WO2009017868A1

WO2009017868A1 - Compositions of thermoplastic polyurethane (tpu), polybutadiene and polydiene-based tpu

Info

Publication number: WO2009017868A1
Application number: PCT/US2008/063814
Authority: WO
Inventors: Xiuhua Cui; Patricia Amsems; Kim L. Walton
Original assignee: Dow Global Technologies Inc.
Priority date: 2007-07-27
Filing date: 2008-05-16
Publication date: 2009-02-05
Also published as: AR066616A1

Abstract

A composition comprising the following; A. A thermoplastic polyurethane (TPU) comprising less than 25 wt% of units derived from a diene; B. A polybutadiene and/or polyisoprene; and C. A polydiene-based TPU that comprises at least 30 wt% of units derived from a diene. Typically and preferably, the TPU of (A) docs not contain any units derived from a diene. These compositions can be cured into thermoplastic vulcanizates. Both the cured and uncured compositions are well-suited for promoting the adhesion between polar (for example, polyester, polycarbonate and polylactic acid) and non-polar materials, and for the manufacture of, among other things, films, fibers, sheets and tie layers, lubes, adhesives, dispersions, protective apparel, footwear, coatings, laminates and foams.

Description

CX)MFOSITiONS OF THERMOPLASTIC POLYU RET BANE (TPU),

BASED TPU

.REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of USSN 60/863,887, filed on November 1, 2006, and USSN No. 60/894,353, filed on March 12, 2007, and USSN 60/952,254, filed on My 27, 2007, and USSN 60/952,266, filed on July 27, 2007; each application is fully incorporated herein by reference.

FIELD_OJiJNVENTiQN

[0002] This invention relates to thermoplastic polyurethanes (TPU). In one aspect, the invention relates to compositions or blends comprising a TPU while in another aspect, the invention relates to both uncrosslinked and crosslinked compositions comprising a TPU, In still another embodiment, the invention relates to an uncrosslinked composition comprising a TPU, a polybutadiene and/or polyisoprenε, and a compatibilizer while yet in another aspect, the invention relates to such a composition that is dynamically crosslinked.

BACKGROUND OF THE INVENTION

[0003] TPU' s are noted for having extremely good abrasion resistance, flexibility and resilience, but they are also noted for having poor to fair hydrolysis resistance and a relatively high cost. Polybutadiene rubber (BR) is noted for having superior dynamic /rebound properties, good abrasion resistance and a relatively low cost. Blends of TPU and BR are known, but come with their own set of problems. For instance, the BR must be crosslinked to produce useful articles, and these therrnoset articles cannot be recycled, i.e.. melt processed. Moreover, the uncrosslinked blends typically exhibit poor optics, i.e., clarity. Accordingly, the polymer industry has a continuing interest in identifying a composition that has the combined performances of TPU and BR, but that exhibits good clarity and that can be recycled.

SUMMARY OF THE INVENTION

The invention provides uncrosslinked and crosslinked compositions comprising the following: a) a thermoplastic polyureihane (TPU) comprising less than 25 weight percent (wt%) of units derived from a diene, b) polybutadiene and/or polyisoprene, and c) a polydiene-based TPU that comprises at least 30 wt% of units derived from a diene. The weight percent of units derived from a diene are based on the weight of the TPU of component A or the weight of the polydiene-based TPU of component C, respectively, The compositions can comprise further components, including one or more crosslinking agents. The uncrosslinked blends exhibit unexpectedly high clarity as compared to similar uncrosslinked polyure thane compositions but without the polydicne-based TPU, Dynamically crossiinked compositions exhibit good melt processability and elasticity as compared to vulcanizatεs made from the same composition but staticly crossiinked. [0005] The TPU of component A typically comprises less than 15, more typically less than 5 and even more typically 0, wt% of units derived from a diene. Typically component B is a polybutadiene, and the TPU of component C typically comprises at least 50 and more typically at least 60 wt% of units derived from a diene, Component C acts as a compatibilizer for components A and B.

[0006] Component A typically comprises at least 30, more typically at least 40 and even more typically at least 50, wl% of the total weight of the composition. The maximum amount of component A in the composition typically does not exceed 75, more typically does not exceed 70 and even more typically does not exceed 65, wt% of the total weight of the composition. Preferably, the composition comprises between 50 and 75 wl% of component

Component B typically comprises at least 30, more typically at least 40 and even more typically at least 50, wi% of the total weight of the composition. The maximum amount of component B in the composition typically does not exceed 70, more typically does not exceed 60 and even more typically does not exceed 50, wt% of the total weight of the composition. Preferably, the composition comprises between 30 and 50 wi% of component

! Component C comprises greater than zero, i.e., at least a corapatibilizing amount, typically at least 1, more typically at least 2 and even more typically at least 5, wt% of the total weight of the composition. The maximum amount of component C in the composition typically does not exceed 30, more typically does not exceed 25 and even more typically does not exceed 20, wf% of the total weight of the composition,

[0009] In one embodiment, the invention provides crossiinked, thermoplastic compositions (also known as vulcanizates) made from the uncrosslinked compositions of the first embodiment. These vulcanizates can be prepared by any suitable technique, e.g., the use of a cure or crosslinking agent, or by exposure to a crossiinking technique, e.g., a crosslinking amount of radiation or moisture under crosslinking conditions. [0010] In. one embodiment, the invention provides a crosslinkcd thermoplastic composition comprising (a) a thermoplastic polyurethane (TPU) comprising less than 25 weight percent (wt%) of units derived from a dienε, and (b) polybutadiene and/or polyisoprene, component (a) and component (b) present at a (a):(b) weight ratio of at least 1.5:1, preferably at least 2:1 and more preferably at least 2.2:1. This crosslinked composition does not contain any polydienε-based TPU that comprises at least 25 wt%₃ preferably at least 30 wt%, of units derived from a diene.

BRIEF DESCRIPTION OF THE FIGURES

[1)0111 Figure 1 is a micrograph of a TFM analysis of a plaque comprising the formulation of Example 2,

[0012] Figure 2 is a micrograph of a TEM analysis of a plaque comprising the formulation of Comparative Example C-3,

Figure 3 is a micrograph of an AFM analysis of the composition of Example 8.

Figure 4 is a micrograph of an AFM analysis of the composition of Example 10.

DETAILED DESCRIPTION OF THE INVENTION Definitions

15] Any numerical range recited herein, includes all values from the lower value to the upper value, in increments of one unit, provided that there is a separation of at least two units between any lower value and any higher value. As an example, if it is stated that a compositional, physical or mechanical property, such as, for example, molecular weight, viscosity, melt index, etc,, is from 100 to 1,000, it is intended that all individual values, such as 100, 101, 102, etc., and sub ranges, such as 100 to 144, 155 to 170, 197 to 200, etc., are expressly enumerated in this specification. For ranges containing values which are less than one, or containing fractional numbers greater than one (for example, 1.1, 1.5, etc.), one unit is considered to be 0.0001. 0.001, 0.01 or 0.1, as appropriate. For ranges containing numbers less than ten (for example, 1 to 5), one unit is typically considered to be 0.1. These are only examples of what is specifically intended, and all possible combinations of numerical values between the lowest value and the highest value enumerated, are to be considered to be expressly stated in this application. In the context of this invention, numerical ranges are used in the description of component amounts and density, crystallinity, haze and other properties of the compositions, both uncrosslinked and crosslinked. All references, specifically including all United States patents. United States patent application publications and allowed United States patent applications, are incorporated herein in their entirety by reference.

[§§16] "Composition" and like terms mean a mixture of two or more materials. Included in compositions are pre-rεaction, reaction and post-reaction mixtures the latter of which will include reaction products and by-products as well as unreacted components of the reaction mixture and decomposition products, if any, formed from the one or more components of the prc-reaction or reaction mixture,

[0017] "Blend", "polymer blend" and like terms mean a composition of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase separated. Such a blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method known in the art. Blends are not laminates, but one or more layers of a laminate may contain a blend,

[0018] "Polymer" means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymcr, usually employed to refer to polymers prepared from only one type of monomer, and the term interpolymer as defined below. The terms "ethylene/α-oiefm polymer" and "propylene/α-olefin polymer" are indicative of intεrpolyraers as described below.

[0019] "Interpolymer" means a polymer prepared by the polymerization of at least two different monomers. This generic term includes copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers, e.g., terpolymers, tetra polymers, etc,

[0Θ20] "Units derived from a diene" and like terms means the units within a TPU that originated from a compound that contained two or more carbon-carbon unsaturated, typically ethylenically unsaturated, functionalities. "Polydiene -based polyαrethane" and like terms mean a polyurethanε polymer formed, in part, from a polydiene containing at least one isocyanatc-reactive group, e.g., hydroxy! and/or amine.

[0022] "Polydiol-based polyiirethane" and like terms mean a polyurethane polymer formed, in part, from a polydiol containing at least two hydroxyl groups. [0023] "Polydiene diol-based polyurethane" and like terms mean a polyurethane polymer formed, in part, from a polydiene containing at least two hydroxyl groups. [0024] "Polyurethane not based on a dienε" and like terms means a polyurethane other than a polydiol-based polyurethanε or a polydienε-bascd polyurethanε, [0025] "Compatibilizing amount" and like terras means an amount of a substance added to a blend such that two or more components of the blend interact with one another to impart to the blend a property, or to enhance an existing property, that is not otherwise evident from the blend. In the context of this invention, a compatibilizing amount of component C is an amount that improves the clarity of an uncrosslinkεd blend of components A and B. [0026] "Catalytic amount" and like terms means an amount of catalyst sufficient to promote the rate of reaction between two or more reactants by a discernable degree. [0027] "Crosslinking amount" and like terms means an amount of crosslinking agent or radiation or moisture or any other crossiinging compound or energy sufficient to impart at least a detectable amount of crosslinking in the composition or blend under crosslinking conditions.

[0028] "Detectable amount of crosslinking" means an amount of crosslinking in the composition or blend that can be measured using any one of known crosslinking detection methods, e.g., gel content, xylene extraction, viscosity or torque increase, and the like. These methods are well know to those of ordinary skill the art.

[0029] "Unerossliπked" and like terms mean that the composition or blend is free of detectable crosslinking,

[0030] "Crosslinked", "vulcanized", "cured" and like terms mean that the composition contains detectable crosslinking.

[0031] "Dynamically crosslinked" and like terms means that a composition or blend is at last partially crosslinked while the blend is subjected to mechanical action, e.g., melt blending through the action of the screws of an extruder or the mixing elements of another mixing device, stirring, etc. Dynamically crosslinked is opposed to statically crossliriked in which the composition or blend is crosslinked without mechanical action, e.g., by exposure to heat, radiation, moisture, etc. Dynamic erosslinMng typically involves subjecting a composition or blend to a shear force, preferably a high shear force, at a temperature above the melting temperature of the component A TPU.

Overview

[0032] In one embodiment, the at least one thermoplastic polyurethane of component A comprises chemical units derived from a polyester or polyether, and at least one aromatic diisocyanate or at least one aliphatic diisocyanate.

[0033] In one embodiment, the at least one thermoplastic polyurethane of component A comprises chemical units derived from a polyester or polyether, and at least one aromatic diisocyanate.

[Θ034J In one embodiment, the at least one thermoplastic polyurethane of component A comprises chemical units derived from a polyester or polyether, and at least one aliphatic diisocyanate.

[0035] In one embodiment, the at least one thermoplastic polyurethane of component Λ comprises chemical units derived from a polyester or polyether and a mixture of l ,3-bis(isocyanatomethyl)~cyclohexane and l,4-bis(isoeyanatomcthyl)eyclohexane, In a further embodiment, the weight ratio of the l,3-bis(isocyanatoraethyl)cyclohexanε to the l,4-bis(isocyanatomethyl)cyclohexanc is about 1 to 1.

[0036] In one embodiment, the polyester is formed from caprolactone.

[0037] In one embodiment, the thermoplastic polyurethane of component A comprises a monomeric unit derived from caprolactone, In one embodiment, the thermoplastic polyurethane comprises a monomeric unit derived from diol derivative which is derived from

N-octyl pyrrolidone. In one embodiment, the thermoplastic polyurethane comprises a monomeric unit derived from poiytetramethylεne ether glycol. In one embodiment, the thermoplastic polyurethane comprises a monomeric unit derived from a polyether.

[0038] In one embodiment, the thermoplastic polyurethane of component A is

PELLETHANE™ polyurethane.

|0039] In one embodiment, the at least one thermoplastic polyurethane of component A has a density from 0,90 grams per cubic centimeter (g/cc) to 1,3 g/cc. In one embodiment. the at [east one thermoplastic polyurεthaαe of component A has a melt index (I₂) from 1 gram per 10 minutes (g/10 min) to 1 G g/10 min.

[0040] In one embodiment, the polybutadieπe and/or or polyisoprene of component B is present in an amount greater than 30, typcially greater than 40 and more typcially greater than 50, wl%. Typically, the poly butadiene and/or polyisoprene is present in the composition in an amount less than or equal to 75, typically less than 70 and more typically less than 65, wl% based on the total weight of the composition.

[0041] In one embodiment component C is a polydiene-based polyurethane. In a preferred embodiment, the polydiene-based polyurethane is a polydiene diol-based polyurethane. In a farther embodiment, the polydiene diol-based polyurethane is a polybutadiene diol and/or polyisoprene diol, and preferably a polybutadiεne diol, [0042] In another embodiment component C is a polydiol-based polyurethane comprising at least one ethylcnic unsaturation. In a further embodiment, the polydiol-based polyurethane comprises at least one diol made from one or more seed oil triglycerides selected from the group consisting of palmitic, stearic, oleic, linoleic and linolcnic acid or ester, [0043] Examples of the polydiol-based polyurethanes include, but are not limited to, polyurεthanes formed from polyester or polyether polyols and seed oil-based polyols, [0044] In one embodiment, the polydiene-based polyurethane and, preferably, a polydiene diol-based polyurethane, is formed from at least one aliphatic or cyclo-aliphatic diisocyanate. In a further embodiment, both the polydiene-based polyurethane, and preferably a polydiene diol-based polyurethane, and the thermoplastic polyurethane are each, independently;, formed from at least one aliphatic diisocyanate.

[0045] In another embodiment, the polydiol-based polyurethane is formed from at least one aliphatic or cyclo-aliphatic diisocyanate. In a further embodiment, both the polydiol- based polyurethane and the thermoplastic polyurethane of (A) are each, independently, formed from at least one aliphatic diisocyanate. In yet a further embodiment, the polydiol- based polyurethane comprises at least one diol made from one or more seed oil triglycerides selected from the group consisting of palmitic, stearic, oleic, linoleic and linoienic acid or ester.

