferably greater than or equal to 0.84 g/cc, and most preferably greater than or equal to 0.85 g/cc. DISPLAY.

In another embodiment, the propylene/α-olefin interpolymer has a density of 0.83 g/cm³a 0,90 g/cm³and preferably 0.84 g/cm³a 0,89 g/cm³and more preferably 0.85 g/cm³a 0,88 g/cm³. All individual values and partial areas of 0.83 g/cm³a 0,90 g/cm³, are included in this document and are disclosed in this document.

In another embodiment, the propylene-based polymer is a propylene/ethylene interpolymer having a molecular weight distribution of less than or equal to 5, and preferably less than or equal to 4, and more preferably less than or equal to 4 to 3. More preferably, the propylene/ethylene interpolymer has a molecular weight distribution of from 1.1 to 5, and more preferably from 1.5 to 4.5, and most preferably from 2 to 4. In another embodiment, the weight distribution molecular weight molecular weights are preferably less than about 3.5, less than 3.0, more preferably less than 2.8, more preferably less than 2.5, and most preferably less than 2.3. All individual values and sub-ranges from approx. 1 to 5 are included here and described here.

In another embodiment, the propylene/ethylene interpolymer has a melt flow rate (MFR) less than or equal to 2000 g/10 min, preferably less than or equal to 1000 g/10 min, and most preferably less than or equal to 1000 g/10 min . at 500 g/10 min and more preferably less than or equal to 100 g/10 min measured according to ASTM D 1238 at 230°C/2.16 kg. In another embodiment, the propylene/α-olefin interpolymer has a melt flow rate (MFR) greater than or equal to 0.01 g/10 min, preferably greater than or equal to 0.1 g/10 min, most preferably greater than or equal to 0.5 g/10 min or greater than or equal to 1 g/10 min measured according to ASTM D 1238 at 230°C/2.16 kg.

In another embodiment, the propylene/ethylene interpolymer has a melt flow rate (MFR) in the range of 0.01 to 2000 grams/10 minutes, more preferably in the range of 0.1 to 1000 grams/10 minutes, more preferably 0.5 up to 500 grams / 10 minutes. 10 min or 1 to 100 g/10 min measured according to ASTM D 1238 at 230°C/2.16 kg. All individual values and sub-ranges from 0.01 to 2000 grams/10 min are recorded here and described here.

In another embodiment, the propylene/ethylene interpolymer has a melt flow rate (MFR) in the range of 0.01 to 300 grams/10 minutes, more preferably in the range of 0.1 to 200 grams/10 minutes, most preferably 0. 5 to 100 grams / 10 minutes. 10 min or 1 to 50 g/10 min measured according to ASTM D 1238 at 230°C/2.16 kg. All individual values and sub-ranges from 0.01 to 300 grams/10 min are recorded here and described here.

In another embodiment, the propylene/ethylene interpolymer has a percent crystallinity of less than or equal to 50 percent, preferably less than or equal to 40 percent, and most preferably less than or equal to 35 percent as measured by DSC. Preferably such polymers have a percent crystallinity of from 2% to 50%, inclusive of all individual values and sub-ranges of from 2% to 50%. These individual values and sub-areas are described here.

In another embodiment, the propylene/ethylene interpolymer has a density of less than or equal to 0.90 g/cc, preferably less than or equal to 0.89 g/cc, and most preferably less than or equal to 0.88 g/cc . DISPLAY. In another embodiment, the propylene/α-olefin interpolymer has a density greater than or equal to 0.83 g/cc, preferably greater than or equal to 0.84 g/cc, and most preferably greater than or equal to 0.85 g/cc. DISPLAY.

In another embodiment, the propylene/ethylene interpolymer has a density of 0.83 g/cm³a 0,90 g/cm³and preferably 0.84 g/cm³a 0,89 g/cm³and more preferably 0.85 g/cm³a 0,88 g/cm³. All individual values and partial areas of 0.83 g/cm³a 0,90 g/cm³, are included in this document and are disclosed in this document.

In one embodiment, the propylene-based polymers comprise propylene-derived units in an amount of at least about 60%, preferably at least about 80%, and most preferably at least about 85% by weight of the interpolymer (based on the total weight of the monomers). ). polymerizable). ). The typical amount of ethylene-derived units in propylene/ethylene copolymers is at least about 0.1, preferably at least about 1, and most preferably at least about 5 weight percent and the maximum amount of ethylene-derived units is the ethylene present therein Copolymers is usually no more than about 35, preferably no more than about 30, and most preferably no more than about 20 weight percent of the copolymer (based on the total weight of the polymerizable monomers). The amount of units derived from one or more additional unsaturated comonomers, if present, is typically at least 0.01%, preferably at least 1%, and most preferably at least 5% by weight, and the typical maximum amount of units that can be derived from the unsaturated comonomer(s) normally does not exceed about 35, preferably does not exceed about 30, and most preferably does not exceed about 20 weight percent of the interpolymer (based on the total weight of the polymerizable monomers). The total combined number of units derived from ethylene and all unsaturated comonomers usually does not exceed about 40, preferably does not exceed about 30, and most preferably does not exceed about 20 weight percent of the interpolymer (based on the total weight of the polymerizable polymer). monomers).

In another embodiment, the propylene-based polymers comprise propylene and one or more unsaturated comonomers other than ethylene, which typically also comprise propylene-derived units in an amount of at least about 60, preferably at least about 70, and most preferably at least about 80 weight percent interpolymer ( based on the total weight of the polymerizable monomers). The one or more unsaturated comonomers of the interpolymer comprise at least about 0.1, preferably at least about 1, and most preferably at least about 3 weight percent, and the typical maximum amount of unsaturated comonomer does not exceed about 40, and preferably does not exceed about 30 weight percent % of the interpolymer (based on the total weight of the polymerizable monomers).

In one embodiment, propylene-based polymers are prepared using a metal-centered heteroaryl ligand catalyst in combination with one or more activators, such as an alumoxane. In certain embodiments, the metal is one or more of hafnium and zirconium. In particular, in certain catalyst embodiments, it has been found that the use of a hafnium metal is preferred over a zirconium metal for heteroaryl ligand catalysts. Catalysts in certain embodiments are compositions comprising the ligand and the metal precursor, and may optionally additionally contain an activator, combination of activators, or package of activators.

Catalysts used to prepare the propylene-based polymers also include catalysts comprising ancillary ligand hafnium complexes, ancillary ligand zirconium complexes and optionally activators which catalyze polymerisation and copolymerisation reactions, particularly with monomers which are olefins, diolefins or other unsaturated compounds. Zirconium complexes and hafnium complexes can be used. Metal-ligand complexes can exist in the neutral or charged state. The ratio of ligand to metal can also vary, with the exact ratio depending on the nature of the ligand and the metal-ligand complex. The metal-ligand complex(es) can take various forms, for example they can be monomeric, dimeric or even higher order. Suitable catalytic structures and associated ligands are described in US Patent No. 6,919,407 at column 16, line 6 through column 41, line 23, which is incorporated herein by reference. In an additional embodiment, the propylene-based polymer comprises at least 50% by weight propylene (based on the total amount of polymerizable monomers) and at least 5% by weight ethylene (based on the total amount of polymerizable monomers) and has¹³The 13 C NMR peaks correspond to an area error at approximately 14.6 and 15.7 ppm and the peaks are of approximately the same intensity (e.g. see US patent here for reference).

Propylene-based polymers can be prepared by any suitable method. In one embodiment, the process reagents, i. H. (i) propylene, (ii) ethylene and/or one or more unsaturated comonomers, (iii) catalyst and (iv) optionally solvent and/or molecular weight regulator ( , hydrogen). fed to a single reaction vessel of any suitable design, e.g., stirred tank, closed loop, or fluidized bed. Process reagents are contacted within the reaction vessel under appropriate conditions (e.g., solution, slurry, gas phase, slurry, high pressure) to form the desired polymer, and then the reactor output is recovered for post-reaction processing. The entire effluent of the reactor can be recovered at once (as in the case of a single pass or batch reactor) or it can be recovered as an effluent stream constituting only a portion, usually a minor portion. of the reaction mass (as in the case of a continuous process reactor where a reactor exit stream is purged at the same rate as reactants are added to maintain the polymerization at steady state conditions). "Reaction mass" means the contents within a reactor, typically during or after polymerization. The reaction mass includes reagents, solvent (if any), catalyst, and products and by-products. The recovered solvent and unreacted monomers can be returned to the reaction vessel. Suitable polymerization conditions are described in US Patent No. 6,919,407, column 41, line 23 through column 45, line 43, incorporated herein by reference.

A propylene-based polymer may have a combination of two or more suitable embodiments as described herein.

A propylene/α-olefin interpolymer may have a combination of two or more suitable embodiments as described herein.

A propylene/ethylene interpolymer may have a combination of two or more suitable embodiments as described herein.

iii) Olefin multiblock interpolymer for olefin-based functionalized polymer

Multiblock olefinic interpolymers, and preferably copolymers, as described herein can also be base polymers for the functionalized polyolefin.

vi) Olefin-based polymer blends for functionalized olefin-based polymers

In one embodiment of the invention, a blend of two or more functionalized olefin-based polymers can be used as the functionalized olefin-based polymer component, such as a blend of a functionalized ethylene-based polymer, as described below. described herein, and a functionalized propylene-based polymer as described herein.

Alternatively, a blend of one or more functionalized olefin-based polymers, such as described herein, and one or more olefin-functionalized multiblock interpolymers, such as described herein, may be used.

In one embodiment, an ethylene-based polymer functionalized as described herein can be blended with a functionalized olefin multiblock interpolymer as described herein.

In another embodiment, a functionalized propylene-based polymer as described herein can be blended with a functionalized olefin multiblock interpolymer as described herein. Alternatively, an ethylene-based polymer functionalized as described herein and a propylene-based polymer functionalized as described herein may be blended with a functionalized olefin multiblock interpolymer as described herein.

3. Grafting agents and initiators for olefin-based functionalized polymers

The olefin polymers described herein can be modified by typical grafting, hydrogenation, nitrene insertion, or other functionalization reactions well known to those skilled in the art. Preferred functionalizations are grafting reactions using a free radical mechanism.

A variety of radically graftable species can be attached to the polymer, either individually or as relatively short grafts. These species include unsaturated molecules each containing at least one heteroatom. These species include, but are not limited to, maleic anhydride, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride, bromomaleic anhydride, chloromaleic anhydride, nadic anhydride, methylhydroic anhydride, alkenoic anhydride. , maleic acid, fumaric acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid and the corresponding Diels-Alder esters, imides, salts and adducts of these compounds. These types also include silane compounds.

Free radically graftable species of the silane class of materials can be attached to the polymer, individually or as relatively short grafts. These species include, but are not limited to, vinyl alkoxysilanes, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, vinyl trichlorosilane, and the like. In general, materials in this class include, but are not limited to, hydrolyzable groups such as alkoxy, acyloxy, or halide groups bonded to silicon. Materials in this class also include non-hydrolyzable groups such as alkyl and siloxy groups bonded to silicon.

Other radically graftable species can be attached to the polymer, individually or as short to long grafts. These species include methacrylic acid; acrylic acid; acrylic acid Diels-Alder adducts; methacrylates including methyl, ethyl, butyl, isobutyl, ethylhexyl, lauryl, stearyl, hydroxyethyl and dimethylaminoethyl; acrylates including methyl, ethyl, butyl, isobutyl, ethylhexyl, lauryl, stearyl, and hydroxyethyl; glycidyl methacrylate; trialkoxysilane methacrylates such as 3-(methacryloxy)propyltrimethoxysilane and 3-(methacryloxy)propyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane; acrylonitrile; 2-isopropenyl-2-oxazoline; styrene; α-methylstyrene; vinyl toluene; dichlorostyrene; N-vinylpyrrolidinone, vinyl acetate, methacryloxypropyltrialkoxysilanes, methacryloxymethyltrialkoxysilanes and vinyl chloride.

Mixtures of free-radically graftable species comprising at least one of the above species with styrene/maleic anhydride and styrene/acrylonitrile can be used as illustrative examples.

A heat grafting process is a process for the reaction; however, other grafting methods can also be used, such as photoinitiation, including various forms of radiation, electron beam, or generation of redox radicals.

The functionalization can occur via a free radical mechanism, but it can also occur on the terminal unsaturated group (e.g. vinyl group) or on an internally unsaturated group if such groups are present in the polymer. Such functionalization includes, but is not limited to, hydrogenation, halogenation (such as chlorination), ozonation, hydroxylation, sulfonation, carboxylation, epoxidation, and grafting reactions. Any functional groups such as halogen, amine, amide, ester, carboxylic acid, ether, silane, siloxane, etc., or functional unsaturated compounds such as maleic anhydride can be added through terminal or internal unsaturation by known chemistry. Other functionalization methods include those described in the following U.S. Patents 5,849,828 entitled "Metallation and Functionalization of Polymers and Copolymers"; U.S. Patent No. 5,814,708 entitled "Process for Oxidative Functionalization of Alkyl Styrene-Containing Polymers"; and U.S. patent Bei der. 5,717,039 entitled "Functionalization of Polymers Based on Koch Chemistry and Derivatives". Each of these patents is hereby incorporated by reference in its entirety.

There are several types of compounds that can initiate grafting reactions by decomposing to form free radicals, including but not limited to azo-containing compounds, peroxycarboxylic acids and peroxyesters, alkyl hydroperoxides, and dialkyl and diacyl peroxides. Many of these compounds and their properties have been described (Reference: J. Branderup, E. Immergut, E. Grulke, eds. "Polymer Handbook", 4th ed., Wiley, New York, 1999, Section II, pp. 1-76 . ). It is preferred that the species formed by decomposition of the initiator is an oxygen-based free radical. Most preferably the initiator is selected from peroxycarboxylic acid esters, peroxyketals, dialkyl peroxides and diacyl peroxides. Some of the most preferred initiators commonly used to modify the structure of polymers are listed below. The respective chemical structures and theoretical radical yields are also shown below. The theoretical free radical yield is the theoretical number of free radicals generated per mole of initiator.


		Theoretically
		Radicals
Name des Initiators	Launcher-Structure	To produce

Benzoylperoxid		2

Lauroylperoxid		2

Dicumylperoxid		2

t-Butyl-α-cumylperoxid		2

Di-t-butylperoxid		2

di-t-Amylperoxid		2

t-Butylperoxybenzoat		2

t-Amylperoxybenzoat		2

1,1-bis(t-butilperoxi)-3,3,5-trimetilciclohexano		4


α,α'-bis(t-butylperoxy)-1,3-diisopropilbenzeneo		4

α,α'-bis(t-butylperoxi)-1,4-diisopropilbenzeneo		4

2,5-Bis(t-butylperoxy)-2,5-dimethylhexan		4

2,5-Bis(t-butilperoxi)-2,5-dimetil-3-hexino		4

In one embodiment, the invention provides olefin polymers grafted with maleic anhydride. The grafted maleic anhydride-olefin interpolymer may or may not contain small amounts of hydrolysis product and/or other derivatives. In one embodiment, the grafted maleic anhydride-olefin interpolymers have a molecular weight distribution of about 1 to 7, preferably 1.5 to 6, and more preferably 2 to 5. All individual values and sub-ranges of about 1 to 7 are included and disclosed herein. those.

In another embodiment, the maleic anhydride-olefin grafted polymers have a density of 0.855 g/cc to 0.955 g/cc, preferably 0.86 g/cc to 0.90 g/cc, and most preferably 0.865 g/cc. at 0.895 g/cc. All individual values and sub-ranges from 0.84 g/cc to 0.955 g/cc are recorded and described here.

In another embodiment, the amount of maleic anhydride used in the grafting reaction is less than or equal to 10 phr (parts per hundred based on the weight of the olefinic interpolymer), preferably less than 5 phr, and most preferably 0.5 phr. 10 phr and more preferably 0.5 to 5 phr. All individual values and sub-ranges from 0.05 phr to 10 phr are recorded and described here.

In another embodiment, the amount of initiator used in the grafting reaction is less than or equal to 10 millimoles of radicals per 100 grams of olefinic interpolymer, preferably less than or equal to 6 millimoles of radicals per 100 grams of olefinic interpolymer, and most preferably less than or equal to 3 millimoles of radicals per 100 grams of olefinic interpolymer. All individual values and sub-ranges from 0.01 mmol to 10 mmol residues per 100 grams of olefinic interpolymer are included and described herein.

In another embodiment, the amount of maleic anhydride moiety grafted onto the polyolefin chain is greater than 0.05 weight percent (based on the weight of the olefinic interpolymer) as determined by titration analysis, FTIR analysis, or any other suitable method. In another embodiment, this amount is greater than 0.25% by weight and in yet another embodiment this amount is greater than 0.5% by weight. In a preferred embodiment, 0.5% to 2.0% by weight of maleic anhydride is grafted. All individual values and sub-ranges greater than 0.05 weight percent are considered within the scope of this invention and are described herein.

Maleic anhydride as well as many other species containing unsaturated heteroatoms can be grafted onto the polymer by any conventional method, typically in the presence of a free radical initiator, e.g. B. peroxide and azo compound classes, etc., or by ionizing radiation. Organic initiators are preferred, such as. any of the peroxide initiators such as e.g. B. dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2 ,5-di(tert-butylperoxy)-3-hexyne, lauryl peroxide and tert-butyl peracetate. A suitable azo compound is 2,2'-azobis(isobutyronitrile). Organic initiators have different reactivities at different temperatures and can generate different types of free radicals for grafting. One skilled in the art can select the appropriate organic primer as needed for the grafting conditions.

The amount and type of initiator, the amount of maleic anhydride, and the reaction conditions including temperature, time, shear, environment, additives, diluents, and the like used in the grafting process can affect the final structure of the maleate. Polymer. For example, the level of maleic anhydride/succinic anhydride, its oligomers and its derivatives, including hydrolysis products, that are grafted onto the grafted polymer can be affected by the above considerations. In addition, the degree and type of branching and the degree of crosslinking can also be influenced by reaction conditions and concentrations. In general, it is preferred that crosslinking be minimized during the maleating process. The composition of the base olefin interpolymer can also play a role in the final structure of the maleated polymer. The resulting structure, in turn, affects the properties and use of the final product. Normally, the amount of initiator and maleic anhydride used will not exceed that determined to provide the desired level of maleation and melt flow each required for the functionalized polymer and its subsequent use.

The grafting reaction must be conducted under conditions that maximize grafting onto the polymer structure and minimize side reactions such as homopolymerization of the grafting agent that does not graft onto the olefinic interpolymer. It is not uncommon for some proportion of the maleic anhydride (and/or its derivatives) to be grafted onto the olefin interpolymer, and it is generally desirable that unreacted grafting agent be minimized. The grafting reaction can be carried out in a molten state, in a solution, in a solid state, in a swollen state and the like. Male infusion can be performed on a wide variety of devices such as: B. but is not limited to twin screw extruders, single screw extruders, Brabenders, batch reactors and the like.

Additional embodiments of the invention provide olefin interpolymers grafted with other carbonyl containing compounds. In one embodiment, such grafted olefin interpolymers can have the same molecular weight distributions and/or similar densities as described above for grafted maleic anhydride-olefin interpolymers. Alternatively, such grafted olefin interpolymers are prepared using the same or similar amounts of grafting compound and initiator as are used for the grafted maleic anhydride-olefin interpolymers described above. Alternatively, such grafted olefinic interpolymers contain the same or similar amounts of grafted compound as the grafted maleic anhydride as described above.

Additional carbonyl-containing compounds include, but are not limited to, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride, bromaleic anhydride, chloromaleic anhydride, nadic anhydride, methylnadium anhydride, alkenyl succinic anhydride, maleic acid, fumaric acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid, their Esters, their imides, their salts and their Diels-Alder adducts.

In one embodiment, the invention provides olefin interpolymers grafted with at least one silane compound. The silane-grafted olefin interpolymer may or may not contain small amounts of hydrolysis product and/or other derivatives.

In another embodiment, the silane-grafted olefin interpolymers have a molecular weight distribution of about 1-7, preferably 1.5-6, and more preferably 2-5. All individual values and sub-ranges from about 1 to 7 are included and disclosed herein. those.

In another embodiment, the silane-grafted olefinic interpolymers have a density of from 0.855 g/cc to 0.955 g/cc, and preferably from 0.86 g/cc to 0.90 g/cc, and more preferably from 0.865 g/cc to 0.895 g/cc cc All individual values and sub-ranges from 0.84 g/cc to 0.955 g/cc are recorded and described here.

In another embodiment, the amount of silane used in the grafting reaction is greater than or equal to 0.05 phr (based on the amount of olefin interpolymer), more preferably from 0.5 phr to 6 phr, and even more preferably from 0.5 phr to 4 fr. All individual values and sub-ranges from 0.05 phr to 6 phr are recorded here and described here.

In another embodiment, the amount of initiator used in the grafting reaction is less than or equal to 4 millimoles of radicals per 100 grams of olefinic interpolymer, preferably less than or equal to 2 millimoles of radicals per 100 grams of olefinic interpolymer. and most preferably less than or equal to 1 millimole of free radicals per 100 grams of olefin interpolymer. All individual values and sub-ranges from 0.01 mmol to 4 mmol residues per 100 grams of olefinic interpolymer are included and described herein.

In another embodiment, the amount of the silane component grafted onto the polyolefin chain is greater than or equal to 0.05% by weight (based on the weight of the olefinic interpolymer) as determined by FTIR analysis or other suitable method. In another embodiment, this amount is greater than or equal to 0.5 percent by weight, and in yet another embodiment, this amount is greater than or equal to 1.2 percent by weight. In a preferred embodiment, the amount of silane builder grafted onto the olefinic interpolymer is from 0.5% to 4.0% by weight. All individual values and sub-ranges greater than 0.05 weight percent are considered within the scope of this invention and are described herein.

Suitable silanes include, inter alia, those of the general formula (I):
CH2=CR-(COO)x(CnH2Norte)jSiR'3 (I).

In this formula, R is a hydrogen atom or a methyl group; x and y are either 0 or 1, provided that when x is 1, y is 1; n is an integer from 1 to 12 inclusive, preferably from 1 to 4, and each R' is independently an organic group including but not limited to an alkoxy group having from 1 to 12 carbon atoms (e.g. methoxy, ethoxy, butoxy ), an aryloxy group (e.g. phenoxy), an araloxy group (e.g. benzyloxy), an aliphatic or aromatic siloxy group, an aromatic acyloxy group, an aliphatic acyloxy group having 1 to 12 carbon atoms (e.g. formyloxy, acetyloxy, propanoyloxy), amino or substituted Amino groups (alkylamino, arylamino) or a lower alkyl group having 1 to 6 carbon atoms.

In one embodiment, the silane compound is selected from vinyltrialkoxysilanes, vinyltriacyloxysilanes or vinyltrichlorosilane. In addition, any silane or mixture of silanes that is effectively grafted and/or crosslinked with the olefin interpolymers can be used in the practice of this invention. Suitable silanes include unsaturated silanes containing an ethylenically unsaturated hydrocarbyl group such as vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or γ-(meth)acryloxyallyl and a hydrolyzable group such as hydrocarbyloxy, hydrocarbyloxy or hydrocarbylamino group, or a halide. Examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, chloro, and alkyl or arylamino groups. Preferred silanes are unsaturated alkoxysilanes that can be grafted onto the polymer. These silanes and their method of preparation are described in more detail in Meverden et al., US Patent No. 5,266,627, which is incorporated herein by reference in its entirety. Preferred silanes include vinyltrimethoxysilane, vinyltriethoxysilane, 3-(trimethoxysilyl)propyl methacrylate (γ-(meth)acryloxypropyltrimethoxysilane), and mixtures thereof.

The silane can be grafted onto the polymer by any conventional method, generally in the presence of a free radical initiator, e.g. peroxides and azo compounds, etc., or by ionizing radiation. Organic initiators are preferred, such as any of the peroxide initiators, for example dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone, 2,5-dimethyl-2,5-di(tert- butylperoxy)hexane, lauryl peroxide and tert-butyl peracetate. A suitable azo compound is 2,2'-azobis(isobutyronitrile).

The amount of initiator and silane used affects the final structure of the silane-grafted polymer, such as the degree of grafting in the grafted polymer and the degree of crosslinking in the cured polymer. The resulting structure, in turn, affects the physical and mechanical properties of the end product. Typically, the amount of initiator and silane used will not exceed that determined to provide the desired degree of crosslinking and resulting properties in the polymer.

The grafting reaction must be conducted under conditions that maximize grafting onto the polymer backbone and minimize side reactions such as homopolymerization of the grafting agent that does not graft onto the polymer. Some silane agents undergo minimal or no homopolymerization due to steric properties in the molecular structure, low reactivity, and/or other reasons.

Curing (crosslinking) of a silanated graft is promoted with a crosslinking catalyst, and any catalyst effective to promote crosslinking of the particular grafted silane can be used. These catalysts generally include acids and bases and organometallic compounds including organic titanates, organic zirconates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin.

Dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, tin acetate, tin octoate, lead naphthenate, zinc caprylate, cobalt naphthenate, and the like can be used. The amount of catalyst depends on the particular system.

In certain embodiments of the claimed invention, dual crosslinking systems can be effectively employed using a combination of radiation, heat, moisture and crosslinking steps. For example, it may be desirable to use peroxide crosslinkers in conjunction with silane crosslinkers, peroxide crosslinkers in conjunction with radiation, or sulfur-containing crosslinkers in conjunction with silane crosslinkers. Dual crosslinking systems are described in US Patent Nos. 5,911,940 and 6,124,370, the entire contents of which are incorporated herein by reference.

4. In situ amine functionalization and in situ hydroxyl functionalization for functionalized olefin-based polymers

In a preferred embodiment of the invention, the functionalized olefin-based polymer is an amine-functionalized olefin-based polymer or a hydroxyl-functionalized olefin-based polymer. The process for preparing amine-functionalized or hydroxy-functionalized olefin-based polymer can be carried out as an extrusion step, i. H. Maleic anhydride (grafting agent) can be grafted onto the olefin-based polymer in the first section of the extruder, followed by imidization with a diamine or primary-secondary alkanolamine in the last section before pelletizing.

Alternatively, two extruders or melt mixers can be operated in series to carry out both chemical steps.

In order to prepare an amino-functionalized olefin-based polymer without concurrent crosslinking reactions in the molten state from anhydride-grafted olefin-based polymer, it is necessary to use a primary-secondary diamine of general formula H₂NR-NH-R”, where R is at least one C2 hydrocarbyl group. The diamine can be used in stoichiometric excess or stoichiometric equivalent.

Suitable secondary primary diamines include compounds of structure (I) below:
H₂NR₁—NH—R₂(JO).

In Struktur (I), R₁is a divalent hydrocarbon radical and preferably a linear hydrocarbon of the formula -(CH₂)_Norte-, where n is greater than or equal to 2 and preferably n is from 2 to 10, more preferably from 2 to 8 and even more preferably from 2 to 6. R₂is a monovalent hydrocarbon radical having at least 2 carbon atoms and may optionally be substituted by a heteroatom-containing group such as OH or SH. Preferably R² is a linear hydrocarbon of the formula -(CH₂)_Norte-CH₃, where n is from 1 to 10, and preferably n is from 1 to 9, more preferably from 1 to 7, and even more preferably from 1 to 5.

Additional primary and secondary diamines include, but are not limited to, N-ethylethylenediamine, N-phenylethylenediamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, and N-(2-hydroxyethyl)ethylenediamine . . Examples of preferred primary-secondary diamines are shown below.

Alkanolamine is a compound containing an amine group and at least one hydroxyl group, preferably only one hydroxyl group. The amine can be a primary or secondary amine and is preferably a primary amine. The polyamine is a compound containing at least two amine groups, preferably only two amine groups.

Suitable alkanolamines are those of structure (II) below:
H₂NR₁-OH(II).

In structure (II), R₁is a divalent hydrocarbon radical and preferably a linear hydrocarbon of the formula -(CH₂)_Norte-, where n is greater than or equal to 2 and preferably n is from 2 to 10, more preferably from 2 to 8 and even more preferably from 2 to 6.

Additional alkanolamines include, but are not limited to, ethanolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol, and 2-aminobenzyl alcohol.

Examples of preferred alkanolamines are shown below.

Additional examples of suitable alkanolamines and suitable diamines are represented by the following formula (III):

In formula (III), X is O or X = NR' (R' = alkyl); and each R is independently H, CH₃, the only₂CH₃; and n is 0-50. The description and preparation of hydroxylamines can be found in US Patent Nos. 3,231,619; 4,612,335; and 4,888,446; the teachings of which are incorporated herein by reference. Examples of preferred alkanolamines include 2-aminoethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 2-(2-aminoethoxy)ethanol, 1-amino-2-butanol, 2-amino-3-butanol and polyoxyalkylene glycol amines. A preferred alkanolamine is 2-aminoethanol.

In one embodiment, a maleic anhydride olefin-based polymer is functionalized with a primary secondary diamine or alkanolamine.

In another embodiment, the amount of maleic anhydride used is from 0.10% to 5.0%, preferably from 0.50% to 3.0%, and most preferably 1.0% by weight % to 2.0% by weight based on the weight of the non-functionalized grafted olefin-based polymer.

In another embodiment, the amount of peroxide used is from 0.01% to 0.5%, preferably from 0.05% to 0.3%, and most preferably 0.1% by weight. % to 0.2% by weight, based on the weight of the non-functionalized substance. Olefin based grafted polymer.

In yet another embodiment, the amount of primary-minor diamine or alkanolamine used is 1 to 10 molar equivalents, preferably 2 to 8 molar equivalents, and more preferably 4 to 6 molar equivalents of amine based on the grafted anhydride.

5. In situ functionalization reactions using maleamic acid for functionalized olefin-based polymers

The hydroxy and amino functionalized ethylene-octene copolymers can also be prepared in a single step by peroxide-initiated grafting of the corresponding maleamic acids or derivatives thereof formed by the reaction of maleic anhydride and primary alkanolamine or secondary diamine.

Maleamic acids are shown in structure (IV) below:

In structure (IV), R1 and R2 are independently hydrogen or a linear or branched C1-C20 hydrocarbyl group; R3 is hydrogen or a linear or branched C1-C20 hydrocarbyl radical; R4 is a hydrocarbyl diradical, linear or branched; X is OH or NHR₅, where R5 is a linear or branched hydrocarbon radical or a hydroxyethyl group. In a preferred embodiment, R1 and R2 are independently hydrogen or a C1-C10, preferably C1-C8, and more preferably C1-C6 hydrocarbyl radical that is linear or branched. In a preferred embodiment, R3 is hydrogen or a C1-C10, preferably C1-C8, and most preferably C1-C6 hydrocarbyl radical that is linear or branched. In a preferred embodiment, R4 is a C1-C20, preferably C1-C10, and more preferably C1-C8, and even more preferably C1-C6, hydrocarbyl radical that is linear or branched.

