Patent Description:
Embodiments of the present disclosure generally relate to polymer compositions, and more particularly to polymer compositions for use in foams.

Polymer compositions are utilized in foams for various applications including athletic shoes and automotive applications. Conventional foams may contain base polymers such as ethyl vinyl acetate copolymers (EVA), polyolefin elastomers (POE), olefin block copolymers (OBC), ethylene-propylene-diene-monomer copolymers (EPDM).

Conventional foams may be formed from polyolefin elastomers, which typically are continuous phase materials that good for melt processibility. However, there is a desire for improved rheological, mechanical, and thermal properties. Thus, cross-linked thermoplastic materials are often utilized to add these properties; however, these cross-linked thermoplastics may require cross-linking agents to achieve desirable final foam properties, and these crosslinking agents often include peroxides, which are not environmentally friendly and require special treatment for transportation and storage. Accordingly, there are needs for polymer compositions that produce foams with improved elasticity and modulus properties, where the polymer compositions may include polyolefin elastomers, but may not require additional cross-linking agents.

Embodiments of the present disclosure meet those needs by providing a polymer composition, which includes at least <NUM> wt. %, based on the total weight of the polymer composition, of a polyolefin elastomer having an ethylene content of from greater than <NUM> wt. % to less than <NUM> wt. %; and a cross-linkable blend. The cross-linkable blend includes (i) from <NUM> wt. % to <NUM> wt. %, based on the total weight of the cross-linkable blend, of an E/X/Y polymer and (ii) from <NUM> wt. % to <NUM> wt. %, based on the total weight of the cross-linkable blend, of an epoxy-containing polymer. E is ethylene monomer; X is a monomer selected from the group consisting of C<NUM> to C<NUM> unsaturated carboxylic acids, esters of C<NUM> to C<NUM> unsaturated carboxylic acids, and anhydrides of C<NUM> to C<NUM> unsaturated carboxylic acids; and Y is an alkyl (meth)acrylate monomer. X is present in an amount of from <NUM> wt. % to <NUM> wt. %, based on the total amount of monomers present in the E/X/Y polymer. Y is present in an amount of from <NUM> wt. % to <NUM> wt. %, based on the total amount of monomers present in the E/X/Y polymer. The epoxy-containing polymer includes copolymerized monomers of ethylene, from <NUM> wt. % to <NUM> wt. %, based on the total amount of monomers present in the epoxy-containing polymer, of a monomer containing one or more epoxy groups, and from <NUM> wt. % to <NUM> wt. %, based on the total amount of monomers present in the epoxy-containing polymer, of an alkyl meth(acrylate) monomer.

These and other embodiments are described in more detail in the following Detailed Description.

Specific embodiments of the present application will now be described. These embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the claimed subject matter to those skilled in the art.

Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percent values are based on weight, all temperatures are in °C, and all test methods are current as of the filing date of this disclosure.

The term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of a same or a different type. The generic term polymer thus embraces the term "homopolymer," which usually refers to a polymer prepared from only one type of monomer as well as "copolymer," which refers to a polymer prepared from two or more different monomers. The term "interpolymer," as used herein, refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes a copolymer or polymer prepared from more than two different types of monomers, such as terpolymers.

"Polyolefin," "polyolefin polymer," "polyolefin resin," and like terms refer to a polymer produced from a simple olefin (also called an alkene with the general formula CnH2n) as a monomer. Polyethylene is produced by polymerizing ethylene with or without one or more comonomers, polypropylene by polymerizing propylene with or without one or more comonomers. Thus, polyolefins include interpolymers such as ethylene-alpha-olefin copolymers and propylene-alpha-olefin copolymers.

"Polyethylene" or "ethylene-based polymer" refers to polymers comprising greater than <NUM>% by mole of units derived from ethylene monomer. This includes ethylene-based homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene-based polymers known in the art include Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m- LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

As used herein, an "elastomer" refers to a polymeric material that will substantially resume its original shape after being stretched.

"(Meth)acrylic acid" includes methacrylic acid and/or acrylic acid and "(meth)acrylate" includes methacrylate and/or acrylate.

The term "composition," as used herein, refers to a mixture of materials which comprises the composition, as well as reaction products and decomposition products formed from the materials of the composition.

"Blend," "polymer blend," and like terms refer to 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. Such blends can be prepared as dry blends, formed in situ (e.g., in a reactor), melt blends, or using other techniques known to those of skill in the art.

"Foam" and like terms refer to a substance that is formed by trapping many gas bubbles in a liquid or solid.

The terms "comprising," "including," "having," and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of" excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically delineated or listed.

Reference will now be made in detail to embodiments of a polymer composition as further described herein. In embodiments, the polymer composition may include a polyolefin elastomer and a cross-linkable blend comprising an E/X/Y polymer and an epoxy-containing polymer.