[0046] In one embodiment, the at least one polydiene-based polyurethane compatibilizεr is present in an amount greater than zero, typically greater than 1 and more typically greater than 5, wt%. Typically, this compatibilizer is present in the composition in an amount less than or equal to 30, more typically less than 25 and even more typically less than 20, wt% based on the total weight of the composition.

[0047] In one embodiment, the at least one polydiene-based polyurεthane compatibilizer has a density from 0.90 g/cc to 1.3 g/cc. In one embodiment, the at least one polydiene- based polyurethane has a melt index (h) from 1 g/10 min to 300 g/10 min. In one embodiment, the at least one polydiene-based polyurethane has a number average molecular weight from 500 grams per mole (g/mole) to 1,000,000 g/mole.

[0048] Jn one embodiment, the at least one polydiene-based polyurεthane is formed from a composition that comprises from 15 to 40 wt% of a diisocyanate based on the total weight of the composition. In one embodiment, the diisocyanate is an aromatic diisocyanate, [0049] In another embodiment, the at least one polydiene-based polyurethane is formed from a composition that comprises from 50 to 75 wt% of a polydiene diol based on the total weight of the composition.

[0050] In another embodiment, the at least one polydiene-based polyurethane is formed from a composition that comprises from 5 to 15 wt% of a chain extender based on the total weight of the composition.

[0051] In one embodiment, an inventive composition comprises one or more additives. In one embodiment, the inventive composition is filled. In one embodiment, an inventive composition is foamed.

[0052] In one embodiment, an inventive composition further comprises a polar polymer selected froiυ the group consisting of polyesters, polyamides, polyethers, polyetherirπidεs, polyvinylalcohois, polycarbonates, polyurethanεs, polylactic acids, and polyamide esters. |0053] The invention also provides an article comprising at least one component formed from an inventive composition.

[0054] In one embodiment, the article is an sheet, a carpet, an adhesive, a wire sheath, a cable, a protective apparel, an automotive part, a footwear component, a coating, or a foam laminate, an automotive skin, an awning, a tarp, a roofing construction article, a steering wheel, a powder coating, a powder slush molding, a consumer durable, a grip, a handle, a computer component, a belt, an applique, a footwear component, a conveyor or timing belt, or a fabric. in another embodiment, the article is a tie layer between extruded sheets, a tie layer between extruded films, a tie layer between extruded profiles, a tie layer between cast sheets, tie layer between cast films, or tie layer between east profiles.

[0056] The invention also provides an extruded sheet formed from an inventive composition. In a further embodiment, the sheet has a surface energy greater than, or equal to, 30 dynes per centimenter (dyne/cm), preferably greater than, or equal to, 33 dyne/cm, more preferably greater than, or equal to 35 dyne/cm, Fn another embodiment, the sheet has a thickness from 10 mil to 1000 mil, preferably from 15 mil to 500 mil, and more preferably from 20 mil to 100 mil,

[Θ0S7] The invention also provides a painted substrate comprising an inventive composition. Tn one embodiment, the paint comprises at least one additive of selected from the group consisting of an acrylic polymer, an alkyd resin, a cellulose-based material, a melamine resin, a urεthane resin, a carbamate resin, a polyester resin, a vinyl acetate resin, a polyol and an alcohol In another embodiment, the paint is a water-based paint. In another embodiment the paint is an organic solvent-based paint.

[0058] The invention also provides an over-molded article comprising the following: (a) a substrate formed from a composition comprising a polar polymer, and (b) a molded overlay formed from an inventive composition. In one embodiment, the polar polymer is a polycarbonate.

[0059] The invention also provides an over-molded article comprising the following: (a) a substrate formed from an inventive composition, and (b) a molded overlay formed from a composition comprising a polar polymer. In one embodiment, the article is in the form of a grip, handle or belt.

[0060] The invention also provides a laminated structure comprising a first layer and a second layer, and wherein the first layer is formed from an inventive composition, and wherein the second layer is formed from a composition comprising a polar polymer. In one 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, tarp or automobile skin or steering wheel, In another embodiment, the second layer is formed from a composition comprising a polycarbonate. [0061] The invention also provides a molded 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 an inventive composition, In one embodiment, Ihε article is in the form of an automobile skin, an applique, a footwear component, a conveyor belt, a timing belt or a consumer durable. »?^"* The invention also provides a dispersion comprising an inventive composition.

In one 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 ureihane resin, a carbamate resin, a polyester resin, a vinyl acetate resin, an epoxy a 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,

[0064] The invention also provides an injection molded article comprising at least one component formed from an inventive composition.

[0Θ65] The invention also provides a radio frequency (RF) welded article comprising at least one component formed from an inventive composition,

[0066] The invention also provides a molded 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 an Inventive composition, in one embodiment, the article is in the form of an automobile skin, an applique, a footwear component, a conveyor belt, a timing belt, artificial leather, or a consumer durable.

[0067] The invention also provides a footwear article comprising at least one component formed from an inventive composition. In one embodiment, the article is selected from the group consisting of shoe outsole, shoe midsole, shoe unitsole, an overmolded article, a natural leather article, a synthetic leather article, an upper, a laminated article, a coated article, a boot, a sandal, galoshes, a plastic shoe, and combinations of two or more of the preceding,

[0068] The invention also provides a thermoformed sheet comprising at least one layer formed from an inventive composition. The invention also provides an automotive part comprising at least one layer formed from an inventive composition. In one embodiment, the part is an instrument panel or a door panel.

[007Oj The invention also provides artificial leather comprising at least one component formed from an inventive composition,

[0071] The invention also provides an artificial turf comprising at least one component formed from an inventive composition,

[0072] The invention also provides an adhesive comprising at least one component formed from an inventive composition. The invention also provides a coated substrate comprising an inventive adhesive, and at least one component formed from KEVLΛR*' aromatic poiyamide fiber.

[0073] The invention also provides a method of making an inventive composition, said method comprising melt mixing Components A, B and C, In one embodiment, components A, B and C are mixed simultaneously, In another embodiment, components A, B and C are mixed sequentially, in any order. In another embodiment, the melt mixing takes place in an extruder, In another embodiment, the melt mixing takes place in an "in-line" compounding process, "In-line compounding process" and like terms mean a process, typically continuous, in which the components of the composition are continuously fed to and mixed within an extruder or like piece of equipment from which a composition comprising the mixed components is discharged and, optionally, is further processed into an article of manufacture, e.g., a film, sheet, fiber, etc.

[0074] In one embodiment the inventive composition is dynamically crosslinked through in an extruder, In one embodiment, the inventive composition is dynamically crosslinked using sulfur, peroxide, heat, moisture and/or radiation,

[0075] An inventive composition may comprise a combination of two or more of the previously described embodiments,

[0076] A polymer component of an inventive composition may comprise a combination of two or more of the previously described embodiments.

[0077] An inventive article may comprise a combination of two or more of the previously described embodiments, An inventive method may comprise a combination of two or more of the previously described embodiments. Thermoplastic Polyurethanes (Component A)

[0079] The polyurethane of component A has no limitation in respect of its formulation, oilier than (i) it comprises no more than 25 wt% of units derived from a diene, and (ii) it is thermoplastic in nature, which means it is prepared from substantially di functional ingredients, for example, organic diisocyanates and components being substantially di functional in active hydrogen containing groups. However, some times minor proportions of ingredients with functionalities higher than two may be employed. This is particularly true when using extenders such as glycerin, trimethyioipropane, and the like. Such thermoplastic polyurethane compositions are generally referred to as TPU materials. Accordingly, any of the TPlJ materials known in the art can be employed in the present compositions. For representative teaching on the preparation of TPU materials see Polyurethanes: Chemistry and Technology, Part 11, Saunders and Frisch, 1964 pp 767 to 769, Interscieαce Publishers, New York, N. Y. and Polyurethane Handbook, Edited by G. Oertel 1985, pp 405 to 417, Hanser Publications, distributed in U.S.A. by MacmiSlan Publishing Co.. Inc., New York, N.Y. For particular teaching on various TPU materials and their preparation see USP 2,929,800; 2,948,691; 3,493,634; 3,620,905; 3,642,964: 3,963.679; 4,131 ,604; 4,169,196; Re 31,671; 4,245,081 ; 4,371,684; 4,379,904; 4,447,590; 4,523,005; 4,621 ,1 13; and 4,631,329.

[0080] The preferred TPU is a polymer prepared from a mixture comprising an organic diisocyanate, at least one polymeric diol and at least one d {functional extender. The TPU may be prepared by the prepolymcr, quasi-prepolymer, or one-shot methods in accordance with the methods described in the incorporated references above.

[008Ϊ] Di-isocyanates suitable for use in preparing the hard segment of the polyurethanes according to this invention include aromatic, aliphatic, and cycloaliphatic di-isocyanates and combinations of two or more of these compounds. Λn example of a structural unit derived from di-isocyanate (OCN-R-NCO) is represented by formula (ϊ) below:

O p

- -C— i-lN ^~- R^~- NH C — ,_{I t} in which R is an aikylene, cycloalkylene, or arylene group, Representative examples of these di-isocyanates can be found in USP 4,385,133, 4,522,975 and 5,167,899. Preferred di-isoeyanates include, but are not limited to, 4,4'~di~isocyanatodipheny-lmcthane, p- phenylene di-isocyanate, l,3-bis(isocyanatomethyl)-cyciohcxane, 1 ,4-di-isocyanato- cyclohexane, hexam ethylene di-isocyanate, 1,5 -naphthalene di-isocyanate, 3,3'~dimethyl- 4,4'-biphenyl di-isocyanate, 4,4'-di-isocyanato-dicyclohεxylmethane, and 2,4-toluene di-isocyanate. More preferred are 4,4'-di~isocyanato-dicyclohexylrnethane and 4,4'-di-isoeyanato-diphenylmethane. A preferred is 4,4'-di-isocyanatodiphenylmεthane.

[0082] Di-isocyanates also include aliphatic and cycloaliphatic isocyanate compounds, such as 1 ,6-hexaniethylene-di-isocyanate; ethylene di-isocyanate; 1 -isocyanato- 3,5,5-triiBεthyl-l-3-isocyanaiomethylcyelohexane; 2,4- and 2,6-hexahydrotoluenedi- isocyanate, as well as the corresponding isomeric mixtures; 4,4'-, 2,2'- and 2,4'-dicyclohexyl- rnethanedi-isocyanate, as well as the corresponding isomeric mixtures. Also, 1,3- tetram ethylene xylene di-isocyanatε can be used with the present invention. The isocyanate may be selected from organic isocyanates, modified isocyanates, isocyanate-based pre- polymers, and mixtures of two or more of these isocyanates.

[0083] Any of the organic diisocyanates previously employed in IPU preparation can be employed, including aromatic, aliphatic, and cycloaliphatic diisocyanates, and mixtures thereof. Illustrative isocyanates include, but are not limited to, methylenebis(phenyl isocyanate), including the 4,4'-isomer, the 2,4'-isomer and mixtures thereof; m-and p- phεnylene diisocyanates; chlorophenylene diisocyanates; α₅α^!-xylylene diisocyanate; 2,4-and 2,6-toluene diisocyanate and the mixtures of these latter two isomers, which are available commercially; tolidine diisocyanate; hexamethylene diisocyanate; 1,5 -naphthalene diisocyanate; isophorone diisocyanate and the like; cycloaliphatic diisocyanates, such as methylεnebisCcyclohεxyl isocyanate), including the 4,4'-isomer, the 2_;4'-isomer and mixtures thereof, and all the geometric isomers thereof, including trans/trans, cis/trans, cis/cis, and mixtures thereof; cyelohexylεnε diisocyanates (1,2-; 1,3-; or 1,4-); l-methyl-2,5- cyclohexylene diisocyanate; l-rnethyl-2,4-cyclohexylenε diisocyanate: l-methyl-2,6- cyelohexylene diisocyanate; 4, 4'~isopropylidenebis-(cyclohcxyl isocyanate); 4,4'~ diisocyanatodicyclohexyh and all geometric isomers and mixtures thereof and the like. Also included are the modified forms of methylenebls(phenyl isocyanate). By the latter are meant those forms of methyl enebis(phenyl isocyanate) which have been treated to render them stable liquids at ambient temperature (circa 20⁰C). Such products include those which have been reacted with a minor amount (up to about 0.2 equivalents per equivalent of polyisocyanale) of an aliphatic glycol or a mixture of aliphatic glycols, such as the modified methylenebis(phenyl isocyanat.es) described in USP 3,394,164; 3,644,457; 3,883,571 ; 4,031 ,026; 4.1 15,429; 4,118,411; and 4,299,347. The modified raelhylenebis(phenyl isocyanates) also include those, which have been treated so as to convert a minor proportion of the diisocyanatε to the corresponding carbodiimide, which then interacts with further diisocyanate to form uretone-iminε groups, the resulting product being a stable liquid at ambient temperatures as described, for example, in USP 3,384,653. Mixtures of any of the above-named polyisocyanates can be employed if desired,

[0085] Suitable classes of organic diisocyanates include the aromatic and cycloaliphatic diisocyanates. Preferred species within these classes are methylεnebis(phenyl isocyanate) including the 4,4'-lsomer, the 2,4'-isomer, and mixtures thereof, and methylεnebisCcyclohexyl isocyanate), inclusive of the isomers described above, In a preferred embodiment the isocyanate is a mixture of l₅3-bis(isocyanatomethyl)cyclohexane and 1,4- bis(isocyanatomethyl)cyclohexane. In a further embodiment, these two isocyanates are present in a weight ratio of about 1 to 1 ,

[0086] In one embodiment, the polydiene-based polyurethane and, preferably, a polydiene diol-based polyurethane, is formed from at least one aliphatic or cyclo-aliphatic diisocyanate, In a further embodiment, both the polydiene-based polyurethane, and preferably a polydiene diol-based polyurethane, and the thermoplastic polyurethane are each, independently, formed from at least one aliphatic diisocyanate.