In a preferred embodiment, R5 is a C1-C20, preferably C1-C10, and more preferably C1-C8, and even more preferably C1-C6, hydrocarbyl radical that is linear or branched. In another embodiment, R5 is a linear -(CH2)_Norte-CH₃, where n is greater than or equal to 1 and preferably n is 1-9, more preferably 1-7 and even more preferably 1-5. Additional examples of R5 include but are not limited to the following structures: -CH₃, -CH₂CH₃, -CH₂CH₂CH₃,

-CH₂CH₂CH₂CH₃, -CH(CH₃)CH₃, -CH(CH₃)CH₂CH₃, -CH₂CH(CH₃)CH₃,

—CH(CH₃)CH₂CH₂CH₃, -CH₂CH(CH₃)CH₂CH₃, y-CH₂CH₂CH(CH₃)CH₃.

Additional structures of maleic acid are shown below. In each structure, R3 and R4 are as defined above.

Maleamic acid is preferably shown in structure (V) below:

The polyolefin is functionalized with a maleamic acid as shown in structure (V).

In one embodiment, the amount of maleamic acid used is from 0.10% to 5.0%, preferably from 0.50% to 3.0%, and most preferably 1.0% by weight. -% to 2.0% by weight, based on the weight of the non-functionalized compound. grafted polyolefin.

In another embodiment, the peroxide level used is from 0.01% to 1%, preferably from 0.01% to 0.5%, and most preferably from 0.01% to 1% by weight 0.3% by weight. and even more preferably 0.1% to 0.2% by weight based on the amount of unfunctionalized grafted polyolefin.

6. Diamine uptake process for functionalized olefin-based polymers

The olefin-based polymers described herein can also be functionalized using a diamine incorporation process. First, an olefin-based polymer is functionalized with an amine-functional reactive group. Preferably, the olefin-based polymer is functionalized with an anhydride group. At least one diamine is mixed with the functionalized olefin-based polymer at a temperature below the melting point of the olefin-based polymer and preferably at room temperature. The diamine is absorbed or incorporated into the olefin-based polymer and reacts with the reactive group of the diamine to form a succinic acid. The reaction of the diamine with the reactive functional group of the diamine to form the imide ring can then be completed by subjecting the mixture to heat treatment, for example in a melt extrusion process. Suitable diamines include the diamines discussed herein. The dipping process helps ensure that the diamine is fully mixed with the olefin-based polymer for an efficient functionalization reaction.

Suitable secondary primary diamines include compounds of structure (VI) below:
H₂NR₁—NH—R₂(VI).

Na-Struktur (VI), R₁is a divalent hydrocarbon radical and preferably a linear hydrocarbon of the formula -(CH₂)_Norte-, where n is greater than or equal to 2 and preferably n is from 2 to 10, more preferably from 2 to 8 and even more preferably from 2 to 6. R₂is a monovalent hydrocarbon radical containing at least 1 carbon atom and may optionally be substituted by a heteroatom-containing group such as OH or SH. Preferably R² is a linear hydrocarbon of the formula -(CH₂)_Norte-CH₃, where n is from 0 to 10, and preferably n is from 0 to 9, more preferably from 0 to 7, and even more preferably from 0 to 5.

Suitable primary and secondary diamines include, but are not limited to, N-methylethylenediamine, N-ethylethylenediamine, N-phenylethylenediamine, N-methyl-1,3-propanediamine, N-methylethylenediamine, N-phenyl-1,2-phenylenediamine, N - Phenyl-1,4-phenylenediamine, 1-(2-aminoethyl)piperazine and N-(2-hydroxyethyl)ethylenediamine. Examples of preferred primary-secondary diamines are shown below.

Olefin-Multiblock-Interpolymere

Multiblock olefin interpolymers are described in International Application No. PCT/US05/008917, filed March 17, 2005, U.S. Publication No. 2006/0199914, U.S. Provisional Application No. 60/876,287, U.S. Provisional Application No. 60/876,287, U.S. Application No. 11/376,873 (Dow 64405B), filed March 15, 2006, and U.S. Provisional Application No. 60/553,906, filed March 17, 2004, each of which is incorporated herein by reference in its entirety are included.

In a preferred embodiment, the olefin multiblock interpolymer is an ethylene/α-olefin multiblock interpolymer. In another embodiment, the ethylene/α-olefin multiblock interpolymer comprises greater than 50 mole percent ethylene (based on total moles of polymerizable monomers).

The ethylene/α-olefin multiblock interpolymer has one or more of the following properties:

(1) an average number of blocks greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3; any

(2) at least one molecular fraction that elutes between 40°C and 130°C when fractionated by TREF, characterized in that the fraction has a blocking index of at least 0.5 and up to about 1; any

(7) a 25°C storage modulus G'(25°C) and a 100°C storage modulus G'(100°C), where the ratio of G'(25°C) to G' ( 100°C) ranges from about 1:1 to about 9:1.

In one embodiment, the ethylene/α-olefin multiblock interpolymer has any of properties (1) through (7) discussed above. In another embodiment, the ethylene/α-olefin multiblock interpolymer has at least property (1) discussed above.

In another embodiment, the ethylene/α-olefin multiblock interpolymer has a combination of two or more properties (1) through (7) discussed above. In another embodiment, the ethylene/α-olefin multiblock interpolymer has at least property (1) as described above in combination with two or more additional properties (2) to (7) as described above.

In another embodiment, the ethylene/α-olefin multiblock interpolymer is characterized by one or more of the following features:

(a) has an Mw/Mn of from about 1.7 to about 3.5, at least one melting point Tm in degrees Celsius and a density d in grams/cubic centimeter, where the numerical values of Tm and d satisfy the relationship:
T _Metro>−2002,9+4538,5(d)−2422,2(d)², Ö

(b) has a Mw/Mn of from about 1.7 to about 3.5 and is characterized by a heat of fusion, ΔH in J/g, and a delta amount, ΔT, in degrees Celsius, defined as the temperature difference between the highest DSC peak and the highest CRYSTAF peak, where the numerical values of ΔT and ΔH have the following relationships:
DT>-0,1299(DH)+62.81 paragraph DHgreater than zero and up to 130 J/g,
DT≧48°C for DHbetter than 130 J/g,
where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; any

(c) is characterized by a percent elastic recovery, Re, at 300 percent elongation and 1 cycle, measured with a die cast ethylene/α-olefin interpolymer film, and has a density, d, in grams/cubic centimeter, where the numerical values of Re and d satisfy the following relationship when the ethylene/α-olefin interpolymer is essentially free of a crosslinked phase:
Re>1481-1629(d); Ö

(d) has a molecular fraction that elutes between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a molar comonomer content that is at least 5% greater than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, the comparable random ethylene interpolymer having the same comonomers and having a melt index, density and molar comonomer content (on a total polymer basis) within 10 percent of the ethylene/α-interpolymer olefin; any

(e) is characterized by a storage modulus at 25 °C, G' (25 °C), and a storage modulus at 100 °C, G' (100 °C), where the ratio of G' (25 °C) in G '(100°C) is from about 1:1 to about 10:1; any

(f) at least one molecular fraction that elutes between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a blocking index of at least 0.5 and up to about 1 and a molecular weight distribution Mw/ Mn having greater than about 1.3 or

(g) an average number of blocks greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3.

In one embodiment, the ethylene/α-olefin multiblock interpolymer has any of properties (a) through (g) discussed above. In another embodiment, the ethylene/α-olefin multiblock interpolymer has at least property (g) discussed above.

In another embodiment, the ethylene/α-olefin multiblock interpolymer has a combination of two or more properties (a) through (g) as discussed above. In another embodiment, the ethylene/α-olefin multiblock interpolymer has at least property (g) as described above in combination with two or more additional properties (a) to (f) as described above.

Ethylene/α-olefin multiblock interpolymers typically comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene/α-olefin interpolymers are block interpolymers, preferably multiblock interpolymers or copolymers. The terms "interpolymer" and "copolymer" are used interchangeably in this document. In some embodiments, the multiblock copolymer can be represented by the following formula:
(AB)Norte,
where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more, "A" "B" represents a rigid block or segment and "B" represents a flexible block or segment. Preferably, A and B are connected in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped manner. In other embodiments, the A-blocks and the B blocks are randomly distributed along the polymer chain In other words, block copolymers generally do not have a structure like the following.
AAA-AA-BBB-BB

In still other embodiments, block copolymers typically lack a third type of block comprising different comonomers. In still other embodiments, each A block and B block has monomers or comonomers that are substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of different composition, such as e.g. B. a leading edge segment that has a substantially different composition than the rest of the block.

Multiblock polymers typically include varying amounts of "hard" and "soft" segments. "Rigid" segments refer to blocks of polymerized units in which ethylene is present in an amount greater than 95% and preferably greater than 98% by weight based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 5% by weight and preferably less than 2% by weight based on the weight of the polymer. In some embodiments, the rigid segments comprise all or substantially all ethylene. "Soft" segments, on the other hand, refer to blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than 5% by weight, preferably greater than 8% by weight, greater than 10% by weight Weight. Percent or greater than about 15% by weight based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments may be greater than 20% by weight, greater than 25% by weight, greater than 30% by weight, greater than 35% by weight, greater than 40% by weight, greater than about 45% by weight, greater than about 50% by weight or greater than about 60 percent by weight.

Soft segments can often be present in a block interpolymer from about 1% to about 99% by weight of the total weight of the block interpolymer, preferably from about 5 to about 95% by weight, per weight percent, from about 10% by weight up to about 90 percent by weight. wt%, from about 15 wt% to about 85 wt%, from about 20 wt% to about 80 wt%, from about 25 wt% to about 75 wt%, from about 30 wt% to about 70 wt%, from about 35 wt% to about 65 wt%, from about 40 from about 45% to about 55% by weight of the total weight of the block interpolymer. On the other hand, hard segments can be present at similar intervals. The soft segment weight percentage and hard segment weight percentage can be calculated based on data obtained from DSC or NMR. Such methods and calculations are described in a co-pending US patent application, serial number. 11/376,835 (insert where known) entitled "Ethylene/α-Olefin Block Interpolymers" filed March 15, 2006 in the name of Colin L.P. Shan, Lonnie Hazlitt, et al. Alabama. and Dow Global Technologies Inc., the disclosures of which are incorporated herein by reference in their entirety.

The term "crystalline", when used, refers to a polymer having a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or an equivalent technique. The term can be used interchangeably with the term "semicrystalline". The term "amorphous" refers to a polymer that does not have a crystalline melting point as determined by differential scanning calorimetry (DSC) or an equivalent technique.

The term "multiblock copolymer" or "segmented copolymer" refers to a polymer that comprises two or more chemically distinct regions or segments (referred to as "blocks") that are preferably connected in a linear fashion, i. H. a polymer comprising two or more regions or chemically distinct segments of units attached end-to-end to polymerized ethylenic functionality, rather than being dangling or grafted. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated therein, in density, in the amount of crystallinity, in the crystallite size attributable to a polymer of such a composition, in the type or degree of tacticity (isotactic or syndiotactic ). , Regio - the regularity or regioirregularity, the amount of branching, including long chain branching or hyperbranching, homogeneity, or any other chemical or physical property. Multiblock copolymers are characterized by unique polydispersion index (PDI or Mw/Mn) distributions, block length distribution, and/or block number distribution due to the unique manufacturing process of the copolymers. In particular, when prepared in a continuous process, the polymers desirably have a PDI of from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably 1. 8 to 2.1. When prepared in a batch or semi-continuous process, the polymers have a PDI of from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.4 1.8 on.

The ethylene/α-olefin multiblock interpolymers (sometimes referred to as "inventive interpolymer" or "inventive polymer") used in embodiments of the invention comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form. , Characterized by several blocks or segments of two or more polymerized monomer units that differ in chemical or physical properties (block interpolymer), preferably a multiblock copolymer. Ethylene/α-olefin interpolymers can be characterized by one or more of the features described below.

In one aspect, the ethylene/α-olefin multiblock interpolymers used in embodiments of the invention have an M_W/METRO_Nortefrom about 1.7 to about 3.5, and at least one melting point, T_Metro, in degrees Celsius and density, d, in grams/cubic centimeter, where the numerical values of the variables correspond to the relationship:
T _Metro>−2002,9+4538,5(d)−2422,2(d)², and prefer
T _Metro≧−6288,1+13141(d)−6720,3(d)², and more preferred
T _Metro≧858,91−1825,3(d)+1112,8(d)².

Such a melting point/density relationship is shown in FIG. 1. In contrast to conventional ethylene/α-olefin random copolymers, whose melting points decrease with decreasing density, the interpolymers of the present invention (represented by diamonds) have melting points that are essentially independent of density, particularly when the density is between about 0 .87 g/cm³ is about 0.95 g/cc. For example, the melting point of such polymers ranges from about 110°C to about 130°C when the density ranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, the melting point of such polymers ranges from about 115°C to about 125°C when the density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, ethylene/α-olefin multiblock interpolymers, in polymerized form, comprise ethylene and one or more α-olefins and are characterized by a ΔT in degrees Celsius, defined as the highest differential scanning calorimetry ("DSC") temperature. minus the temperature for the highest fractionation peak of the crystallization analysis ("CRYSTAF") and the heat of fusion in J/g, ΔH and ΔT and ΔH satisfy the following relationships:
DT>-0,1299(DH)+62.81 and preferably
DT≧−0,1299(DH)+64.38 and more preferred
DT≧−0,1299(DH)+65,95,
for ΔH up to 130 J/g. In addition, ΔT is equal to or greater than 48°C for ΔH greater than 130 J/g. The CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (ie, the peak must represent at least 5 percent of the cumulative polymer), and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF 30° temperature C and ΔH is the numerical value of the heat of fusion in J/g. More preferably, the highest CRYSTAF peak contains at least 10 percent of the cumulative polymer. COWARD. 2 shows plotted data for olefin multiblock polymers and comparative examples. Integrated peak areas and peak temperatures are calculated using the computer drawing program provided by the instrument manufacturer. The diagonal line shown for the comparative ethylene-octene random polymers corresponds to the equation ΔT = -0.1299 (ΔH) + 62.81.

In yet another aspect, the ethylene/α-olefin multiblock interpolymers have a molecular fraction that elutes between 40°C and 130°C when fractionated by temperature elevation elution fractionation ("TREF"), characterized in that the fraction a larger molar comonomer, preferably at least 5 percent larger, more preferably at least 10 percent larger, than a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein the comparable random ethylene interpolymer O contains the same comonomers and has a melt index and density and molar comonomer content (based on the total polymer) within 10% of the block interpolymer. Preferably, the Mw/Mn of the comparable interpolymer is also within 10% by weight of the block interpolymer and/or the comparable interpolymer has a total comonomer content within 10% by weight of the block interpolymer.

In yet another aspect, ethylene/α-olefin multiblock interpolymers are characterized by a percent elastic recovery, Re, at 300 percent elongation and 1 cycle as measured on a compression molded film of an ethylene/α-interpolymer olefin. - Olefin, e has a density, d, in grams/cubic centimeter and where the numerical values of Re and d satisfy the following relationship when the ethylene/α-olefin interpolymer is essentially free of a crosslinked phase:
Re>1481-1629(d); and prefer
Re≧1491-1629(d); and more preferred
Re≧1501-1629(d); and even more preferred
Re≧1511-1629(d).

COWARD. Figure 3 shows the effect of density on elastic recovery for unoriented films made from certain interpolymers of the invention and conventional random copolymers. At the same density, the interpolymers according to the invention have significantly higher elastic recoveries.

In some embodiments, the ethylene/α-olefin multiblock interpolymers have a tensile strength of greater than 10 MPa, preferably a tensile strength of ≥ 11 MPa, more preferably a tensile strength of ≥ 13 MPa, and/or an elongation of at least 600 percent, or more preferably at least 700 percent, more preferably at least 800 percent, and most preferably at least 900 percent failure at a crosshead propagation rate of 11 cm/minute.

In other embodiments, the ethylene/α-olefin multiblock interpolymers have (1) a storage modulus ratio G'(25°C)/G'(100°C) of from 1 to 50, preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a compression set at 70°C of less than 80 percent, preferably less than 70 percent, more preferably less than 60 percent, less than 50 percent or less than 40 percent down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin multiblock interpolymers have a compression set at 70 of less than 80 percent, less than 70 percent, less than 60 percent, or less than 50 percent. Preferably, the 70°C compression set of the interpolymers is less than 40 percent, less than 30 percent, less than 20 percent, and can be as low as about 0 percent.

In some embodiments, the ethylene/α-olefin multiblock interpolymers have a heat of fusion of less than 85 J/g and/or a bead blocking power of less than or equal to 100 lbs/ft.²(4800 Pa), preferably less than or equal to 50 lbs/ft²(2400 Pa), especially less than or equal to 5 lbs/ft²(240 Pa) and as low as 0 lbs/ft²(0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers, in polymerized form, comprise at least 50 mole percent ethylene and have a compression set at 70°C of less than 80 percent, preferably less than 70 percent or less to 60 percent. more preferably less than 40 to 50 percent and up to almost zero percent.

In some embodiments, the multiblock copolymers have a PDI that conforms to a Schultz-Flory distribution rather than a Poisson distribution. The copolymers are further characterized as having a polydisperse block distribution and a polydisperse block size distribution and a most likely block length distribution. Preferred multiblock copolymers are those containing 4 or more blocks or segments, including endblocks. More preferably, the copolymers contain at least 5, 10, or 20 blocks or segments, including endblocks.

Comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance ("NMR") spectroscopy being preferred. Furthermore, for polymers or polymer blends with relatively broad TREF curves, the polymer is desirably fractionated using TREF into fractions, each with an elution temperature range of 10°C or less. That is, each eluted fraction has a collection temperature window of 10°C or less. Using this technique, such block interpolymers will have at least one of these fractions with a higher molar comonomer content than a corresponding fraction of the comparable interpolymer.

In another aspect, the multiblock interpolymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks (i.e., at least two blocks) or segments of two or more polymerized monomer units that are chemically different or physical properties (blocked interpolymer), most preferably a multiblock copolymer. Preferably, the block interpolymer has a peak (but not just a molecular fraction) that elutes between 40°C and 130°C (but without collecting and/or isolating individual fractions), characterized in that the peak has a comonomer content estimated by infrared spectroscopy if it is expanded using a maximum width/half area (FWHM) calculation, has a higher molar average comonomer content, preferably at least 5 percent greater, more preferably at least 10 percent greater than the peak of a comparable random ethylene interpolymer elution temperature and expands using a Full width/half maximum (FWHM) area calculation, and wherein the comparable random ethylene interpolymer has the same comonomers and has a melt index, density and molar comonomer content (based on the full polymer) within 10 percent of the blocked interpolymer. Preferably, the Mw/Mn of the comparable interpolymer is also within 10% by weight of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10% by weight of the blocked interpolymer. The maximum half/full width (FWHM) calculation is based on the ratio of the reaction area of methyl to methylene [CH₃/CH₂] of the ATREF infrared detector, where the highest (highest) peak from the baseline is identified, and then the FWHM range is determined. For a distribution measured with an ATREF peak, the FWHM area is defined as the area under the curve between T₁e T₂, onde T₁e T₂are points determined to the left and right of the ATREF peak by dividing the height of the peak by two and drawing a horizontal line to the baseline crossing the left and right parts of the ATREF curve. A calibration curve for comonomer content is generated using ethylene/α-olefin random copolymers, plotting comonomer content from NMR versus area ratio. FWHM of the TREF peak. For this infrared method, the calibration curve is established for the same type of comonomer of interest. The comonomer content of the TREF peak of the olefin multiblock polymer can be determined by reference to this calibration curve using its methyl:methylene area ratio FWHM [CH₃/CH₂] tun pico TREF.

Comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy being preferred. Using this technique, such blocked interpolymers have a higher molar comonomer content than a corresponding comparable interpolymer.

For ethylene-1-octene interpolymers, the block interpolymer preferably has a comonomer content of the TREF fraction eluting between 40 and 130°C greater than or equal to the amount (-0.2013) T + 20.07, plus preferably greater than or equal to the amount (-0.2013) T+21.07, where T is the numerical value of the peak elution temperature of the compared TREF fraction, measured in °C.

COWARD. Figure 4 graphically depicts an embodiment of ethylene-1-octene block interpolymers wherein a plot of comonomer content versus TREF elution temperature for various comparable ethylene/1-octene interpolymers (random copolymers) is fitted to a line containing (-0, 2013) T+ represents 20.07 (solid line). The equation line (-0.2013) T+21.07 is represented by a dotted line. Also shown are comonomer contents for fractions of various ethylene/1-octene block interpolymers of the invention (several block copolymers). All interpolymer block fractions have significantly higher 1-octene content than each line at equivalent elution temperatures. This result is characteristic of the interpolymer of this invention and is believed to be due to the presence within the polymer chains of discrete blocks that are crystalline and amorphous in nature.

COWARD. Figure 5 graphically shows the TREF curve and the comonomer content of the polymer fractions for an example 5 (a multiblock copolymer) and a comparative polymer F (physical blending of two copolymerizing polymers using two catalysts). The peak eluting at 40-130°C, preferably 60-95°C for both polymers, is fractionated into three parts, each part eluting over a temperature range of less than 10°C. Actual data in Example 5 is represented by triangles. One skilled in the art will recognize that a suitable calibration curve can be constructed for interpolymers containing different comonomers and a line used as a fitted comparison with TREF values obtained from comparative interpolymers of the same monomers, preferably random copolymers made using of a metallocene or others. homogeneous. catalyst composition. The interpolymers of this invention are characterized by a molar comonomer content that is greater than the value determined from the calibration curve at the same TREF elution temperature, preferably at least 5 percent greater, more preferably at least 10 percent greater.

In addition to the aspects and properties described above in this document, olefin multiblock polymers can be characterized by one or more additional features. In one aspect, the olefin multiblock polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer ). , more preferably a multiblock copolymer, wherein the block interpolymer has a molecular fraction that elutes between 40°C and 130°C when fractionated using TREF increments, characterized in that the fraction has a molar content of greater, preferably at least 5 percent more, more preferably at least 10, 15, 20 or 25 percent higher than that of a comparable ethylene random interpolymer fraction eluting between the same temperatures at which the comparable ethylene random interpolymer comprises the same comonomer(s), preferably the same Comonomer is ( s) o(s) and a melt index, density and molar comonomer content (based on the total polymer) within 10 percent of the blocked interpolymer. Preferably, the Mw/Mn of the comparable interpolymer is also within 10% by weight of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10% by weight of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and at least one alpha-olefin, especially those interpolymers having a total polymer density of from about 0.855 to about 0.935 g/cm.³and particularly for polymers having greater than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130°C greater than or equal to the amount (-0.1356) T+ 13.89, more preferably greater greater than or equal to (-0.1356) T+14.93 and most preferably greater than or equal to (-0.2013) T+21.07, where T is the numerical value of the ATREF peak elution temperature of the compared TREF fraction is measured in °C.

Preferred for the above interpolymers of ethylene and at least one alpha-olefin, especially those interpolymers having a total polymer density of from about 0.855 to about 0.935 g/cm³, and in particular for polymers with more than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 °C greater than or equal to the amount (−0.2013) T+20.07, more preferably greater than or equal to (-0.2013) T + 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared, measured in °C.

In yet another aspect, the olefin multiblock polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. (blocked interpolymer), more preferably a multiblock copolymer, wherein the block interpolymer has a molecular fraction eluting between 40°C and 130°C when fractionated using TREF increments, characterized in that each fraction has a comonomer content of at least about 6 mole percent has a melting point greater than about 100°C. For fractions having a comonomer content of from about 3 mole percent to about 6 mole percent, each fraction has a DSC melting point of about 110°C or greater. More preferably, the polymer fractions having at least 1 mole percent comonomer have a DSC melting point that satisfies the equation:
Tm≧(-5.5926) (mole percent comonomer in the fraction) + 135.90.

In yet another aspect, the olefin multiblock polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. (blocked interpolymer), more preferably a multiblock copolymer, wherein the block interpolymer has a molecular fraction that elutes between 40°C and 130°C when fractionated using TREF increments, characterized in that each fraction has an ATREF elution temperature greater than or equal to about 76 °C has an enthalpy of fusion (heat of fusion) measured by DSC that conforms to the equation:
Heat of fusion (J/g) ≤ (3.1718) (ATEF elution temperature in Celsius) - 136.58.

The block interpolymers of the invention have a molecular fraction that elutes between 40°C and 130°C when fractionated using TREF increments, characterized in that each fraction has an ATREF elution temperature between 40°C and less than about 76° c has , has an enthalpy of fusion (heat of fusion) measured by DSC, which conforms to the equation:
Heat of fusion (J/g) ≤ (1.1312) (ATEF elution temperature in Celsius) + 22.97.
Measurement of ATREF peak comonomer composition by infrared detector

The comonomer composition of the TREF peak can be measured using an IR4 infrared detector available from Polymer Char, Valencia, Spain (http://www.polymerchar.com/).

The "Composition Mode" detector is equipped with a measurement sensor (CH₂) and composition sensor (CH₃), which are fixed narrow-band infrared filters in the range of 2800-3000 cm⁻¹. The measurement sensor detects methylene (CH₂) carbons in the polymer (which is directly related to the concentration of the polymer in solution), while the composition sensor is methyl (CH₃) polymeric groups. The mathematical relationship of the composition signal (CH₃) divided by the measurement signal (CH₂) is sensitive to the comonomer content of the polymer measured in solution and its response is calibrated against known standards of ethylene-alpha-olefin copolymers.

The detector, when used with an ATREF instrument, provides a concentration (CH₂) and composition (CH₃) Response of the eluted polymer signal during the TREF process. A polymer specific calibration can be made by measuring the area ratio of the CH₃a CH₂for polymers with known comonomer content (preferably measured by NMR). The comonomer content of an ATREF peak from a polymer can be estimated by applying an area ratio reference calibration to the single CH₃and CH₂Answer (i.e. area ratio CH₃/CH₂versus Comonomergehalt).

The peak area can be calculated using a full width/half maximum (FWHM) calculation after applying the appropriate baselines to integrate the individual signal responses from the TREF chromatogram. The full/half maximum calculation is based on the methyl to methylene response area ratio [CH₃/CH₂] of the ATREF infrared detector, where the highest (highest) peak from the baseline is identified, and then the FWHM range is determined. For a distribution measured with an ATREF peak, the FWHM area is defined as the area under the curve between T1 and T2, where T1 and T2 are given points to the left and right of the ATREF peak, representing the height of the peak divide by two. and then draw a horizontal line to the baseline that intersects the left and right parts of the ATREF curve.

The application of infrared spectroscopy to measure the comonomer content of polymers in this ATREF infrared method is in principle similar to that of GPC/FTIR systems as described in the following references: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley; "Development of Gel Permeation Chromatography Fourier Transform Infrared Spectroscopy for the Characterization of Ethylene-Based Polyolefin Copolymers." Science and Engineering of Polymeric Materials (1991), 65, 98-100.; and Deslauriers, P.J.; Rohlfing, DC; Shieh, E.T.; "Quantification of Short Chain Branching Microstructures in Ethylene-1-Olefin Copolymers Using Size Exclusion Chromatography and Fourier Transform Infrared Spectroscopy (SEC-FTIR)", Polymer (2002), 43, 59-170., both incorporated herein by reference in their entirety .

In other embodiments, the ethylene/α-olefin multiblock interpolymer is characterized by an average block index ABI greater than zero and up to about 1.0 and a molecular weight distribution M_W/METRO_Norte, greater than about 1.3. The mean block index, ABI, is the weighted average of the block index ("BI") for each of the polymer fractions obtained in the preparative TREF at 20°C and 110°C, with an increment of 5°C:
ABI=S(W,BI_EU),
Donde BI_EUis the block index for fraction i of the ethylene/α-olefin interpolymer of the present invention obtained in the preparative TREF, and w_EUis the weight percentage of the i-th fraction.

For each polymer fraction, the BI is defined by one of the following two equations (both give the same BI value):

$BI = \frac{1 / T_{x} - 1 / T_{XO}}{1 / T_{A} - 1 / T_{AB}} Ö BI = - \frac{{LnP}_{x} - {LnP}_{XO}}{{LnP}_{A} - {LnP}_{AB}},$
Onde T_xis the preparative ATREF elution temperature for fraction i (preferably expressed in Kelvin), P_xis the mole fraction of ethylene for the ith fraction, which can be measured by NMR or IR as described above. P_ABis the ethylene mole fraction of the total ethylene/α-olefin interpolymer (before fractionation), which can also be measured by NMR or IR. your_AE P_Aare the ATREF elution temperature and ethylene mole fraction for pure "hard segments" (relative to the crystalline segments of the interpolymer). As a first-order approximation, the T_AE P_AValues are set to those of high density polyethylene homopolymer when actual "hard segment" values are not available. For the calculations performed here, T_Ais 372°K,P_Aes 1

T_ABis the ATREF temperature for a random copolymer of the same composition and with an ethylene mole fraction of P_AB. T_ABcan be calculated from the following equation:
LnPAG _AB =a/T _AB+b,
where α and β are two constants that can be determined by calibration using various known random ethylene copolymers. It should be noted that α and β may vary from instrument to instrument. In addition, it would be necessary to create your own calibration curve with the polymer composition of interest and also in a molecular weight range similar to that of the fractions. There is a slight molecular weight effect. If the calibration curve were derived from similar molecular weight ranges, such an effect would be essentially negligible. In some embodiments, ethylene random copolymers satisfy the following relationship:
LnP=−237,83/T _CASA+0,639.
T_XOis the ATREF temperature for a random copolymer of the same composition and with an ethylene mole fraction of P_x. T_XOcan be calculated from the LnP_x=a/T_XO+β. On the contrary, Mrs._XOis the mole fraction of ethylene for a random copolymer of the same composition and with an ATREF temperature of T_x, which can be calculated from Ln P_XO=a/T_x+b.

Once the block index (BI) has been obtained for each TREF preparative fraction, the weighted average block index ABI for the entire polymer can be calculated. In some embodiments, the ABI is greater than zero but less than about 0.3, or from about 0.1 to about 0.3. In other embodiments, the ABI is greater than about 0.3 and up to about 1.0. Preferably, the ABI should range from about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9. In some embodiments, the ABI ranges from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about 0.3 to about 0, 6, about 0.3 to about 0.5 or about 0.3 to about 0.4. In other embodiments, the ABI ranges from about 0.4 to about 1.0, from about 0.5 to about 1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1, 0, about 0.8 to about 1.0 or about 0.9 to about 1.0.

Another feature of the ethylene/α-olefin multiblock interpolymer is that the ethylene/α-olefin multiblock interpolymer comprises at least one polymer fraction obtainable by preparative TREF, the fraction having a number of blocks greater than about 0 ,1. and up to about 1.0, and a molecular weight distribution, M_W/METRO_Nortegreater than about 1.3. In some embodiments, the polymer fraction has a blocking index of greater than about 0.6 and up to about 1.0, greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0 or greater to about 0.9 and greater to about 1.0. In other embodiments, the polymer fraction has a blocking index of greater than about 0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to about 1.0 , greater than about 0.4 and up to about 1.0 , or greater than about 0.4 and up to about 1.0. In still other embodiments, the polymer fraction has a blocking index of greater than about 0.1 and up to about 0.5, greater than about 0.2 and up to about 0.5, greater than about 0.3 and up to about 0. 0.5 or greater than about 0.4 and up to about 0.5. about 0.5. In still other embodiments, the polymer fraction has a blocking index greater than about 0.2 and up to about 0.9, greater than about 0.3 and up to about 0.8, greater than about 0.4 and up to about 0. 7 or greater than about 0.5 and greater to about 0.7. about 0.6.

For copolymers of ethylene and an alpha-olefin, the multiblock interpolymers preferably (1) have a PDI of at least 1.3, more preferably at least 1.5, at least 1.7, or at least 2.0, and most preferably at least minus 2.6 bis to a maximum value of 5.0, more preferably to a maximum value of 3.5 and especially to a maximum value of 2.7; (2) a heat of fusion of 80 J/g or less; (3) an ethylene content of at least 50% by weight; (4) a glass transition temperature T_Grammatik, less than -25°C, more preferably less than -30°C and/or (5) one and only one T_Metro.

Additionally, alone or in combination with any other property described herein, the multiblock interpolymers may have a storage modulus G' such that log(G') is greater than or equal to 400 kPa, preferably greater than or equal to 400 kPa. equal to 1.0 MPa at a temperature of 100 °C. In addition, multiblock interpolymers have a relatively flat storage modulus as a function of temperature in the range 0 to 100°C (shown in Figure 6), which is characteristic of block copolymers and hitherto unknown for an olefin copolymer, particularly a copolymer of olefin, ethylene and one or more c_3-8aliphatic α-olefins. (The term "relatively flat" in this context means that log G' (in pascals) decreases by less than an order of magnitude between 50 and 100 °C, preferably between 0 and 100 °C).

Multiblock interpolymers can be further characterized by a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 90 °C and a flexural modulus of 3 kpsi (20 MPa) to 13 kpsi (90 MPa). Alternatively, the multiblock interpolymers may have a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 104°C and a flexural modulus of at least 3 kpsi (20 MPa). They are characterized by an abrasion resistance (or volume loss) of less than 90 mm³. COWARD. 7 shows the TMA (1 mm) vs. flexural modulus for the multiblock interpolymers compared to other known polymers. Multiblock interpolymers have a significantly better balance between flexibility and heat resistance than other polymers.

In addition, ethylene/α-olefin multiblock interpolymers can have an I melt index₂B. 0.01 to 2000 g/10 minutes, preferably 0.01 to 1000 g/10 minutes, more preferably 0.01 to 500 g/10 minutes and especially 0.01 to 100 g/10 minutes. In certain embodiments, the ethylene/α-olefin interpolymers have a melt index of I₂0.01 to 10 g/10 minutes, 0.5 to 50 g/10 minutes, 1 to 30 g/10 minutes, 1 to 6 g/10 minutes or 0.3 to 10 g/10 minutes. In certain embodiments, the melt index for ethylene/α-olefin polymers is 1 g/10 minutes, 3 g/10 minutes, or 5 g/10 minutes.

Multiblock interpolymers can have M molecular weights_W, from 1,000 g/mol to 5,000,000 g/mol, preferably from 1,000 g/mol to 1,000,000, particularly preferably from 10,000 g/mol to 500,000 g/mol and in particular from 10,000 g/mol to 300,000 g/mol. The density of olefin multiblock polymers can be 0.80 to 0.99 g/cm³and preferably for polymers containing 0.85 g/cm ethylene³a 0,97 g/cm³. In certain embodiments, the density of the ethylene/α-olefin polymers ranges from 0.860 to 0.925 g/cm³o 0.867 to 0.910 g/cm³.

The manufacturing process of multiblock interpolymers has been described in the following patent applications: US Provisional Application no. 60/553,906, filed March 17, 2004; U.S. Provisional Order No. 60/662,937, filed March 17, 2005; U.S. Provisional Order No. 60/662,939, filed March 17, 2005; U.S. Provisional Order No. 60/566,2938, filed March 17, 2005; PCT Application No. PCT/US2005/008916, filed March 17, 2005; PCT Application No. PCT/US2005/008915, filed March 17, 2005; and PCT Application No. PCT/US2005/008917, filed Mar. 17, 2005, all of which are incorporated herein by reference in their entirety. For example, one such process comprises contacting ethylene and optionally one or more addition-polymerizable monomers other than ethylene under addition-polymerization conditions with a catalyst composition comprising:

the mixture or reaction product resulting from the combination:

- (A) a first olefin polymerization catalyst having a high comonomer incorporation rate,
- (B) a second olefin polymerization catalyst having a comonomer incorporation rate of less than 90 percent, preferably less than 50 percent, more preferably less than 5 percent of the comonomer incorporation rate of catalyst (A), Y
- (C) a chain transport agent.

Representative catalysts and chain supports are as follows.

The catalyst (A1) is [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl prepared according to the teachings of WO 03/40195, 2003US0204017, U.S. His. In the. 10/429,024, filed May 2, 2003 and WO 04/24740.

The catalyst (A2) is [N-(2,6-Di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafnium dimethyl , manufactured according to the teachings of WO 03/40195, 2003US0204017, U.S. His. In the. 10/429,024, filed May 2, 2003 and WO 04/24740.

Catalyst (A3) is bis[N,N'''-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafnium dibenzyl.

The catalyst (A4) is bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium(IV) dibenzyl , made substantially in accordance with the teachings of US-A-2004/0010103.

Catalyst (B1) is 1,2-bis(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)imino)methyl)(2-oxoyl)zirconium dibenzyl

The catalyst (B2) is 1,2-bis(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)imino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (C1) is dimethyl(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitanium dimethyl prepared substantially according to the techniques of U.S. Patent No .US No. 6,268,444:

Catalyst (C2) is (t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitanium dimethyl prepared substantially in accordance with the teachings of USA - A-2003/004286:

Catalyst (C3) is (t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-indacen-1-yl)silanetitanium dimethyl prepared substantially in accordance with the teachings of USA - A-2003/004286:

Catalyst (D1) is bis(dimethyldisiloxane)(inden-1-yl)zirconium dichloride available from Sigma-Aldrich:

Transport Agents Transport agents used include diethyl zinc, di(i-butyl) zinc, di(n-hexyl) zinc, triethyl aluminum, trioctyl aluminum, triethyl gallium, i-butyl aluminum bis(dimethyl(t-butyl)siloxane), i-butyl aluminum bis(di)(trimethylsilyl )amide), n-octylaluminum di(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum, i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis( 2 6 -di-t-butylphenoxide , n-octylaluminum di(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7)-dibenzo-1-azacycloheptanoamide), n-Octylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptanoamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide, (2,7)6-diphenylphenoxide) of ethylzinc and ethylzinc (t -butoxide).

Preferably the above process takes the form of a continuous solution process to form block copolymers, particularly multiblock copolymers, preferably linear multiblock copolymers, of two or more monomers, most particularly ethylene and a C_3-20olefin or cycloolefin and especially ethylene and a C_4-20α-Olefin using different catalysts that cannot be interconverted. That means the catalysts are chemically different. Under continuous solution polymerization conditions, the process is ideal for polymerizing monomer mixtures with high monomer conversions. Under these polymerization conditions, passage of the chain binder to the catalyst is advantageous compared to chain growth, and multiblock copolymers, particularly linear multiblock copolymers, are formed with high efficiency.

Multiblock interpolymers can be distinguished from traditional random copolymers, physical blends of polymers, and block copolymers made by sequential addition of monomers, flow catalysts, anionic or cationic live polymerization techniques. In particular, when compared to a random copolymer of the same monomers and monomer content with equivalent crystallinity or modulus, the interpolymers of the invention have better (higher) heat resistance as measured by melting point, higher TMA penetration temperature, higher high temperature tensile strength and/or increased torsional storage modulus at high temperature determined by dynamic mechanical analysis. Compared to a statistical copolymer with the same monomers and the same monomer content, the interpolymers according to the invention have lower compression hardening, especially at elevated temperatures, lower stress relaxation, higher creep resistance, higher tear propagation resistance, higher blocking resistance, faster setting due to increased crystallization (solidification) . ), higher recovery (particularly at elevated temperatures), better abrasion resistance, higher shrinkage resistance, and better oil and load absorption.

Multiblock interpolymers also exhibit a unique branching distribution and rate of crystallization. That is, the interpolymers of this invention have a relatively large difference between the highest peak temperature measured using CRYSTAF and DSC as a function of heat of fusion, particularly when compared to random copolymers containing the same monomers and monomer content or physical mixtures of polymers such as z is a blend of a high density polymer and a lower density copolymer at an equivalent overall density. It is believed that this unique feature of the interpolymers of the invention is due to the unique distribution of the comonomer in blocks within the polymer backbone. In particular, the interpolymers of the invention may comprise alternating blocks with different comonomer contents (including homopolymer blocks). The interpolymers according to the invention can also have a number and/or block size distribution of polymer blocks of different density or comonomer content, which is a type of Schultz-Flory distribution. In addition, the interpolymers of the present invention also have a unique maximum melting point and crystallization temperature profile that are essentially independent of polymer density, modulus, and morphology. In a preferred embodiment, the microcrystalline order of the polymers shows characteristic spherulites and lamellae, distinguishable from random or block copolymers, even at PDI values of less than 1.7 or even less than 1.5, even less than 1. , 3.

In addition, multiblock interpolymers can be made using techniques to affect the degree or level of blocking. That is, the amount of comonomer and the length of each polymer block or segment can be modified by controlling the level and type of catalyst and transfer agent, as well as the polymerization temperature and other polymerization variables. A surprising benefit of this phenomenon is the discovery that as the level of blocking increases, the optical properties, tear strength and high temperature recovery properties of the resulting polymer improve. In particular, as the average number of blocks in the polymer increases, haze decreases while clarity, tear strength, and high temperature recovery properties increase. By selecting combinations of transfer agents and catalysts that have the desired chain transfer capability (high transfer rates with low chain termination), other forms of polymer termination are effectively suppressed. Consequently, little or no β-hydride removal is observed in the polymerization of ethylene/α-olefin comonomer mixtures according to embodiments of the invention, and the resulting crystal blocks are highly linear or essentially completely linear and have little or no length chain branching. .

Polymers with highly crystalline chain ends can be selectively prepared according to embodiments of the invention. In elastomeric applications, reducing the relative amount of polymer that results in an amorphous block reduces the effect of intermolecular thinning in crystalline regions. This result can be achieved by selecting chain translation agents and catalysts that have an appropriate response to hydrogen or other chain terminating agents. In particular, if the catalyst producing a highly crystalline polymer segment is more prone to chain termination (e.g. through the use of hydrogen) than the catalyst responsible for the production of the less crystalline polymer segment (e.g. through more incorporation of comonomer, defect area or atactic polymer). formation), then highly crystalline polymer segments preferentially fill the end portions of the polymer. Not only are the resulting terminated groups crystalline, but upon termination, the site of the catalyst that forms the highly crystalline polymer is again available to resume polymer formation. The polymer initially formed is thus another highly crystalline polymer segment. Consequently, both ends of the resulting multiblock copolymer are preferably highly crystalline.

The ethylene/α-olefin multiblock interpolymers used in embodiments of the invention are preferably ethylene interpolymers having at least one C₃-C₂₀α-Olefin. Copolymers of ethylene and a C₃-C₂₀Alpha-olefins are particularly preferred. The interpolymers may also include C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or non-conjugated dienes, polyenes, alkenylbenzenes, and the like. Examples of such comonomers include C₃-C₂₀α-Olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. 1-Butene and 1-octene are particularly preferred. Other suitable monomers include styrene, halo- or alkyl-substituted styrenes, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenes (e.g., cyclopentene, cyclohexene, and cyclooctene).

Although ethylene/α-olefin multiblock interpolymers are preferred polymers, other ethylene/olefin polymers can also be used. Olefins, as used herein, refer to a family of compounds based on unsaturated hydrocarbons having at least one carbon-carbon double bond. Depending on catalyst selection, any olefin can be used in embodiments of the invention. Preferred suitable olefins are C₃-C₂₀aliphatic and aromatic compounds containing vinyl unsaturation, as well as cyclic compounds such as cyclobutene, cyclopentene, dicyclopentadiene and norbornene, including but not limited to 5- and 6-C-substituted norbornene₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures of such olefins as well as mixtures of such olefins with C₄-C₄₀diolefinic compounds

Examples of olefin monomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene, Vinylcyclohexene, Norbornadiene, Ethylidenenorbornene, Cyclopentene, Cyclohexene, Dicyclopentadiene, Cyclooctene, C₄-C₄₀Dienes including but not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀α-olefins and the like. In certain embodiments, the α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or a combination thereof. While any hydrocarbon containing a vinyl group could potentially be used in embodiments of the invention, practical issues such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer can become more problematic as molecular weight increases. increases. very high.

The polymerization processes described herein are well suited for the production of olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene, p-methyl styrene, t-butyl styrene and the like. In particular, interpolymers comprising ethylene and styrene can be prepared by following the teachings described herein. Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀alpha-olefin optionally comprising a C₄-C₂₀A diene with improved properties can be produced.

Suitable non-conjugated diene monomers can be a straight chain, branched chain, or cyclic hydrocarbyl diene having from 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include straight chain acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched acyclic dienes such as 5-methyl-1,4-hexadiene ; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene and dihydroocines, single ring alicyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene and fused alicyclic ring and multi-ring bridged dienes such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo-(2,2,1)hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene. Of the dienes typically used to make EPDM, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2- norbornene (MNB) and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

A class of desirable polymers that can be prepared according to embodiments of the invention are elastomeric ethylene interpolymers, a C₃-C₂₀α-Olefin, especially propylene, and optionally one or more diene monomers. Preferred alpha-olefins for use in this embodiment of the present invention are denoted by the formula CH₂=CHR*, where R* is a linear or branched alkyl group having 1 to 12 carbon atoms. Examples of suitable alpha-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. A particularly preferred alpha-olefin is propylene. Propylene based polymers are commonly referred to in the art as EP or EPDM polymers. Dienes suitable for use in preparing such polymers, particularly multiblock EPDM-type polymers, include conjugated or non-conjugated straight or branched chain cyclic or polycyclic dienes containing from 4 to 20 carbon atoms. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene.

Because diene-containing polymers comprise alternating segments or blocks containing greater or lesser amounts of diene (including none) and α-olefin (including none), the total amount of diene and α-olefin can be reduced without loss of properties. Polymer. That is, since the diene and α-olefin monomers are preferentially incorporated into a block type of polymer rather than uniformly or randomly throughout the polymer, they are used more efficiently and subsequently the crosslink density of the polymer is increased. can control better. These crosslinkable elastomers and cured products have beneficial properties including increased tensile strength and improved elastic recovery.

In some embodiments, the interpolymers of this invention made with two catalysts containing different amounts of comonomer have a weight ratio of the blocks they form from 95:5 to 5:95. Elastomeric polymers desirably have an ethylene content of 20 to 90 percent, a diene content of 0.1 to 10 percent, and an alpha-olefin content of 10 to 80 percent, based on the total weight of the polymer. More preferably, the elastomeric multiblock polymers have an ethylene content of 60 to 90 percent, a diene content of 0.1 to 10 percent, and an alpha-olefin content of 10 to 40 percent, based on the total weight of the polymer. Preferred polymers are high molecular weight polymers having an average molecular weight (Mw) of from 10,000 to about 2,500,000, preferably 20,000 to 500,000, more preferably 20,000 to 350,000, and a polydispersion of less than 3.5, more preferably less than 3.0 , and a Mooney viscosity (ML (1+4) 125°C) from 1 to 250. More preferably, such polymers have an ethylene content of 65 to 75 percent, a diene content of 0 to 6 percent and an α-olefin content of 20 to 35 percent.

catalysts

The term "overnight" when used refers to a time of about 16-18 hours, the term "room temperature" refers to a temperature of 20-25°C, and the term "mixed alkanes" refers to im Commercially available mixture of C6-9 aliphatic hydrocarbons available under the tradename Isopar ES from ExxonMobil Chemical Company. When a compound's name in this document does not match its structural representation, the structural representation takes precedence. The synthesis of all metal complexes and the preparation of all selection experiments were performed in a dry nitrogen atmosphere using dry box techniques. All solvents used were HPLC grade and dried prior to use.

MMAO refers to modified methylalumoxane, a triisobutyl aluminum modified methylalumoxane commercially available from Akzo-Noble Corporation.

The preparation of catalyst (B1) is carried out as follows.

- a) Preparation of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine
- Add 3,5-di-t-butylsalicylaldehyde (3.00 g) to 10 mL of isopropylamine. The solution quickly turns light yellow. After stirring at room temperature for 3 hours, the volatiles are removed in vacuo to give a light yellow crystalline solid (97% yield).
- (b) Preparation of 1,2-bis(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)imino)methyl)(2-oxoyl)zirconium dibenzyl
- A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605 mg, 2.2 mmol) in 5 mL of toluene was slowly added to a solution of Zr(CH).₂PH value)₄(500 mg, 1.1 mmol) in 50 mL of toluene. The resulting dark yellow solution is stirred for 30 min. The solvent is removed under reduced pressure to give the desired product as a reddish brown solid.

The preparation of the catalyst (B2) is carried out as follows.

- (a) Preparation of (1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine
- 2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol (90 mL) and di-t-butylsalaldehyde (10.00 g, 42.67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -25°C over 12 hours. The resulting yellow solid precipitate is collected by filtration and washed with cold methanol (2 x 15 mL) and then dried under reduced pressure. The yield is 11.17 g of a yellow solid.¹H NMR consistent with the desired product as a mixture of isomers.
- (b) Preparation of bis(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imino)zirconium dibenzyl
- A solution of (1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63 g, 23.2 mmol) in 200 mL of toluene slowly becomes a Solution of given Zr(CH₂PH value)₄(5.28 g, 11.6 mmol) in 600 mL of toluene. The resulting dark yellow solution is stirred at 25°C for 1 hour. The solution is further diluted with 680 mL of toluene to give a solution with a concentration of 0.00783 M.

Cocatalyst 1 A mixture of methyldi(C_14-18Alkyl)ammonium salts of tetrakis(pentafluorophenyl)borate (hereinafter armenium borate) prepared by the reaction of a long-chain trialkylamine (Armeen TM M2HT, available from Akzo-Nobel, Inc.), HCl and Li[B(C)₆F₅)₄], substantially as disclosed in U.S. Patent No. 5,919,9883, ex. two.

Cokatalysator 2 Mixto C_14-18Bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide alkyldimethylammonium salt prepared according to US Patent No. 6,395,671, e.g. sixteen.

Means of transport The means of transport used include diethyl zinc (DEZ, SA1), di(i-butyl) zinc (SA2), di(n-hexyl) zinc (SA3), triethyl aluminum (TEA, SA4), trioctyl aluminum (SA5), triethyl aluminum (SA6 ), i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminum bis(di(trimethylsilyl)amide) (SA8), n-octylaluminum di(pyridine-2-methoxide) (SA9 ), bis(n-octadecyl)i-butylaluminum (SA10), i-butylaluminum bis(di(n-pentyl)amide (SA11), n-octylaluminum bis(2,6-di-t-butylphenoxide) (SA12), n- Octylaluminum di(ethyl(1-naphthyl)amide) (SA13), ethylaluminum bis(t-butyldimethylsiloxide) (SA14), ethylaluminum di(bis(trimethylsilyl)amide) (SA15), ethylaluminum bis(2,3,6); . , 7) -dibenzo-1-azacycloheptanoamide) (SA16), bis(2,3,6,7-dibenzo-1-azacycloheptanoamide) of n-octyl aluminum (SA17), bis(dimethyl(t-butyl) siloxide of n-octyl aluminum (SA18 ), ethylzinc (2,6-diphenylphenoxide) (SA19) and ethylzinc (t-butoxide) (SA20).

Polymerizations were carried out using a high performance parallel polymerization reactor (PPR) available from Symyx Technologies, Inc. and in substantial accordance with US Patent No. Ethylene copolymerizations are carried out at 130°C and 200 psi (1.4 MPa) with ethylene as needed using 1.2 equivalents of cocatalyst 1 based on the total catalyst used (1.1 equivalents if any). MMAO). A series of polymerizations are carried out in a parallel pressure reactor (PPR) consisting of 48 individual reactor cells in a 6x8 matrix fitted with a pre-weighed glass tube. The working volume in each reactor cell is 6000 µL. Each cell is temperature and pressure controlled, with agitation provided by individual stirring paddles. Monomer gas and extinguishing gas are connected directly to the PPR unit and controlled by automatic valves. Liquid reagents are automatically syringed into each reactor cell, and the solvent in the reservoir is a mixture of alkanes. The order of addition is solvent blend of alkanes (4 mL), ethylene, 1-octene comonomer (1 mL), cocatalyst 1 or cocatalyst blend 1/MMAO, displacer and catalyst or catalyst blend. When using a mixture of Cocatalyst 1 and MMAO or a mixture of two catalysts, the reagents are premixed in a small vial just prior to addition to the reactor. If a reagent is omitted from an experiment, the previous order of addition is retained. The polymerizations are run for about 1-2 minutes until the predetermined ethylene consumptions are reached. After quenching with CO, the reactors are cooled and the glass tubes are unloaded. The tubes are transferred to a spin/vacuum drying unit and dried at 60°C for 12 hours. Tubes containing dry polymer are weighed and the difference between this weight and the tare weight gives the net yield of polymer. The results are contained in Table 1. In Table 1 and elsewhere in the application, comparative compounds are often marked with an asterisk (*).

Examples 1-4 demonstrate the synthesis of linear block (multiblock) copolymers by the present invention as by the formation of an essentially monomodal copolymer with a very narrow MWD when DEZ is present and a product with a broad bimodal molecular weight distribution (a mixture separately prepared polymers) in the absence of DEC. Due to the fact that Catalyst (A1) is known to incorporate more octene than Catalyst (B1), the different blocks or segments of the copolymers resulting from the invention differ based on branching or density.

TABLE 1

	Cat. (A1)	cat (B1)	sleeve	MMAO	Transport
Ex.	(μmol)	(μmol)	(μmol)	(μmol)	Active ingredient (μmol)	Yield (g)	Minnesota	MW/Mn	Hexilos¹


A*	0,06	—	0,066	0,3	—	0,1363	300502	3.32	—
B*	—	0,1	0,110	0,5	—	0,1581	36957	1.22	2.5
C*	0,06	0,1	0,176	0,8	—	0,2038	45526	5.30²	5.5
1	0,06	0,1	0,192	—	DEZ (8,0)	0,1974	28715	1.19	4.8
2	0,06	0,1	0,192	—	DEZ (80,0)	0,1468	2161	1.12	14.4
3	0,06	0,1	0,192	—	TEE (8,0)	0,208	22675	1,71	4.6
4	0,06	0,1	0,192	—	TEE (80,0)	0,1879	3338	1.54	9.4

¹C₆or higher chain content per 1000 carbons
²Bimodal molecular weight distribution

It can be seen that the multiblock polymers made according to the invention have a relatively narrow polydispersion (Mw/Mn) and a higher content of block copolymers (trimer, tetramer or higher) than polymers made without the transfer agent.

Additional characterization data for the polymers in Table 1 is provided with reference to FIGS. 1-7 and figures in WO/2005/090427, filed March 17, 2005, incorporated herein by reference. More specifically, the DSC and ATREF results show the following:

The DSC curve for the polymer from Example 1 shows a melting point (Tm) of 115.7°C with a heat of fusion of 158.1 J/g. The corresponding CRYSTAF curve shows the highest peak at 34.5°C with a peak area of 52.9 percent. The difference between DSC Tm and Tcrystaf is 81.2 °C.

The DSC curve for the polymer of Example 2 shows a peak with a melting point (Tm) of 109.7°C at a heat of fusion of 214.0 J/g. The corresponding CRYSTAF curve shows the highest peak at 46.2°C with a peak area of 57.0 percent. The difference between DSC Tm and Tcrystaf is 63.5 °C.

The DSC curve for the polymer of Example 3 shows a peak with a melting point (Tm) of 120.7°C at a heat of fusion of 160.1 J/g. The corresponding CRYSTAF curve shows the highest peak at 66.1°C with a peak area of 71.8 percent. The difference between DSC Tm and Tcrystaf is 54.6 °C.

The DSC curve for the polymer of Example 4 shows a peak with a melting point (Tm) of 104.5°C at a heat of fusion of 170.7 J/g. The corresponding CRYSTAF curve shows the highest peak at 30°C with a peak area of 18.2 percent. The difference between DSC Tm and Tcrystaf is 74.5 °C.

The DSC curve for Comparison A shows a melting point (Tm) of 90.0°C with a heat of fusion of 86.7 J/g. The corresponding CRYSTAF curve shows the highest peak at 48.5°C with a peak area of 29.4 percent. Both values are consistent with a low density resin. The difference between DSC Tm and Tcrystaf is 41.8 °C.

The DSC curve for Comparison B shows a melting point (Tm) of 129.8°C with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curve shows the highest peak at 82.4°C with a peak area of 83.7 percent. Both values are consistent with a high density resin. The difference between DSC Tm and Tcrystaf is 47.4 °C.

The DSC curve for Comparison C shows a melting point (Tm) of 125.3°C with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curve shows the highest peak at 81.8 °C with a peak area of 34.7%, and a lower crystalline peak at 52.4 °C. The separation between the two peaks is consistent with the presence of a highly crystalline peak and a low crystalline polymer. The difference between DSC Tm and Tcrystaf is 43.5 °C.

Continuous solution polymerizations were performed in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar™ E, available from ExxonMobil Chemical Company), 2.70 lbs/hr (1.22 kg/hr) ethylene, 1-octene and hydrogen (if used) are charged to a 3 gallon reactor . Equipped with 0.8L with temperature control jacket and internal thermocouple. The solvent feed to the reactor is metered by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. On discharge from the pump, a side stream is withdrawn to provide wash streams to the catalyst and cocatalyst injection lines 1 and to the reactor agitator. These flows are measured with Micro-Motion mass flow meters and controlled by check valves or by manually adjusting needle valves. The remaining solvent is combined with 1-octene, ethylene and hydrogen (if used) and fed to the reactor. A mass flow controller is used to add hydrogen to the reactor as needed. The temperature of the solvent/monomer solution is controlled using a heat exchanger before it enters the reactor. This stream enters through the bottom of the reactor. Catalyst component solutions are metered using pumps and mass flow meters and combined with the catalyst wash solvent and introduced at the bottom of the reactor. The reactor is operated full of liquid at 500 psig (3.45 MPa) with vigorous agitation. The product is removed through exit lines at the top of the reactor. All reactor exit lines are steam-lined and insulated. The polymerization is stopped by adding a small amount of water to the outlet line along with any stabilizers or other additives and passing the mixture through a static mixer. The product stream is then heated by passing it through a heat exchanger prior to degassing. The polymer product is obtained by extrusion using a devolatilizing extruder and a water-cooled pelletizer. Procedure details and results can be found in Table 2. The properties of selected polymers are given in Table 3.