[0087] in another embodiment, the polydiol-based polyurethane is formed from at least one aliphatic or cyclo-aliphatic diisocyanate. In a further embodiment, both the poly diol- based polyurethane and the thermoplastic polyurethane are each, independently, formed from at least one aliphatic diisocyanate. In yet a further embodiment, the polydiol-based polyurethane comprises at least one diol made from one or more seed oil triglycerides selected from the group consisting of palmitic, stearic, oleic, linoieic and linolenic acid or ester. The polymeric diols which can be used include those conventionally employed in the art for the preparation of TPU elastomers. The polymeric diols arc responsible for the formation of soft segments in the resulting polymer, and preferably have molecular weights (number average) falling in the range from 200 to 10,000 g/mole, preferably from 400 to 4,000 g/mole, and, more preferably from 500 to 3,000 g/mole. It is not unusual, and, in some cases, it can be advantageous, to employ more than one polymeric diol. Exemplary of the diols are polyεther diols, polyester diols, hydroxy-terminated polycarbonates, hydroxy - terminaled polybutadienes, hydroxy-terminated polybutadiene-acrylonitrile copolymers, hydroxy-terminated copolymers of dialkyl siloxane and alkylene oxides, such as ethylene oxide, propylene oxide, and the like, and mixtures, in which any of the above poiyols are employed as major component (greater than 50% weight by weight (w/w)) with amine- terminated polyethers and amino-terminated polybutadiene-acrylonitrile copolymers. Additional examples of the diols include the natural oil diols.

[0089] Suitable polyether poiyols include poiyoxyethylenε glycols, polyoxypropylcne glycols, which, optionally, have been capped with ethylene oxide residues; random and block copolymers of ethylene oxide and propylene oxide; polytetramethylεnc glycol; random and block copolymers of tetrahydrofuran and ethylene oxide and/or propylene oxide; and products derived from any of the above reaction with di-funetional carboxylic acids or esters derived from said acids, in which latter case, ester interchange occurs, and the esterifying radicals are replaced by polyether glycol radicals. The preferred polyether poiyols are random and block copolymers of ethylene and propylene oxide of functionality about 2.0 and polytetramethylene glycol polymers of functionality about 2.0,

[0090] Suitable polyester poiyols include those prepared by polymerizing cpsilon- caprolactone using an initiator such as ethylene glycol, efhanoiamme, and the like; and those prepared by esterification of polycarboxylic acids such as phthalic, terephthalic, succinic, glutaric, adipic azεlaic, and the like acids, with polyhydric alcohols, such as ethylene glycol, butanediol, cyclohexanedimethanol, and the like.

[0091] Suitable amme-terramatεd polyethers are the aliphatic primary diamines structurally derived from polyoxypropylene glycols. Polyether diamines of this type were available from Jefferson Chemical Company under the trademark JEFFAMlNF. (now available from Basell). Suitable polycarbonates containing hydroxy! groups include those prepared by reaction of diols, such as propane- 1,3-ch^'ol, butane- 1,4-diol, hexan~l,6-diol, 1,9-nonanedio), 2-mcihyloctane-l,8-diol, diethylεne glycol, triethylenc glycol, dipropylene glycol, and the like, with diarylcarbonates, such as diphenylcarbonate, or with phosgene, [0093] Suitable silicon-containing polyethers include the copolymers of alkylcne oxides with dialkylsiloxan.es, such as dimcthylsiloxane, and the like (see, for example, USP 4,057,595 or 4,631, 329).

[0094] Suitable hydroxy-terminated polybutadiene copolymers include the compounds available under the trade name Poly BD Liquid Resins from Areo Chemical Company. Hydroxy-terminated polybutadiene copolymers arc also available from Sartomer. Illustrative of the hydroxy-and amine-terminated butadiεne/acrylonitrile copolymers are the materials available under the trade name HYCAR hydroxy l-lerminated (HT) liquid polymers and amine-terminated (AT) liquid polymers, respectively. Preferred diols are the polyether and polyester diols set forth above.

[0095] The difunctional extender employed can. be any of those known in the TPU art disclosed above. Typically the extenders can be aliphatic straight and branched chain diols having from 2 to 10 carbon atoms, inclusive, in the chain, Illustrative of such diols are ethylene glycol, L3~ρropanediol₅ 1 ,4-butanediol, 1,5-pentanediol, 1,6-hexanedioi, neopentyl glycol, and the like; 1 ,4-eyelohexanedirnethanol: hydroquinonebis-(hydroxyethyl)et3ier; cyclohexylεnεdiols (1,4--, 1,3-, and 1,2-isomcrs), isopropylidenebis(cyclohexanols); diethylenc glycol, dipropylene glycol, εthanolaminc. N-methyl-diethanolamine, and the like; and mixtures of any of the above. As noted previously, in some cases, minor proportions (less than about 20 equivalent percent) of the difunctional extender may be replaced by trifunctional extenders, without detracting from the thermoplasticity of the resulting TPlJ; illustrative of such extenders are glycerol, trimcthylolpropane, and the like. [0096] While any of the diol extenders, described and exemplified above, can be employed alone, or in admixture, it is preferred to use 1,4-butanediol, 1 ,6-hexanediol, neopentyl glycol, 1,4-cyclohexaiiedimethanoi, ethylene glycol, and diethylenc glycol, either alone, or in admixture, with each other, or with one or more aliphatic diols previously named. Particularly preferred diols are 1 ,4-butanediol, 1 ,6-hexanediol and 1 ,4- cyclohexanedira ethanol . The chain extender is incorporated into the polyurethane in amounts determined by the selection of the specific reactant components, the desired amounts of the hard and soft segments, and the index 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 more preferably from 4 to 18, wt% of the chain extender component.

[0098] ϊf desired, optionally, small amounts of monohydroxylfunctional or monoamine functional compounds, often termed "chain stoppers," may be used to control molecular weight, Illustrative of such chain stoppers are the propanols, butanols, pentanols, and hexanois. When used, chain stoppers are typically present in minor amounts from 0, 1 to 2 weight percent of the entire reaction mixture leading to the polyurethane composition. [0099] The equivalent proportions of polymeric diol to said extender can vary considerably depending on the desired hardness for the TPU product. Generally speaking, the equivalent proportions fall within the respective range of from about 1 :1 to about 1 :20, preferably from about 1 :2 to about 1 :10. At the same time the overall ratio of isocyanate equivalents to equivalents of active hydrogen containing materials is within the range of 0.90:1 to 1.10:1, and preferably, 0.95:1 to 1 .05:1.

[ΘΘIOOJ 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 of from 125°C to 25O⁰C, preferably from 16O⁰C to 225°C.

[00101] It is frequently desirable, but not essential, to include a catalyst in the reaction mixture employed to prepare the compositions of the invention. Any of the catalysts, conventionally employed in the art, to catalyze the reaction of an isocyanate with a reactive hydrogen containing compound, can be employed for this purpose; see, for example, Saunders ct al., Polyurethanes, Chemistry and Technology, Part I, ϊnlerscience, New York, 1963, pages 228-232; see also, Britain et al., J. Applied Polymer Science, 4, 207-211, 1960. Such catalysts include organic and inorganic acids salts of, 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 stannous octoate, stannous olεate, dibutyltiii dioctoate, dibutyltin dilaurate, and the like. Representative tertiary organic amine catalysts are triethylaminε; triethylenedi amine; N, N,N\N'4etrarnethylethylenediamine; N,N,N^p _;N'~tetracthylethy3enedianiinc, N- metliylmorpholine; N-ethylmoφholine; N,N,M'₅N'-tetramethylguanidine; N,N,N',Nf'~ tetramεthyl-1 ,3-butanediamine; N,N-dimethylethanolamine; N,N-diethylethanolamine; and the like. The amount of catalyst employed, is generally within the range of 0,02 to 2.0 wt%, based on the total weight of the reactants.

[00102] As discussed above, the polyure thanes can be prepared by mixing all ingredients, at essentially the same time in a "one-shot" process, or can be prepared by step-wise addition of the ingredients in a "prepolymer process," with the processes being carried out in the presence of, or without the addition of, optional additives, The polyurethane forming reaction can take place in bulk, or in solution, with, or without, the addition of a suitable catalyst that would promote the reaction of isocyanates with hydroxyl or other functionality. Examples of a typical preparation of these polyurethanes are described in USP 5,864,001. [00103] As discussed above, the other main component of the hard segment of the polyurethanes of the present invention is at least one chain extender, which are well know in this technology field. As is known, when the chain extender is a diol, the resulting product is a thermoplastic polyurethane (TPU). When the chain extender is a diamine or an amino alcohol, the resulting product is technically a thermoplastic polyurεa (TPlJU). [00104] The chain extenders that may be used in the invention are characterized by two or more, preferably two, functional groups, each of which contains "active hydrogen atoms," These 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 hydrogen atoms" refers to hydrogen atoms that, because of their placement in a molecule, display activity according to the Zerewitinoff test as described by Kohier in J. Am. Chemical Soc, 49, 31-81 (1927), [00105] The chain extenders may be aliphatic, cycloaliphalic, or aromatic and are exemplified by diols, diamines, and amino alcohols. Illustrative of the di functional chain extenders arc ethylene glycol, dieihylene glycol, propylene glycol, dipropylene glycol, 1,3- propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol and other pentane diols, 2-ethyl- 1,3-hexanediol, 2~ethyl~l,6-hexanediol, other 2-ethyl-liexanediols. 1 ,6-hexanediol and other hexanediois, 2,2,44rimetliylpεntane-] ,3-diol, decanediols, dodecanediols, bisphεnol A₅ hydrogenated bisphenol A₅ 1 ,4-eyelohexanediol, l,4~his(2-hydroxyethoxy)~cyclohexane₅ 1 ,3-cyciohexanedimethano!, 1 ,4-cyclohcxanediol, 1 ,4-bis(2-hydroxyethoxy)benzene, Esterdiol 204 (propanoic acid, 3-lrydroxy~2,2~dimethyi-₅ 3-hydroxy-2,2~dimethylpropyl ester available from TCI America), N-methylethanolamine, N-methyl iso-propylamine, 4~ aminocyclo-hexanol, 1,2-diaminotheane, 1,3-diaroinopropane, diethylenetriaminε, toluenc- 2,4-diamine, and toluene-l,6-diaminc. Aliphatic compounds containing from 2 to 8 carbon atoms are preferred. If thermoplastic or soluble polyurethanεs are Io be made, the chain extenders will be difunetional in nature, Amine chain extenders include, but are not limited to, εthylenediamine, monomeihanolaminε, and propylenεdiamine.

[Θ0106] Commonly used linear chain extenders are generally diol, diamine or amino alcohol compounds characterized by having a molecular weight of not more than 400 g/mol (or Dalton). In this context, by "linear" it is meant that no branching from tertiary carbon is included. Examples of suitable chain extenders are represented by the following formulae: HO-(CH₂VOH, H₂N-(CI-I₂J_n-NH₂, and H₂N-(CH₂VOH. where "n' is typically a number from 1 to 50.

[ΘΘ107] One common chain extender is 1 ,4-butane diol ("butane diol" or "BDO"), and is represented by the following formula: HO-CII₂CH₂CM₂CI]₂-OH. Other suitable chain extenders include ethylene glycol; diethylene glycol; 1,3-propanedioi; 1,6-hexanediok 1,5- heptanediol; triethyleneglycoh 1.2-efhyl hcxenediol (EHL) diol); and combinations of two or more of these extenders. In one embodiment, the chain extender is 1 ,2-ethyl hcxenediol (EHD diol).

[00108] Also suitable, are cyclic chain extenders which are generally diol, diamine or amino alcohol compounds characterized by having a molecular weight of not more than 400 g/mol. In this context, by "cyclic^"' it is meant a ring structure, and typical ring structures include, but are not limited to, the 5 to 8 member ring structures with hydroxyl-alkyl branches. Examples of cyclic chain extender are represented by the following formulae: HO- R-(ring)-R'-OH and HO-R-O-(ring)-O-R'-OH, where R and R^! are one to live carbon alkyl chains, and each ring has 5 to 8 members, preferably all carbons, In these examples, one or both of the terminal -Oil can be replaced with -NH₂, Suitable cyclic chain extenders include cyclohexane dimethano! ("CHDM") and hydroquinone bis-2-hydrxyeτhyl ether (HQEE). A structural unit of CI-IDM, a preferred cyclic chain extender, is represented by the following formula: HO-CH₂-(cγciohεxane OrIg)-CH₂-OH. ⁾} The chain extender is incorporated into the polyurethane in amounts determined by the selection of the specific reactant components, the desired amounts of the hard and soft segments and the index 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 more preferably from 4 to 18, wt% of the chain extender component.

[001 10] If desired, optionally, small amounts of monohydroxylfunctional or monoaniinofunctional compounds, often termed "chain stoppers," may be used to control molecular weight. Illustrative of such chain stoppers are the propanols, butanols, pentanols, and hexanois. When used, chain stoppers are typically present in minor amounts from 0.1 to 2 wt% of the entire reaction mixture leading to the polyurethane composition. [C)OJ lIj As is well 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 slight excess of isocyanate,

[00112] For linear, high Mn polymers, starting materials with two functional groups per chain are desirable. However, it is possible to accommodate starting materials with a range of functionality. For example, a poiydiene with one functional end could be used to cap both ends of a polyurethane with the middle portion consisting of repeating isoeyanate-ehain extender moieties. Polydienes with more than two functional groups will form branched polymers. Although crosslinking and gels can be a problem, if the degree of functionality is too high, this can usually be controlled by process conditions. Such branched polymers will exhibit some theological characteristics that are desirable in soniε cases, such as high melt strength.

[00113] As discussed above, catalysts that will promote or facilitate the formation of urelhanε groups may optionally be used in the formulation. Illustrative of useful catalysts are stannous octanoate, dibutyltin dilaurate, stannous oleate, tcirabutyltin titanate, tributyltin chloride, cobalt naphthenate, dibutyltin oxide, potassium oxide, stannic chloride, N₅N₃N₅N'- ιetramethyl~l,3~butancdiaminc. bis[2-(N₅N-dimcthylamino)ethyl] ether, 1,4- diazabicyclo[2.2.2]octane; zirconium chelates, aluminum chelates and bismuth carbonates. The catalysts, when used, are typically employed in catalytic amounts that may range from 0.001 wt%, and lower, to 2 wt%, and higher, based on the total amount of polyurε thane- forming ingredients.

[00114] Additives may be used to modify the properties of the polyuretbane used in the practice of this invention. Additives may be included in the conventional amounts as already known in the art and literature. Usually additives are used to provide specific desired properties to the polyurethanes such as various antioxidants, ultraviolet inhibitors, waxes, thickening agents and fillers. When fillers are used, they may be either organic or inorganic, but are generally inorganic such as clay, talc, calcium carbonate, silica and the like. Also, fibrous additives, such as glass or carbon fiber, may be added to impart certain properties. [00115] The polyurethane used in the practice of the present invention is preferably prepared by reacting the functional polyester with an isocyanate, and optionally a chain extender. In the 'prepolymer method, typically one or more functional polydiencs are reacted with one or more isoeyanates to form a prepolymer. The prepolymer is further reacted with one or more chain extenders. Alternatively, the polyurethanes may be prepared by a one-shot reaction of all of the reactants. Typical polyurethanes have a number average molecular weight from 5.,QQO to 1,000,000 g/mol, and more preferably from 20,000 to 100,000 g/mol.