TABLE 2

Process details for preparing sample polymers
					gato	Cat. A1	gato	B2		DEZ	sleeve	sleeve		Polytechnic School
	C₈H_sixteen	solution	H₂	T	A1²	Flow	B2³	Flow	DEZ	Flow	conc.	Flow	[C₂H₄]/	Index⁵		fest
Ex.	kg/Std	kg/Std	sccm¹	°C	ppm	kg/Std	ppm	kg/Std	concentration %	kg/Std	ppm	kg/Std	[DEZ]⁴	kg/Std	% of conversation⁶	%	Box⁷

D*	1.63	12.7	29,90	120	142.2	0,14	—	—	0,19	0,32	820	0,17	536	1.81	88,8	11.2	95,2
MI*	″	9.5	5,00	″	—	—	109	0,10	0,19	″	1743	0,40	485	1.47	89,9	11.3	126,8
F*	″	11.3	251,6	″	71,7	0,06	30.8	0,06	—	—	″	0,11	—	1,55	88,5	10.3	257,7
5	″	″	—	″	″	0,14	30.8	0,13	0,17	0,43	″	0,26	419	1,64	89,6	11.1	118.3
6	″	″	4,92	″	″	0,10	30.4	0,08	0,17	0,32	″	0,18	570	1,65	89,3	11.1	172,7
7	″	″	21.70	″	″	0,07	30.8	0,06	0,17	0,25	″	0,13	718	1,60	89.2	10.6	244.1
8	″	″	36,90	″	″	0,06	″	″	″	0,10	″	0,12	1778	1.62	90,0	10.8	261.1
9	″	″	78,43	″	″	″	″	″	″	0,04	″	″	4596	1.63	90.2	10.8	267,9
10	″	″	0,00	123	71.1	0,12	30.3	0,14	0,34	0,19	1743	0,08	415	1,67	90,31	11.1	131.1
11	″	″	″	120	71.1	0,16	″	0,17	0,80	0,15	1743	0,10	249	1,68	89,56	11.1	100,6
12	″	″	″	121	71.1	0,15	″	0,07	″	0,09	1743	0,07	396	1,70	90.02	11.3	137,0
13	″	″	″	122	71.1	0,12	″	0,06	″	0,05	1743	0,05	653	1,69	89,64	11.2	161,9
14	″	″	″	120	71.1	0,05	″	0,29	″	0,10	1743	0,10	395	1.41	89,42	9.3	114.1
fifteen	2.45	″	″	″	71.1	0,14	″	0,17	″	0,14	1743	0,09	282	1,80	89,33	11.3	121.3
sixteen	″	″	″	122	71.1	0,10	″	0,13	″	0,07	1743	0,07	485	1,78	90.11	11.2	159,7
17	″	″	″	121	71.1	0,10	″	0,14	″	0,08	1743	″	506	1,75	89.08	11,0	155,6
18	0,69	″	″	121	71.1	″	″	0,22	″	0,11	1743	0,10	331	1.25	89,93	8.8	90.2
19	0,32	″	″	122	71.1	0,06	″	″	″	0,09	1743	0,08	367	1.16	90,74	8.4	106,0

*Comparison, not an example of the invention
¹Standard cm³/Minimum
²[N-(2,6-Di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalin-2-diyl(6-pyridin-2-diyl)methan)]háfniodimethyl
³Bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imino)zirconiumdibenzyl
⁴molar ratio in the reactor
⁵polymer production rate
⁶Percentage of ethylene conversion in the reactor
⁷Efficiency, kg polymer/g M where g M = g Hf + g Zr

TISCH 3

Properties of examples of polymers
								heat from				Tm-	CRYSTALLF
	density				molecular weight	Minnesota		merger	T_Metro	T_C	T_CRYSTALLF	T_CRYSTALLF	peak area
Ex.	(g/cm³)	she₂	she₁₀	she₁₀/YO₂	(g/mol)	(g/mol)	MW/Mn	(J/g)	(°C.)	(°C.)	(°C.)	(°C.)	(Percent)

D*	0,8627	1,5	10,0	6.5	110.000	55.800	2.0	32	37	45	30	7	99
MI*	0,9378	7,0	39,0	5.6	65.000	33.300	2.0	183	124	113	79	45	95
F*	0,8895	0,9	12.5	13.4	137.300	9.980	13.8	90	125	111	78	47	20
5	0,8786	1,5	9.8	6.7	104.600	53.200	2.0	55	120	101	48	72	60
6	0,8785	1.1	7.5	6.5	109600	53300	2.1	55	115	94	44	71	63
7	0,8825	1,0	7.2	7.1	118.500	53.100	2.2	69	121	103	49	72	29
8	0,8828	0,9	6.8	7.7	129.000	40.100	3.2	68	124	106	80	43	13
9	0,8836	1.1	9.7	9.1	129600	28700	4.5	74	125	109	81	44	sixteen
10	0,8784	1.2	7.5	6.5	113.100	58.200	1.9	54	116	92	41	75	52
11	0,8818	9.1	59.2	6.5	66.200	36.500	1.8	63	114	93	40	74	25
12	0,8700	2.1	13.2	6.4	101.500	55.100	1.8	40	113	80	30	83	91
13	0,8718	0,7	4.4	6.5	132.100	63.600	2.1	42	114	80	30	81	8
14	0,9116	2.6	15.6	6.0	81.900	43.600	1.9	123	121	106	73	48	92
fifteen	0,8719	6.0	41.6	6.9	79.900	40.100	2.0	33	114	91	32	82	10
sixteen	0,8758	0,5	3.4	7.1	148.500	74.900	2.0	43	117	96	48	69	Sixty-five
17	0,8757	1.7	11.3	6.8	107.500	54.000	2.0	43	116	96	43	73	57
18	0,9192	4.1	24,9	6.1	72.000	37.900	1.9	136	120	106	70	50	94
19	0,9344	3.4	20.3	6.0	76.800	39.400	1.9	169	125	112	80	45	88

The resulting polymers are tested by DSC and ATREF as in the previous examples. The results are as follows:

The DSC curve for the polymer of Example 5 shows a peak with a melting point (Tm) of 119.6°C at a heat of fusion of 60.0 J/g. The corresponding CRYSTAF curve shows the highest peak at 47.6°C with a peak area of 59.5%. The delta between DSC Tm and Tcrystaf is 72.0 °C.

The DSC curve for the polymer of Example 6 shows a peak with a melting point (Tm) of 115.2°C at a heat of fusion of 60.4 J/g. The corresponding CRYSTAF curve shows the highest peak at 44.2°C with a peak area of 62.7 percent. The delta between DSC Tm and Tcrystaf is 71.0 °C.

The DSC curve for the polymer from Example 7 shows a peak with a melting point of 121.3°C at a heat of fusion of 69.1 J/g. The corresponding CRYSTAF curve shows the highest peak at 49.2°C with a peak area of 29.4 percent. The delta between DSC Tm and Tcrystaf is 72.1 °C.

The DSC curve for the polymer of Example 8 shows a peak with a melting point (Tm) of 123.5°C at a heat of fusion of 67.9 J/g. The corresponding CRYSTAF curve shows the highest peak at 80.1°C with a peak area of 12.7 percent. The delta between DSC Tm and Tcrystaf is 43.4 °C.

The DSC curve for the polymer of Example 9 shows a peak with a melting point (Tm) of 124.6°C at a heat of fusion of 73.5 J/g. The corresponding CRYSTAF curve shows the highest peak at 80.8°C with a peak area of 16.0 percent. The delta between DSC Tm and Tcrystaf is 43.8 °C.

The DSC curve for the polymer of Example 10 shows a peak with a melting point (Tm) of 115.6°C at a heat of fusion of 60.7 J/g. The corresponding CRYSTAF curve shows the highest peak at 40.9°C with a peak area of 52.4 percent. The delta between DSC Tm and Tcrystaf is 74.7 °C.

The DSC curve for the polymer of Example 11 shows a peak with a melting point (Tm) of 113.6°C at a heat of fusion of 70.4 J/g. The corresponding CRYSTAF curve shows the highest peak at 39.6°C with a peak area of 25.2 percent. The delta between DSC Tm and Tcrystaf is 74.1 °C.

The DSC curve for the polymer of Example 12 shows a peak with a melting point (Tm) of 113.2°C at a heat of fusion of 48.9 J/g. The corresponding CRYSTAF curve shows no peaks at or above 30°C (hence Tcrystaf is defined as 30°C for further calculation purposes). The delta between DSC Tm and Tcrystaf is 83.2 °C.

The DSC curve for the polymer of Example 13 shows a peak with a melting point (Tm) of 114.4°C at a heat of fusion of 49.4 J/g. The corresponding CRYSTAF curve shows the highest peak at 33.8°C with a peak area of 7.7 percent. The delta between DSC Tm and Tcrystaf is 84.4 °C.

The DSC for the polymer of Example 14 shows a peak with a melting point (Tm) of 120.8°C at a heat of fusion of 127.9 J/g. The corresponding CRYSTAF curve shows the highest peak at 72.9°C with a peak area of 92.2 percent. The delta between DSC Tm and Tcrystaf is 47.9 °C.

The DSC curve for the polymer of Example 15 shows a peak with a melting point (Tm) of 114.3°C at a heat of fusion of 36.2 J/g. The corresponding CRYSTAF curve shows the highest peak at 32.3°C with a peak area of 9.8 percent. The delta between DSC Tm and Tcrystaf is 82.0 °C.

The DSC curve for the polymer of Example 16 shows a peak with a melting point (Tm) of 116.6°C at a heat of fusion of 44.9 J/g. The corresponding CRYSTAF curve shows the highest peak at 48.0°C with a peak area of 65.0 percent. The delta between DSC Tm and Tcrystaf is 68.6 °C.

The DSC curve for the polymer of Example 17 shows a peak with a melting point (Tm) of 116.0°C at a heat of fusion of 47.0 J/g. The corresponding CRYSTAF curve shows the highest peak at 43.1°C with a peak area of 56.8 percent. The delta between DSC Tm and Tcrystaf is 72.9 °C.

The DSC curve for the polymer of Example 18 shows a peak with a melting point (Tm) of 120.5°C at a heat of fusion of 141.8 J/g. The corresponding CRYSTAF curve shows the highest peak at 70.0°C with a peak area of 94.0 percent. The delta between DSC Tm and Tcrystaf is 50.5 °C.

The DSC curve for the polymer of Example 19 shows a peak with a melting point (Tm) of 124.8°C at a heat of fusion of 174.8 J/g. The corresponding CRYSTAF curve shows the highest peak at 79.9 °C with a peak area of 87.9 percent. The delta between DSC Tm and Tcrystaf is 45.0 °C.

The DSC curve for the polymer of Comparative Example D shows a peak with a melting point (Tm) of 37.3°C at a heat of fusion of 31.6 J/g. The corresponding CRYSTAF curve shows no peak equal to or greater than 30 °C. Both values are compatible with a low density resin. The delta between DSC Tm and Tcrystaf is 7.3 °C.

The DSC curve for the polymer of Comparative E shows a peak with a melting point (Tm) of 124.0°C at a heat of fusion of 179.3 J/g. The corresponding CRYSTAF curve shows the highest peak at 79.3°C with a peak area of 94.6 percent. Both values are consistent with a high density resin. The delta between DSC Tm and Tcrystaf is 44.6 °C.

The DSC curve for Comparative Polymer F shows a peak with a melting point (Tm) of 124.8°C at a heat of fusion of 90.4 J/g. The corresponding CRYSTAF curve shows the highest peak at 77.6°C with a peak area of 19.5%. The separation between the two peaks is consistent with the presence of both a highly crystalline polymer and a poorly crystalline polymer. The delta between DSC Tm and Tcrystaf is 47.2 °C.

Physical property tests

Polymer samples are analyzed for their physical properties, such as B. High temperature strength properties as evidenced by TMA temperature tests, insert seizure resistance, high temperature recovery, high temperature strain compression, and the storage modulus ratio, G'(25°C)/G'. (100°C). Several commercially available polymers were included in the tests: Comparative G* is a substantially linear ethylene/1-octene copolymer (AFFINITY®, available from The Dow Chemical Company), Comparative H* is a substantially linear ethylene/1- octene copolymer and (AFFINITY® EG8100, available from The Dow Chemical Company), Comparison I is a substantially linear ethylene/1-octene copolymer (AFFINITY® PL1840, available from The Dow Chemical Company), Comparison J is a substantially linear elastomeric styrene copolymer/butadiene/hydrogenated styrene triblock (KRATON™ G1652, available from KRATON Polymers), Comparative K is a thermoplastic vulcanizate (TPV, a blend of polyolefins containing a dispersed crosslinked elastomer). The results are shown in Table 4.

TABLE 4

High temperature mechanical properties
		Ball		300%
		Block		Print
	TMA-1 mm	Fortaleza		recreation	Compression
	Penetration	pounds/foot²	G' (25°C)/	(80 °C)	Fiji (70° C)
Ex.	(°C.)	(kPa)	G’ (100 °C)	(Percent)	(Percent)

D*	51	—	9	He failed	—
MI*	130	—	18	—	—
F*	70	141 (6,8)	9	He failed	100
5	104	0 (0)	6	81	49
6	110	—	5	—	52
7	113	—	4	84	43
8	111	—	4	He failed	41
9	97	—	4	—	66
10	108	—	5	81	55
11	100	—	8	—	68
12	88	—	8	—	79
13	95	—	6	84	71
14	125	—	7	—	—
fifteen	96	—	5	—	58
sixteen	113	—	4	—	42
17	108	0 (0)	4	82	47
18	125	—	10	—	—
19	133	—	9	—	—
GRAMM*	75	463 (22,2)	89	He failed	100
H*	70	213 (10.2)	29	He failed	100
AND*	111	—	11	—	—
J*	107	—	5	He failed	100
K*	152	—	3	—	40

In Table 4, Comparison F (which is a physical blend of the two polymers resulting from simultaneous polymerizations using catalysts A1 and B1) has a 1 mm penetration temperature of about 70°C, while Examples 5-9 have a temperature of 1 mm penetration. 100°C or higher. In addition, examples 10-19 all have a 1mm soak temperature greater than 85°C and most have a 1mm TMA temperature greater than 90°C or even greater than 100°C. This shows that multiblock polymers have better dimensional stability at elevated temperatures compared to a physical blend. Comparison J (a commercial SEBS) has a good 1 mm TMA temperature of about 107 °C, but a very poor compression set (high temperature of 70 °C) of about 100% and has not recovered either (the sample was Broken). ) during 300% stress relaxation at high temperature (80°C). Therefore, the polymers exemplified have a unique combination of properties not available even in some commercially available high performance thermoplastic elastomers.

Likewise, Table 4 shows a low (good) storage modulus ratio G'(25°C)/G'(100°C) for multiblock polymers of 6 or less, while a physical blend (Comparison F) has a storage modulus ratio of 9 and a random ethylene /octene copolymer (Comparison G) of similar density has an order of magnitude higher storage modulus ratio (89). It is desirable for the storage modulus ratio of a polymer to be as close to 1 as possible. Such polymers are relatively unaffected by temperature, and articles made from such polymers can be usefully employed over a wide range of temperatures. This property of low modulus storage rate and temperature independence is particularly useful in elastomeric applications such as pressure sensitive adhesive formulations.

The data in Table 4 also show that the multiblock polymers of this invention have improved pellet blocking resistance. In particular, Example 5 has a bead blocking force of 0 MPa, meaning that it flows freely under the conditions tested, compared to Comparative Samples F and G, which show significant blocking. Block resistance is important because bulk shipping of polymers with high block forces can cause the product to agglomerate or stick during storage or shipping, resulting in poor handling properties.

High temperature (70°C) compression set for olefin multiblock polymers is generally good, which generally means less than 80 percent, preferably less than 70 percent, and more preferably less than 60 percent. In contrast, Comparative Samples F, G, H, and J have a 70°C compression set of 100 percent (the maximum possible value that indicates no recovery). Good high temperature compression set (low numbers) is particularly required for applications such as gaskets, window profiles, gaskets and the like.

TABLE 5

Mechanical properties at room temperature
								traction	100%	300%	retractable	To-	Emphasize
							abrasion:	written down	Print	Print	Emphasize	Print	Eras-
	To bend	traction	traction	strain	traction	strain	Volume	tear	recreation	recreation	at 150%	Put on	laxative
	Module	Module	Fortaleza	I am not resting¹	Fortaleza	I am not resting	Loss	Fortaleza	21 Grad	21 Grad	Print	21 Grad	at 50%
Ex.	(MPa)	(MPa)	(MPa)¹	(%)	(MPa)	(%)	(mm³)	(mJ)	(Percent)	(Percent)	(kPa)	(Percent)	Print²

D*	12	5	—	—	10	1074	—	—	91	83	760	—	—
MI*	895	589		—	31	1029	—	—	—	—	—	—	—
F*	57	46	—	—	12	824	93	339	78	Sixty-five	400	42	—
5	30	24	14	951	sixteen	1116	48	—	87	74	790	14	33
6	33	29	—	—	14	938	—	—	—	75	861	13	—
7	44	37	fifteen	846	14	854	39	—	82	73	810	20	—
8	41	35	13	785	14	810	45	461	82	74	760	22	—
9	43	38	—	—	12	823	—	—	—	—	—	25	—
10	23	23	—	—	14	902	—	—	86	75	860	12	—
11	30	26	—	—	sixteen	1090	—	976	89	66	510	14	30
12	20	17	12	961	13	931	—	1247	91	75	700	17	—
13	sixteen	14	—	—	13	814	—	691	91	—	—	21	—
14	212	160	—	—	29	857	—	—	—	—	—	—	—
fifteen	18	14	12	1127	10	1573	—	2074	89	83	770	14	—
sixteen	23	20	—	—	12	968	—	—	88	83	1040	13	—
17	20	18	—	—	13	1252	—	1274	13	83	920	4	—
18	323	239	—	—	30	808	—	—	—	—	—	—	—
19	706	483	—	—	36	871	—	—	—	—	—	—	—
GRAMM*	fifteen	fifteen	—	—	17	1000	—	746	86	53	110	27	50
H*	sixteen	fifteen	—	—	fifteen	829	—	569	87	60	380	23	—
AND*	210	147	—	—	29	697	—	—	—	—	—	—	—
J*	—	—	—	—	32	609	—	—	93	96	one thousand nine hundred	25	—
K*	—	—	—	—	—	—	—	—	—	—	—	30	—

¹Tested at 51 cm/minute
²measured at 38°C for 12 hours

Table 5 shows the results of the mechanical properties of the new polymers as well as several comparative polymers at room temperature. Multiblock polymers show very good abrasion resistance when tested according to ISO 4649 and generally show a volume loss of less than about 90 mm.³, preferably less than about 80 mm³, and especially less than about 50 mm³. In this test, larger numbers mean greater volume loss and, consequently, lower abrasion resistance.

The tenacity at break measured by the tensile notched tenacity of olefin multiblock polymers is generally 1000 mJ or more as shown in Table 5. The tear strength for olefin multiblock polymers can be as high as 3000 mJ or even as high as 5000 mJ. Comparative polymers generally have a tear strength of no more than 750 mJ.

Table 5 also shows that the multiblock polymers of the invention have better shrink stress at 150% elongation (shown by higher shrink stress values) than some of the comparative samples. Comparative Examples F, G and H have shrink stress values at 150 percent elongation of 400 kPa or less, while the olefin multiblock polymers have shrink stress values at 150 percent elongation of 500 kPa (Ex. 11) at about 1100 kPa (Ex. 17). Polymers with shrinkage stress values greater than 150 percent would be very useful for elastic applications such as elastic fibers and fabrics, particularly nonwovens. Other applications include diapers, sanitary and medical garment waistbands such as flaps and elastics.

Table 5 also shows that the stress relaxation (at 50 percent strain) is also improved (less) for olefin multiblock polymers compared to, for example, Comparative G. Less stress relaxation means the polymer better retains its durability in applications such as diapers. and other garments where retention of stretch properties over long periods of time at body temperature is desirable.

An olefin multiblock interpolymer, and preferably an ethylene/α-olefin multiblock interpolymer, may comprise a combination of two or more suitable embodiments as described herein.

Alternatively, a combination of one or more olefin-based polymers, such as as described herein, and one or more olefin multiblock interpolymers, such as as described herein, may be used.

In another embodiment, an ethylene-based polymer as described herein can be blended with an olefin multiblock interpolymer as described herein.

In another embodiment, a propylene-based polymer as described herein can be blended with an olefin multiblock interpolymer as described herein.

In another embodiment, an ethylene-based polymer as described herein and a propylene-based polymer as described herein can be blended with an olefin multiblock interpolymer as described herein.

Thermoplastic Polyurethane

The polyurethane component which may optionally be used in the compositions is not subject to any restriction as to its formulation other than the requirement that it be thermoplastic in nature, which means that it is made from essentially bifunctional ingredients, for example organic diisocyanates and components containing it are essentially difunctional in groups containing active hydrogen. However, sometimes smaller proportions of components with functionalities greater than two can be used. This is especially true when using diluents such as glycerin, trimethylolpropane and the like. These thermoplastic polyurethane compositions are commonly referred to as TPU materials. Accordingly, all TPU materials known in the art can be used in the present compositions. For a representative teaching on the preparation of TPU materials, see Polyurethanes: Chemistry and Technology, Part II, Saunders and Frisch, 1964, pp. 767-769, Interscience Publishers, New York, N.Y. and Polyurethane Handbook, edited by G. Oertel 1985, pp. 405-417, Hanser Publications, distributed in the USA by Macmillan Publishing Co., Inc., New York, N.Y. 2,929,800; 2,948,691; 3,493,634; 3,620,905; 3,642,964; 3,963,679; 4,131,604; 4,169,196; rev 31671; 4,245,081; 4,371,684; 4,379,904; 4,447,590; 4,523,005; 4,621,113; and 4,631,329; the descriptions of which are incorporated herein by reference.

The preferred TPU is a polymer made from a blend comprising an organic diisocyanate, at least one polymeric diol, and at least one difunctional diluent. TPU can be made by prepolymer, quasi-prepolymer, or one-shot processes according to the methods described in the references included above.

Diisocyanates suitable for use in preparing the hard segment of polyurethanes of this invention include aromatic, aliphatic and cycloaliphatic diisocyanates and combinations of two or more of these compounds. An example of a structural unit derived from diisocyanate (OCN-R-NCO) is represented by the formula (I) below:

wherein R is an alkylene, cycloalkylene or arylene group. Representative examples of these diisocyanates can be found in US Patent Nos. 4,385,133, 4,522,975 and 5,167,899. Preferred diisocyanates include, but are not limited to, 4,4'-diisocyanatodiphenylmethane, p-phenylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-diisocyanatocyclohexane, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'- dimethyl 4,4'-biphenyl diisocyanate, 4,4'-diisocyanate dicyclohexylmethane and 2,4-toluene diisocyanate. More preferred are 4,4'-diisocyanate dicyclohexylmethane and 4,4'-diisocyanate diphenylmethane. A preferred one is 4,4'-diisocyanatodiphenylmethane.

Diisocyanates also include aliphatic and cycloaliphatic isocyanate compounds such as 1,6-hexamethylene diisocyanate; ethylene diisocyanate; 1-isocyanato-3,5,5-trimethyl-1-3-isocyanatomethylcyclohexane; 2,4- and 2,6-hexahydrotoluene diisocyanate and the corresponding isomer mixtures; 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures. Furthermore, 1,3-tetramethylenexylene diisocyanate can be used with the present invention. The isocyanate can be selected from organic isocyanates, modified isocyanates, isocyanate-based prepolymers and mixtures of two or more such isocyanates.

Any of the organic diisocyanates used above in the manufacture of TPUs can be used, including aromatic, aliphatic and cycloaliphatic diisocyanates and mixtures thereof. Illustrative isocyanates include, but are not limited to, methylene bis(phenyl isocyanate), which includes the 4,4'-isomer, the 2,4'-isomer, and mixtures thereof; m- and p-phenylene diisocyanates; chlorophenylene diisocyanates; α,α'-xylylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these last two isomers which are commercially available; tolidine diisocyanate; hexamethylene diisocyanate; 1,5-naphthalene diisocyanate; isophorone diisocyanate and the like; cycloaliphatic diisocyanates such as methylene bis(cyclohexyl isocyanate) including the 4,4'-isomer, 2,4'-isomer and mixtures thereof, and all geometric isomers thereof including trans/trans, cis/trans, cis/cis and mixtures thereof cyclohexylene diisocyanates (1,2-, 1,3- or 1,4-); 1-methyl-2,5-cyclohexylene diisocyanate; 1-methyl-2,4-cyclohexylene diisocyanate; 1-methyl-2,6-cyclohexylene diisocyanate; 4,4'-isopropylidenebis-(cyclohexyl isocyanate); 4,4'-diisocyanatodicyclohexyl and all geometric isomers and mixtures thereof and the like.

Modified forms of methylene bis(phenyl isocyanate) are also included. The latter are to be understood as those forms of methylene bis(phenyl isocyanate) which have been treated to convert them to stable liquids at room temperature (about 20°C). Such products include those reacted with a small amount (up to about 0.2 equivalents per polyisocyanate equivalent) of an aliphatic glycol or mixture of aliphatic glycols, such as the modified methylene bis(phenyl isocyanates) described in the US patent; 3,644,457; 3,883,571; 4,031,026; 4,115,429; 4,118,411; and 4,299,347; each incorporated herein by reference. Modified methylene bis(phenyl isocyanates) also include those that have been treated to convert a minor portion of the diisocyanate to the corresponding carbodiimide, which then interacts with more of the diisocyanate to form uretonimine groups, with the resulting product being a stable liquid. at room temperature, such as in US Pat. 3,384,653; paste here by reference. If desired, mixtures of any of the above mentioned polyisocyanates can be used.

Suitable classes of organic diisocyanates include aromatic and cycloaliphatic diisocyanates. Preferred species within these classes are methylene bis(phenyl isocyanate), including the 4,4'-isomer, 2,4'-isomer and mixtures thereof, and methylene bis(cyclohexyl isocyanate), including the isomers described above. In a preferred embodiment, the isocyanate is a mixture of 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane. In another embodiment, these two isocyanates are present in an approximately 1 to 1 weight ratio.

Polymeric diols that can be used include those conventionally used in the art for making TPU elastomers. The polymeric diols are responsible for the formation of soft segments in the resulting polymer and preferably have molecular weights (number average) falling in the range of 200 to 10,000 g/mol, preferably 400 to 4,000 g/mol and most preferably 500 to 3000 g/mol. mol. It is not uncommon, and in some cases it may be advantageous, to use more than one polymeric diol. Examples of diols are polyether diols, polyester diols, hydroxy-terminated polycarbonates, hydroxy-terminated polybutadienes, hydroxy-terminated polybutadiene-acrylonitrile copolymers, hydroxy-terminated copolymers of dialkylsiloxane and alkylene oxides such as ethylene oxide, propylene oxide and the like, and mixtures in which any of the above polyols can be used as the main component (greater than 50% by weight) with amine-terminated polyethers and amine-terminated polybutadiene-acrylonitrile copolymers. Additional examples of the diols include natural oil diols.

Suitable polyether polyols include polyoxyethylene glycols, polyoxypropylene glycols, optionally capped with ethylene oxide residues; random and block copolymers of ethylene oxide and propylene oxide; polytetramethylene glycol; random and block copolymers of tetrahydrofuran and ethylene oxide and/or propylene oxide; and products derived from any of the above reactions with difunctional carboxylic acids or esters derived from these acids, in which latter case ester interchange takes place and the esterifying groups are replaced by glycol polyether groups. Preferred polyether polyols are random and block copolymers of ethylene and propylene oxide having a functionality of about 2.0 and polytetramethylene glycol polymers having a functionality of about 2.0.

Suitable polyester polyols include those made by polymerizing epsilon-caprolactone using an initiator such as ethylene glycol, ethanolamine, and the like; and those prepared by esterifying polycarboxylic acids such as phthalic acid, terephthalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid and the like with polyhydric alcohols such as ethylene glycol, butanediol, cyclohexanedimethanol and the like.

Suitable amine terminated polyethers are primary aliphatic diamines structurally derived from polyoxypropylene glycols. Polyetherdiamines of this type were available from Jefferson Chemical Company under the trademark JEFFAMINE (now available from Basell).

Suitable hydroxyl-containing polycarbonates include those prepared by the reaction of diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyloctane- 1,8-diol, diethylene glycol, triethylene glycol, dipropylene glycol and the like, with diaryl carbonates such as diphenyl carbonate, or with phosgene.

Suitable silicon-containing polyethers include copolymers of alkylene oxides with dialkylsiloxanes such as dimethylsiloxane and the like (see, for example, U.S. Patent No. 4,057,595 or U.S. Patent No. 4,631,329 cited above and incorporated herein).

Suitable hydroxyl-terminated polybutadiene copolymers include those available under the tradename Poly BD Liquid Resins from Arco Chemical Company. Hydroxy terminated polybutadiene copolymers are also available from Sartomer. Illustrative of the hydroxyl and amine terminated butadiene/acrylonitrile copolymers are the materials available under the trade name HYCAR Hydroxyl Terminated Liquid Polymers (HT) and Amine Terminated Liquid Polymers (ΔT), respectively. Preferred diols are the polyether and polyester diols shown above.

The bifunctional stent deployed can be any of the TPUs described above that are known in the art. Typically, the extenders can be straight and branched chain aliphatic diols having from 2 to 10 carbon atoms in the chain, inclusive. Examples of such diols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol and the like; 1,4-cyclohexanedimethanol; hydroquinone bis(hydroxyethyl) ether; cyclohexylene diols (1,4-, 1,3- and 1,2-isomers), isopropylidene bis(cyclohexanols); diethylene glycol, dipropylene glycol, ethanolamine, N-methyldiethanolamine and the like; and mixtures of any of the foregoing. As noted above, in some cases, minor portions (less than about 20 percent equivalent) of the bifunctional stent can be replaced with trifunctional stents without reducing the thermoplasticity of the resulting TPU; exemplary of such diluents are glycerin, trimethylolpropane, and the like.

Although any of the diol extenders described and illustrated above can be used alone or in a mixture, it is preferred to use 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethylene glycol and diethylene glycol, alone or mixed with each other or with one or more of the above mentioned aliphatic diols. Particularly preferred diols are 1,4-butanediol, 1,6-hexanediol and 1,4-cyclohexanedimethanol.

The chain extender is incorporated into the polyurethane in amounts determined by selection of specific reactive components, desired amounts of hard and soft segments, and in an amount sufficient to provide good mechanical properties such as modulus and tear strength. The polyurethane compositions used in the practice of this invention may contain from 2 to 25%, preferably from 3 to 20% and most preferably from 4 to 18% by weight of the chain extender component.

Optionally, small amounts of monohydroxy or monoamino functional compounds, often referred to as "chain blockers", can be used to control molecular weight. Examples of such chain terminators are propanols, butanols, pentanols and hexanols. When used, chain brakes are typically present in amounts of less than 0.1 to 2% by weight of the total reaction mixture resulting in the polyurethane composition.

Equivalent proportions of polymeric diol to diluent can vary considerably depending on the desired hardness of the TPU product. Generally, the ratios fall within the respective range of about 1:1 to about 1:20, preferably about 1:2 to about 1:10. At the same time, the general ratio of isocyanate equivalents to active hydrogen-containing material equivalents ranges from 0.90:1 to 1.10:1, and preferably from 0.95:1 to 1.05:µm.

The TPU-forming ingredients can be reacted in organic solvents, but are preferably reacted in the absence of solvent by melt extrusion at a temperature from about 125°C to about 250°C, preferably about 160°C. . . at about 225°C.

It is often desirable, but not essential, to include a catalyst in the reaction mixture used to prepare the compositions of the invention. Any of the catalysts conventionally used in the art for catalyzing the reaction of an isocyanate with a compound containing reactive hydrogen can be used for this purpose; see, for example, Saunders et al., Polyurethanes, Chemistry and Technology, Part I, Interscience, New York, 1963, pp. 228-232; see also Britain et al., J. Applied Polymer Science, 4 , 207-211, 1960; each incorporated herein by reference. These catalysts include organic and inorganic acid salts and organometallic derivatives of bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese. and zirconium, as well as phosphines and tertiary organic amines. Representative organotin catalysts are tin octoate, tin oleate, dibutyltin dioctoate, dibutyltin dilaurate, and the like. Representative organic tertiary amine catalysts are triethylamine; triethylenediamine; N,N,N',N'-tetramethylethylenediamine; N,N,N',N'-tetraethylethylenediamine, N-methylmorpholine; N-ethylmorpholine; N,N,N',N'-tetramethylguanidine; N,N,N',N'-tetramethyl-1,3-butanediamine; N,N-dimethylethanolamine; N,N-diethylethanolamine; That's similar. The amount of catalyst employed generally ranges from about 0.02 to about 2.0 weight percent based on the total weight of the reactants.

As discussed above, polyurethanes can be made by mixing all of the ingredients at substantially the same time in a "one-step" process, or they can be made by gradually adding ingredients in a "prepolymer process" where the processes are performed are the presence or without the addition of optional additives. The polyurethane-forming reaction can be carried out in bulk or in solution, with or without the addition of a suitable catalyst that promotes the reaction of isocyanates having hydroxyl or other functionalities. Examples of a typical preparation of these polyurethanes are given in US Patent No. 5,864,001.

As discussed above, the other major hard segment component of the polyurethanes of the present invention is at least one chain extender, both of which are well known in this technological field. When the chain extender is a diol, the resulting product is known to be a thermoplastic polyurethane (TPU). Technically, when the chain extender is a diamine or an amino alcohol, the resulting product is a thermoplastic polyurea (TPUU).

Chain extenders that can be used in the invention are characterized by two or more, preferably two, functional groups, each of which contains "active hydrogen atoms". Such functional groups are preferably in the form of hydroxyl, primary amino, secondary amino, or mixtures of two or more of these groups. The term "active hydrogens" refers to hydrogens which, because of their location in a molecule, exhibit activity according to the Zerewitinoff test described by Kohler in EPJelly. chemical society,49, 31-81 (1927).

Chain extenders can be aliphatic, cycloaliphatic or aromatic and are exemplified by diols, diamines and amino alcohols. Examples of bifunctional chain extenders are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol and other pentanediols, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, other 2-ethylhexanediols, 1,6-hexanediol and other hexanediols, 2,2,4-trimethylpentane-1,3-diol, decanediols, dodecanediols, bisphenol A, bisphenol hydrogenated A, 1 ,4-cyclohexanediol, 1,4-bis(2-hydroxyethoxy)cyclohexane, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(2-hydroxyethoxy)benzene, ester diol 204 (propanoic acid, 3-hydroxy -2,2-dimethyl, 3-hydroxy-2,2-dimethylpropyl ester available from TCI America), N-methylethanolamine, N-methylisopropylamine, 4-aminocyclohexanol, 1,2-diaminothene, 1,3-diaminopropane, diethylenetriamine, toluene-2,4-diamine and toluene-1,6-diamine. Aliphatic compounds having 2 to 8 carbon atoms are preferred. When preparing thermoplastic or soluble polyurethanes, chain extenders are difunctional in nature. Amine chain extenders include, but are not limited to, ethylenediamine, monomethanolamine, and propylenediamine.

Commonly used linear chain extenders are usually diol, diamine or amino alcohol compounds characterized as having a molecular weight not exceeding 400 g/mol (or daltons). In this context, "linear" means that no tertiary carbon branching is included. Examples of suitable chain extenders are represented by the following formulas: HO-(CH₂)_Norte-OH₂N-(CH₂)_Norte-N.H₂, eH₂N-(CH₂)_Norte—OH, where “n” is usually a number from 1 to 50.

A common chain extender is 1,4-butanediol ("butanediol" or "BDO") and is represented by the following formula: HO-CH₂CH₂CH₂CH₂-Oh. Other suitable chain extenders include ethylene glycol; diethylene glycol; 1,3-propanediol; 1,6-hexanediol; 1,5-heptanediol; triethylene glycol; 1,2-ethylhexenediol (EHD diol); and combinations of two or more of these extenders. In one embodiment, the chain extender is 1,2-ethylhexenediol (EHD diol).

Also suitable are cyclic chain extenders, which are generally diol, diamine or amino alcohol compounds characterized as having a molecular weight of not more than 400 g/mol. In this context, "cyclic" means a ring structure, and typical ring structures include, but are not limited to, 5- to 8-membered ring structures having hydroxyl-alkyl branches. Examples of cyclic chain extenders are represented by the following formulas: HO-R-(Ring)-R'-OH and HO-R-O-(Ring)-OR'-OH, where R and R' are one to five carbon alkyl chains and each ring has 5 to 8 members, preferably all carbons. In these examples, one or both of the -OH ends can be replaced with -NH₂. Suitable cyclic chain extenders include cyclohexanedimethanol ("CHDM") and hydroquinone bis-2-hydroxyethyl ether (HQEE). A CHDM moiety, a preferred cyclic chain extender, is represented by the following formula: HO-CH₂— (Cyclohexanring)-CH₂-OH.

Optionally, small amounts of monohydroxy or monoamino functional compounds, often referred to as "chain blockers", can be used to control molecular weight. Examples of such chain terminators are propanols, butanols, pentanols and hexanols. When used, chain blockers are typically present in amounts of less than 0.1 to 2% by weight of the total reaction mixture resulting in the polyurethane composition.

As known to those skilled in the art, the ratio of isocyanate to total functional groups determines the Mn of the polymer. In some cases it is desirable to use a very small excess of isocyanate.

For linear polymers with high Mn content, starting materials with two functional groups per chain are desirable. However, it is possible to accommodate starting materials with a range of functionalities. For example, a functional end polydiene can be used to cap both ends of a polyurethane with the medium consisting of repeating fractions of isocyanate chain extension. Polydienes with more than two functional groups form branched polymers. While crosslinking and gels can be a problem, too much functionality can usually be controlled by process conditions. These branched polymers exhibit some rheological properties that are desirable in some cases, such as high melt strength.

As discussed above, catalysts that promote or facilitate the formation of urethane groups can optionally be used in the formulation. Examples of suitable catalysts are tin octanoate, dibutyltin dilaurate, tin oleate, tetrabutyltin titanate, tributyltin chloride, cobalt naphthenate, dibutyltin oxide, potassium oxide, tin chloride, N,N,N,N'-tetramethyl-1,3-butanediamine, bis [2-(N,N-dimethylamino) ethyl] ether, 1,4-diazabicyclo[2.2.2]octane; zirconium chelates, aluminum chelates and bismuth carbonates. Catalysts, if used, are typically employed in catalytic amounts ranging from 0.001% by weight and less, up to 2% by weight and more, based on the total amount of polyurethane-forming ingredients.

Additives can be used to modify the properties of the polyurethane used in the practice of this invention. Additives can be included in conventional amounts known in the art and in the literature. Additives are commonly used to impart specific desired properties to polyurethanes, such as various antioxidants, UV inhibitors, waxes, thickeners and fillers. When fillers are used, they can be organic or inorganic, but generally they are inorganic, such as clay, talc, calcium carbonate, silica, and the like. In addition, fibrous additives such as fiberglass or carbon fiber can be added to impart specific properties.

The polyurethane used in the practice of the present invention is preferably made by reacting the functional polyester with an isocyanate and optionally a chain extender. In the "prepolymer" process, one or more functional polydienes are typically reacted with one or more isocyanates to form a prepolymer. The prepolymer is further reacted with one or more chain extenders. Alternatively, polyurethanes can be prepared by a single reaction of all the reagents. Typical polyurethanes have a number average molecular weight of 5,000 to 1,000,000 g/mol and more preferably 20,000 to 100,000 g/mol.

In a preferred embodiment of the invention, the polyurethane is formed from a polyester, an isocyanate and a chain extender, and preferably an aliphatic chain extender. In a preferred embodiment, these polyesters have at least one, and more preferably at least two, ester groups in the molecule and typically have an Mn of 500 to 10,000, more preferably 1,000 to 5,000, and most preferably 1,500 to 3,000 g/m 2 .

In another embodiment, the polyurethane is formed from a composition comprising 10 to 40% by weight diisocyanate, preferably 15 to 35% by weight diisocyanate; from 50% to 85% by weight of a polyester, preferably from 55% to 80% by weight of a polyester, and more preferably from 60% to 80% by weight of a polyester; and 2 to 15% by weight of a chain extender, preferably 2 to 10% by weight of a chain extender (each weight percentage is based on the total weight of the reactants). In another embodiment, the diisocyanate is an aliphatic or aromatic diisocyanate, and more preferably 4,4'-diphenylmethane diisocyanate. In yet another embodiment, the chain extender is an aliphatic diol. In another embodiment, the polydiene diol has an Mn of 500 to 10,000, more preferably 1,000 to 5,000, and even more preferably 1,500 to 3,000 g/mol.

In one embodiment, the polyurethane has a density greater than or equal to 0.90 g/cc, preferably greater than or equal to 0.95 g/cc, and most preferably greater than or equal to 1.00 g/cc. In another embodiment, the polyurethane has a density of less than or equal to 1.30 g/cc, preferably less than or equal to 1.25 g/cc, and most preferably less than or equal to 1.20 g/cc. In another embodiment, the polyurethane has a density of 0.90 g/cc to 1.30 g/cc, preferably 0.95 g/cc to 1.25 g/cc, and most preferably 1.00 g/cc to 1 .20g/cc. All individual values and sub-ranges from 0.90 g/cc to 1.30 g/cc are recorded and described here.

In another embodiment, the polyurethane has a melt index greater than or equal to 0.1 g/10 min, preferably greater than or equal to 0.5 g/10 min, and most preferably greater than or equal to 1 g/10 min 10 minutes (ASTM D -1238-04, 190°C, 8.7kg). In another embodiment, the polyurethane has a melt index of less than or equal to 100 g/10 min, preferably less than or equal to 50 g/10 min, more preferably less than or equal to 20 g/10 min, and even more preferably less than or equal to 10 g/10 min (ASTM D-1238-04, 230°C, 8.7 kg). In another embodiment, the polyurethane has a melt index of from 0.1 g/10 min to 100 g/10 min, preferably from 0.5 g/10 min to 50 g/10 min, more preferably 1 g/10 min at 20 g/10 min. 10 mins and even more preferably from 1 g/10 min to 10 g/10 min. In a preferred embodiment, the polyurethane has a melt flow rate of from 6 g/10 min to 10 g/10 min and preferably from 7 g/10 min to 9 g/10 min. All individual values and partial ranges from 0.1 g/10 min to 100 g/10 min are contained and described in this document.

Preferred polyurethanes include Pellethane™ thermoplastic polyurethane elastomers available from The Dow Chemical Company.

Additional polyurethanes suitable for use in the invention include, but are not limited to, ESTANE thermoplastic polyurethanes, TECOFLEX thermoplastic polyurethanes, CARBOTHANE thermoplastic polyurethanes, TECOPHILIC thermoplastic polyurethanes, TECOPLAST thermoplastic polyurethanes, and TECOTHANE thermoplastic polyurethanes, all available from Noveon; thermoplastic polyurethanes ELASTOLLAN and other thermoplastic polyurethanes available from BASF; and commercial thermoplastic polyurethanes available from Bayer, Huntsman and Merquinsa.

The polyurethane component can contain a combination of two or more suitable embodiments as described above.

If desired, additives such as pigments, fillers, lubricants, stabilizers, antioxidants, dyes, flame retardants, and the like, commonly used in connection with polyurethane elastomers, can be incorporated into polyurethanes at any convenient stage in their manufacture. .

fillings

A composition according to the invention may contain one or more fillers. Such fillers include, but are not limited to, silicates, aluminates, aluminosilicates, aluminas, talc, mica, calcium carbonate, titanium dioxide and magnesium hydroxide. Fillers also include surface modified fillers including but not limited to surface modified silicas and surface modified silicates (preferably talc).

In one embodiment, the filler is a silicate whose surface is modified with a hydroxysilane. In another embodiment, the filler is talc whose surface is modified with a hydroxysilane.

In another embodiment, the filler is a silicate whose surface is modified with an aminosilane. In another embodiment, the filler is talc whose surface has been modified with an aminosilane.

In another embodiment, the aminosilane is selected from the following structures:

For Structure I, each of R1, R2, and R3 is independently alkyl (preferably methyl or ethyl), hydrogen, or chloro.

For Structure II, each of R1, R2, R3, R4, and R5 is independently alkyl (preferably methyl or ethyl), hydrogen, or chloro.

For Structure III, each of R1, R2, R3, R4, R5, R6 and R7 is independently an alkyl (preferably methyl or ethyl), hydrogen or chlorine and n is 0 to 50, preferably 0 to 20 and more preferably from 0 to 10

In another embodiment, a composition according to the invention comprises 0 to 60 percent by weight, preferably 5 to 50 percent by weight and particularly preferably 10 to 40 percent by weight, based on the total weight of the composition, of at least one filler. In another embodiment, the filler is a silicate. In another embodiment, the filler is talc. In another embodiment, the filler is a silicate whose surface is modified with an aminosilane. In another embodiment, the filler is talc whose surface has been modified with an aminosilane.

inventive compositions

Compositions of the invention typically comprise a) at least one olefin multiblock interpolymer; b) at least one functionalized olefin-based polymer; and optionally c) at least one thermoplastic polyurethane.

1. Compositions comprising two or more components

For compositions comprising (a) at least one olefin multiblock interpolymer; and b) at least one functionalized olefin-based polymer; it is preferred that the olefin multiblock interpolymer is an ethylene/α-olefin multiblock interpolymer.

In one embodiment, the functionalized olefin-based polymer is present in an amount less than or equal to 20% by weight, more preferably less than or equal to 15% by weight, most preferably less than or equal to 10% by weight. percent and more preferably less than or equal to 5% by weight based on the total weight of the composition.

In another embodiment, the functionalized olefin-based polymer is present in an amount greater than or equal to 50% by weight, more preferably greater than or equal to 60% by weight, and even more preferably greater than or equal to 60% by weight. . . 70% by weight based on the total weight of the composition.

In another embodiment, the composition comprises from 75% to 95%, and preferably from 80% to 75% by weight of the olefin multiblock interpolymer, preferably an ethylene/α-olefin multiblock interpolymer, based on the total weight of the composition. composition . . Preferably the α-olefin is a C3-C10 α-olefin and more preferably is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.

In another embodiment, the composition comprises from 1% to 10% by weight of the functionalized olefin-based polymer; and 99 to 90 weight percent of the olefin multiblock interpolymer, preferably an ethylene/α-olefin multiblock interpolymer, based on the weight of the sum of these two components. Preferably the α-olefin is a C3-C10 α-olefin and more preferably is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.

In another embodiment, the composition comprises from 70% to 100% by weight of an olefin-based functional polymer and from 0% to 30% by weight of an olefin multiblock interpolymer; each percentage by weight based on the sum of the weights of these two components.

In another embodiment, the composition comprises from 5% to 40%, preferably from 10% to 35%, and more preferably from 12% to 30% by weight of a functionalized olefin-based polymer, based on the total weight of the composition.

In another embodiment, the composition comprises greater than or equal to 50%, preferably greater than or equal to 55% by weight of an olefin multiblock interpolymer, based on the total weight of the composition.

In another embodiment, the composition comprises from 45% to 60%, preferably from 50% to 55% by weight of an olefin multiblock interpolymer; 5 to 20% by weight, preferably 10 to 15% by weight, of a functionalized olefin-based polymer; and 25 to 45% by weight, preferably 30 to 40% by weight, of a filler; each weight percentage is based on the total weight of these three components. In another embodiment, the filler is a silicate. In another embodiment, the filler is talc.

In another embodiment, the composition comprises from 45% to 60%, preferably from 50% to 55% by weight of an olefin multiblock interpolymer; 5 to 20% by weight, preferably 10 to 15% by weight, of a functionalized olefin-based polymer; and from 25% to 45%, preferably from 30% to 40% by weight of a modified surface filler; each weight percentage is based on the total weight of these three components. In another embodiment, the filler is a silicate whose surface is modified with an aminosilane. In another embodiment, the filler is talc whose surface has been modified with an aminosilane.

A composition according to the invention may optionally contain one or more additives. Additives such as plasticizing oils, lubricants, antiblocking agents, AO, UV fillers can be added to the compositions according to the invention. Typically, a composition of the invention will contain one or more stabilizers, for example antioxidants such as Irganox™ 1010 and Irgafos™ 168, both available from Ciba Specialty Chemicals. Polymers are typically treated with one or more stabilizers prior to extrusion or other melt processing. Other polymeric additives include, but are not limited to, UV light absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, lubricants, flame retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents, antioxidants -blocking agents, mold release agents , flame retardants, abrasion and scratch agents, antimicrobial agents, antistatic agents and crosslinking agents.

A composition according to the invention may comprise a combination of two or more suitable embodiments as described herein.

2. Compositions containing at least three components

For compositions comprising (a) at least one olefin multiblock interpolymer; b) at least one functionalized olefin-based polymer; and c) at least one thermoplastic polyurethane, it is often preferred that the functionalized olefin-based polymer is present in an amount less than or equal to 20% by weight, more preferably less than or equal to 15% by weight and even more. preferably less than or equal to 10% by weight based on the total weight of the composition.

In one embodiment, the composition comprises from 15% to 35%, and preferably from 20% to 30%, by weight of the thermoplastic polyurethane, based on the total weight of the composition.

In another embodiment, the composition comprises from 55% to 80%, and preferably from 60% to 75%, by weight of the olefin multiblock interpolymer, based on the total weight of the composition. Preferably, the olefin multiblock interpolymer is an ethylene/α-olefin interpolymer. Preferably the α-olefin is a C3-C10 α-olefin and is more preferably selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene and most preferably 1-octene.

In one embodiment, the composition comprises from 5% to 10% by weight of the functionalized olefin-based polymer; from 15 to 35 percent by weight of the thermoplastic polyurethane; and from 55% to 80% by weight of the olefin multiblock interpolymer based on the total weight of the composition. Preferably, the olefin multiblock interpolymer is an ethylene/α-olefin interpolymer. Preferably the α-olefin is a C3-C10 α-olefin and is more preferably selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene and most preferably 1-octene.

In another embodiment, the composition comprises from 5% to 10% by weight of the functionalized olefin-based polymer; from 20 to 30 percent by weight of the thermoplastic polyurethane; and 60 to 75 weight percent of the olefin multiblock interpolymer based on the total weight of the composition. Preferably, the olefin multiblock interpolymer is an ethylene/α-olefin interpolymer. Preferably the α-olefin is a C3-C10 α-olefin and is more preferably selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene and most preferably 1-octene.

3. Additives for compositions according to the invention

The compositions described above, which comprise two or more components or at least three components, may optionally contain one or more additives. Additives such as plasticizing oils, lubricants, antiblocking agents, AO, UV fillers can be added to the compositions according to the invention. Typically, a composition of the invention may contain one or more stabilizers, for example antioxidants such as Irganox™ 1010 and Irgafos™ 168, both available from Ciba Specialty Chemicals. Polymers are typically treated with one or more stabilizers prior to extrusion or other melt processing. Other polymeric additives include, but are not limited to, UV light absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, lubricants, flame retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents, antioxidants -blocking agents, mold release agents , flame retardants, abrasion and scratch agents, antimicrobial agents, antistatic agents and crosslinking agents.

A composition according to the invention may comprise a combination of two or more suitable embodiments as described herein.

5. Compositions of the invention comprising an olefin-based polymer and at least one anhydride-containing compound and/or at least one carboxylic acid-containing compound

Preferred compositions of the invention contain the following: a) at least one olefin multiblock interpolymer; b) at least one thermoplastic polyurethane; and c) at least one functionalized olefin-based polymer formed from an olefin-based polymer and at least one anhydride-containing compound and/or at least one carboxylic acid-containing compound.

In one embodiment, the functionalized olefin-based polymer is present in an amount less than or equal to 20% by weight, preferably less than or equal to 15% by weight, more preferably less than or equal to 10% by weight. and even more preferably less than or equal to 5% by weight based on the total weight of the composition. In a preferred embodiment, the functionalized olefin-based polymer is present in an amount less than or equal to 10% by weight, and preferably less than or equal to 5% by weight, based on the total weight of the composition.

In another embodiment, the composition comprises 10% to 90% by weight of the thermoplastic polyurethane, preferably as described herein, and 90% to 10% by weight of at least one olefin multiblock interpolymer, based on the total weight of the components. In another embodiment, the composition comprises 1 to 10% by weight of the functionalized olefin-based polymer.

In another embodiment, the composition comprises from 10% to 50%, preferably from 25% to 40%, and more preferably from 25% to 37% by weight of the thermoplastic polyurethane, preferably as described herein, based on the total weight of the composition. .

In another embodiment, the composition comprises from 55% to 80%, preferably from 60% to 75%, and even more preferably from 63% to 75% by weight of the olefin multiblock interpolymer, based on the total weight of the composition.

In another embodiment, the composition comprises from 55% to 80%, preferably from 60% to 75%, and more preferably from 63% to 75% by weight of an olefin multiblock interpolymer, preferably as described herein, based on total weight . Preferably, the olefin multiblock interpolymer is an ethylene multiblock interpolymer and the α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and more preferably 1-octene.

In one embodiment, the composition comprises from 1% to 10% by weight of the functionalized olefin-based polymer; from 15 to 50 percent by weight of the thermoplastic polyurethane; preferably as described herein, and from 55% to 80% by weight of the olefin multiblock interpolymer, based on the total weight of the composition. Preferably, the olefin multiblock interpolymer is an ethylene multiblock interpolymer and the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and most preferably 1-octene.

In another embodiment, the composition comprises from 1% to 10% by weight of the functionalized olefin-based polymer; from 25% to 40% by weight of the thermoplastic polyurethane, preferably as described herein, and from 60% to 75% by weight of the olefin multiblock interpolymer, based on the total weight of the composition. Preferably, the olefin multiblock interpolymer is an ethylene multiblock interpolymer and the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and most preferably 1-octene.

In one embodiment, the composition comprises from 1% to 10% by weight of the functionalized olefin-based polymer; 15 to 50% by weight thermoplastic polyurethane, preferably as described herein, and 55 to 80% by weight of an ethylene multiblock interpolymer, preferably as described herein, based on the total weight of the composition. Preferably the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and most preferably 1-octene.

In another embodiment, the composition comprises from 1% to 10% by weight of the functionalized olefin-based polymer; 25 to 40% by weight thermoplastic polyurethane, preferably as described herein, and 60 to 75% by weight of an ethylene multiblock interpolymer, preferably as described herein, based on the total weight of the composition. Preferably the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and most preferably 1-octene.

In another embodiment, the olefin multiblock interpolymer is present in an amount greater than or equal to 50% by weight and the polyurethane is present in an amount less than or equal to 50% by weight, both percentages being based on combined weight. the polyurethane-olefin multiblock interpolymer. The amounts are preferably 50 to 90% by weight olefin multiblock interpolymer and 45 to 10% by weight thermoplastic polyurethane, and more preferably 55 to 85% by weight olefin multiblock interpolymer and 45 to 15% by weight thermoplastic polyurethane. . In another embodiment, the composition comprises 55 to 80% by weight of the olefin multiblock interpolymer and 45 to 20% by weight of the polyurethane. The amounts are chosen to total 100% by weight. All individual values and sub-ranges from 50 to 90 weight percent olefin multiblock interpolymer are included and described herein. All individual values and partial ranges from 50 to 10% by weight polyurethane are included and described herein. Preferably, the olefin multiblock interpolymer is an ethylene multiblock interpolymer and the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and most preferably 1-octene.

In another embodiment, the compositions of this invention comprise 50% by weight or more and preferably 60% by weight or more olefin multiblock interpolymer and 50% by weight or less and preferably 40% by weight or less thermoplastic polyurethane. In one embodiment, the composition comprises from 50% to 80%, and preferably from 55% to 77%, by weight of the olefin multiblock interpolymer; and from 20% to 50%, preferably from 23% to 45%, by weight of the thermoplastic polyurethane; and both percentages are based on the combined weight of the polyurethane-olefin multiblock interpolymer. Preferably, the olefin multiblock interpolymer is an ethylene multiblock interpolymer and the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and most preferably 1-octene.

In another embodiment, compositions of the invention comprise greater than 85%, preferably greater than 90%, and most preferably greater than 95% by weight, based on the total weight of the composition, of the combined weight of the olefinic multiblock interpolymer . and thermoplastic polyurethane. Preferably, the olefin multiblock interpolymer is an ethylene multiblock interpolymer and the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and most preferably 1-octene.

When the compositions used in the practice of this invention comprise components other than the polymeric components as discussed above, e.g., filler, pigment, etc., then the combination of olefin multiblock interpolymer, thermoplastic polyurethane, and olefin-based polymer is preferably more than 85, preferably more than 90 and most preferably more than 95% by weight based on the total weight of the mixture.

In one embodiment, the compositions used in the practice of the invention have a melt flow index (I₂) from 0.01 to 100, preferably from 0.1 to 50 and more preferably from 1 to 40 and even more preferably from 5 to 40 g/10 min, determined using ASTM D-1238 (190°C, 2, 16 kg load) . In another embodiment, the composition has an I₂greater than or equal to 0.01, preferably greater than or equal to 1, and most preferably greater than or equal to 5 g/10 min. In another embodiment, the composition has an I₂less than or equal to 100, preferably less than or equal to 50, and most preferably less than or equal to 20 g/10 min. Me₂of composition is measured in a pure mixture, i.e. H. a mixture with no other components that could significantly affect the measurement of I₂.

In another embodiment, the compositions have a percent crystallinity of less than or equal to 50, preferably less than or equal to 30, and most preferably less than or equal to 20 percent as measured by DSC. In one embodiment, these polymers have a percent crystallinity of 2 to 50 percent, inclusive of all individual values and sub-ranges of 2 to 50 percent. The crystallinity of the composition is measured in a neat mixture, i.e. H. a mixture with no other components that could significantly affect the crystallinity measurement.

In another embodiment, the compositions have a density greater than or equal to 0.855, preferably greater than or equal to 0.86, and greater than or equal to 0.87 grams per cubic centimeter (g/cm³or g/cc). In another embodiment, the composition has a density of less than or equal to 1, preferably less than or equal to 0.97, more preferably less than or equal to 0.96, and even more preferably less than or equal to 0.95 g/cm 2³. In one embodiment, the density is from 0.855 to 0.97, preferably from 0.86 to 0.95, and most preferably from 0.865 to 0.93 g/cm³. The density of the composition is measured in a neat mixture, i.e. H. a mixture with no other components that could significantly affect the density measurement. In those embodiments where the composition comprises one or more fillers, e.g. barium sulfate, talc, etc., the maximum density may exceed 1 g/cm³For example, the maximum density can reach or exceed 1.4 g/cm³depending, among other things, on the type and amount of the fee.

In another embodiment, the compositions neat and as prepared have a tensile strength of 5 to 40, preferably 8 to 30, and more preferably 9 to 20 megapascals (MPa).

In another embodiment, the compositions neat and as prepared have a machine direction or cross-machine direction elongation of 50 to 600 or 50 to 500 as measured according to ASTM D-638-03.

In another embodiment, the compositions when neat have a melt strength of from 0.5 to 50, more preferably from 0.5 to 20, and even more preferably from 0.5 to 10 centiNewtons (cN).

In another embodiment, the compositions in neat form have a surface tension of from 10 to 100, and more preferably from 20 to 70, and even more preferably from 30 to 50 dynes per centimeter at room temperature or 23°C (dynes/cm).

In another embodiment, the compositions in neat form have a surface tension greater than or equal to 32, more preferably greater than or equal to 33, and even more preferably greater than or equal to 35 dynes/cm at room temperature or 23°C.

In another embodiment, a composition of the invention, when extruded at a die temperature of 200°C (zone temperatures of 180°C-190°C) at 80 lbs/hr through a flat web having a thickness of 40 mils of a Customs. and 2 feet wide, generates surface energies >35 dynes/cm.

In another embodiment, a composition of the invention is formed into an extruded sheet that retains at least 50, preferably at least 60 percent, of its original elongation after heat aging at 120°C for 500 hours (ASTM D-882-02).

In another embodiment, the invention provides such compositions as discussed above, wherein the multiblock olefin interpolymer, and preferably an ethylene/α-olefin multiblock interpolymer, is present as a continuous or co-continuous phase with the thermoplastic polyurethane .

In another embodiment, the invention provides such compositions as discussed above and wherein the multiblock olefin interpolymer, and preferably an ethylene/α-olefin multiblock interpolymer, is present as a continuous phase with the thermoplastic polyurethane.

The compositions of the invention can be made by blending one or more multiblock olefin interpolymers, and preferably one or more ethylene/α-olefin multiblock interpolymers, with one or more thermoplastic polyurethanes. Typically, the compositions of the invention are prepared by post-reactor blending of the polymeric components (the olefin multiblock interpolymer, the polyurethane, and the functionalized olefin-based polymer). Extrusion is exemplary of post-reactor blending in which two or more solid polymers are fed into an extruder and physically mixed into a substantially homogeneous composition. Compositions of the invention can be crosslinked and/or foamed. In a preferred embodiment, the compositions of the present invention are made by blending the components in a melt process. In another embodiment, the melt process is a melt extrusion process, and preferably an "on-line" compounding process.

In another embodiment, the compositions further contain a polypropylene polymer component, such as a homopolymer of propylene, a copolymer of propylene with ethylene or at least one α-olefin, or a mixture of a homopolymer and a copolymer, a nucleated homopolymer, a copolymer, or a nucleated one Mixture of a homopolymer and a copolymer. The α-olefin in the propylene copolymer can be 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or 4-methyl-1-pentene. Ethylene is the preferred comonomer. The copolymer can be a random copolymer or a block copolymer or a blend of a random copolymer and a block copolymer. Polymers can also be branched. As such, this component is preferably selected from the group consisting of polypropylene homopolymers and propylene/ethylene copolymers or mixtures thereof. This component can have a melt flow rate (MFR) (230°C and 2.16 kg weight) of 0.1 g/10 min to 150 g/10 min, preferably 0.3 g/10 min to 60 g/10 min, stronger preferably from 0.8 g/10 min to 40 g/10 min and most preferably from 0.8 g/10 min to 25 g/10 min. All individual values and partial ranges are from 0.1 to 150 g/10 min recorded here and described here. This component can also have a density of from 0.84 g/cc to 0.92 g/cc, more preferably from 0.85 g/cc to 0.91 g/cc, and most preferably from 0.86 g/cc to 0.90 g/cc. All individual values and sub-ranges from 0.84 g/cc to 0.92 g/cc are recorded and shown here. This component can have a melting point greater than 125°C.

As used herein, "nucleated" refers to a polymer that has been modified by the addition of a nucleating agent such as Millad®, a dibenzyl sorbitol commercially available from Milliken. Other conventional nucleating agents can also be used.

Additives such as process oils, slip agents, anti-block agents, AO, UV fillers can be added to any inventive composition described herein. Typically the composition will contain one or more stabilizers, for example antioxidants such as Irganox™ 1010 and Irgafos™ 168, both supplied by Ciba Specialty Chemicals. An example of a hindered phenolic antioxidant is Irganox® 1076 antioxidant available from Ciba-Geigy Corp. Polymers are typically treated with one or more stabilizers prior to extrusion or other melt processing. Other polymeric additives include, but are not limited to, UV light absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, lubricants, flame retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents, and anti-blocking agents. Additional additives include, but are not limited to, surface tension modifiers, pigments, process oil, wax, blowing agents, antiblock agents, foaming agents, antistatic agents, release agents, blowing agents, blowing agents, antistatic agents, release agents, resistance, abrasion and scratch additives, antimicrobials, antistatic agents, and crosslinking agents.