[00J16] 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 a Mn from 500 to 10,00O₅ more preferably from 1 ,000 to 5,000 and even more preferably from 1,500 to 3,000 g/mol. [00117] In another embodiment, the polyurethane is formed from a composition comprising 10 to 40 wt% of di-isoeyanate, preferably 15 to 35 wt% of di-isocyanate; 50 to 85 wt% of a polyester, preferably 55 to 80 wt% of a polyester, and more preferably 60 to 80 wt% of a polyester; and 2 to 15 wt% of a chain extender, preferably 2 to 10 wt% of a chain extender (each weight percentage based on the total weight of reactants). In a further embodiment, the di-isocyanate is an aliphatic or aromatic di-isocyanate, and more preferably 4,4'-diphεnyimethane di-isocyanate. In yet a further embodiment, the chain extender is an aliphatic diol. In another embodiment, the poJydienε diol has a Mn from 500 to 10,000, more preferably from I₅OOO to 5,000 and even more preferably from 1,500 to 3,000, g/mol. In one embodiment, the poJyurethane has a density greater than, or equal to, 0,90 g/cc, preferably greater than, or equal to, 0,95 g/cc, and more preferably greater than, or equal to, 1.00 g/cc. In another embodiment, the polyurethane has a density less than, or equal to, 1.30 g/cc, preferably less than, or equal to, 1 .25 g/cc, and more preferably less than, or equal to, 1.20 g/cc. In another embodiment, the polyurethane has a density from 0.90 g/cc to 1,30 g/cc, preferably from 0.95 g/cc to 1,25 g/cc, and more preferably from 1 ,00 g/cc to 1.20 g/cc.

[001 J 9] In another embodiment, the polyurethane has a melt index greater than, or equal to, 0.1 g/10 irrin, preferably greater than, or equal to, 0.5 g/10 mm, and more preferably greater than, or equal to, 1 g/l ϋ min (as measured by ASTM D-1238-04, I^QO⁰C, 8.7kg). In another embodiment, the polyurethane has a melt index less than, or equal to, 100 g/10 min, preferably less than, or equal to, 50 g/10 min, and more preferably less than, or equal to, 20 g/10 min, (ASTM D-1238-04, 19O⁰C₃ 8,7kg). In another embodiment, the polyurethane has a melt index 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 from 1 g/10 min to 20 g/10 min.

[00120] Preferred polyurethanεs include the Peliethanε^m thermoplastic polyurethane elastomers available from The Dow Chemical Company.

[00121] Additional polyurethanεs suitable for use in the invention include, but are not limited to, ESTANE thermoplastic polyurethanes, TECOFLEX thermoplastic polyurethanes, CARBOTHANE thermoplastic polyurethanes, TECOPHfLlC thermoplastic polyurethanes, TlECOP LAST thermoplastic polyurethanes, and TECOTHΛNE thermoplastic polyurethanes, all available from Noveon; ELASTO LLAN thermoplastic polyurethanes and other thermoplastic polyurethanes available from BASF; and commercial thermoplastic polyurethanes available from Bayer, Huntsman and Mcrquinsa.

[00122] The polyurethane component of the compatibilized blends used in the practice of the invention may contain a combination of two or more suitable embodiments as described above.

[00123] If desired, the polyurethanεs can have incorporated in them, at any appropriate stage of preparation, additives such as pigments, fillers, lubricants, stabilizers, antioxidants, coloring agents, fire retardants, and the like, which are commonly used in conjunction with polyurethane elastomers. Polybutadiene (Component B)

[00J24] Suitable polybυtadienes include, but are not limited to, natural cis-1,4- polybutadiene, trans- 1 ,4-polybutadiene, vinyl- 1,2-polybutadiene, copolymers of styrene and butadiene, copolymers of isoprene and butadiene, and interpolymcrs of styrene, isoprcne and butadiene, Preferred poiybutadienes include natural cis-l,4-poiybutadiene, trans- 1 ,4- polybutadiene, vinyl -1 ,2 -polybutadiene, and copolymers of isoprcne and butadiene. More preferred poiybutadienes are cis-l ,4-polybutadiεne and trans- 1 ,4-polybutadiene, [Θ0125] In one embodiment, the polybutadiene has a Mooney Viscosity (ML 1+4 at 100⁰C) from 10 to 100, preferably from 15 to 9O₃ and more preferably from 20 to 80. [0OJ 26] Examples of suitable poiybutadienes include EUROPRENE NEOCIS BR 40 from Polimeri Europa, BlJNA CB 24 from Lanxess, and FIRESTONE 40ΛC10. [00127] A polybutadiene may comprise a combination of two or more appropriate embodiments as described above,

[00128] Polyisoprenes include both natural poiyisprenε and synthetic polyisoprcne, Suitable polyisoprenes include, but are not limited to, natural cis-l,4-polyisoprene, synthetic cis-l_s4-polyisoprene, high vinyl 3,4-polyisoprene and 3,4-poiyisoprene. |00129] In one embodiment, the polyisoprene has a Mooney Viscosity (ML 1+4 at K⁾O⁰C) from 20 to 100, and preferably from 40 to 80,

[Θ013Θ] Suitable examples of polyisoprenes include the following technical grades: SMR (Standard Malaysian Rubber), such as SRM 5 and SMR 20; TSR (Technical Specified Rubber) and RSS (Ribbed Smoked Sheets).

[00131] A polyisoprene may comprise a combination of two or more appropriate embodiments as described above. Diene-Based TPU Companbillzers (Component C)

|00132] Suitable diene-basεd TPU for use in the inventive compositions are described in International Publication No. WO 2007/033117 and International Application No, PCT/US2006/035384. As here used, "diene-hased TPU", "polydiene-based thermoplastic polyurethanc", "polydiene -based polyurethanε", "pd-TPU" and like terms mean a polyurεthane polymer formed, in part, from a polydiene containing at least one isocyanate- reaetive group, e.g., hydroxy] and/or amine, preferably a hydroxyl group, and specifically include polydioi-based TPU. ^Polydiene diol-based thermoplastic polyurethane'^", "polydiene diol-based polyurethanε" and like terms mean a polyurethane polymer formed, in part, from a polydicne diol containing ai least two hydroxyl groups and at least one unsaturation, preferably ethyl enic unsaturation. "T)iol-bascd thermoplastic polyurethane", "d-TPU" and like terms mean a polyurethane polymer formed, in part, from a diol. The diol can be either a natural-sourced diol or a pd-TPU.

[00133] Tn one embodiment, component C is a polydiene-based polyurethane. In a preferred embodiment, the polydiene-based polyurethane is a polydiene dioi-based polyurethane. In a further embodiment, the polydiene diol-based polyurεthane is a polybutadiene diol and/or polyisoprene diol, and preferably a polybutadiene diol. In a further embodiment, the polydiene diol-based polyurethane comprises at least one diol made from one or more seed oil triglycerides that contain diεnic unsaturation e.g., palmitic, stearic, oleic, linoleic and linolenic acid or εster,

[00134] In one embodiment, component C is a polydiene diol-based TPU comprising at least 30 wt% units derived from an unsaturated diol.

[00135] In one embodiment, the polydiene-based polyurethane has a density less than or equal to 1.30 g/cc, preferably less than or equal to 1.00 g/cc, and more preferably less than or equal to 0.98 g/cc. In another embodiment, the polydiene-based polyurethane has a density- greater than or equal to 0.94 g/cc, preferably greater than or equal to 0.95 g/cc, and more preferably greater than or equal to 0.96 g/cc. In another embodiment, the polydiene-based polyurethane has a density from 0.94 g/cc to 1,30 g/cc₅ preferably from 0,96 g/cc to 0,99 g/cc, and more preferably from 0.96 g/cc to 0,98 g/cc.

[00136] In one embodiment, the polydiene-based polyurethane has a melt index (I₂) less than or equal to 300 g/10 min, preferably less than or equal to 100 g/10 min, more preferably- less than or equal to 20 g/10 min, and even more preferably less than or equal to 15 g/10 min. In another embodiment, the polydiene-based polyurethane has 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 more preferably greater than or equal to 2 g/10 min. In another embodiment, the polydiene-based polyurethanε has a melt index (I₂) from 0.5 g/10 min to 300 g/10 min, preferably from 1 g/cc to 100 g/10 min, and more preferably from 2 g/cc to 20 g/10 min. [Θ0137] In one embodiment, the polydiene-based polyurethane contains units formed from a polydiene, preferably a polydiene diol, in an amount from 30 to 75 wt%, and preferably from 50 to 75 wt%, based on the total weight of the polyurethane.

[00138] In a one embodiment, the polydiene-based polyurethane is a polydiene diol that is formed from conjugated dienes having 4 to 24 carbons, and preferably having 4 to 8 carbons, Typical dienes include butadiene and isoprεne, and typical polydienes include polybutadiene and polyisoprene, and hydrogenaied polybutadiene and hydrogenaiεd polyisoprene. In a preferred embodiment, these polydienes have at least one, and more preferably at least two, hydroxy! groups in the molecule, and typically have a number average weight average (Mn) from 500 to 1,000,000, more typically from 500 to 10,00O₅ even more typically 1,000 to 5,000, and still more typically from l_;500 to 3,000 g/mol. Preferably, the polydiene diol is a polybutadiene diol or a polyisoprene diol, and more preferably a polybutadiene diol. [00139] In another embodiment, the polydiene-based polyurethane is a polydiene diol- based polyurethane, and is formed from a composition comprising 15 to 40 wt% of di-isocyanate, 50 to 75 wt% of a polydiene diol, and 5 to 15 wt% of a chain extender, each weight percent based on the total weight of the composition, In a further embodiment, the polydiene diol is a polybutadiene diol or a polyisoprεnc diol, and preferably is a polybutadiene diol, In a further embodiment, the di-isocyanate is an aliphatic or aromatic di- isocyanate, preferably an aromatic di-isocyanate, and more preferably 4,4'-diphenylmethane di-isocyanate. In yet a further embodiment, the chain extender is an aliphatic diol. In another embodiment, the polydiene diol has a Mn from 500 to 10,000, more preferably from 1,000 to 5,000 and even more preferably from 1.500 to 3,000, g/mol, In another embodiment, the polydiene diol is non-hydrogεnated, In another embodiment, the polydiene diol is hydrogenated. In another embodiment, the polydiene diol is partially hydrogcnated. [00140] In another embodiment, the polydiol-based polyurethane is formed from a natural-sourced diol. As here used, "natural-sourced diol". "natural oil polyols" and like terms mean a diol derived from an agricultural product, e.g., seed oils such soy, sunflower, com and canola. The composition of seed oil triglycerides is well understood. Triglycerides are fatty acid esters of glycerin, and the composition depends on the source of the oil. The nomenclature used is standard in the fats and oils industry, with the number of carbons in the fatty acid indicated first, followed by the number of sites of unsaturation in parentheses. Representative oils include palmitic, stearic, oleic, linoleic and linolemc. For the puφosc of making polyols from these triglycerides, oils which contain a high level of υnsaturation are desirable. Oils such as soy, canola and sunflower are acceptable due to the relatively low levels of saturated fatty acids that they contain, while feedstocks such as palm oil are considered unusable without further purification or refinement due to high levels of saturated fatty acids.

[1)0141] The polydiene-based polyurethane may contain a combination of two or more embodiments as described above.

[§0142] The dicnε-based polyurethanes of the present invention are each independently prepared from a polydiol or a functional polydiene containing at least one (preferably about two) ''isocyanate-reactivε grouρ(s)" attached at the ends of the molecule or attached pendanlly within the molecule. This functionality may be any of the groups that react with isocyanales to form covalent bonds. This functionality preferably contains ''active hydrogen atoms," with typical examples being hydroxyl, primary amine, secondary amine, sulfliydryl, and mixtures thereof. The terni "active hydrogen atoms" refers to hydrogen atoms that, because of their placement in a molecule, display activity according to the Zerewitinoff test, as described by Kohler in J. Am. Chemical Soc, 49, 31-81 (1927). The content of the unsaturated segment in the polyurethane is from 30 to 75 wl%, preferably from 50 to 70 Λvt%. and preferably from 50 to 65 wt%, based on the total weight of the polyurethane. In a preferred embodiment, the polyurethane component is prepared from a polydiene diol. In another embodiment, the polyurethane is prepared from a functionalized polydiene, which contains "isocyanate reactive groups" other than hydroxyl,

[00143] One method for preparing such functional polydienes is a two-step process in which a conjugated diene is grown by anionic polymerization from both ends of a difimctional initiator. The molecular weight of the polydiene is controlled by the molar ratio of the conjugated diεnc to the initiator. In the second step, the ends are then capped with alkylene oxide (such as ethylene oxide or propylene oxide) to produce an unsaturated diol. This particular process is described in USP 4,039,593. In such processes, it is possible to add excess alkylene oxide and form short polyfalkylenε oxide) chains at the ends of the polydiene. Such materials are within the scope of this invention. [Θ0144] The conjugated dienes used to prepare the functional polydiene typically contains from 4 to 24 carbons, and preferably from 4 to 8 carbons. Typical dienes include butadiene and isoprenε, and typical functional polydienes are polybυtadiene and polyisoprεne, each capped at each end with ethylene oxide. These polydienes have at least one functional group per molecule, and typically have a Mn from 500 to 10,000 g/mol, and preferably from 500 Io 5,000 g/mol, The functional group is preferably a hydroxy! group. Two preferred polydiene diols are polybuiadieiie dio! and polyisoprene diol, and more preferably polybutadienc diol. [00145] In one embodiment, the at least one polydiene diol-basεd polyurethane is formed from a non-liydrogenated polydiene diol. In another embodiment_., the at least one polydiene diol-based polyurethane is formed from a hydrogenated polydiene dioi. In another embodiment, the at least one polydiene diol-bascd polyurcthane is formed from a partially hydrogenated polydiene diol.