A composition according to the invention may comprise a combination of two or more suitable embodiments as described herein.

to shape

The compositions described above, comprising two or more components or at least three components, can be used for a wide variety of applications. For example, the invention provides an article comprising at least one component formed from a composition according to the invention as described herein. The compositions of the invention are particularly suitable for injection molded articles, blow molded articles, overmolded articles, extruded films, adhesives and tie layers between extruded sheets, tie layers between cast sheets, tie layers between films and tie layers between profiles, fibers and dispersions. (aqueous and non-aqueous). Additional items include a carpet component; Leatherette; Artificial grass; an adhesive; A tissue; a dispersion; a wire wrap; A cable; a protective suit; a lining; a coated article; a laminated article; a foam laminate; a shoe component such as a shoe outsole, a shoe midsole, and a shoe sole; Plastic shoes in general (e.g. boots, sandals and galoshes); o artificial and natural leather items; or automotive products (e.g. airbags, headrests, armrests, carpet covers, paintable auto parts, etc.) and adhesives for KEVLAR.

In another embodiment, the article is an automotive finish, such as an instrument panel finish or a door trim finish; an awning; a tarpaulin a roof structural element (e.g. adhesives for epoxy, urethane or acrylic substrates for all roofing applications such as insulation bonding, liquid roofing, facade waterproofing, expansion joints, wet room waterproofing, pitched roofs, acrylic bonded roofs, bituminous joints and renovations bonded with PUR); a steering wheel; a powder coating; a molding of powdered mud; a durable consumable; a handle; a handle; a computer component; a strap; wall lamps; a shoe component; a conveyor belt or toothed belt; lubricants and engine oil components; fibers; Foils, foil sleeves of various sizes; fabrics; Leatherette; injection molded items such as injection molded and/or paintable toys; Artificial grass; Leatherette; Adhesives for Kevlar; Foil (n; film casings of various sizes; dispersions; powder coatings, powdered slurry casts, or rotomoulded (typically each with a particle size less than 950 microns), durable goods, cables, belts, computer hardware components (e.g. keyboards), belts, adhesives for Fabric/polyurethane (PU) foam laminates (e.g. appliques and shoes), adhesives (hot melt or other) e.g., for bonding a wear layer to an extruded article, conveyor and timing belts, fabrics, carpets, artificial turf, coatings , wire and cable, and raincoats and similar protective clothing.

Specific applications include adhesives for polyurethane films and foams and adhesives for polyesters; dyes, adhesives for paints and adhesion promoters for paints; weldability applications; Interior and exterior fittings for motor vehicles; compatibilizers for polymer compositions; and curing agents for polymeric compositions.

In particular, the compositions of the invention can be used in the following applications: (a) soles, midsoles, unit soles and reinforcements to be assembled with standard polyurethane adhesive systems currently used in the footwear industry, (b) painting of soles and intermediate soles with polyurethane paints currently used in the footwear industry, and (c) over-molding of polyolefins and two-component polyurethanes for soles and multi-layer midsoles. In addition, the compositions of the present invention can be used in other applications such as automotive applications and construction applications. Automotive applications include but are not limited to the manufacture of bumper panels, vertical panels, soft TPO liners, interior panels, and sheet metal panels. Construction applications include but are not limited to furniture and toy manufacturing.

Other uses include bonding coextruded films where one or more substrates are compatible or reactive with functional groups such as hydroxyl groups, and laminating polyolefin-based films to other polar substrates (e.g., laminating glass). Other uses include synthetic leather for bonding to polar substrates such as polyurethane, polyvinyl chloride (PVC), and others. Faux leather is used for car interiors and is bonded to polyurethane for seats and headliners.

The compositions according to the invention are also suitable for health and hygiene products such as towels, cleaning towels, foams or directly dyeable fibers. The compositions of this invention can be used to improve the hydrophilicity of elastomers for new membrane structures for separation or breathability. The compositions according to the invention are also suitable for use as self-adhesive elastomers in metallic structures or automotive textiles. As discussed above, the compositions of this invention are useful for interaction-enhanced blends and compatibilizers with polar polymers such as TPU, EVA, PVC, PC, PET, PLA (polylactic acid), polyamide esters, and PBT. These compositions can be used for new compounds for footwear, automobiles, consumer products, durable goods, household appliances, electronic boxes, apparel and conveyor belts.

The compositions of the invention can also serve as compatibilizers between natural fibers and other polyolefins for use in applications such as wood binder formulations or cellulosic binder formulations. The inventive compositions are also useful in blends with one or more polyether block amides such as the Pebax® polymers available from Arkema. The compositions of this invention can also be used as impact modifiers for nylon. In addition, the amino groups of the compositions of the invention can be protonated or alkylated to form quaternary or ionomeric nitrogen atoms for use as antimicrobial agents.

Compositions of the invention can also be used to improve interaction with fillers such as silica, carbon black or clay for use in formulations for toners, tires, coatings or other compounds. The compositions of this invention can also be used in motor oil viscosity modifiers, motor oil dispersants, dyeable or printable fibers for clothing, paint adhesion promoters, adhesives for glass, metal and PVDC barrier resins, dispersions, components in primers and sizing agents.

Therefore the invention also provides a painted substrate, the substrate being formed from a composition according to the invention as described herein and the paint comprising at least one of an acrylic polymer, alkyd resin, cellulosic material, melamine resin, urethane resin, carbamate resin, polyester resin, vinyl acetate resin, polyol and alcohols. In another embodiment, the ink is a water-based ink. In another embodiment, the ink is an organic solvent based ink.

This embodiment of the invention works well with a wide variety of paint formulations. The main components of solvent-based paints and varnishes are solvents, binders, pigments and additives. In paints, the combination of binder and solvent is called the paint carrier. The pigment and additives are dispersed within the vehicle. The amount of each component varies depending on the specific ink, but solvents traditionally make up around 60% of the total formulation. Typical solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and water. Binders make up about 30% by weight, pigments 7 to 8% by weight and additives 2 to 3% by weight. Some of the polymers and other additives used in paint formulations include: acrylic polymers, alkyd resins, cellulosic based materials such as cellulose acetate butyrate, melamine resins, carbamate resins, polyester resins, acetate resins, vinyl, urethane resins, polyols, alcohols, materials such as titanium dioxide (rutile), mica flake, iron oxide, silica, aluminum and the like.

The invention also provides an overmolded article, the article formed from a polar substrate, and a shaped liner formed from a composition according to the invention as described herein. In another embodiment, the invention provides an overmolded article, the article being formed from a substrate comprising a composition according to the invention as described herein and a molded liner comprising a nonwoven material. In another embodiment, the article is in the form of a handle, handle or belt.

In another embodiment, the invention provides an overmolded article comprising a polycarbonate base sheet of variable thickness and preferably having at least one textured surface to which the composition of the invention can be adhered, typically by a molding process. temperature of 140° C. These items have excellent adhesion. This article can be further laminated to polyolefin using conventional welding techniques such as pressure and heat, or a second sheet of polycarbonate having a textured surface can be adhered to the exposed surface of the film of the composition of the invention.

The invention also provides a laminated structure comprising a first layer and a second layer, the first layer being formed from a composition according to the invention as described herein and the second layer being formed from a composition comprising a polar material. In another embodiment, one of the layers is in the form of a foam. In another embodiment, one of the layers is in the form of a fabric. In another embodiment, the laminated structure is in the form of an awning, a tarpaulin, or a car wrap, or a steering wheel.

In another embodiment, the invention provides a laminated structure comprising a polycarbonate base sheet of varying thickness and preferably having at least one textured surface to which a composition of the invention can be adhered, typically by a bonding process. Moderate temperature compression molding. temperature of 140ºC. These laminates have been shown to have excellent adhesion; for example, a peel strength of 1 N/mm for a polyolefin functionalized with secondary amino groups at a concentration of 1.1 percent by weight. This article can also be laminated to polyolefin using conventional welding techniques such as pressure and heat. In addition, a second sheet of polycarbonate having a textured surface can be laminated over the composition of the invention (having a textured surface at the interface).

Another embodiment of this invention is a multilaminate structure of polycarbonate and polyolefin films interleaved to increase the toughness of the final structure. Another embodiment would be an elastomeric coating composition of the invention deposited on the polycarbonate surface to provide a scratch resistant assembly coating that could be readily thermoformed, for example at a thermoforming temperature of about 160°C or higher.

The invention also provides a shaped article comprising a first component and a second component, the first component being formed from a polar material and the second component being formed from a composition according to the invention as described herein. In another embodiment, the article is in the form of an automobile cover, applique, shoe, conveyor belt, timing belt, or consumable.

"Laminate", "lamination" and similar terms mean two or more layers, e.g. B. Film layers that are in close contact with each other. Laminates include moldings that carry a coating. Laminates are not blends, although one or more layers of a laminate may comprise a blend.

"Polar", "polar polymer" and similar terms mean that the polymer molecules have a permanent dipole, that is, the polymer molecule has a positive end and a negative end. In other words, the electrons in a polar molecule are not evenly shared between the atoms in the molecule. In contrast, "non-polar", "non-polar polymer" and similar terms mean that the polymer molecules do not have a permanent dipole, that is, the polymer has no positive end and no negative end. The electrons in a nonpolar molecule are shared essentially equally among the atoms in the molecule. Most hydrocarbon liquids and hydrocarbon polymers are non-polar.

Carboxyl, hydroxyl substituted polymers and the like are often polar polymers. Articles made from non-polar polymers have a relatively low surface energy, i. H. less than about 32 dynes/cm (dynes/cm), and articles made from polar polymers have relatively high surface energies, i. H. 32 or more dynes/cm. . The non-polar material of this invention typically comprises one or more non-polar, typically elastomeric, thermoplastic olefinic polymers devoid of any significant amount of polar functionality, e.g. hydroxyl, carboxyl, carbonyl, ester, ether, amide, mercaptan, halide , and the same. . The polar material of this invention typically includes one or more polymers that include one or more polar functionalities. Typical polymers containing one or more polar functionalities include, but are not limited to, polyesters, polyethers, polylactic acid, polycarbonates, nylon, polysulfides, polysulfones, polyurethanes, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, acrylonitrile, ABS, esters of polyamide, and polysiloxanes.

"Insignificant amount of polar functionality" and similar terms mean that a polymer does not include a sufficient amount of polar functional groups to impart a surface energy of at least about 32 dynes/cm to an article made therefrom.

"Overmolding" and similar terms refer to a process in which a resin is injected into a mold containing a previously placed substrate and poured onto that substrate. Overmolding is commonly used to improve the performance and properties of an end product by injecting a resin onto another polymeric substrate. Overmolding can be used to form seamless and integrated parts. Examples of overmolded parts include flexible handles on power tools and cookware that provide additional gripping properties without the hygienic concerns normally associated with mechanical assemblies. The substrate can be any suitable material, such as a piece of plastic, metal, or ceramic.

"Cast liner" and similar terms refer to an article that includes at least two parts (an injection molded part and a substrate) that are bonded together. The injection molded part is placed on the substrate outside the injection mold. An adhesive may be used to bond the molded part to the substrate. The substrate can be any suitable material, such as a piece of plastic, metal, or ceramic.

Substrates to which the compositions of the invention can be applied include a wide range of materials, both polar and non-polar, such as, but not limited to, polymers, metal, wood, concrete, glass, ceramics and various composites two or more more of these materials. Alternatively, these materials can be applied to an article formed from a composition of the invention containing them.

Methods of application include brushing, printing, coloring, overmolding, and the like, including many variations of each, for example, applying, spraying, dipping, extruding, and other methods. Compositions of the invention can be crosslinked before, during or after application to a substrate and can be crosslinked in any suitable manner, for example by peroxide, sulfur, moisture, silane, radiation, heat and the like. In one embodiment, the composition of the invention is applied to a substrate and the composition of the invention is crosslinked during application and/or after application. For crosslinking, compositions of the invention typically contain unsaturation, for example a diene-containing PO.

In one embodiment, the compositions of the invention can be used to form an adhesive layer between polar and non-polar materials, in particular between polar and non-polar polymeric materials, for example between a film layer of a non-polar PO such as polyethylene or polypropylene. , and a film layer of a polar polymer such as polylactic acid (PLA) or polyamide or polyester. The inventive compositions of this invention are particularly useful as make coats for bonding a) a polyethylene or polypropylene film or a polyethylene or polypropylene molded article surface to b) a film or molded article surface of an ethylene/acrylic acid copolymer (EAA) material or a Copolymer of PLA or polyethylene terephthalate (PET). Any process combining coextrusion, extrusion lamination, adhesive lamination, and/or foam casting or extrusion can be used to create such laminated structures, including structures where one layer comprises a foam.

The compositions of this invention can also be used in dispersions, such as water-based dispersions for use as olefinic shoe primers to improve adhesion to polyurethane and leather adhesives; Fabric Coating Adhesion (adhesion to PET, Nylon, PP, elastomer rich TPO including POE, EPDM or other non-polar elastomers or a combination thereof, etc.).

In general, compositions of the invention can be used for adhesion applications such as overmolding, painting and printing applications. The compositions can also be used in coloring applications. Particular bonding applications include adhesives for polyurethanes in automotive applications such as instrument panel and door panel coatings, adhesives in footwear applications such as various shoe components, and adhesives for polyesters in EPDM conveyor belts. Water-based dispersions made from the compositions of this invention can be used as adhesives in footwear to bond layers of polyolefin and polyurethane. Aqueous dispersions based on the compositions of the invention can also be used as primers on olefinic footwear components to promote adhesion to polyurethane adhesives and adhesion to leather. Other applications include adhesives for fabric coatings (e.g. adhesion to PET, nylon, PP, elastomer rich TPO including POE, EPDM, other non-polar elastomers or a combination thereof). The compositions of the present invention can also be used as an ingredient in coatings, inks, adhesives, adhesives, films, printable surfaces, dyeable films and fibers, artificial leather, protective clothing, artificial turf, carpet fibers, textiles, medical supplies (e.g. blood bags and tubing), toys, overmolded flexible products, soft touches, athletic apparel and the like, or in any application where adhesion to polyolefin is desired. Other applications are described in this document.

Other particularly preferred applications include thermoformed automotive coatings, PU foam bonding (preferably without the use of water-based primers based on maleated chlorinated polyolefins), home coating where a high moisture vapor transmission rate (100% PELLETHANE TM 2103-70A meets the required requirements) and is good adhesion to fabric; adhesive films (blown or cast); co-extruded films where POE/TPU is used as a thin adhesive layer (e.g. a roof membrane that needs to be bonded with PU adhesives). In these situations, the composition of the invention is often used with an appropriate diol, isocyanate, POE and/or compatibilizer. The composition of the invention can result in increased surface energy (>37 dynes/cm) for adhesion to polar materials. If TPU were fully aliphatic (no aromaticity, no lack of saturation), the POE/TPU system could function as a weather-resistant skin layer (as opposed to an adhesive tie layer).

In one embodiment, the invention is a method of imparting radio frequency (RF) solderability and/or printability to an article comprising a low surface energy material, e.g. H. a non-polar material. HF weldability can allow the use of polyolefin sheets or films in applications such as roofing membranes, stationery, synthetic leather, etc. where polyolefins are desirable due to cost/performance advantages and recyclability. HF welding materials and methods are known in the art and are generally described in US2004/0077791. Known methods include adding a zeolite or a resin containing a polar functionality, for example a MAH-grafted resin or an EAA, EEA, EMA, EBA or EMAA copolymer, to a non-polar olefin resin prior to addition of the polymer . -polar is subjected to HF welding or printing. However, these methods generally provide poor weldability and/or printability results relative to the results of this embodiment of the invention under similar conditions using similar amounts of similar materials.

In another embodiment, the invention is a method of imparting at least one of paintability, printability, dyeability, and overmoldability to an article comprising a low surface energy material.

This embodiment of the invention works well with a wide variety of paint formulations. The main components of solvent-based paints and varnishes are solvents, binders, pigments and additives. In paints, the combination of binder and solvent is called the paint carrier. The pigment and additives are dispersed within the vehicle. The amount of each component varies depending on the specific ink, but solvents traditionally make up around 60% of the total formulation. Typical solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and water. Binders make up about 30% by weight, pigments between 7 and 8% by weight and additives between 2 and 3% by weight. Some of the polymers and other additives used in paint formulations include: acrylic polymers, alkyd resins, cellulosic based materials such as cellulose acetate butyrate, melamine resins, carbamate resins, polyester resins, vinyl acetate resins, urethane resins, polyols, alcohols, inorganic resins, and materials such as titanium dioxide (rutile), mica flake, iron oxide, silica, aluminum and the like.

As non-limiting examples, the compositions of the invention can be used to promote adhesion between (i) thermoset PU foams and polyolefin elastomers (POE), in particular as a bonding layer between sheets, films or extruded profiles, (ii) POE / pd-TPU -blown film; (iii) pure TPU and POE, (iv) butadiene rubber and TPU or a thermoplastic vulcanate (TPV) such as those described in EP 0 468 947; (v) nylon or other polar plastics and cross-linked chlorinated polyethylene or EPDM in extrusion or molding processes, (vi) polypropylene and TPU fibers, e.g. in carpets, artificial turf, etc. (vii) polar fillers and non-polar materials, e.g. wire and cable insulation, coatings, etc., (viii) hot melt adhesives and polar substrates, (ix) POE and pd-TPU in molded articles, e.g. B. shoes and automobiles, and (x) aqueous dispersions from which various articles can be made, eg film.

Substrates to which the compositions of the invention may be applied include a wide variety of materials, both polar and non-polar, including but not limited to polymers, metal, wood, concrete, glass, ceramic, and various bi- or bimetallic composites more of these materials. Alternatively, these materials can be applied to an article comprising the mixture. Methods of application include brushing, printing, coloring, overmoulding, and the like, including many variations of each, for example, brushing, spraying, dipping, extruding, etc. Compositions of the invention may be crosslinked before, during, or after application to a substrate. B. peroxide, sulfur, moisture, silane, radiation, heat and the like. In one embodiment, the composition is applied to a substrate and the composition is crosslinked during application and/or after application. For crosslinking, the composition of the invention will normally contain unsaturation, for example a PO containing non-hydrogenated diene and/or TPU.

In one embodiment, the composition of the invention serves as an adhesive layer between polar and non-polar materials, in particular between polar and non-polar polymeric materials, for example between a film layer of a polyolefin such as polyethylene or polypropylene and a layer of a polyolefin sheet. of a polar polymer such as polylactic acid (PLA) or polyamide or polyester. The pd-TPUs of this invention are particularly useful as tie layers for bonding a polyethylene or polypropylene film or a molded article surface to an ethylene/acrylic acid copolymer (EAA) or PLA film or molded article surface. or polyethylene. terephthalate (PET). Any process combining coextrusion, extrusion lamination, adhesive lamination, and/or foam casting or extrusion can be used to create these laminated structures, including structures where they are made of foam.

In another embodiment of the invention, an article is provided that includes a film formed from a composition of the invention and a polyurethane foam, and wherein the film is adhered to a surface of the polyurethane foam. Such an article can be a dashboard. In another embodiment, the adhesion between the film of the invention and the polyurethane foam is stronger than the adhesion between the foam and another film made from a composition comprising the same components as the film of the invention except for the functionalized polyethylene.

In one embodiment of the invention there is provided a film formed from a composition of the invention. In another embodiment there is provided a film containing at least two layers or layers and in which at least one layer or layer is formed from a composition according to the invention as described herein. In another aspect of the invention, the film is formed by coextrusion or lamination. Such a film may contain one or more morphological features as described herein and preferably contains a continuous phase of the ethylene and polyurethane based polymer. Also provided is an article that includes at least one component that includes or is formed from the film. These articles include, but are not limited to, automotive interiors, trim, fabric covers, vacuum formed profiles, shoe components, laminated panels, and other articles. These articles can be made by the respective methods described herein.

In another embodiment of the invention there is provided a film comprising at least three layers or layers and in which at least one layer or layer is formed from a composition according to the invention as described herein. In another aspect of the invention, the film is formed by coextrusion or lamination. Such a film may contain one or more morphological features as described herein and preferably contains a continuous phase of the ethylene and polyurethane based polymer. Also provided is an article that includes at least one component that includes or is formed from the film. These articles include, but are not limited to, automotive interiors, trim, fabric covers, vacuum formed profiles, shoe components, laminated panels, and other articles. These articles can be made by the respective methods described herein.

In another embodiment, the invention provides a film containing at least two layers and having at least one layer formed from a composition of the invention and having at least one other layer formed from a composition comprising ethylene/α-olefin . Interpolymer having a melt strength greater than or equal to 5 cN. The invention further provides an article comprising or formed from such a film.

The invention also provides articles containing at least one component formed from a composition according to the invention as described herein. These articles can be made by any one or more appropriate operations including, but not limited to, extrusion, thermoforming, blow molding, injection molding, foaming, and calendering processes. In one embodiment, the items described herein are non-automotive items and are used in non-automotive applications.

The invention also provides methods of making the compositions and articles described herein. The invention also provides various embodiments and combinations of two or more embodiments of the compositions, articles and methods described herein.

Each range of numbers mentioned in this document includes all values from the lowest value to the highest value in increments of one unit, provided that there is a gap of at least two units between each lower value and each higher value. For example, if a compositional physical or mechanical property such as molecular weight, viscosity, melt index, etc., 102, etc. and subsidiary ranges such as 100-144, 155-170, 197-200, etc. are specifically listed in this specification. For ranges containing values less than one or fractions greater than one (e.g. 1.1, 1.5, etc.), a unit is rendered as 0.0001, 0.001, 0.01, or 0.1, as appropriate considered. For ranges containing numbers less than ten (e.g. 1 to 5), a unit is usually assumed to be 0.1. These are only examples of what is specifically intended, considering all possible combinations of numerical values between the smallest value and the largest value listed as expressly provided in this application. Numerical ranges, as discussed herein, have been listed with reference to melt index, melt flow rate, molecular weight distribution, percent crystallinity, density, and other properties.

The term "composition" as used herein includes a mixture of materials comprising the composition and reaction products and decomposition products formed from the materials of the composition.

The terms "blend" or "polymer blend" as used herein mean a blend of two or more polymers. Such a mixture may or may not be miscible (no phase separation at the molecular level). Such a mixture may or may not be phase separated. The mixture may or may not contain one or more domain configurations as determined by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art.

The term "polymer" as used herein refers to a polymeric compound made by the polymerisation of monomers, whether of the same or a different type. The generic term polymer thus includes the term homopolymer, which is generally used to refer to polymers made from a single type of monomer, and the term interpolymer, as defined below. The terms "ethylene/alpha-olefin polymer" and "propylene/alpha-olefin polymer" refer to the interpolymers described below.

The term "interpolymer" as used herein refers to polymers made by polymerizing at least two different types of monomers. Therefore, the generic term interpolymer includes copolymers, which are generally used to denote polymers made from two different monomers and polymers made from more than two different types of monomers.

As used herein, the term "olefin-based polymer" refers to a polymer containing greater than 50 mole percent polymerized olefin monomer, e.g. B. ethylene or propylene (based on the total amount of polymerizable monomers), and may optionally comprise one or more comonomers.

The term "ethylene-based polymer" as used herein refers to a polymer comprising greater than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and may optionally include one or more comonomers. As used herein, this term does not refer to an olefin multiblock interpolymer as described herein.

As used herein, the term "ethylene/alpha-olefin interpolymer" refers to an interpolymer comprising greater than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and at least one alpha-olefin. As used herein, this term does not refer to an olefin multiblock interpolymer as described herein.

The term "propylene-based polymer" as used herein refers to a polymer comprising greater than 50 mole percent polymerized propylene monomer (based on the total amount of polymerizable monomers) and may optionally include one or more comonomers. As used herein, this term does not refer to an olefin multiblock interpolymer as described herein.

As used herein, the term "propylene/alpha-olefin interpolymer" refers to an interpolymer comprising greater than 50 mole percent polymerized propylene monomer (based on the total amount of polymerizable monomers) and at least one alpha-olefin. As used herein, this term does not refer to an olefin multiblock interpolymer as described herein.

As used herein, the term "propylene/ethylene interpolymer" refers to an interpolymer comprising greater than 50 mole percent polymerized propylene monomer (based on the total amount of polymerizable monomers), ethylene, and optionally at least one alpha-olefin. As used herein, this term does not refer to an olefin multiblock interpolymer as described herein.

As used herein, the term "amine-reactive group" refers to a chemical group or moiety capable of reacting with an amine group.

As used herein, the terms "hydroxyl-reactive group" or "hydroxyl-reactive group" refer to a chemical group or moiety capable of reacting with a hydroxyl group.

As used herein, the term "anhydride-containing compound" refers to a chemical compound that includes at least one anhydride group.

As used herein, the term "carboxylic acid-containing compound" refers to a chemical compound that includes at least one carboxylic acid group.

As used herein, the term "amine-containing compound" refers to a chemical compound that includes at least one amine group.

The terms "hydroxyl-containing compound" or "hydroxyl-containing compound" as used herein refer to a chemical compound that includes at least one -OH group.

As used herein, the term "functionalized olefin-based polymer" refers to a polymer formed from an olefin-based polymer and one or more compounds each containing at least one functional group such as anhydride, carboxylic acid, amine, hydroxyl, or imide

The term "amine-functionalized olefin-based polymer" as used herein refers to a polymer formed from an olefin-based polymer and one or more compounds, and at least one compound contains at least one amine group.

As used herein, the term "hydroxyl-functionalized olefin-based polymer" refers to a polymer formed from an olefin-based polymer and one or more compounds, and at least one compound contains at least one hydroxyl group.

The term "imide-functionalized olefin-based polymer" as used herein refers to a polymer formed from an olefin-based polymer and one or more compounds, and at least one compound contains at least one imide precursor capable of forming an imide . (see for example the experimental examples below).

The test method

Density is determined according to ASTM D792-00, American Society for Testing and Materials (ASTM) Method B.

The melt index (I 2 ) in g/10 min is measured using ASTM D-1238-04 (version C), condition 190°C/2.16 kg. The 110" notation refers to a melt index in g/10 min measured using ASTM D-1238-04, 190°C/10.0 kg condition. The 121" notation refers to a melt index in g /10 min measured using ASTM D-1238-04, condition 190°C/21.6 kg. Polyethylene is typically measured at 190°C while polypropylene is typically measured at 230°C. MFR stands for Melt Flow Rate for Propylene-Based Polymers and is measured using ASTM D-1238 condition at 230°C/2.16 kg. For urethane-based polymers, including the blend comprising such polymers, with the exception of PELLETHANE™ polymers, melt index is measured according to ASTM D-1238 condition 190°C/2.16 kg. For PELLETHANE ™ (Pellethan ™ 2102-80A AND 2103-70A) the melt index is measured according to ASTM D-1238, 190°C/8.7 kg condition.

The differential scanning calorimeter (DSC) is performed using a model TAI Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 cc/min is used. The sample is pressed into a thin film and melted in the press at about 175°C and then air cooled to room temperature (25°C). The material (3-10 mg) is then cut into a 3 mm diameter disc, accurately weighed, placed in a light aluminum tray (ca. 50 mg) and then sealed. The thermal behavior of the sample is examined with the following temperature profile. The sample is rapidly heated to 180°C and held isothermally for 3 minutes to remove any previous thermal history. The sample is then cooled to -90°C at a cooling rate of 10°C/min and held at -90°C for 3 minutes. The sample is then heated to 150°C at a heating rate of 10°C/min. The cooling and second heating curves are recorded. The melting temperature (Tm) is determined from the second heating curve. The crystallization temperature (Tc) is determined from the first cooling curve.

Ultimate tensile strength and elongation at break are measured according to ASTM D-638-03. Both measurements are performed at 23°C on stamped D638 Type IV samples.

The surface tension is measured according to ASTM D2578-04a, method B and DIN 53364 (1986). ARCOTEC test inks are used, which are liquids with a defined surface tension and are available in ranges from 28 to 56 mN/m. The tests are carried out at room temperature (23°C).

Surface energy is measured using ARCOTEC™ test inks and test pens available from Lotar Enterprises. As a starting point for each test, a test ink or test pen should be applied with a mean value, eg 38 mN/m (dyne/cm). If the line of ink remains unchanged on the surface of the material for at least 2 seconds without becoming a drip, the surface energy of the material is equal to or greater than the surface tension of the liquid. The test ink/test pen with the next higher value is applied to the surface, eg 40 mN/m (dyne/cm). This test should be repeated with the next higher surface tension value until within 2 seconds the liquid line becomes discrete drops. If droplets form from the liquid line at the starting point (38 mN/m (dyne/cm)), the test is continued with test inks/test pens with lower values, which is usually the case with metals. 32 mN/m (dyne/cm) is often mentioned as the general limit. Below this value of surface energy, the adhesion is poor, above this value, the adhesion is good or fair.

Sheet hardness properties are measured according to ASTM D2240-05. Tensile properties are determined by standard test method ASTM D638-03.

Melt strength is measured on selected polymer samples in a Goettfert Rheotens Melt Tensile Tester at a temperature of 190°C. The Rheotens tester consists of two counter-rotating wheels that pull a molten wire that is extruded from a capillary matrix. , at constant speed. . The wheels are fitted with a scale to measure the stress response of the casting when accelerating the wheels. The wheels can accelerate until the line breaks. The force to break the wire is given as the melt tension in centiNewtons (cN).

The RR (V0.1/V100) is determined by examining samples using fusion rheology techniques on a Rheometric Scientific, Inc. ARES (Advanced Rheometric Expansion System) Dynamic Mechanical Spectrometer (DMS). The samples are tested at 190°C using the dynamic frequency mode and parallel plate fixtures with 25 millimeter (mm) diameter and a 2 mm gap. With a strain rate of 8% and a gradually increasing oscillation rate from 0.1 to 100 rad/s, five data points are obtained for each decade of analyzed frequency. Each sample (pellets or bales) is formed into plaques 3 inches (7.62 centimeters (cm)) in diameter and ⅛ inch (0.049 cm) thick at 20,000 psi (137.9 megapascals (MPa)) pressure for one minute at 180° C Compression Molded The panels are set aside and allowed to cool (over a period of 1 minute) to room temperature. The "25mm boards" are cut from the middle of the larger boards. These 25mm diameter aliquots are then introduced into the ARES at 190°C and allowed to equilibrate for five minutes before beginning the assay. Samples are kept in a nitrogen environment during analyzes to minimize oxidative degradation. Data reduction and manipulation is performed by the Windows 95-based ARES2/A5:RSI Orchestrator software package. RR measures the relationship of the viscosity curve to the shear rate.

The Mooney viscosity of the interpolymer, MV, (ML 1+4 at 125°C) is measured according to ASTM D1646-04. The processing rheology ratio PRR is calculated from MV and RR according to the formula; PRR = RR + [3.82 - Mooney viscosity of the interpolymer (ML₁₊₄at 125°C)]x0.3. ML refers to the large Mooney rotor. The viscometer is a Monsanto MV2000 instrument.