[00146] The term "hydrogenation" is known in the art, and is used in reference to the hydrogenation (reaction of hydrogen with alkene groups) of double bonds within the polydiene diol, and is in reference to the final (hydrogenated) product, The term "hydrogenation" refers to the complete hydrogenation of all the double bonds, or the near complete hydrogenation (approximately greater than 95 mole percent (mol%) of the double bonds, within the polydiene diol. The term "partial hydrogenation," is used in reference to a hydrogenation reaction, and the final product, both in which a significant amount (approximately greater than 5 mol%) of the double bonds, within the polydiene diol, are not hydrogenated,

[00147] The polydiene-based polyurethane used in the practice of the present invention is prepared by the reaction of the functional polydiene with an isocyanate and optionally a chain extender. In the 'prepolymer method, typically one or more functional polydienes are reacted with one or more isocyanatcs to form a prepolymer. The prepolymer is further reacted with one or more chain extenders. Alternatively, the polyurethanes may be prepared by a one-shot reaction of all of the reaetants. Typical polyurethanes have a number average- molecular weight from 5,000 to 1,000,000 g/mol, preferably from 10,000 to 500,000 g/mol, and more preferably from 20,000 io 100,000 g/mol.

[00148] Some examples of polydiene diols, and corresponding polyurethanes, are described in Pytεla et al, "Novel Polybutadiene Diols for Thermoplastic Polyurethanes.^"' International Polyurεthanc Conference, PU LaL Am. 2001; and in Pytela el al, "'Novel Thermoplastic Polyurethanes for Adhesives and Sealants," Adhesivεs & Sealant Industry, June 2003, pp. 45-51, Sonic examples of some hydrogenated polydiene diols, and corresponding polyurethanes, are described in WO 99/02603, and corresponding European Patent EP 0 994 919 Bl . As discussed in these references, the hydrogenation may be carried out by a variety of established processes, including hydrogenation in the presence of catalysts as Raney Nickel, noble metals, such as platinum, soluble transition metal catalysts and titanium catalysts, as in USP 5,039,755. Also, the polymers may have different dicnε blocks and these dienε blocks may bε selectively hydrogenated as described in USP 5,229,464. [00149J The di-isocyanates suitable for use in preparing the hard segment of the diene- bascd poly ore thane compatibilizers of component C are the same as those described for component A above.

[00Ϊ50] In one embodiment the polydiene -based poivurethanc and, preferably, a polydiene diol-based polyυr ethane, is formed from at least one aliphatic or cyclo-aliphatic diisocyanatc, In a further embodiment, both the polydiene-based poiyurethane, and preferably a polydiene diol-based poiyurethane, and the thermoplastic poiyurethane are each, independently, formed from at least one aliphatic diisoeyanate.

[00151] In another embodiment, the polydiol-based poiyurethane is formed from at least one aliphatic or cyclo-aliphatic diisoeyanate. In a further embodiment, both the poly diol- based poiyurethane and the thermoplastic poiyurethane are each, independently, formed from at least one aliphatic diisoeyanate. Ln yet a further embodiment, the polydiol-based poiyurethane comprises at least one diol made from one or more seed oil triglycerides selected from the group consisting of palmitic, stearic, oleic, linoleic and linoienic acid or ester.

[00152] As discussed above, the polyurethanes can be prepared by mixing all ingredients, at essentially the same time, in a "one-shot" process, or can be prepared by step- wise addition of the ingredients, in a "prepoiymer process," with the processes being carried out in the presence of, or without the addition of, optional additives. The polyurεthane forming reaction can take place in bulk, or in solution, with, or without, the addition of a suitable catalyst that would promote the reaction of isocyanates with hydroxy! or other functionality. Hxamples of a typical preparation of these polyurethanes are described in IJ SP 5,864,001. [00153] The other main component of the hard segment of the diεnc-based polyurethane compatibilizεrs of component C is also the same as that described for component A above. As is known, when the chain extender is a diol, the resulting product is a thermoplastic polyurethane (TPU). When the chain extender is a diamine or an amino alcohol, the resulting product is technically a thermoplastic polyurea (TPUU), Likewise, the chain extenders that may be used in the compatibϊlizers of component C are the same as those described for component A.

[0OJ 54] Optionally, catalysts that will promote or facilitate the formation of urethane groups may he used in the formulation. Illustrative of useful catalysts are stannous octanoate, dibutyltin dϋaurate, stannous olcate, tetrabutyltin titanate, tributyldn chloride, cobalt naphthεnate, dibutyltin oxide, potassium oxide, stannic chloride, N,N,K,N'- tetramethyl-i₅3-butanediaminε, bis[2-(N,N-dimεthylamino)ethyl] ether, 1 ,4- diazabicyclo[2.2.2]octane; zirconium chelates, aluminum chelates and bismuth carbonates. ^'The catalysts, when used, are typically employed in catalytic amounts that may range from 0.001 wt%, and lower, to 2 wt%, and higher, based on the total amount of polyurethane- forming ingredients.

[00155] The optional additives that may be used to modify the properties of component C are the same as those described for use with component A.

[00156] In a preferred embodiment of the invention, the polyurethane is formed from a polydiene diol. an isocyanate and a chain extender, and preferably an aliphatic chain extender. In another embodiment, the polydiene diol-based polyurethane is hydrogenatεd. [00157] in a further embodiment, the polydiene diol is formed from conjugated dienes having 4 to 24 carbons, and preferably having 4 to 8 carbons. As discussed above, typical dienes include butadiene and isoprene, and typical poiydienes include polybutadiene and polyisoprene, and hydrogenated polybutadiene and hydrogenated polyisoprene. In a preferred embodiment, these poiydienes have at least one, and more preferably at least two, hydroxy! groups in the molecule, and typically have a Mn from 500 to 1O₅OOO₅ more preferably from 1,000 to 5,000 and even more preferably from 1,500 to 3,000 g/mol. Preferably, the polydiene diol is a polybutadiene diol or a polyisoprene diol, and more preferably a polybutadiene diol. [00158] In another embodiment, the polydiene diol-based polyurethane is formed from a composition comprising 15 to 40 wt% of di-isocyanate, 50 to 75 wt% of a polydiene diol, and 5 to 15 wt% of a chain extender, based on the weight of the composition. In a further embodiment, the polydiene diol is a polybutadiene diol or a poiyisoprene diol. and preferably is a polybutadiene diol, In a further embodiment, the di-isocyanate is an aliphatic or aromatic di-isocyanate, and more preferably 4,4'-diphenylmethane di-isocyanate. In yet a further embodiment, the chain extender is an aliphatic diol. In another embodiment, the polydiene diol has a Mn from 500 to 10,000, more preferably from 1 ,000 to 5,000, and even more preferably from 1,500 to 3,000, g/mol, In another embodiment, the polydiene diol is non-hydrogεnated. In another embodiment, the polydiene diol is hydrogεnated. In another embodiment, the polydiene diol is partially hydrogεnated.

[00159] The polydiene- or polydiol based polyurethane used in the practice of the invention may comprise a combination of two or more embodiments as described above. Uncrosslinked Compositions

[00160] The uncrosslinked compositions of the invention comprise: a) at least one TPU comprising less than 25 wt% of units derived from a diene, b) at least one of polybutadiene and poiyisoprene, and e) at least one polydiene-based TPU that comprises at least 30 wt% of units derived from a diene. Typically, the compatibilizer is present in an amount less than or equal to 30, more lypciaily less than or equal to 25 and even more typically less than or equal to 20, wt% based on the total weight of the composition.

[00161] In one embodiment, the unerosslinked composition comprises from 30 to 75, and typcially from 50 to 70, wt% of the thermoplastic polyurethane of component A. [00162] In another embodiment, the uncrosslinked composition comprises from 30 to 70 wt%, and typically from 30 to 50, wt% of polybutadiene and/or poiyisoprene. [00163] In one embodiment, the uncrosslinked composition comprises from greater than zero to 25 wt% of the component C polydienc-based polyurethane; from 30 to 75 wt% of the component A thermoplastic polyurethane; and from 30 to 70 wt% of polybutadiene, [00164] In one embodiment, the uncrosslinked composition comprises from greater than zero to 20 wt% of the component C polydiene-based polyurethane; from 50 to 70 wt% of the component A thermoplastic polyurethane; and from 30 to 50 wt% of polybutadiene. I In one embodiment, the weight ratio of the TPU of component A to the polybutadieiie and/or polyisoprene of component B in the uncrosslinked composition is at least 1.5:1, preferably at least 2:1 and more preferably 2.2:1.

[§0166] Additives such as process oils, slip agents, anti-block, antioxidants (AO), IJV₅ fillers, may bε added to the inventive compositions. Typically the composition will contain one or more stabilizers, for example, antioxidants, such as Irganox^®1 1010 and Irgafos^® 168, both supplied by Ciba Specialty Chemicals Corp. An example of a hindered phenolic antioxidant is Irganox^® 1076 antioxidant, available from Ciba Speciality Chemicals Corp. Polymers are typically treated with one or more stabilizers before an extrusion or other melt processes. Other polymeric additives include, but arc not limited to, ultraviolet light absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, fire retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents and anti-blocking agents. Additional additives include, but not limited to, surface tension modifiers, pigments, process oil, wax, blowing agents, anti-block agents, foaming agents, antistatic agents, release agents, blowing agents, foaming agents, antistatic agents, release agents, flame resistant agents, abrasion and scratch mar additives, antimicrobial agents, antistatic agents, and crosslink ing agents.

[00167] In one embodiment, the compositions of this invention further comprise a styrenic block copolymer. These styrenic block copolymer may be a triblock copolymer including but not limited to styrene-butadiene-styrene triblock copolymers (SBS) and hydrogenated SBS copolymers, styrene-butadienε diblock copolymers and hydrogenated styrene-butadiene dibloek copolymers, styrene-isoprene-styrene triblock copolymers (SlS) and hydrogenated SlS copolymers, styrene-isoprene dibloek copolymers and hydrogenated styrcne-isoprene diblock copolymers, styrene-cthylene-butylene-styrene (SEBS) tctrablock copolymers and hydrogenated SEBS copolymers, styrene-acrylonitrilc copolymers (SAN), and elastomer- modified SAN. The styrenic. polymer may be a hydrogenated styrene-butadienc-styrene triblock copolymer, available from Shell Chemical under the trade name KRATON G-1652. [0OJ 68] In another embodiment, the compositions, neat and in fabricated form, have a tensile strength from 5 to 40, preferably from 8 to 30 and even more preferably from 9 to 20, MegaPascal (MPa). In another embodiment, the compositions, neat, and in fabricated form, have an elongation in the machine direction or the cross machine direction from 50 to 600, or from 50 to 500, as measured according to ASTM D-638-Q3.

[00170] In another embodiment, the compositions in neat form have a melt strength from 0.5 to 50, and more preferably from 0.5 to 20 and even more preferably from 0.5 to 10, eentiNewton (cN).

Crosslinked Compositions or Vulcanizates

[00171] The crosslinked or cured composition contains essentially the same components in the same proportions as the uncrosslinked composition but further comprises a crosslinking or cure package before cure and the remnants of the same after cure. The cure system, the mechanism and degree of cure, and the amount and degree of mixing are all known to those of ordinary skill in the art. Preferably, upon completion of cure, rubber component, i.e., the polybutadiene and/or poiyisoprene, is fully or near fully cured and the thermoplastic component, i.e., the TPU of component A and the corapatibilizer, are only minimally cured.

[00172] In one embodiment, the crosslinked compositions of the invention comprise: a) at least one TFlJ comprising less than 25 wt% of units derived from a diεnc, b) at least one of polybutadiene and polyisoprene, and c) at least one polydiene-based TPIJ that comprises at least 30 wl% of units derived from a diene. Typically, the compatibilizer is present in an amount less than or equal to 30, more typcially less than or equal to 25 and even more typically less than or equal to 20, wt% based on the total weight of the composition. [§0173] In one embodiment, the crosslinked composition comprises from 30 to 75, and typcially from 50 to 70, wt% of the thermoplastic polyurethane of component A. |00174] In another embodiment, the crossiinked composition comprises from 30 to 70 wt%, and typically from 30 to 50, wt% of polybutadiene and/or polyisoprene. [§0175] In one embodiment, the crosslinked composition comprises from greater than zero to 25 wt% of the component C polydiene-based polyurethane; from 30 to 75 wt% of the component A thermoplastic polyurethane; and from 30 to 70 wt% of poly butadiene. [00176] In one embodiment, the crosslinked composition comprises from greater than zero to 20 wt% of the component C polydiene-based polyurethane; from 50 to 70 wt% of the component A thermoplastic polyurethane; and from 30 to 50 wt% of polybutadiene. [1)0177] In one embodiment, the weight ratio of the TPU of component A to the polybutadiene and/or polyisoprene of component B in the crosslinked composition is at least 1 .5:1, preferably at least 2: 1 and more preferably 2.2: 1.

[00178] in one embodiment, the erosslinked composition does not contain any polydiεnε- based TPU that comprises at least 25 wt%, preferably at least 30 wt%, of units derived from a diene, and components A and B are present at a weight ratio of component A to component B of at least 2:1, preferably at least 2.1 :1 and more preferably 2,2:1,

[00179] Crosslinking can be achieved by adding an appropriate curative or curative system to the composition, and curing the rubber component to the desired degree under conventional curing conditions. In a preferred embodiment, the composition is crosslinked or cured by the process of dynamic vulcanization. The term '"dynamic vulcanization" means a vulcanization or curing process for a rubber contained in a thermoplastic composition in which the curable rubber (here the polybutadiene and/or polyisoprene) is vulcanized under conditions of sufficiently high shear at a temperature above the melting point of the thermoplastic component. Under dynamic vulcanization conditions, the rubber is simultaneously crosslinked or cured and dispersed as particles within the thermoplastic matrix. Dynamic vulcanization is effected by mixing the εlastomεric and thermoplastic components at elevated temperature in the presence of a curative in conventional mixing equipment such as roll mills, Moriyama mixers, B anbury mixers, Brabender mixers, continuous mixers, mixing extruders such as single and twin-screw extruders, and the like. An advantageous characteristic of dynamically cured compositions is that, notwithstanding the fact that the elastomeric component is fully cured, the compositions can be processed and reprocessed by conventional plastic processing techniques such as extrusion, injection molding and compression molding. Scrap or flashing can be salvaged and reprocessed. [00180] Heating and mixing or mastication at vulcanization temperatures are generally adequate to complete the vulcanization reaction in a few minutes or less, but if shorter vulcanization times are desired, higher temperatures and/or higher shear may be used. A suitable range of vulcanization temperature is from about the melting temperature of the thermoplastic material (typically 12O⁰C) to about 300^clC or more. Typically, the range is from about 15O⁰C to about 25O⁰C. A preferred range of vulcanization temperatures is from about 18O⁰C to about 22O⁰C, Preferably mixing continues without interruption until vulcanization of the rubber occurs or is complete.