Tensile strength and elongation were measured according to ASTM D-882-02. The samples were extruded films.

Type C tear was measured according to ASTM D-882-02. The samples were extruded films.

Gloss (60 degrees) was measured according to ASTM D-2457-03. The samples were extruded films.

Thermal Aging Study. For each analysis, the sample (extruded sheet) was heat treated at 120°C in a convection oven (Lindberg Blue Oven, Model ESP-400C-5, circulating air) for the time periods indicated, for example, in Tables 9 and 10 in the following examples . After this heat treatment, the sample was equilibrated at room temperature (16 h - 96 h 9 see ASTM D573, 10.5)). Tensile strength and elongation were then measured according to ASTM D-882-02.

Moisture Vapor Transmission Rate Test (ASTM E 96/E 96M-05, Imperial Method): Used to determine Moisture Vapor Transmission Rate (MVT) and permeability using the desiccant method. The temperature and relative humidity for the evaluation were 72°F and 50%, respectively. The unlaminated films were sealed in the open mouth of a test pan containing a desiccant and the assembly placed in a controlled atmosphere of 72°F and 50% relative humidity. Periodic weighings determine the rate of movement of water vapor through the sample into the desiccant. At a deviation of 13.3 from ASTM E 96/E 96M-05, MVT and permeability were normalized to film thickness, yielding the normalized MVT and permeability coefficient, respectively, by multiplying MVT and permeability by the film thickness measurement. This happened because permeance and MVT are directly related to the sample thickness and the thickness variability resulted in the film manufacturing process.

Fourier-Transformations-Infrarotspektroskopie-Analyse (FTIR)

Maleic anhydride content

The concentration of maleic anhydride is determined by the ratio of the peak heights of maleic anhydride at the 1791 cm wavenumber⁻¹to the polymer reference peak, which in the case of polyethylene is at wavenumber 2019 cm⁻¹. The maleic anhydride content is calculated by multiplying this ratio by the appropriate calibration constant. The equation used for maleic-grafted polyolefins has the following form.
MAH (% on pesos) =A*{[FTIR peak area at 1791 cm⁻¹]/[FTIR PeakArea 2019 cm⁻¹ ]+B* [Maximum FTIR range at 1712 cm⁻¹]/[FTIR PeakArea@2019 cm⁻¹]} (equation 1)

The calibration constant A can be determined using C13 NMR standards. Actual calibration constant may vary slightly depending on instrument and polymer. The second component at wave number 1712 cm⁻¹explains the presence of maleic acid, which is negligible for the newly grafted material. However, over time, maleic anhydride readily converts to maleic acid in the presence of moisture. Depending on the surface, significant hydrolysis can occur within a few days under ambient conditions. The acid has a clear peak at wave number 1712 cm⁻¹. The constant B in Equation 1 is a correction for the difference in extinction coefficients between the anhydride and acid groups.

The sample preparation procedure begins with pressing the sample, typically 0.05 to 0.15 millimeters thick, in a heated press between two protective sheets at 150-180°C for 1 hour. MYLAR and TEFLON are suitable protective films to protect samples from dishes. Aluminum foil should never be used (maleic anhydride reacts with aluminum). The boards must be under pressure (~10 tons) for about 5 minutes. The sample is cooled to room temperature, placed in a suitable sample holder and then examined in the FTIR. A background check should be performed prior to each sample run or as needed. Test accuracy is good with inherent variability of less than ±5%. Samples should be stored under desiccant to avoid excessive hydrolysis. Moisture content in the product has been measured to be as low as 0.1% by weight. However, the conversion of anhydride to acid is reversible with temperature, but it can take up to a week for the conversion to complete. Inversion is best performed in a vacuum oven at 150°C and a good vacuum (about 30 inches Hg) is required. If the vacuum is insufficient, the sample tends to oxidize, resulting in an infrared peak at about 1740 cm.⁻¹making the values very low. Maleic anhydride and acid are represented by peaks at about 1791 cm⁻¹e 1712cm⁻¹, or.

Test method for the characterization of olefin multiblock interpolymers

1. GPC method for Samples 1-4 and A-C

An automated liquid handling robot equipped with a heated needle set at 160°C is used to add 300 ppm ionol-stabilized 1,2,4-trichlorobenzene to each dry polymer sample to give a final concentration of 30 mg/mL. A small glass rod is placed in each tube and the samples are heated at 160°C for 2 hours on a heated orbital shaker rotating at 250 rpm. The concentrated polymer solution is then diluted to 1 mg/mL using the automated liquid handling robot and the heated needle is set at 160°C.

A Symyx Rapid GPC system is used to determine molecular weight data for each sample. A Gilson 350 pump set with a flow rate of 2.0 mL/min is used to pump helium-stabilized purified 1,2-dichlorobenzene containing 300 ppm ionol as the mobile phase through three 10 micrometer (μm) mobile phase. 7.5 mm tubes connected in series and heated to 160 °C. A Polymer Labs ELS 1000 detector is used with the vaporizer set at 250°C, the nebulizer set at 165°C and the nitrogen flow rate at 1.8 SLM at a pressure of 60-80 psi (400-600 kPa). is set.₂. Polymer samples are heated to 160 °C and each sample is injected into a 250 µl loop using the liquid handling robot and a heated needle. Serial analyzes of the polymer samples using two switched loops and overlapping injections are used. Sample data is collected and analyzed using Symyx Epoch™ software. Peaks are manually integrated and molecular weight information is reported uncorrected against a standard polystyrene calibration curve.

2. Standard CRYSTAF Method

Branching distributions are determined by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit commercially available from PolymerChar, Valencia, Spain. Samples are dissolved in 1,2,4-trichlorobenzene at 160°C (0.66 mg/ml) for 1 hour and stabilized at 95°C for 45 minutes. Sample temperatures range from 95 to 30 °C at a cooling rate of 0.2 °C/min. An infrared detector is used to measure polymer solution concentrations. The accumulated soluble concentration is measured as the polymer crystallizes while the temperature is reduced. The analytical derivation of the sum profile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak area and temperature are identified by the peak analysis module included in the CRYSTAF software (version 2001.b, PolymerChar, Valencia, Spain). CRYSTAF's peak finder routine identifies a peak temperature as a maximum on the dW/dT curve and the area between the largest positive inflection points on either side of the peak identified on the derived curve. To calculate the CRYSTAF curve, the preferred processing parameters are with a temperature threshold of 70°C and with smoothing parameters above the temperature threshold of 0.1 and below the temperature threshold of 0.3.

3. Standard DSC method (except samples 1-4 and A-C)

Differential scanning calorimetry results are determined using a model TAI Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge flow of 50 mL/min is used. The sample is pressed into a thin film and melted in the press at about 175°C and then air cooled to room temperature (25°C). Next, 3-10 mg of material is cut into a 6 mm diameter disc, weighed accurately, placed in a light aluminum pan (ca. 50 mg), and then sealed. The thermal behavior of the sample is examined with the following temperature profile. The sample is rapidly heated to 180°C and held isothermally for 3 minutes to remove any previous thermal history. The sample is then cooled to -40°C at a cooling rate of 10°C/min and held at -40°C for 3 minutes. The sample is then heated to 150°C at 10°C/min. rate of warming. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum heat flow rate (W/g) versus the linear baseline plotted between -30°C and the end of melting. The heat of fusion is measured as the area under the melting curve between -30°C and the end of melting using a linear baseline.

4. GPC method (without samples 1-4 and A-C)

The gel permeation chromatography system consists of a Polymer Laboratories Model PL-210 or Polymer Laboratories Model PL-220 instrument. The column and carousel chambers operate at 140°C. Three 10 micron Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4-trichlorobenzene. Samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by gently stirring at 160°C for 2 hours. The injection volume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6 "cocktail" mixes with at least a decade weight separation. Standards are obtained from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared at 0.025 g in 50 mL solvent for molecular weights equal to or greater than 1,000,000 and 0.05 g in 50 mL solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80°C with gentle stirring for 30 minutes. Tight standard blends are run first and in descending order of the highest molecular weight component to minimize degradation. Polystyrene standard peak molecular weights are calculated using the following equation (as described in Williams and Ward,J. Polym. Sci., Polím. Dejar.,6, 621 (1968)): M_Polyethylene=0,431(M_polystyrene).

Polyethylene equivalent molecular weight calculations are performed using Viscotek TriSEC software, version 3.0.

5. Compression set

Compression set is measured according to ASTM D 395. The sample is prepared by stacking round discs 25.4 mm in diameter and 3.2 mm, 2.0 mm and 0.25 mm thick for a total thickness of 12.7 mm. Discs are cut from 12.7 cm x 12.7 cm compression molded plaques cast with a hot press under the following conditions: zero pressure for 3 min at 190°C, followed by 86 MPa for 2 min at 190°C, followed by Cool down inside the press with cold running water at 86 MPa.

6th density

Samples for density measurement are prepared according to ASTM D1928. Measurements are made within one hour of pressing the sample using ASTM D792, Method B.

7. Flexural/Drying Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and secant modulus of 2 percent are measured according to ASTM D-790. Storage modulus is measured according to ASTM D 5026-01 or an equivalent technique.

8. Optical Properties

The 0.4 mm thick films are compression molded using a hot press (Carver Model No. 4095-4PR1001R). Pellets are placed between sheets of polytetrafluoroethylene, heated to 190°C at 55 psi (380 kPa) for 3 minutes, followed by 1.3 MPa for 3 minutes, then 2.6 MPa for 3 minutes. The sheet is then pressed in the press chilled under cold tap water at 1.3 MPa for 1 min. Compression molded films are used for optical measurements, tensile behavior, recovery and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D 1746.

Gloss at 45° is measured with BYK Gardner Glossmeter Microgloss 45° as specified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D 1003 Method A. Mineral oil is applied to the surface of the film to remove surface scratches.

9. Mechanical properties: traction, hysteresis and tearing

The stress-strain behavior under uniaxial loading is measured using microtensile specimens according to ASTM D 1708. The specimens are elongated with an Instron at 500% min.⁻¹at 21 degrees. Tensile strength and elongation at break are given for an average of 5 samples.

100% and 300% hysteresis is determined from cyclic loading for 100% and 300% elongations using ASTM D 1708 microtensile specimens with an Instron ™ instrument. The sample is charged and discharged at 267% min.⁻¹for 3 cycles at 21°C. Cycling experiments at 300% and 80°C are performed using a climate chamber. In the 80°C experiment, the sample is allowed to equilibrate at the test temperature for 45 minutes before testing. In the 300% elongation cyclic test at 21°C, the contraction stress at 150% elongation of the first unloading cycle is recorded. The percent recovery for all experiments is calculated from the first discharge cycle using the voltage at which the charge has returned to baseline. The recovery percentage is defined as:

$% recreation = \frac{{mi}_{F} - {mi}_{s}}{{mi}_{F}} \times 100$
where is_Fis the stress taken for cyclic loading and ε_sis the deflection at which the load is released during the 1^{S t}discharge cycle.

Stress relaxation is measured at 50 percent strain and 37°C for 12 hours using an Instron ™ instrument fitted with an environmental chamber. The hole geometry was 76 mm x 25 mm x 0.4 mm. After equilibrating at 37°C in the environmental chamber for 45 minutes, the sample was stretched at 50% strain at 333% min.⁻¹. Stress was recorded as a function of time for 12 hours. The percentage of stress relaxation after 12 hours was calculated using the following formula:

$% Emphasize Relaxation = \frac{{EU}_{0} - {EU}_{12}}{{EU}_{0}} \times 100$
Onde L₀is the load with 50% elongation at time 0 and L₁₂is the load with 50% elongation after 12 hours.

Tensile failure experiments are performed on samples having a density of 0.88 g/cc or less using an Instron™ instrument. The geometry consists of a 76 mm × 13 mm × 0.4 mm gage section with a 2 mm notch cut in the sample halfway along the length of the sample. The sample is stretched to a minimum of 508 mm⁻¹at 21°C until fracture. The energy at break is calculated as the area under the stress-strain curve to elongation at maximum load. An average of at least 3 specimens are reported.

10. TMA

The thermomechanical analysis (soak-through temperature) is performed on 30mm diameter x 3.3mm thick compression molded discs molded at 180°C and a molding pressure of 10 MPa for 5 minutes and then cooled in air. The instrument used is a TMA 7, a brand available from Perkin-Elmer. In the test, a 1.5mm radius tip probe (P/N N519-0416) is applied to the surface of the sample disk with a force of 1N. The temperature increases at 5°C/min from 25°C. The penetration distance of the probe is measured as a function of temperature. The experiment ends when the probe penetrates 1 mm into the sample.

11. DMA

Dynamic Mechanical Analysis (DMA) is measured on compression molded discs that were formed in a hot press at 180°C at a pressure of 10 MPa for 5 minutes and then water quenched in the press at 90°C/min. The test is performed using an ARES Tension Controlled Rheometer (TA Instruments) equipped with dual cantilever fittings for torsion testing.

A 1.5 mm thick sheet is pressed and cut into a bar measuring 32 x 12 mm. The sample is clamped at both ends between fixtures with a distance of 10 mm (clamp opening ΔL) and subjected to successive temperature steps from -100 °C to 200 °C (5 °C per step). At each temperature, the torsional modulus G' is measured at an angular frequency of 10 rad/s while maintaining the strain amplitude between 0.1 percent and 4 percent to ensure that the torque is sufficient and the measurement stays within the linear range.

An initial static force of 10 g (auto-tension mode) is maintained to prevent the sample from loosening when thermal expansion occurs. As a result, the AL adhesion gap increases with temperature, especially above the melting or softening point of the polymer sample. The test ends at maximum temperature or when the distance between accessories reaches 65 mm.

12. Fusionsindex

Fusion Index, the I₂, is measured according to ASTM D 1238, condition 190°C/2.16 kg for polyethylene-based polymers (condition 230°C/2.16 kg for polypropylene-based polymers). Melt index or I₁₀sometimes it is also measured according to ASTM D 1238, condition 190°C/10 kg.

13. CASA

Analytical Temperature Rise Elution Fractionation Analysis (ATREF) is performed according to the procedure described in US Patent No. 4,798,081 and Wilde, L.; Ryle, T.R.; Knobloch, DC; Torf, I.R.;Determination of branching distributions in polyethylene and ethylene copolymers, J. Polym. Sci., 20, 441-455 (1982), which are incorporated herein by reference in their entirety. The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert carrier (stainless steel grit), slowly reducing the temperature to 20°C with a cooling rate of 0.1°C/min. The column is equipped with an infrared detector. An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the elution solvent (trichlorobenzene) from 20 to 120°C at a rate of 1.5°C/min.

14¹³C-NMR-Analyse

The samples are prepared by adding approximately 3 g of a 50/50 mixture of tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mm NMR tube. Samples are dissolved and homogenized by heating the tube and its contents to 150°C. Data is collected using a JEOL Eclipse™ 400MHz spectrometer or a Varian Unity Plus™ 400MHz spectrometer, according to a¹³Resonant frequency C of 100.5 MHz. Data is acquired using 4000 transients per data file with a 6 second pulse repetition delay. Multiple data files are aggregated to obtain minimum signal-to-noise ratio for quantitative analysis. The spectral width is 25,000 Hz with a minimum file size of 32,000 data points. Samples are analyzed at 130°C on a 10mm broadband probe. Comonomer incorporation is determined using the Randall triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which is incorporated herein by reference in its entirety.

15. Fractionation of polymers by TREF

Large scale TREF fractionation is performed by dissolving 15-20 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB) with stirring for 4 hours at 160°C. The polymer solution is forced under 15 psig (100 kPa) of nitrogen into a 3 inch by 4 foot (7.6 cm x 12 cm) steel column filled with a 60:40 (v:v) mixture of glass beads. 30-40 mesh (600-425 μm), spherical engineering grade (available from Potters Industries, HC 30 Box 20, Brownwood, Texas, 76801) and stainless steel, 0.028 inch (0.7 mm) cut diameter (available from Pellets, Inc 63 Industrial Drive, North Tonawanda, N.Y., 14120).The column is immersed in a heat-controlled oil jacket, initially set at 160°C C per minute held and held for one hour. Fresh TCB is introduced at approximately 65 mL/min while the temperature is increased at 0.167°C per minute.

Approximately 2000 mL portions of the eluent from the preparative TREF column are collected in a 16-station heated fraction collector. The polymer in each fraction is concentrated using a rotary evaporator until about 50-100 mL of the polymer solution remains. The concentrated solutions are left overnight before adding excess methanol, filtering and rinsing (ca. 300-500 ml methanol including final rinsing). The filtration step is performed in a 3-position vacuum-assisted filtration station using 5.0 µm polytetrafluoroethylene-coated filter paper (available from Osmonics Inc., Cat. No. Z50WP04750). The filtered fractions are dried overnight in a vacuum oven at 60°C and weighed on an analytical balance before further testing.

16. Fusion Strength

Melt strength (MS) is measured using a capillary rheometer fitted with a 20:1 die having a diameter of 2.1 mm and an entrance angle of about 45 degrees. After equilibrating the samples at 190°C for 10 minutes, the piston is run at a speed of 1 inch/minute (2.54 cm/minute). The standard test temperature is 190 °C. The sample is uniaxially pulled into a set of accelerated contact points located 100 mm below the die at an acceleration of 2.4 mm/s.². The required tensile force is recorded depending on the feed speed of the pressure rollers. The maximum tensile strength achieved during the test is defined as the melt strength. In the case of molten polymer showing strain resonance, the tensile force before strain resonance started was taken as the melt strength. Melt strength is reported in centiNewtons ("cN").

The following examples illustrate the present invention but do not limit it either explicitly or implicitly.

The following components were used in the following examples.

Pellethane ™ 2102-80A is a thermoplastic polyurethane with a density of 1.18 g/cc and a melt index (I2) of 4 g/10 min measured at 190°C and 8.7 kg (available from The Dow Chemical Company) .

Pellethane™ 2103-70A is a thermoplastic polyurethane with a density of 1.06 g/cc (ASTM D 792) and a melt index (I2) of 11 g/10 min measured at 190°C and 8.7 kg (available from The Dow Chemical Company).

Pellethane™ 2355-80AE is a thermoplastic polyurethane with a density of 1.18 g/cc (ASTM D 792) and a melt index (I2) of 7 g/10 min measured at 190 °C and 8.7 kg (available from The Dow Chemical Company).

Pellethane™ 2103-80AEF is a thermoplastic polyurethane with a density of 1.13 g/cc (ASTM D 792) and a melt index (I2) of 13 g/10 min measured at 190 °C and 8.7 kg (available from The Dow Chemical Company).

Isoplast™ 2530 is an engineering thermoplastic polyurethane available from The Dow Chemical Company.

CAPRON is a polyamide (Nylon 6) available from BASF.

Gauge™ 200-14 is a polycarbonate available from The Dow Chemical Company.

Eastman EASTAR EN-001 is a polyethylene terephthalate available from Eastman Chemicals.

GE Plastics 315-1001 is a polybutylene terephthalate available from GE Plastics.

Engage™ 8200 is an ethylene/octene-1 copolymer with a density of 0.870 g/cc and a melt index (I2) of 5 g/10 min measured at 190°C and 2.16 kg (available from The Dow Chemical Company ). .

Engage™ 8100 is an ethylene/octene-1 copolymer with a density of 0.870 g/cm³ and a melt index (I2) of 1 g/10 min measured at 190 °C and 2.16 kg (available from The Dow Chemical Company ). .

Engage ™ 7086 or ENR 7086.01, an ethylene/1-butene copolymer having a density of 0.901 g/cc and a melt index (I 2 ) of <0.5 g/10 min (available from The Dow Chemical Company).

Amplify™ GR-216 is a grafted ethylene/octene-1 copolymer containing about (approximately) 0.8% by weight maleic anhydride and having a density of 0.875 g/cc and a melt index (I 2 ) of 1.3 ( available from The Dow Chemical Company).

EVA 265 is an ethylene vinyl acetate copolymer available from DuPont with 28% by weight vinyl acetate and a melt flow rate of 3.0 dg/min.

SANTOPRENE TPV 191-55PA is a thermoplastic vulcanizate available from Advanced Elastomer Systems.

SANTOPRENE TPV 8291-70PA is a thermoplastic vulcanizate available from Advanced Elastomer Systems.

SANTOPRENE TPV 8271-55B100 is a thermoplastic vulcanizate available from Advanced Elastomer Systems.

LOTADER 8900 is a terpolymer of ethylene, methyl acrylate and glycidyl methacrylate and is available from Arkema.

POLYBD 2035 is a polybutadienediol based TPU with a Tg of -34°C, a specific gravity at 25°C of 0.995 g/cc, a tensile strength of 1711 psi, 12 of 1 g/10 min, a segment content of 35% hard Weight, softening point 90°C and elongation 559% (available from Sartomer Company, Inc.).

Affinity g-amines, also known as AffinityGA1950-g-amines or AffinityGA-g-amines, is made by reacting an Affinity GA 1950 resin prepared with maleic anhydride having a density of 0.87 g/cc and a maleic anhydride content of 0 .7% by weight is grafted by impregnating 2 molar equivalents of ethylene diamine and then melting with mixing through a small REX extruder. Affinity GA1950 resins are ultra-low molecular weight resins typically characterized by viscosity rather than melt index. The Brookfield viscosity of the resin before MAH grafting is 17,000 cps at 177°C (measured by ASTM D 1084).

OBC 9007.10 is an olefin block copolymer available from Dow Chemicals with a melt index of 0.5 and a density of 0.866 g/cc.

8407-g-Amine is an ENGAGE™ 8407-g-(2-[N-ethylamino]ethylsuccinimide (density 0.87 g/cc; melt index about 5; 1.2% by weight [N-ethylamino]ethylsuccinimide). The polymer was prepared by reacting a maleic anhydride-grafted Engage™ 8407 (density 0.87 g/cc, MI 5 g/10 min and MAH graft content about 0.8 wt%) with ethylenediamine using two diamine/anhydride equivalents, is incorporated into Engage™ 8407 granules grafted with maleic anhydride and the embedded granules melt blended in a REX extruder.

8407-g-MAH is made by reacting an ENGAGE 8407 ethylene-octene copolymer having a density of 0.87 g/cc and a melt index of 30 with maleic anhydride. The final melt index is about 5 with a maleic anhydride content of about 0.8% by weight.

Polybond 3150 g-amine is prepared by reacting a Polybond 3150 homopolypropylene-grafted maleic anhydride polymer (50 MFR (230°C/2.16 kg) 0.5 wt% MAH content, available from Chemtura) with 3 molar equivalents of ethyl ethyl diamine.

Amine 8402-g is prepared from an ENGAGE 8402 grafted with 0.8 wt% MAH (density = 0.9, 30 MI before grafting, 5 MI after grafting) by first soaking 2 molar equivalents of ethylenediamine and then the embedded grains are passed through a REX extruder.

AMPLIFY GR216-g-amine refers to an AMPLIFY GR216 maleic anhydride (MAH) graft polymer available from Dow having a density of 0.87 to 1.25 MI, a graft content of 0.8% by weight, which is incorporated into a imidized amine by first immersing 2.0 molar equivalents of ethylenediamine (DEDA) and then melting the mixture in a reagent extruder.

LDPE 662i is a low density polyethylene available from Dow Chemicals having a density of 0.917 g/cc and a melt index of 0.47 (190°C/2.16 kg).

VERSIFY 2000-g-DEDA is made from VERSIFY 2000 propylene-ethylene copolymer grafted with 0.9 wt% MAH with an ethylene content of 5 wt%. The starting VERSIFY copolymer has an MFR of 2 (230°C/2.16 kg) and a density of 0.888 g/cc. The grafted MAH is converted to the imidized amine by reaction with 3 molar equivalents of ethylenediamine.

OBC 9817.10 g-amine is prepared from OBC 9817.10 grafted with 1.17% MAH (density = 0.877, MI 3.04) by a reactive extrusion process using 3 molar equivalents of ethylene diamine.

OBC 9807.10 g-amine is prepared from OBC 9807.10 grafted with 1.13 wt% MAH (density = 0.866, MI 3.80) by a reactive extrusion process using 3 molar equivalents of ethylene diamine.

OBC(32MI) g-amine is prepared from OBC grafted with 1.09 wt% MAH (density = 0.877, MI 7.08) by a reactive extrusion process using 3 molar equivalents of ethylenediamine.

The sample designated 8407-g-amine (A) is ENGAGE 8407-g-(2-[N-ethylamino]butylsuccinimide (0.87 density; ~5 melt index) and has the following structure Engage prepared anhydride 8407 (density 0.87, 5 MI) (~0.74 wt% MAH degree of grafting) with butyl ethylene diamine using 2 eq. diamine/anhydride. The diamine is incorporated into the granules and then passed through a small REX extruder.

8407-g-amine (B) is an ENGAGE™ 8407-g-(2-[N-ethylamino]-ethylsuccinimide (density 0.87 g/cc; melt index ca. 5; 1.2 wt% [N- Ethylamino]ethylsuccinimide) and has the structure shown in Scheme A below. This grafted polymer was prepared by reacting an Engage™ 8407 grafted with maleic anhydride (density 0.87 g/cc, 5 g/10 min MI and about 0.74 wt% graft level MAH) with ethylene diamine using two equivalents Diamine/Anhydride. The embedded granules are melt blended in a small REX extruder.

8407-g-OH is ENGAGE™-g-(2-Hydroxyethylsuccinimide) (density 0.87 g/cc; melt index ca. 5 g/10 min; 1.0% by weight hydroxyethyl succinimide) and was prepared by reaction in an extruder , anhydride-grafted Engage ™ 8407 maleic acid (density 0.87, 5 MI, 0.74% by weight anhydride) with an ethanolamine using 3.5 equivalents of ethanolamine/anhydride. The reaction is shown in Scheme B below.

8407-g-DEDA refers to an Engage 8407 grafted with ~0.8 wt% MAH with a MI of 5 and a density of 0.87 g/cc and then using 3.0 molar equivalents of ethylenediamine (DEDA) was converted to an imidized amine in a reactive extruder.

AMPLIFY GR216-g-DEDA refers to an AMPLIFY GR216 maleic anhydride (MAH) graft polymer available from Dow having a 1.25 MI, density of 0.87, a graft content of 0.8 wt .0 molar equivalents of ethylenediamine is converted to an imidized amine (DEDA) in a reactive extruder.

OBC 9817.10 g-amine is prepared from OBC 9817.10 grafted with 1.17% MAH (density = 0.877, MI 3.04) by a reactive extrusion process using 3 molar equivalents of ethylene diamine.

OBC 9507 is an ethylene/octene-1 multiblock copolymer having a density of 0.866 g/cc and a melt index (I 2 ) of 5 g/10 min (available from The Dow Chemical Company).

OBC 9000 or OBC 9000.00 is an ethylene/octene-1 multiblock copolymer having a density of 0.877 g/cc and a melt index (I 2 ) of 0.5 g/10 min (available from The Dow Chemical Company).

OBC 9500 is an ethylene/octene-1 multiblock copolymer having a density of 0.877 g/cc and a melt index (I 2 ) of 5 g/10 min (available from The Dow Chemical Company).

Fusabond 493D is an ethylene-octene-maleic anhydride graft copolymer available from DuPont having a density of 0.87 g/cc and a melt index (I 2 ) of 1.2 (190°C/2.16 kg).

Amplify GR216 is a maleic anhydride grafted ethylene-octene copolymer available from The Dow Chemical Company having a density of 0.87 g/cc and a melt index (I2) of 1.25 (190°C/2.16 kg) .

OBC 9807.10 is an olefin block copolymer available from The Dow Chemical Company having a density of 0.877 and a melt index (I2) of 15 (190°C/2.16 kg).

Dark gray or ebony concentrate is available from Americhem. The dark gray ID is 53008-H1-101 and the ebony ID is 53169-H1-101. The support resin is Escorene AN 13K.

Examples of compositions according to the invention containing two or more components

Examples in this section typically include (a) at least one olefin multiblock interpolymer and b) at least one functionalized olefin-based polymer, while examples in the following section entitled "Examples of Compositions of the Invention Comprising At Least Three Components" also include c). at least one thermoplastic polyurethane.

Each substrate (Isoplast™ 2530, Pellethane™ 2102-80A, CAPRON (Nylon 6), Polycarbonate Caliber™ 200-14, PET (Eastman Eastar En-001), and PBT GE 315-1001 plastics) was injection molded from Dimensions sheet : 3 x 3.5 x 0.0625 thick. Each panel was then placed in a mold (0.125" thick) and a 0.5" strip of masking tape was attached. wide at one end (along the outside edge, parallel to the 3 inch edge) of the plate to create a non-stick zone. between the substrate and the composition used for the overmolding layer. The compositions used as the overmold layer are shown in Tables 6 and 7. Each composition was overmolded onto each of the substrates described above at a melt temperature of about 250°C and a mold temperature of 18°C. . to form an overmolded substrate.

Each overmolded substrate was die cut with a single groove to create 6-8 stripes parallel to the 3 inch width of the panel. Each strip measured 5.2 mm wide and 3 inches long. of the overmolded substrate was placed in an air gripper in an Instron 4201 tensile tester, equilibrated at 23°C and 50% relative humidity (RH). A schematic of the test equipment is shown in Figure 1.8 securely attached to the base of an Instron Peel Tester and the slide plate movable by means of ball bearings (see Fig. 8) was moved at the same speed as the crosshead, using the peel roller tester to translate the vertical movement of the cross arm into a horizontal movement of the slide plate. This resulted in the application of a full force perpendicular to the plate. The specific increase is referred to as the "90 degree peel test" and referenced in AS TM D6862-04. The rate of displacement was constant at a force of "0.3mm/s" and each displacement was automatically recorded using Bluehill software available from Instron. The load, expressed in Newtons (N), was divided by the width of the strip to give the peel strength in N/mm. The mean and standard deviation of each peel strength over a range of 10-30 mm are reported as "mean plus/minus standard deviation" as shown in Tables 6 and 7 below. Six to eight samples were tested in each run.