[00181] After dynamic vulcanization, a homogeneous mixture is obtained in which the rubber (comprising the crosslinked or cured polybutadiene and/or polyisoprenε) is in the form of small dispersed particles essentially of an average particle size smaller than about 50 microns, typeially of an average particle size smaller than about 25 microns, more typically of an average size smaller than about 10 microns or less, and still more typically of an average particle size of 5 microns or less,

[00182| The progress of the cure during the dynamic vulcanization may be followed by monitoring mixing torque or mixing energy requirements during mixing. The mixing torque, or mixing energy curve generally passes through a maximum, and mixing can continue beyond this point to improve the fabricabiliiy of the blend, ϊf desired, additional ingredients, such as the stabilizer package, can be added after the dynamic vulcanization is complete. The stabilizer package is preferably added to the thermoplastic vulcanizate after vulcanization has been essentially completed, i.e., the curative has been essentially consumed.

[00183] Those skilled in the art appreciate the appropriate quantities, types of cure systems and vulcanization conditions required to cany out the vulcanization of these components. Vulcanization can be carried out using varying amounts of curative, varying temperatures, and varying time of cure in order to obtain optimum crosslink density for any particular application. Any known cure system can be used as long as it is suitable for use under the vulcanization conditions for the components and is compatible with the components. For the purposes of this application, a curative compatible with these components is one that does not degrade any of the components to any significant degree and does not produce excessive evolution of sufficient volatile components which may degrade the physical properties of the resulting thermoplastic vulcanizate. The curatives operable in this invention include MgO, ZnO, sulfur, sulfur donors, N,N'-m-phertylenedimaleimide, 2- mercapto-tolyl-iraidazole, metal oxides, resin systems, maleimides, azonitriies, peroxides, both with and without accelerators and co-agents. Phenolic resin curatives are used for the preparation of thermoplastic vulcanizates of the invention and such cure systems arc well known to the art and literature of vulcanization of elastomers. Curing through hydrosilylation, e.g., USP 5,672,660, can also be used, The use of phenolic curatives is more fully described in USP 4,311,628.

[Θ0Ϊ84] In addition, crosslinking can be effected by the use of any one of a number of different agents, e.g., by the use of thermally activated initiators, e.g., peroxides and azo compounds; photoinitiators, e.g., benzophenone; a vinyl silane, e.g., vinyl tri-ethoxy or vinyl tfi-methoxy silane; and the like. Alternative Iy₅ crosslinking can be obtained by substituting a crosslinking technique for a crosslinking agent, e.g., the use of radiation techniques other than sunlight and UV light, e.g., E-beam and x-ray, and moisture cure although both of these techniques can benefit from the use of an initiator, These crosslink ing agents and techniques are used in known amounts and using known equipment and procedures, [00185] In one embodiment, the compositions, either crosslinkεd or not, have a percent crystallinity of less than or equal to 50. preferably less than or equal to 30 and more preferably Sεss than or equal to 20, percent as measured by DSC. Preferably, these polymers have a percent crystallinity from 2 to 50 percent, including all individual values and subranges from 2 to 50 percent. The crystallinity of the composition as described above is measured on a neat blend, i.e., a blend without other components that may significantly affect the measurement of the crystallinity,

[00186] In another embodiment the compositions, either crosslinked or not, have a density greater than, or equal to, 0,855, preferably greater than, or equal to, 0.86 and more greater than, or equal to, 0.87, g/cc. in another embodiment, the composition has a density less than or equal to 1.15, preferably less than or equal to 1.10, more preferably less than or equal to 1.05 and even more preferably less than or equal to 1 , g/cc. ϊn one embodiment, the density is from 0.855 to 0.97, preferably from 0.86 to 0.95 and more preferably from 0.865 to 0.93. g/cc. The density of the blend as described above is measured on a neat blend, i.e., a blend without other components that may significantly affect the measurement of the density. In those embodiments in which the composition comprises one or more filler, e.g., barium sulfate, talc, etc., the maximum density can exceed 1 g/cc, for example, the maximum density can approach or exceed 1.4 g/cc depending upon, among other things, the nature and amount of filler. In another embodiment, the compositions, either crosslinked or not, in neat form have a surface tension from 10 to 100, and more preferably from 20 to 70 and even more preferably from 30 to 50, dyne per centimeter (dyn/cm) at room temperature (23⁰C). [00188] In another embodiment, the compositions, cither crosslinked or not, 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, dyn/cm at 23⁰C. [§0189] In another embodiment, an inventive composition is formed into an extruded sheet, which maintains at least 50 percent, preferably at least 60 percent of its original elongation after heat aging at 12O⁰C for 500 hours (ASTM D-882-02).

[00190] The compositions of the invention may be prepared by combining one or more thermoplastic polyurethanεs with one or more polybutadienes. Typically, the inventive compositions are prepared by post-reactor blending the polymer components (for example, the thermoplastic polyurethane, polybutadiene and polydiene- or polydiol-based polyurethane). Illustrative of a post-reactor blending is an extrusion, in which two or more solid polymers are fed into an extruder, and physically mixed into a substantially homogeneous composition. The inventive compositions may be crosslinked and/or foamed. In a preferred embodiment, the inventive compositions are prepared by blending the εthylcne/u-olelϊn mteipolymεr and the polydiene diol-basεd polyurethane in a melt process. In a further embodiment, the melt process is a melt extrusion process, and preferably an "inline" process,

[00191] An inventive composition may comprise a combination of two or more suitable embodiments as described above. Applications

[00192] The invention provides an article comprising at least one component formed from an inventive composition that is either crosslinked or uncrosslinked. The inventive compositions are particularly suitable for extruded sheets and tie layers between extruded sheets, tie layers between cast sheets, tie layers between films, and tie layers between profiles. Additional articles include a carpet component, an adhesive, a fabric a dispersion, a wire sheath, a cable, a protective apparel, a coating, and a foam laminate. [§0193] Tn another embodiment, the article is an automotive skin; an awning; a tarp; a roofing construction article (for example, adhesives to epoxy, urethanε or acrylic-based sυbslratεs for all roofing applications, such as insulation bonding, liquid roofing, facade sealant, expansion joints, wet-room sealants, pitched roof, acrylics-adhered roof, bitumen bonding, and PUR-adhered refurbishment); a steering wheel; a powder coating; a powder slush molding; a consumer durable; a grip; a handle; a computer component; a belt; an appliques; a footwear component; a conveyor or timing belt: lubricants and engine oil components; fibers; fabrics; artificial leather; injection molded objects, such as injection molded toys; artificial turf; and dispersions.

[00194] Specific applications include adhesives to polyurethane films and foams, adbesivεs to polyesters; dyes; paint adhesives and paint adhesion enablers; weldability applications; automotive interiors and exteriors: compatibilizers for polymer compositions; and toughening agents for polymer compositions.

[00195] In particular, the inventive compositions can be used in the following applications: (a) outsolεs, mid-soles and sliffeners, to be assembled with standard polyurethane adhesive systems currently used by footwear industry, (b) painting of soles and mid-soles with polyurefhanc paints, currently used by footwear industry, and (c) over- molding of polyolcfms and bi-componcnt polyurethanεs for multilayercd soles and mid- soles, fn addition, the inventive compositions 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 fascitis, vertical panels, soft thermoplastic olefinic (TPO) skins, and interior trim. Construction applications include, but arc not limited to, the manufacture of furniture and toys.

[00196] Additional applications include adhesion of co-extruded films, where one or more substrates arc compatible or reactive with hydroxyl groups, and the lamination of polyolcfm based films to other polar substrates (for example, glass lamination). Further applications include artificial leather to be adhered to polar substrates, such as polyureihane, polyvinyl chloride (PVC), and others substrates. Artificial leather is used for automotive interiors adhering to polyurethane for seating, head liners.

[00197] The inventive compositions are also suitable for health and hygiene products, such as wipes, cleaning tissues, foams or directly dyeable fibers. The inventive compositions can be used to enhance hydrophillcity of the elastomer for novel membrane structures for separation or breathability. The inventive compositions are also suitable for use as self- adhearable elastomers onto metal or textile structures for automotive. As discussed above, the inventive compositions are well suited for blends and compatibilizers with enhanced interaction towards polar polymers, such as TPU, ethylene vinyl acetate (EVA), PVC, polycarbonate (PC), polyethylene ierephthalate (PETj, polylactic acid (PLA). polyarnide esters, and polybutene terephthalate (PBT). Such bends can be used for novel compounds for footwear, automotive, consumer, durables, appliances, electronic housing, apparel, and conveyor belts. The inventive compositions can also serve as compatibilizers between natural fibers and other polyolefms for use in applications, such as wood binding formulations or cellulose binding formulations. The compositions of the invention are also useful in blends with one or more polyεther block amides, such as PEBAX polymers available from Arkema. The inventive compositions may also be used as impact modifiers for nylon.

[I)OJ 98] The inventive compositions can also be used to enhance the interaction to fillers, such as silica, carbon black or clay, for use in formulations for toners, tires, coatings or other compounds. The inventive compositions may also be used in engine oil viscosity modifiers, engine oil dispcrsants, dyεable or printable fibers for apparel, paint adhesion promoters, adhesives for glass, metal and polyvinylidene chloride (PVDC) barrier resins, dispersions, components in primers and sizing agents.

[00199] Thus the invention also provides a painted substrate, the substrate formed from an inventive composition, and the paint comprising at least one of an acrylic polymer, alkyd resin, cellulose-based material, melaminc resin, urefhane resin, carbamate resin, polyester resin, vinyl acetate resin, polyol and alcohol, in a further embodiment, the paint is a water- based. In another embodiment, the paint is an organic solvent based. This embodiment of the invention works well with a wide variety of paint formulations. The major components of solvent-borne paints and coatings are solvents, binders, pigments, and additives. In paint, the combination of the binder and solvent is referred to as the paint vehicle. Pigment and additives are dispersed within the vehicle. The amount of each constituent varies with the particular paint, but solvents traditionally make up about 60 percent of the total formulation. Typical solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone and water. Binders account for about 30 wi%, pigments for 7 to 8 wt%, and additives for 2 to 3 wt%. Some of the polymers and other additives used in paint formulations include: acrylic polymers, alkyd resins, cellulose based materials, such as cellulose acetate butyrate, melamine resins, carbamate resins, polyester resins, vinyl acetate resins, urethane resins, polyols, alcohols, inorganic materials such as titanium dioxide (rutile), mica flakes, iron oxide, silica, aluminum, and the like.

[00200] The invention also provides an over-molded article, the article formed from a polar substrate and a molded overlay formed from an inventive composition, In another embodiment, the invention provides an over-molded article, the article formed from a substrate comprising an inventive composition, and a molded overlay comprising a polar material, In further embodiment, the article is in the form of a grip, handle or belt. |00201] In another embodiment, the invention provides an over molded article comprising a polycarbonate, as the base sheet having variable thickness, and preferably having at least textured face on which inventive compositions can be adhered, typically by a compression molding process, at a moderate temperature of 140⁰C. This article can be further laminated with polyolelϊn using conventional welding techniques, such as by pressure and heat, or a second polycarbonate sheet with a textured surface can be adhered to the exposed surface of the inventive composition.

[002Θ2] The invention also provides a laminated structure comprising a first layer and a second layer, the first layer is formed from an inventive composition, and the second layer is formed from a composition comprising a polar material. In a further embodiment, one of the layers is in the form of a foam, (n another embodiment, one of the layers is in the form of a fabric. In a further embodiment, the laminated structure is in the form of an awning, a tarp, an automobile skin or a steering wheel.

[00203] In another embodiment, the invention provides a laminate structure comprising a polycarbonate, as the base sheet having variable thickness, and preferably having at least one textured surface on which an inventive composition of the invention can be adhered, typically by a compression molding process at moderate temperature of 14O⁰C. This article can be further laminated with polyolefm using conventional welding techniques, for example, by pressure and heat. In addition, a second polycarbonate, sheet with a textured surface, interfacing the inventive composition, can be laminated over the compatibilized blends. Another embodiment of this invention is a multi-laminate structure of polycarbonate and polyolefin films, intercalated for increased toughness of the final structure. Another embodiment would be a compatibilized blend coating deposited on the surface of polycarbonate to provide a scratch resistant assembly coat, which could be therraofbrmed, for example at a thermoforming temperature of 160⁰C. [§0205] The invention also provides a molded article comprising a first component and a second component, the first component is formed from a polar material, and the second component formed from an inventive composition. In a further embodiment, the article is in the form of an automobile skin, applique, footwear, conveyor belt, timing belt or consumer Ie.

"Laminates", 'laminations" and like terms mean two or more layers, for example, film layers, in intimate contact with one another. Laminates include molded articles bearing a coating. Laminates are not blends, although one or more layers of a laminate may comprise a blend.

[00207] "Polar", '"polar polymer" and like terms mean that the polymer molecules have a permanent dipolε, i.e., the polymer molecule has a positive end and a negative end. In other words, the electrons in a polar molecule arc not shared equally among the atoms of the molecule, Jn contrast, "nonpolar", "nonpolar polymer" and like terms mean that the polymer molecules do not have a permanent dipole, i.e., the polymer does not have a positive end and a negative end. The electrons in a nonpolar molecule are essentially equally shared among the atoms of the molecule. Most hydrocarbon liquids and polymers are nonpolar. [00208] Polymers substituted with carboxyl, hydroxy!, and the like, are often polar polymers. Articles prepared from nonpolar polymers have relatively low surface energy, that is, less than about 32 dyne/cm, and articles prepared from polar polymers have relatively high surface energy, that is, 32, or more, dyne/cm. The nonpolar material of this invention typically comprises one or more nonpolar thermoplastic olefmic polymers, typically elastomers, free of any significant amount of polar functionality, for example, hydroxyl, carboxyl, carbonyl, ester, ether, amide, mereaptan. halide, and the like groups. The polar material of this invention typically comprises one or more polymers comprising one or more polar functionalities. Typical polymers comprising one more polar functionalities include, but are not limited to, polyesters, polyethers, polylactic acid, polycarbonates, nylons, polysulfides, polysulfones, poiyurethanes, polyvinyl alcohol, poly(vinyl acetate), polyvinyl chloride), acrylonitrile, ABS, polyamide esters, and polysiloxanes.

[00209] "Insignificant amount of polar functionality," and like terms, mean that a polymer does not comprise a sufficient number of polar functional groups to impart a surface energy of at least about 32 dyne/cm to an article made from it.

[002.10] "Over-molding," and like terms, refer to a process in which one resin is injection into a mold containing a pre-placed substrate, and the resin is molded over this substrate. Over-molding is typically used to improve the performance and properties of a final product by over-molding one resin over another polymer substrate. Over-molding can be used to form seamless, integrated parts. Examples of over-molded parts include flexible grip handles on power tools and kitchen utensils, which provide additional gripping properties, without the hygienic concern normally associated with mechanical assemblies. The substrate may be any suitable material, such as a plastic, metal or ceramic part,

[00211] '"Molded overlay." and like terms, refer to an article comprising at least two parts (an injection molded part and a substrate) that are bound together, The injection molded part is placed on top of the substrate, outside the injection mold. An adhesive may be used to bind the injection molded part to the substrate, The substrate may be any suitable material, such as a plastic, metal or ceramic part,

[00212] The substrates to which an inventive composition can be applied, include a wide range of materials, both polar and nonpolar, such as, but not limited to, polymers, metal, wood, concrete, glass, ceramic, and various composites of two or more of these materials. Alternatively, these materials can be applied to an article formed from an inventive composition.

[002 J 3] As discussed above, application methods include painting, printing, dying, over- molding, and the like, including the many variations on each, for example, spreading, spraying, dipping, extrusion, and other processes. The inventive compositions can be crosslinkεd before, during or after application to a substrate, and they can be crosslinked in any convenient manner, for example, peroxide, sulfur, moisture, silane, radiation, heat and the like. In one embodiment, the inventive composition is applied to a substrate, and the inventive composition is crosslinked, as it is applied, and/or after it is applied. For crosslinking, the inventive composition will usually contain unsaturation, for example, a diene-eontairπng polyoiefm (PO).

[00214] Λs discussed above, the inventive compositions can be used to form a tie layer between polar and nonpolar materials, particularly between polar and nonpolar polymeric materials, for example, between a film layer of a nonpolar polyoJefm, such as polyethylene or polypropylene, and a film layer of a polar polymer, such as PLA or poiyamide or polyester. The compositions of this invention are particularly well suited as tie layers for binding together the following: (a) a polyethylene or polypropylene film, or a polyethylene or polypropylene surface of a molded article, to (b) a film, or surface of a molded article, of an ethylene/acrylic acid copolymer (IEAA) or a copolymer of PLA or PET. Any processes that combine co-extrusion, extrusion lamination, adhesive lamination, and/or foam casting or extrusion can be used to create tSiese laminated structures, including structures in which one layer comprises a foam.

[002 J 5] The inventive compositions may also be used in dispersions, such as aqueous- based dispersions for use as primers in olefmic-bascd footwear that promote adhesion to polyurethaiie (PlJ) glues and leather, and fabric coating adhesion (adhesion to PET, nylon, polypropylene, elastomer-rich TPO comprising polyoiefm elastomer (POE), ethyl ene/propylene/diene monomer tεrpolymer (EPDM) and other non-polar elastomers or combinations of such materials). |002t6] In other embodiments, the dispersion can be prepared by: a) Preparing a polyurethane prcpolymer using a non-polar polyol such as polybutadiene diol or a seed-oil based polyester polyol, and a diisocyanate, or b) Dispersing the polyurethane prepolymer in an aqueous phase comprising a polybutadiene dispersion and chain extender; the polyurethane prepolymer can be dispersed in the aqueous phase by incorporating a suitable surfactant or by making the prepolymer self- dispersing using a conventional functionalization approach, or c) Physically blending a polybutadiene dispersion and a polyurethane dispersion prepared using a non-polar polyol, such as polybutadiene diol or a seed-oil based polyol, or d) Following the procedures of US 2005/0100754, or e) Dispersing a prε-blend of an inventive composition, or post blending two or more dispersions. [ΘΘ217J In one embodiment, each polyurethane component of the dispersion is formed, independently, from an aliphatic isoeyanatε.

[00218] The dispersions of these compositions can also be used as paint adhesion promoters for non-polar thermoplastic and thermoset parts for automotive exteriors and interiors, They can also be used as primers for painting or printing of non-polar plastic pans for toys, and other molded or extruded parts and films.

[00219] In one embodiment, the polydie-nc-based polyurethane and, preferably, a polydiene diol-based polyurethane, is formed from at least one aliphatic or cyelo-aliphatic diisocyanate. In a further embodiment, both the polydiene -based polyurethane, and preferably a polydiene diol-based polyurethane, and the thermoplastic polyurethane are each, independently, formed from at least one aliphatic diisocyanate.

[00220] In another embodiment, the poly diol-based poiyurethane is formed from at least one aliphatic or cyelo-aliphatic diisocyanate. In a further embodiment, both the poly diol- based polyurethane and the thermoplastic polyurethane arc each, independently, formed from at least one aliphatic diisocyanate. In yet a further embodiment, the polydiol-based polyurethane comprises at least one diol made from one or more seed oil triglycerides selected from the group consisting of palmitic, stearic, oleic, linoleic and linolenic acid or ester,

[00221] Additional preferred applications include automotive theπnoformed skins for PU foam adhesion without the use of current water based primers based on chlorinated maleatcd polyolefins), house wrap - where high moisture vapor transmission rate is required and good adhesion to polypropylene woven fabric (scrim); adhesive films {blown or cast); co-extruded films, where the POK/TPU is used as a thin adhesive tie layer (for example, roofing membrane that needs adhesion using PIJ glues). The compositions, with proper choice of diol, isocyanate, POE and compatibilizer, can be used in coatings, paints, adhesivεs, glues, films, printability, dyeability, artificial leather, protective clothing, artificial turf, carpet fibers, textiles, medical (blood bags, tubing), toys, flexible overmolded goods, soft grips, sportwear, and the like, where adhesion to the polyolefin is crucial, and the inventive composition results in increased surface energy (>37 dyne/cm) for adhesion to polar materials. If the polyurethane components were completely aliphatic (no aromaticity, no un- saturation), the POE/TPU composition can be used to form a weathcrable coating layer (as opposed to adhesive tie layer). Test Methods

[00222] Density is determined in accordance with American Society for Testing and Materials (ASTM) procedure ASTM D792-00, Method B.

[00223] Melt index (12) in g/10 min, is measured using ASTM D-1238-04 (version C), Condition 190°C/2,16 kg. The notation "UO" refers to a melt index, in g/10 min, measured using ASTM D-1238-04, Condition 190°C/10.0 kg. The notation "121" refers to a melt index, in g/10 min, measured using ASTM D-1238-04, Condition 19()°C/21.6 kg. Polyethylene is typically measured at 190C while polypropylene is typically measured at 23O⁰C. MFR means melt flow rate for propylene based polymers and is measured using ASTM D-1238 condition 23()°C/2.16kg. For urethane based polymers, including blend comprising such polymers, except PELLETH ANE^{1 M} polymers, melt index is measured according to ASTM D-1238 condition 190°C/2.16kg. For PELLETH ANE™ (Pellethane™ 2102-80A AND 2103-70A) melt index is measured according to ASTM D-1238 condition 190°C/8.7kg.

[00224] Differential Scanning Calorimeter (DSC) is performed using a TAI model QiOOO DSC equipped with an RCS cooling accessory and an auto-sampler. A nitrogen purge gas flow of 50 cc/rnin is used. The sample is pressed into a thin film and melted in the press at about 175⁰C and then air-cooled to room temperature (25⁰C), Material (3-10 mg) is then cut into a 3 mm diameter disk, accurately weighed, placed in a light aluminum pan (ca 50 mg), and then crimped shut. The thermal behavior of the sample is investigated with the following temperature profile. The sample is rapidly heated to 18O⁰C and held isothermally for 3 minutes in order to remove any previous thermal history. The sample is then cooled to -9O⁰C at 10°C/min cooling rate and held at -9O⁰C for 3 minutes. The sample is then heated to 15O⁰C at 10°C/min heating rate. The cooling and second heating curves are recorded. [00225] Ultimate tensile strength and elongation at break are measured according to ASTM D-638-03. Both measurements are performed at 23⁰C on die-cut D638-type IV specimens. Melting temperature (Tm) is determined from the second heating curve. Crystallization temperature (Tc) is determined from the first cooling curve. Surface tension is measured in accordance with ASTM D2578-04a, Method B, and DIN 53364 (1986). ARCOTEC test inks are used, which are fluids of defined surface tension, and are available in ranges from 28 to 56 mN/m. Tests are run at room temperature (23C),

[0Θ227J Surface energy is measured using ARCOTEC ^lM test inks and test pens available from Lotar Enterprises. As a starting point for each check, a test ink or test pen with a medium value should be applied, e.g., 38 mN/m (dyne/cm). If the line of ink stays unchanged, for at least 2 seconds on the surface of the material, without turning into droplets, the surface energy of the material is the same, or higher, than the surface tension of the fluid. In this case, the test ink/test pen with the next higher value is applied Io die surface, e.g., 40 mN/m (dyne/cm), This check has to be repeated with the next higher value of surface tension, up to the point, at which, within 2 seconds, the line of fluid turns into separate droplets. If already at the starting point (38 mN/m (dyne/cm)) droplets are formed from the line of fluid, the check is continued with test Inks/test pens of lower values, which is often the case with metals. As a general limit often 32 mN/m (dyne/era) are mentioned. If the surface energy level is below this value, the adhesion will be poor, above this value the adhesion will be good or sufficient.

[§0228] Sheet hardness properties are measured according to ASTM D2240-05. The tensile properties are determined according to standard test method ASTM 13638-03. [00229] Melt tension is measured on selected polymer samples on a Goettfert Rheotcns melt tensile tester at a temperature of 39O⁰C. The Rheotens tester is composed of two counter rotating wheels, which pull a molten strand, extruded from a capillary die, at a constant velocity. The wheels are equipped with a balance to measure the stress response of the melt, as the wheels accelerate. The wheels are allowed to accelerate until strand rupture, The force to break the strand is taken as the melt tension in eentiNewton (cN). [0023Θ] rnterpolymer Mooncy Viscosity, MV, (ML 1+4 at 125°C) is measured in accordance with ASTM D 1646-04, The processing rheology ration, PRR₅ is calculated from the MV and the RR in accordance with the formula; PRR = RR + [3,82 - interpolymer Mooney Viscosity (ML_t+4 at 125⁰C)] x 0.3. ML refers to Mooney Large Rotor. The viscometer is a Monsanto MV2000 instrument. Stress @ 2, 50, 100, 200, 300 and 400% is measured using ASTM D-1708. Samples are stretched with a mechanical tester (Instron mode! 5564) at 500% min^{" 1} at 21⁰C. The samples arc pressed plaques of 0,5 ram thickness.

[00232] Tensile strain (S), break (standard) (%) is measured in accordance with ASTM D- 1708, The reported data are averages of five specimens. Samples are stretched with a mechanical tester (Instron model 5564) at 500% min^"1 at 21 °C. The samples are pressed plaques of 0.5mm thickness,

[00233] Modulus is measured in accordance with ASTM D-] 708. The reported data are averages of five specimens. Samples are stretched with a mechanical tester (Instron model 5564) at 500% rain^"1 at 21⁰C, The samples are pressed plaques of 0.5mm thickness, [Θ0234J Haze is measured in accordance with ASTM D-1003, The samples are pressed plaques,

[00235] Morphology determined by either transmission electron microscopy (TEM) or atomic force microscopy (AFM) analysis according to the following procedures. [00236] TE¹M procedure: Small pieces are cut from compression molded plaques and trimmed near the core region. The trimmed blocks are cryo-sectioncd at -140°C using a diamond knife on a Leica FC6 microtome equipped with a UC6 ctyosectioning chamber. Sections of approximately 90 nanometers in thickness are placed on virgin 1000 mesh copper TEM grids for observation. The sections are post stained at ambient temperature using the vapor phase of a 2% aqueous osmium tctraoxide solution for 20 minutes, Images are collected on a JEOI, JEM-1230 operated at 10OkV accelerating voltage and captured with Gatan-791 and 794 digital cameras and post processed using Adobe Photoshop 7,0. [00237] AFM method: A 0.5cm X 0,5cm piece of the material is eryo-microtomed at -150⁰C to reveal a view from the core of the bulk material. Sections are microtomed to a thickness of 160 nra using a diamond knife and placed on freshly cleaved mica surfaces. The specimens are scanned with a Digital Instruments NanoScope IV₅ MultiMode J ΛFM in Tapping Mode with phase detection. Software version is 5.12r46. Nano-scnsor tips are used in all experiments. The parameters of the tip are: L=235um, tip ratio = 5-1 Onm, Spring constant - 37-55 N/m, Fo=] 59-164 kHz, Tapping ratio is: 0.7-0.33. Tuning voltage is set to 3.0v, Post processing of images is conducted with Adobe Photoshop v7.0. E38] The following examples illustrate, but do not, either explicitly or by implication, limit the present invention.

EXAMPLES

[00239] The following materials were used in the examples reported below. [00240] Pellethane^® 2103-70A! is a polyεther-basεd thermoplastic polyurelhane, with a density of 1.06 g/cc. and a melt index (12) of 11 g/10 min as measured at 19O⁰C and 8.7 kg (available from The Dow Chemical Company).

[00241] Pellethane^® 2102-80A is a polyester-based thermoplastic pojyurethane, with a density of 1,18 g/cc, and a melt index (12) of 4 g/10 min as measured at 190 ⁰C and 8.7 kg (available from The Dow Chemical Company),

[0Θ242] Firestone 40AC 10 is a polybutadiene with a density of 0.90 g/cc and 40% cis-1,4 content available from Firestone Polymers,

[00243] Sartomer Poly-pd^® 2035 is a polybutadiene thermoplastic urεthane available from Sartomer Company, Inc.

[00244] Buna cis 132 is a polybutadiene with 95% cis-1 ,4 content available from The Dow Chemical Company.

[00245] SE PB 5800 is a polybutadiene with 37% cis-1,4 content available from The Dow Chemical Company.

[00246] SH PB 5901 is a polybutadiene with a density of 0.89 g/cc with 37% cis-1,4 content under development by The Dow Chemical Company. [00247] AC 629A is a releasing agent available from Honeywell International Inc. [00248J Irganox 1076 is octadecyl 3,5-Di-(tert)-butyl-4-hydroxyhydrocinnamate, an antioxidant available from Ciba Specialty Chemicals Corporation. [00249] Stearic acid was obtained from J.T. Baker. [00250] Sulfur was obtained from Λldrich Chemical Company in the form of powder.