TABLE 6

Peel Adhesion (n=6-8)
			Polycarbonate	Peletano
		Isoplast 2530	Caliber 200-14	2102-80A
	overmoulded	big fall	big fall	big fall
	composition	(N/mm)	(N/mm)	(N/mm)

compensation 1	add 8900	0,37 ± 0,11	1,32 ± 0,18	0,022 ± 0,005
compensation 2	Eva 265	0,26 ± 0,11	3,33 ± 0,09	0,091 ± 0,020
EX. 5	5 % 8407-g-Amin	1,02 ± 0,34	0,012 ± 0,002	0,61 ± 0,15
	(A) of ENGAGE 8200
EX. 6	5 % 8407-g-Amin	1,67 ± 0,77	0,11 ± 0,04	0,39 ± 0,08
	(A) im OBC 9507
EX. 7	5% 8407-g-OH um	0,017 ± 0,010	0,18 ± 0,06
	HOOK 8100
EX. 8	5% 8407-g-OH um	0,07 ± 0,11
	OBC9000
EX. 3	5 % 8407-g-Amin	1,86 ± 0,41	0,11 ± 0,03	0,24 ± 0,03
	(B) um ENGAGE 8100
EX. 4	5 % 8407-g-Amin	4,62 ± 0,26	0,35 ± 0,04	3,30 ± 0,06
	(B) im OBC 9000
EX. 1	5% affinity g-amine	1,61 ± 0,28	0,08 ± 0,01
	an ENGAGE 8100
EX. 2	5% affinity g-amine	3,05 ± 0,05		2,30 ± 0,17
	im OBC 9000
EX. 6A	8407-g-OH	0,05 ± 0,01	0,55 ± 05
compensation 6	GR 216 REINFORCE	0,90 ± 0,16	0,19 ± 0,04
EX. 5A	8407-g-Amina (B)	2,58 ± 0,14	0,16 ± 0,02
compensation 7	Participate ™	0,25 ± 0,04	0,44 ± 0,07
	7086/Polybd 2035 63:37

TABLE 7

Peel Adhesion (n=6-8)
			PBT GE
		MASCOT	Plastics 315-
		(Easter EN-001)	1001	Nylon 6 Kapron
	overmoulded	big fall	big fall	big fall
	composition	(N/mm)	(N/mm)	(N/mm)

Comp 1	add 8900	0,28 ± 0,07	0,081 ± 0,012	0,038 ± 0,008
Comp 2	Eva 265	0,37 ± 0,02	0,043 ± 0,014	0,029 ± 0,009
EX. 5	5 % 8407-g-Amin	0,023 ± 0,002		0,019 ± 0,012
	(A) PARTICIPATE
	8200
EX. 6	5 % 8407-g-Amin			0,064 ± 0,008
	(A) im OBC 9507
EX. 7	5% 8407-g-OH um			0,023 ± 0,009
	HOOK 8100
EX. 8	5% 8407-g-OH um	0,077 ± 0,011	0,026 ± 0,011	0,027 ± 0,007
	OBC9000
EX. 3	5 % 8407-g-Amin	0,054 ± 0,004	0,048 ± 0,007	0,023 ± 0,013
	(B) PARTICIPATE
	8100
EX. 4	5 % 8407-g-Amin	0,15 ± 0,02	0,12 ± 0,02	0,033 ± 0,005
	(B) im OBC 9000
EX. 1	5% affinity-g-	0,19 ± 0,02	0,14 ± 0,02	0,042 ± 0,021
	Love me
	HOOK 8100
EX. 2	5% affinity-g-		0,045 ± 0,012	0,046 ± 0,015
	Amin in OBC
	9000
compensation 3	Santoprene TPV			0,24 ± 0,06
	191-55PA
compensation 4	Santoprene TPV			0,13 ± 0,02
	8291-70PA
compensation 5	Santoprene TPV			0,082 ± 0,028
	8271-55B100
EX. 6A	8407-g-OH	0,02 ± 0,00		0,02 ± 0,01
compensation 6	GR 216 REINFORCE	0,09 ± 0,02	0,02 ± 0,01	0,90 ± 0,43
EX. 5A	8407-g-Amina (B)	0,28 ± 0,02		0,39 ± 0,05
compensation 7	Participate ™	0,17 ± 0,02	0,37 ± 0,03	0,17 ± 0,02
	7086/Polybd 2035
	63:37

As discussed above, Tables 6 and 7 list the peel strengths and standard deviations of pure functionalized samples, comparative samples, blends with low levels of OBC functionalized samples, and random EO matrices.

The compositions of the examples according to the invention show good adhesion to polar substrates. Overmolded compositions containing OBC result in very high peel adhesion values for the ISOPLAST 2530 substrate and the PELLETHANE substrate.

The compositions of the invention can also be used in aqueous and non-aqueous dispersions. Aqueous dispersions can be prepared by melt blending the compatibilized composition and water in an extruder to produce a stable, uniform dispersion having an average particle size of typically about 300 nm. The solids content of dispersions is typically 35 to 50 percent by weight based on the total weight of the dispersion. A dispersing agent such as UNICID™ Acid 350 (6% by weight on solids; derived from a synthetic C26 carboxylic acid converted to potassium salt and available from Baker Petrolite) is added to the dispersion. The dispersions are then applied as a cast film to a sheet of biaxially oriented polypropylene (BOPP) and the surface energy is measured.

The compositions of this invention can also be used as an adhesion promoter for polyurethane, neat or in blends, extruded to provide artificial grass (or artificial grass yarn).

For example, a composition of the present invention can be extruded and stretched five times on a ribbon extrusion line. The pattern tapes can then be grouped and stacked as five strands on top of each other, mimicking bundles of artificial grass strands after forming a mat. The packages can be held in a mold and a diol-isocyanate polycondensation mixture, for example as shown in Table 8 below, injected into the mold in a portion of the package. After curing for about 30 minutes at 25°C, adhesion to a polyurethane can be evaluated on a sample of the resulting polymer.

TABLE 8

Formulation of diols


	Voranol EP 1900	90 parts by weight
	1,4HAB	10 pounds
	Silosiva P3	5 parts by weight
	DABCO33LV	0.2 parts by weight
Isocianatos
	M143 isonate proportion	40:100

Thus the composition according to the invention can be used as an adhesion promoter for polyurethane, in artificial turf and other applications and can be reactively incorporated into polyolefins, the latter being used in the manufacture of artificial turf in order to improve the adhesion of the yarn to the artificial turf carpet.

Adhesion is promoted by the fact that the functional group reacts with the polyurethane coating applied to the carpet backing as a polymerizing mixture. On the back of the mat, the surface of the tufted artificial grass yarn/tape is exposed and the coating applied to it. The concentration of the adhesion promoter can be 100 percent of a composition of the invention and can be up to 10 percent of a composition of the invention in a blend with any polyethylene or propylene deemed suitable for use in artificial turf yarn applications.

A composition of the present invention can also be used in the manufacture of hydrophilic artificial turf yarn to create more "player friendly" surface characteristics. In particular, blends of thermoplastic polyurethanes with polyethylenes compatible with a composition of the invention can be used to form artificial turf.

The colors typically used in the footwear industry were obtained from Kenda Colors S.P.A., Italy. 5 parts by weight of an isocyanate prepolymer (NCO), also purchased from Kendra, was premixed with the paint. A paint thickness of less than 20 microns was applied to the samples using a spray gun. The samples were then heated in a hot oven at 110°C for 15 minutes. A crosshatch ink adhesion test was performed 24 hours later according to ASTM D 3359-02. A knife device was used to obtain 10×10 2 mm square grids. An adhesive tape of the TESA Tesafix type (04970-00154-00) was pressed on firmly. After about 60 seconds, the tape was peeled off perpendicular to the sample in one quick motion. This was repeated 2-3 more times while the ink squares came out of the sample. The highlighted squares were counted and the percent adhesion was reported in the table below.


Adhesion of paint to paint for shoes
	which one
	Sergeant

	Engage ™ 8200	0
	Lose 8900	40
	Eva 265	45
	Engage 8407-g-Amin	100	100
	Include 8407-g-OH	100	45
	Participation 8407-g-OH 25%, 75% OBC	99
	9500
	Participation 8407-g-OH 5%, 95% OBC	95
	9500
	Proportion 8407 g amine 25%, 75%	95
	OBC9500
	5 % 8407-g-Amin in OBC 9507	100

The blends shown were blended in a Hakke ¾'' twin screw extruder. Panels 0.125 inch thick were prepared and subjected to the adhesion test with PU glue used in the footwear industry. Typically, polymer samples used in the footwear industry must have a peel strength of 5 N/mm. The polymer surface was cleaned with toluene and sanded with 60 grit sandpaper. The PET backing and polymer surface were brush primed with a mixture of MEK, Forestali Poligrip M328 shoe glue and Desomdur RFE. These were allowed to dry at room temperature, followed by heating at 100°C for 30 seconds. A mixture of adhesive and Deomdur RFE was then applied to both parts and allowed to dry at room temperature. The polymer sheet was heated in an oven at 110°C for 5 minutes and the PET support was heated for 1 minute. The sticky sides of the PET holder and polymer were pressed together and hammered lightly. This sandwich was placed in a hot press and pressed between two sheets of 2 cm thick foam for 1 minute at 10 bar at room temperature. The resulting sample was then subjected to a peel test and the peel adhesion numbers are given in the table below.


Polymer	Weight %	Weight %	Weight %	Weight %


Engage ™ 8200	0	0	0	0
Strengthen GR	0	20	100	0
216-g-DEDA
8407-g DEDA	20	0	0	100
OBC9500	80	80	0	0
Adhesion [N/mm]	7.5	8.5	4.3	8.9

For all samples in the table below, the tiles were first injection molded and then Isoplast, Pellethane 2102-80A, Pellethane 2355-80AE and Pellethane 2103-70A were cast onto these tiles. A 90 degree peel test was used to generate the peel adhesion data shown in N/mm in the table below.


	Isoplast	Peletano	Peletano	Peletano
	2530	2102-80A	2355-80AE	2103-70A


OBC9500	Very low	Very low	Very low	Very low
5 % 8407-g-Amin in	4.7	3.7	3.9	2.5
OBC 007.10
5% affinity GA1950-g-	2.4	2.8	1.9	3.4
Amin in BC 9007.10
5 % 8407-g-Amin in	3.1	3.1	2.8	1.9
OBC9000
5% affinity GA1950-g-	3.4	2.7	2.6	3.9
Amine in 9000 BC
5 Gew.-% 8407-g-MAH	0,2	Very low	Very low	0,3
im OBC 9000
5 Gew.-% Polybond3150-	1,5	3.9	5.1	4.9
G-Amin em 9000 v
5 Gew.-% 8402-g-Amin	3.1	2.8	3.9	2.5
im OBC 9000
5 Gew.-% GR216-g-Amin	4.2	3.9	4.1	4.8
im OBC 9500
8407-g-reines Amin	3.3	4.4	6.5	10,0
8402-g-reins Amin	3.3	1.1	8.7	6.8
Reines 8407-g-MAH	Very low	Very low	Very low	Very low
5 wt% Participate 8407-g-	5.3	4.8	6.1	2.5
95 wt% amine
OBC9000
5 wt% Participate 8407-g-	2.3	3.7	7,0	3.5
amine at 15 wt%
PEBD 662i and 80
Gew.-% OBC 9000
5% by weight	2.4
2000 DEDA
with 95% by weight OBC 9000
5 Gew.-% OBC 9817.10-g-	3.2
95 wt% amine
OBC 9,000.00
5 Gew.-% OBC 9807.10-	2.5	4.9	3.6	5.6
g-amine at 95% by weight
OBC 9,000.00
5 Gew.-% OBC (32MI)-g-	1.9	3.1	3.6	2.1
95 wt% amine
OBC 9,000.00

As the table above shows, a wide range of functional polyolefin elastomers covering a range of crystallinity and MI are suitable candidates in OBC matrices into which the functional elastomer is blended. Grafted PO made with very high MI materials like AffinityGA1950 has negative impact adhesion. In general, blends of OBC with functional POE's containing 5 to 10% by weight of functional POE are at least equivalent to or better in peel strength than pure functional POE. They are also better than MAH-grafted polymers. In addition, OBC blends with functional polymers tend to perform better than blends of functional polymers with BO or P/E random copolymers.

The paint adhesion with other paint systems was tested. Sherman Williams G55N2096 soft-touch polyurethane paint with V66VM100 catalyst, commonly used on airbag covers, was another paint system tested on these samples. A mix ratio of 3.5:1 by volume was used and a target coating thickness of 1.8 mils was used. NB 04172R798 2K Mono Black Coatings with C775 monocatalyst polyurethane paint system used at a 100:14 mix ratio by weight with a target thickness of 1.0 mil was another paint system evaluated. This is commonly used on car exteriors. A crosshatch paint adhesion test was performed on five samples from each lot and the percentage adhesion failure was noted and an average value reported in the table below.

Farbaftung


		Sherman
	NB coatings	Williams
	livery	livery


5 Gew.-% AffinityGA-g-Amin in OBC	100	100
9000,00
5 Gew.-% AffinityGA-g-Amin in OBC	93,5	98
9007.10
8407-g-Amina	92,5	100
5 Gew.-% Polybond3150-g-Amin in OBC 9000	86	100
5 Gew.-% 8407-g-Amin in OBC 9000	82,5	100
5 Gew.-% Polybond3150-g-Amin in ENGAGE	69	100
8100
5 Gew.-% 8407-g-Amin in ENGAGE 8100	37,5	94,3

As can be seen from the table above, blends of POE with functional POE containing 5-10 wt% functional POE are at least equal to or better than pure functional materials in terms of ink adhesion. In addition, OBC blends have better ink adhesion than MI and EO copolymers of equivalent random density. High MI functional materials like Affinity GA1950 that are grafted promote ink adhesion.

Examples of compositions according to the invention containing at least three components

Examples in this section typically include (a) at least one olefin multiblock interpolymer; b) at least one functionalized olefin-based polymer; and c) at least one thermoplastic polyurethane. The components are described above.

Extruded films can be formed from compositions of the invention. Extruded films were formed from the compositions shown in Tables 9 and 10. All weight percentages are based on the total weight of the composition.

The components were fed individually or together in a dry blend into the hopper of a WP-ZSK twin screw extruder. The manner of addition did not affect the properties of the extruded film. The extruder speed was about 500 rpm and the zone temperatures were as follows: 140°C and zones 2-8 = ca. 170°C. The extruded yarn was pelletized upon exiting the extruder to form composite pellets.

The composite grains were dried overnight in a conventional static oven at about 80°C to remove residual moisture. The dried pellets were fed into a Killion extruder (3 roll stack) and extruded into a 20-40 mil thick film. The films used in Tables 9-10 were extruded to a thickness of 20-40 mils. The extruder speed was about 75-100 rpm and the zone temperatures were as follows: Zone 1 = 180°C, Zone 2-4 = 190°C. It is 20-40 mils thick and 2 feet wide. Results in cutting times of approx. 96 s⁻¹(for 40 mil thickness) and 385 s⁻¹(for 20 mil thickness). Processing yielded extruded films with relatively high surface energies.

Surface energy, thermal stability, elongation, tear strength and gloss were measured on each film and are reported in Tables 9 and 10 below. The permeability parameters of the moisture vapor transmission test (ASTM E 96/E 96M-05, Imperial method) are also given in Table 9.

TABLE 9

Blends of POE/PELLETHABE/functionalized polyolefins.
	4	5	6	7	8	9

Engage ™ 7086	57	69,5	57	69,5	59,5	63,8
Peletano 2102-80A	36	25	36	25	36	30
8407-g-OH	5	3.5	0	0	0	0
8407-g-Amina	0	0	5	3.5	2.5	4.2
Dark gray concentrate.	2	2	2	2	2	2
	100	100	100	100	100	100
surface energy	36	36	41	38	43	41
extruded sheets
surface energy	Mercado	Mercado	Mercado	Mercado	Mercado	Mercado
approved criteria
(>35 dyn/cm) or exposed
maximum tensile strength	14.4	16.7	17.9	23.3	19.9	22.2
(MPa)DM
Elongation (%) MD	527.1	582,0	599,1	700,3	628,2	619,8
C The tear strength	83,9	94,7	89,8	72,4	85,5	94,4
(N/mm)
60 degree brightness	19.3	5.4	3.4	30.7	26,8	4.3
Thermal aging at 120°C.	New Mexico	New Mexico		New Mexico		New Mexico
draw stock			27.07		31.56
72 hours			25.56		39,56
7 dia			28.53		New Mexico
14 dia			26.31		New Mexico
21 dia					New Mexico
original stretch			749		551
72 hours			706		644
7 dia			694		New Mexico
14 dia			746		New Mexico
21 dia					New Mexico

TABLE 10

Blends of POE/PELETAN/functionalized polyolefin
					Compare 63:37
	10	11	12	Clean 2103-70A	Engage ™ 7086

Engage ™ 7086	57	69,5	41	0
Peletano 2103-70A	36	25	50	100
8407-g-Amina	5	3.5	7	0
Dark gray concentrate.	2	2	2	0
Surface Energy (dyne/cm)	40	40	39	New Mexico
thickness (inches)	0,016	0,019	0,02	0,006	0,0090
Permeability (Permian Inch)	0,014	0,004	0,038	0,128	0,0000
Pattern of development continuity	0,002	0,00005	0,0001	0,015	0,0000
persistence (permanent)	0,878	0,197	1.914	23.3	0,2000
Transmission (grains/hour * feet {caret over ( )}2)	0,355	0,079	0,773	9.284	0,0820
Maximum Tensile Strength (MPa) MD	13.5	13.3	17.6
Elongation (%) MD	605,0	581,3	790,9
Tear strength Matrix C (N/mm)	69,5	70.3	62,6
60 degree brightness	4.1	3,84	36,5
Aging in heat 120°C.		New Mexico	New Mexico	New Mexico	New Mexico
draw stock	23.48
72 hours	23.33
7 dia	New Mexico
14 dia	New Mexico
21 dia	New Mexico
original stretch	653
72 hours	700,8
7 dia	New Mexico
14 dia	New Mexico
21 dia	New Mexico

Water vapor transmission rate data according to the imperial method ASTM E 96

In addition to good mechanical properties and gloss, the mixtures according to the invention also have very good surface energies.

The dependence of permeability on polyurethane content can be seen by plotting the data from Examples 10-12 in Table 10. The linear dependence fairly accurately predicts the permeability of neat Pellethane™ 2103-70A, which is about 0.13 (inch permanent).

The inventive compositions used to form the extruded films of Tables 9 and 10 above and Table 11 below (or virtually any other inventive composition) can also be used in aqueous and non-aqueous dispersions.

aqueous dispersions

Aqueous dispersions can be prepared by melt blending a composition of the invention as described herein and water in an extruder to produce a stable, uniform dispersion having an average particle size, typically around 300 nm. The solids content of dispersions is typically 35 to 50 percent by weight based on the total weight of the dispersion. A dispersing agent such as UNICID™ Acid 350 (6% by weight on solids; derived from a synthetic C26 carboxylic acid converted to potassium salt and available from Baker Petrolite) is added to the dispersion. The dispersions are then applied as a cast film to a sheet of biaxially oriented polypropylene (BOPP) and the surface energy is measured.

adhesion promoter

Compositions of the invention as described herein can also be used as an adhesion promoter for polyurethane, neat or in blends, extruded to provide artificial grass (or artificial grass yarn).

TABLE 8

Formulation of diols


	Voranol EP 1900	90 parts by weight
	1,4HAB	10 pounds
	Silosiva P3	5 parts by weight
	DABCO33LV	0.2 parts by weight
Isocianatos
	M143 isonate proportion	40:100

Extruded Sheets

Extruded films comprising the compositions identified as A-I in the table immediately below were prepared by blending the composition in a zsk-25 at a temperature profile of 140°C, 170°C, 170°C and 170°C, respectively for the Zones 1 through 4 made. The resulting composition was then dried and extruded into 20 ml thick sheets using a temperature profile of 175°C, 185°C, 190°C and using a three plate Killion line with a Maddock screw mixer.


	A	B	C	D	mi	F	GRAMM	H	she
Components	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)


OBC9000	84	73.3	60,5	58	53	60,5	60,5	60,5	60,5
Peletano 2103-70A	fifteen	25	37	37	37	37	0	0	0
Peletano 2355-80AE	0	0	0	0	0	0	0	0	37
Peletano 2103-80AEF	0	0	0	0	0	0	0	37	0
Peletano 2102-80A	0	0	0	0	0	0	37	0	0
Reinforce GR216-g-	1.01	1.7	2.5	5	10	0	2.5	2.5	2.5
DEDA
OBC 9817.10-g-Amina	0	0	0	0	0	2.5	0	0	0
In total	100	100	100	100	100	100	100	100	100

The test performed on the leaves labeled A-I gave the following results.


test	A	B	C	D	mi	F	GRAMM	H	she


60 degrees brightness - average of five films read (%)	10	7	23	14	13	19	31	18	14
Tear strength: Thermoplastic type C-CD with medium tear strength	264	253	236	269	308	181	315	320	312
(lbf/Zoll)
Tear: Thermoplastic Type C- MD Avg-Tear	269	290	280	286	304	253	370	390	372
Resistance (lbf/in)
Traktion - CD - D638 Avg-STRESS@BREAK (psi)	1708	1201	1893	2805	2640	1626	2575	2140	2567
Traktion - CD - D638 Avg-STAIN@BREAK(%)	911	746	744	630	812	740	638	681	589
Spannung - MD - D638 STRESS@BREAK (psi)	2580	2435	2785	2351	3366	2588	3961	3464	4168
Traktion - MD - D638 Avg-STAIN@BREAK(%)	589	623	751	814	721	686	661	599	592
Surface Energy (dyne/cm)	34	34	34	34	34	34	30	34	34
Crosshatch Paint Adhesion Test Qualification for coating with	5	5	5	5	5	5	5	5	5
PU coating United Paint AWOF-0082 (classification)
Haftung von „Dow Great Stuff Insulating Foam“	Fail	Fail	Mercado	Fail	Fail	Mercado	Mercado	Mercado	Mercado
(Cohesion Failure) (Pass/Fail)

In the example below, extruded films were formed from the compositions of the invention as shown in Table 11. All weight percentages are based on the total weight of the composition.

The composite grains were dried overnight in a conventional static oven at about 80°C to remove residual moisture. The dried pellets were fed into a Killion extruder (3 roll stack) and extruded into a 20-40 mil thick film. The films used in Table 11 were extruded to a thickness of 20-40 mils. The extruder speed was about 75-100 rpm and the zone temperatures were as follows: Zone 1 = 180°C, Zone 2-4 = 190°C. is 20-40 mils thick and 2' wide resulting in cutting speeds of around 96s⁻¹(for 40 mil thickness) and 385 s⁻¹(for 20 mil thickness). Compositions 1, 2 and 4 were extruded to a thickness of 40 mils and Composition 3 was extruded to a thickness of 20 mils. Processing yielded extruded films with relatively high surface energies.

Surface energy, thermal stability, elongation, tear strength and gloss were measured on each film and are reported in Table 11 below.

TABLE 11

POE/PELLETHANE™/compatible examples
	1	2	3	4

ENR7086	57	69,5	59,5	51,74
Peletano 2102-80A	36	25	36	36.26
Reinforce GR216	5	3.5	2.5
FUSABOND 493D				10
(injects 1% MAH)
Ebony concentrate.	2	2	2	2
	100	100	100
surface energy	36	36	41	32
extruded sheets
surface energy	Mercado	Mercado	Mercado	Fail
Pass/Fail Criterion (>35 dyn/cm)
Maximum Tensile Strength (MPa) MD	22.2	22,9	25.6
Elongation (%) MD	656,9	668,8	619,1
C The tear strength	93,4	91,8	94,4	47.3
(N/mm)
60 degree brightness	2.5	5.0	29,9	3.6
Thermal aging at 120°C.	New Mexico	New Mexico
Original Tensile Force(MPa)			38,5	26
72 hours			45,0	New Mexico
7 dia			New Mexico	30.8
14 dia			New Mexico	27.6
21 dia			New Mexico	28
% original elongation			482	600
72 hours			636	New Mexico
7 dia			New Mexico	593
14 dia			New Mexico	548
21 dia			New Mexico	623

NM = NOT MEASURED

In addition to good mechanical properties and gloss, the compositions according to the invention in the table above also have very good surface energies.

Extruded films comprising the compositions designated J-Q in the table immediately below were prepared by blending the composition in a zsk-25 at a temperature profile of 140°C, 170°C, 170°C and 170°C for zones 1 made up to 4. The resulting composition was then dried and extruded into 20 ml thick sheets using a temperature profile of 175°C, 185°C, 190°C and using a three plate Killion line with a Maddock screw mixer.


	j	k	EU	METRO	Norte	Ö	PAG	q
Components	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)


OBC9000	84	73.3	60,5	58	53	60,5	60,5	60,5
Peletano 2103-70A	fifteen	25	37	37	37	0	0	0
Peletano 2355-80AE	0	0	0	0	0	0	0	37
Peletano 2103-80AEF	0	0	0	0	0	0	37	0
Peletano 2102-80A	0	0	0	0	0	37	0	0
Amplifiziere GR216-g-MA	1.01	1.7	2.5	5	10	2.5	2.5	2.5
In total	100	100	100	100	100	100	100	100

The test performed on leaves marked J-Q gave the following results.


test	j	k	EU	METRO	Norte	Ö	PAG	q


60 degrees brightness - average of five films read (%)	18	22	20	31	28	25	10	fifteen
Tear strength: Thermoplastic type C-CD with medium tear strength	250	254	251	275	293	338	258	304
(lbf/Zoll)
Tear: Thermoplastic Type C- MD Avg-Tear	252	299	327	295	290	380	386	420
Resistance (lbf/in)
Traktion - CD - D638 Avg-STRESS@BREAK (psi)	2307	2283	2088	2806	2763	1543	1506	1819
Traktion - CD - D638 Avg-STAIN@BREAK(%)	822	833	743	815	826	564	542	485
Spannung - MD - D638 STRESS@BREAK (psi)	2914	3719	3254	3597	3496	4123	2805	3693
Traktion - MD - D638 Avg-STAIN@BREAK(%)	710	769	623	768	756	455	532	434
Surface Energy (dyne/cm)	34	34	34	34	34	30	35	32
Crosshatch Paint Adhesion Test Qualification for coating with	3	5	5	5	5	5	5	5
PU coating United Paint AWOF-0082 (classification)
Haftung von „Dow Great Stuff Insulating Foam“	Fail	Fail	Mercado	Mercado	Mercado	Fail	Mercado	Mercado
(Cohesion Failure) (Pass/Fail)

Extruded films comprising the compositions identified as R-W in the table immediately below were prepared by blending the composition in a zsk-30 at a temperature profile of 140°C, 170°C, 170°C and 170°C for zones 1 made up to 4. The resulting composition was then dried and extruded into 20 ml thick sheets using a temperature profile of 175°C, 185°C, 190°C in a Haake ¾'' extruder.


	R	S	T	Tu	v	C
Components	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)	(% by weight)


OBC D9000	51,75	50,5	48	0	0	60,5
rheology	0	0	0	60,5	0	0
modified CBO
(70 Gew.-% COB
9100 years 30
wt% DS6D82
impostor
Trigonox 101
1500 ppm ano
Coagent SR
350 1500 ppm)
rheology	0	0	0	0	60,5	0
modified CBO
(OBC 9100
impostor
Trigonox 101
1500 ppm ano
Coagent SR350
1500 ppm)
PEBD 662i	10	10	10	0	0	0
Peletano	37	37	37	37	37	37
2103-70A
Strengthen	1.25	2.5	5	2.5	2.5	2.5
GR216
In total	100	100	100	100	100	100

The test performed on sheets marked R-W gave the following results.


test	R	S	T	Tu	v	C


60 degree brightness - film average from five readings	13.6	15.58	7,94	15.64	4,76	6.68
(%)
Tear: Thermoplastic Type C- MD Avg-Tear	224	241	282	313	230	243
Resistance (lbf/in)
ASTM D 1708 Micro Traction (Average Final psi)	343	509	658	1096	530	635
Microstress ASTM D 1708 (% Average	238	334	363	500	335	496
stretch)
Surface Energy (dyne/cm)	35	35	35	35	35	35
Crosshatch Coating Paint Adhesion Test Qualifikation	5	5	5	5	5	5
with PU coating AWOF-0082 from United Paint
(Classification)
Haftung von „Dow Great Stuff Insulating Foam“	Mercado	Mercado	Mercado	Fail	Mercado	Mercado
(Cohesion Failure) (Pass/Fail)

Examination of injection molded plates

The inventive compositions in the table below were prepared by blending 5% by weight of the total composition of a functionalized polyolefin at various weight percentages and grades of olefin multiblock interpolymer (OBC), SBS 401 and thermoplastic polyurethane. Thermoplastic polyurethane, TPU, is a TPU based on polycaprolactam polyester diol with methylene diisocyanate and has a density of 1.18 g/cm³, an MFR (190°C/2.16 kg) of 5 g/10 min and a Shore A hardness of 80. SBS 401 is a styrene-butadiene-styrene rubber manufactured by Total Petrochemicals with a styrene/ Butadiene weight ratio of 22:28 wt% and a density of 0.93 g/cm³. The functionalized polyolefin is 8407 g amine prepared by reactive extrusion of a MAH-grafted Engage 8407 (-0.8 wt% MAH, MI 5) by reaction with 3 molar equivalents of ethyl ethyl diamine. The OBC used in samples 1, 2 and 6-8 in the table below was OBC 9100, while the OBC used in samples 3-5 and 9-10 was OBC 9500.


OBC	SBS 401	TPU
(% by weight)	(% by weight)	(% by weight)


1	40	0	55
2	0	60	35
3	40	0	55
4	0	40	55
5	25	25	45
6	0	40	55
7	60	0	35
8	25	25	45
9	0	60	35
10	60	0	35

The compositions according to the invention of the above table can be injection molded in an injection molding machine customary in the shoe industry at room temperature as sheets generally about 0.5 to 1 cm thick. right melt temperature (typically around 160-170°C), the right mold temperature (typically around 60-80F) and at an appropriate injection rate.


	Stand up-		load	renewal			melted
Sam-	ness	density	take a rest	dog	abrasion	tear	Index
You're welcome	Rand A	g/cc	kg/cm2	%	mm3	kg/cm	l5


1	73	1.001	17.8	1131	201	43	36
2	63	1	9.9	928	178	37	1.1
3	76	0,991	12	867	197	51	5
4	68	1.048	12.8	922	96	45	4.5
5	72	1.008	10.4	874	164	44	5.7
6	67	1.048	15.3	1056	107	44	4.6
7	75	0,983	9.2	1158	332	43	2.8
8	69	1.004	14.6	1055	179	37	4.8
9	Sixty-five	1.002	6.6	705	143	30	1
10	77	0,968	6.3	817	179	42	8.6

Although the invention has been described in some detail in the above examples, this detail is for illustrative purposes and should not be construed as limiting the invention as set forth in the following claims. All US patents, allowed US patent applications, or published US patent applications are incorporated by reference into this specification.

Polyolefin Compositions and Articles Made Therefrom and Methods of Manufacture Related Patent (2023)

References