E51] Zinc oxide was obtained from CP. Hall Company.

£52 j Λltax is benzothiazyl disulfide, a powdered cure agent available from RT. Vanderbilt Company, Inc.

[0Θ253] Methyl Tuads is tεtramethylthiuram disulfide, a cure agent available from RT. Vanderbilt Company, Inc. Examples 1-6 and Comparative Examples C- / 73

[00254] PELLETHANE^® polyurcthane is added to a small Ilaakε bowl equipped with roller blades operating at 35 revolutions per minute (rpm) and maintained at a temperature of 19O⁰C. The Pellethane^® PU is allowed to flux at which time AC 629 A and IRGAN OX^® 1076 are added to the bowl and allowed to mix with the PlJ for two minutes, In Examples 1- 6 Sartomer poly-pd 2035 and the polybutadiene is then added to the bowl, and the operating speed of the roller blades is increased to 75 rpm and all ingredients are allowed to mix for three minutes after reaching stable torque, In Examples C- 1/3 the procedure is repeated except that Sartomer poly-pd 2035 is not added to the other ingredients. [00255] The mixture is then removed from the bowl and pressed by hand at room temperature (about 23⁰C) into crude plaques. The crude plaques are then pressed into completed plaques using the following protocol: 19O⁰C and 2,000 pounds per square inch (psi) for three minutes, followed by 19O⁰C and 2O₅OOO psi for three minutes, followed by cooling at 15⁰C and 20,000 psi for three minutes. Table 1 and Figures 1 and 2 report the details of the individual formulations, and the haze and morphological properties of the individual completed plaques.

^'TABLE 1

Formulations and Haze and Thickness Values of the Completed Plaques of Examples 1-6 anctC-1/3

As is readily evident from these reported results, the haze values of compositions containing polyεther-basεd TPU and the diene-based TPU Sartomεr poly-pd 2035 exhibit significantly less haze than the compositions that do not contain the diene-based TFU or the polyester-based TPU. Examples 2 and C~3 were submitted for morphology testing, and the results are shown in Figures 1 and 2, respectively. In the absence of Sartoraer poly bd 2035 as the compatibiiizer, the morphology of C-3 consisted of non-oriented agglomerates of Firestone 40AC 10 diene polymer dispersed within a continuous PELLETHANE™ TPU matrix, a result of incompatibility between the two components. The Example 2 blend, however, the blend with Sartomer poly bd 2035, showed much better compatibility as demonstrated by small oriented BR domains dispersed within a continuous PELLETHANE™ matrix.

[00257] Examples 7-10

[00258] PEL! /ETHANE^® polyurethane is added to a small Haake bowl equipped with roller blades operating at 35 revolutions per minute (rpm) and maintained at a temperature of 190T. The Pellethane^® TPU is allowed to flux at which time in Examples 7-10 Firestone Diene 40 AC 10 and Sartomer poly-bd 2.035 TPU are added to the bowl and allowed to mix with the TPU for two minutes, In Example 10, the Sartomer po!y-pd 2035 is not added to the bowl. Stearic acid and zinc oxide arc then added to the bowl and allowed to mix with the other ingredients for an additional two minutes. The operating speed of the roller blades is then increased to 75 rpm and the ingredients mixed for another two minutes. The remainder of the curatives is then added to the bowl, the ingredients mixed for three minutes after reaching maximum torque, and the mixture removed from the bowl and pressed into crude plaques at 3,000 psi for 30 seconds at room temperature. A small portion of the formulations of Examples 8 and 10 were subjected to morphology analysis (AFM) and the results arc shown in Figures 3 and 4, respectively,

[00259] These AFM images show the formation of thermoplastic vulcanizates (TPV) using sulfur curatives. These images images show the formation of small particles distributed within the PELI. BTHAN E™ matrix. The TPV with Sartomer poly bd 2035 (TPV3) shows smaller particle sizes and a more homogeneous distribution. A closer look at the images reveals the existence of small PELLETHANE ^{l M} TPU particles in the rubber phase in the TPV without Sartomer poly bd 2035. This phenomenon is not observed in the TPV with Sartomer poly bd 2035,

[00260] The crude plaques are dried in a vacuum oven at 8O⁰C overnight, and then pressed into finished plaques using the following protocol: 19O⁰C and 3,000 psi for three minutes, followed by 190⁰C and 20,000 psi for three minutes, followed by cooling at 15⁰C and 20,000 psi for two minutes. Table 2 reports the details of the individual formulations, and Table 3 reports the results of micro-tensile analysis of the individual completed plaques. Figures 3 and 4 report the morphological properties of the completed plaques of Examples 8 and 10, respectively. TABLF 2 Formulations of the Completed Plaques

TABLE 3

Tensile Properties of the Completed Plaques

[00261] The results reported in Table 3 shows TPVs with and without Sartomer poiy-ρd 2035 compatibilizer are similar in tensile properties although Sartomer poly-pd 2035 is necessary for good haze property of the blends. Althouth polyesler-extented TPUs do not give as a good haze property as polyether-extended TPUs (sec Table 1), they too can be cured using sulfur to form TPVs (Examples 7 and 9).

[00262] Although the invention has been described in considerable detail in the preceding examples, this detail is for the purpose of illustration and is not to be construed as a limitation on the invention as described in the following claims. All U.S. patents and allowed U.S. patent applications or published U.S. patent applications are incorporated within this specification by reference.

Claims

We claim:

1. A composition comprising at least the follwing components:

Λ. A thermoplastic polyurethane (TPU) comprising less than 25 wt% of units derived from a diene based on the weight of the TPU;

B. A polybutadiene and/or a polyisoprene; and

C. A polydiene-based TPIJ that comprises at least 30 wt% of units derived from a diene based on the weight of the TPU,

2. The composition of Claim 1 wherein the polydiene-based TPlJ is present in an amount less than, or equal to, 25 weight percent, based on the total weight of the composition.

3. The composition of Claim 1 wherein the polydiene-based TPU is present in an amount less than, or equal to, 15 weight percent, based on the total weight of the composition.

4. The composition of Claim 1 wherein the polydiene-based TFlJ has a density from 0.94 g/ec to 1.30 g/cc.

5. The composition of Claim i wherein the polydiene-based TPU has a melt index (I₂) from 0.5 g/10 rain to 300 g/10 min.

6. The composition of Claim 1 wherein the polydiene-based TPU has a number average molecular weight from 500 g/mole to 10,000 g/mole,

7. The composition of Claim 1 wherein the polydiene-based TPU is formed from a composition that comprises 15 to 40 weight percent of a diisocyanate, based on the total weight of the compatibilizer,

8. The composition of Claim 7 wherein the diisocyanate is an aromatic diisocyanate.

9. The composition of Claim 1 wherein the polydiene-based TFU comprises froni 50 to 75 weight percent of units derived from a poiydiεne diol based on the total weight of the compatibilizer.

10. The composition of Claim 1 wherein the polydiene-based TPU comprises from 5 to 15 weight percent of units derived from a chain extender based on the total weight of the composition.

11. The composition of Claim 1 in which the component A TPIJ docs not contain any units derived from a diene.

12. The composition of Claim 1 in which the component A TPU comprises chemical units derived from a polyethεr or a polyester, and at least one aromatic dϋsocyanatε or at least one aliphatic diisocyanate.

13. The composition of Claim 12 wherein the component A TPU comprises chemical units derived from a poiyether or a polyester and at least one aromatic diisocyanate.

14. The composition of Claim 12 wherein the component A TPU comprises chemical units derived from a poiyether or a polyester and at least one aliphatic diisocyanate.

15. The composition of Claim 12 wherein the component A TPU comprises chemical units derived from a poiyether or a polyester and a mixture of 13-bis(isocyanatomethyl)cyclohexane and 1 ,4-bis(isocyanatomethyl)cyc!ohexanc.

16. The composition of Claim 12 wherein the polyester Is formed from caprolactone.

17. The composition of Clam 12 wherein the thermoplastic polyurethane is a PELLETHANE^® polyurethane.

18. The composition of Claim 1 wherein the poly butadiene is at least one of natural cis- 1,4-polybutadiene, trans- 1 ,4-butadiene, vinyl- 1 ,2-polybutadiene, copolymers of styrεnc and butadiene, copolymers of isoprεne and butadiene, and interpolyniers of styrenc, isoprene and butadiene.

) 9, The composition of Claim 1 wherein the polyisoprene is at least one of natural cis-1 ,4-polyisoprene, synthetic cis- 1,4 -polyisoprene, high vinyl-3,4~pαlyisoprene, and 3,4-polyisoprεnε.

20. The composition of any of the preceding claims further comprising one or more additives.

21. The composition of any of the preceding claims, further comprising a polar polymer selected from the group consisting of polyesters, polyarmdεs, polyethers, poSyetherimides, polyvinylalcohols, polycarbonates, polyurethancs, polylactic acids, and polyarnide esters.

22. An article comprising at least one component formed from the composition of any of the preceding claims.

23. The article of Claim 22 wherein the article is an sheet, a carpet, an adhesive, a wire sheath, a cable, a protective apparel, an automotive part, a footwear component, a coating, or a foam laminate, an automotive skin, an awning, a larp, a roofing construction article, a steering wheel, a powder coating, a powder slush molding, a consumer durable, a grip, a handle, a computer component, a belt, an applique, a footwear component, a conveyor or timing belt, or a fabric.

24. The article of Claim 22 wherein the article is a tie layer between extruded sheets, a tie layer between extruded films, a tie layer between extruded profiles, a tie layer between cast sheets, tie layer between cast films, or tie layer between cast profiles.

25. An extruded sheet formed from the composition of any of Claims 1-21.

26. Λ painted substrate wherein the substrate is formed from the composition of any of Claims 1 -21.

An over-molded article comprising the following: (a) a substrate formed from a composition comprising a polar polymer, and (b) a molded overlay formed from the composition of any of Claims 1-21,

28. A laminated structure comprising a first layer and a second layer, and wherein the first layer is formed from the composition of any of Claims 1-21, and wherein the second layer is formed from a composition comprising a polar polymer.

29. The laminated structure of Claim 28 wherein one of the layers is in the form of a foam,

30. A molded 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 the composition of any of Claims 1-2.1.

31. A dispersion comprising the composition of any of Claims 1-21.

32. An injection molded article comprising at least one component formed from the composition of any of Claims 1-21.

33. An RF welded article comprising at least one component formed from the composition of any of Claims 1-21.

34. A molded 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 the composition of any of Claims 1-21.

35. A thermoformed sheet comprising at least one layer formed from the composition of any of Claims 1 -21,

36. An automotive part comprising at least one layer formed from the composition of any of Claims 1-21.

37. An adhesive comprising at least one component formed from the composition of any of Claims 1-21.

38. A method of making the composition of any of Claims 1 -21, the method comprising melt mixing Components A, B and C.

39. The composition of any of Claims 1-21 further comprising at least one cross-Unking agent,

40. The composition of Claim 39 in which the crosslinking agent is at least one of MgO, ZnO, sulfur, a sulfur donor, N,N'-m-pheny!encdimaleimide, 2-mercapto-tolyl-imidazoiε, a metal oxide, a rnaleimide, an azonitrile, a peroxides (with and without accelerators and/or co- agents), a phenolic resin curative and a silicon-based curative.

41. The composition of Claim 39 after dynamic vulcanization.

42. The composition of any of Claims 1-21 after exposure to a cross-linking technique,

43. The composition of Claim 42 in which the crosslinking technique is exposure to at least one of radiation and moisture.

44. The composition of Claim 43 in which the radiation crosslinking technique is exposure to at least one of a crosslinking amount of E-beam and x-ray radiation.

45. The composition of Claim 42 in which the crosslinking technique includes high shear and a temperature above the melting point of the component A TPU.

46. A thermoplastic vulcanizate formed from the composition of any of Claims 1-21.

47. An article comprising at least one component formed from the composition, of Claim 46.

48. The article of Claim 47 wherein the article is an sheet, a carpet, an adhesive, a wire sheath, a cable, a protective apparel, an automotive part, a footwear component, a coating, or a foam laminate, an automotive skin, an awning, a tarp, a roofing construction article, a steering wheel, a powder coating, a powder slush molding, a consumer durable, a grip, a handle, a computer component, a belt, an applique, a footwear component, a conveyor or timing belt, or a fabric,

49. The article of Claim 47 wherein the article is a tie layer between extruded sheets, a tie layer between extruded films, a tie layer between extruded profiles, a tie layer between cast sheets, tie layer between cast films, or tie layer between cast profiles,

50. An extruded sheet formed from the composition of Claim 47.

51. A painted substrate wherein the substrate is formed from the composition of Claim 47.

52. Art over-molded article comprising the following: (a) a substrate formed from a composition comprising a polar polymer, and (b) a molded overlay formed from die composition of Claim 47.

53. A laminated structure comprising a first layer and a second layer, and wherein the first layer is formed from the composition of Claim 47, and wherein the second layer is formed from a composition comprising a polar polymer.

54. The laminated structure of Claim 53 wherein one of the layers is in the form of a foam.

55. A molded 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 the composition of Claim 47.

56. A dispersion comprising the composition of Claim 47.

57. An injection molded article comprising at least one component formed from the composition of Claim 47.

58. An HF welded article comprising at least one component formed from the composition of Claim 47.

59. A molded 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 the composition of Claim 47.

60. A thermofomied sheet comprising at least one layer formed from the composition of Claim 47.

61. An automotive part comprising at least one layer formed from the composition of Claim 47.

62. An adhesive comprising at least one component formed from the composition of Claim 47.

63. The composition of any of Claims 1-21 in which the component A TPU is present in an amount of between 50 and 70 wt% of the composition, and the amount of polybutadiene and/or polyisoprene is present in an amount of between 30 and 50 wt%, both based on the total weight of the composition.

64. The thermoplastic vulcanizate of Claim 46 in which the component Λ TPU is present in an amount of between 50 and 70 wt% of the composition, and the amount of polybutadiene and/or polyisoprene is present in an amount of between 30 and 50 wt%, both based on the total weight of the composition.

65. A erosslinked composition comprising at least the foil wing components:

A, A thermoplastic polyurethane (TPU) comprising less than 25 wt% of units derived from a diene based on the weight of the TPU; and

B, A polybutadiene and/or a polyisoprene.

66. The composition of Claim 65 in which components A and B are present at a weight ratio of component A to component B of at least 2: 1,

67. The composition of Claim 66 in which the composition does not contain a polydiene- based TPU that comprises at least 25 wt% of units derived from a diene based on the weight of the TPU,