The polymer composition includes at least <NUM> weight percent (wt. %), based on the total weight of the polymer composition, of the polyolefin elastomer. In some embodiments, the polymer composition may include from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to about <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, or from <NUM> wt. % to <NUM> wt. % of the polyolefin elastomer based on the total weight of the polymer composition.

Embodiments of the polymer composition may include from <NUM> wt. % to <NUM> wt. %, based on the total weight of the polymer composition, of the cross-linkable blend comprising an E/X/Y polymer and an epoxy-containing polymer. In some embodiments, the polymer composition may include from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, or from <NUM> wt. % to <NUM> wt. % of the cross-linkable blend based on the total weight of the polymer composition.

Embodiments of the polymer composition may have a melt flow index (I<NUM>) of less than <NUM> grams per ten minutes (g/<NUM>) when measured according to according to ASTM D1238 at <NUM>, <NUM>. Without being bound by theory, compositions with an I<NUM> of greater than <NUM> may indicate that the polymer composition does not have sufficient crosslinking needed to produce foams with desirable properties. As such, in embodiments, the polymer compositions may be crosslinked. In embodiments, the polymer composition may have a melt flow index (I<NUM>) of from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, or from <NUM>/<NUM> to <NUM>/<NUM> when measured according to according to ASTM D1238 at <NUM>, <NUM>.

Embodiments of the polymer composition may have a Mooney Viscosity (ML<NUM>+<NUM>) of greater than <NUM> wherein Mooney Viscosity (ML<NUM>+<NUM>) is measured according to ASTM D1646. In embodiments, the polymer composition may have a Mooney Viscosity (ML<NUM>+<NUM>) of from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM> wherein Mooney Viscosity (ML<NUM>+<NUM>) is measured according to ASTM D1646.

Reference will now be made in detail to embodiments of the polyolefin elastomer of the polymer compositions described herein. As stated previously in this disclosure, an "elastomer" refers to a material that substantially resumes its original shape after being stretched. For instance, upon application of a stretching force, an elastomer is stretchable in at least one direction, such as the cross machine direction, and, upon release of the stretching force, contracts and returns to approximately its original dimension. For example, an example elastomer is a stretched material having a stretched length which is at least <NUM> % greater than its relaxed, unstretched length, and which will recover to within at least <NUM> % of its stretched length upon release of the stretching force. A hypothetical example would be a <NUM> (one (<NUM>) inch) sample of a material which is stretchable to at least <NUM> (<NUM> inches) and which, upon release of the stretching force, will recover to a length of not more than <NUM> (<NUM> inches).

As used herein, polyolefin elastomer means a copolymer comprised of at least <NUM> wt. % of ethylene and/or propylene derived units copolymerized with a different alpha olefin monomer unit selected from C<NUM>-C<NUM> alpha olefins, for example, ethylene, <NUM>-butene, <NUM>-hexane, <NUM>-methyl-<NUM>-pentene and/or <NUM>-octene. The polymer compositions described herein include polyolefin elastomers that have an ethylene content of from greater than <NUM> wt. % to less than <NUM> wt. In embodiments, the polyolefin elastomers may have an ethylene content of from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, or <NUM> wt. % to <NUM> wt. Embodiments of the polymer compositions described herein may include polyolefin elastomers that have a comonomer content of at least <NUM> wt. In embodiments, the weight ratio of ethylene and/or propylene derived units to the different alpha olefin monomer unit selected from C<NUM>-C<NUM> alpha olefins may be from <NUM>:<NUM> to <NUM>:<NUM>, from <NUM>:<NUM> to <NUM>:<NUM>, from <NUM>:<NUM> to <NUM>:<NUM>, from <NUM>:<NUM> to <NUM>:<NUM>, from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>. The polyolefin elastomers may be polymerized using constrained geometry catalysts such as metallocene catalysts. The polyolefin elastomers may provide desirable properties, including electrical insulation, good long term chemical stability, as well as high strength, toughness and elasticity.

Embodiments of the polyolefin elastomers utilized in the polymer compositions described herein may have a melt index of less than <NUM>/<NUM>, less than <NUM>/<NUM>, or less than <NUM>/<NUM> when measured according to ASTM D1238. Embodiments of the polyolefin elastomers utilized in the polymer compositions described herein may have a melt index of from <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, <NUM>/<NUM> to <NUM>/<NUM>, when measured according to ASTM D1238.

Exemplary polyolefin elastomers may be obtained from The Dow Chemical Company of Midland, Mich. under the product name INFUSE™ <NUM>. In embodiments, polyolefin elastomers may include ethylene-propylene-diene terpolymer (EPDM), specifically a terpolymer product of ethylene, propylene and ENB. Further exemplary polyolefin elastomers may be obtained from The Dow Chemical Company of Midland, Mich. under the product name NORDEL™ <NUM> XFC EPDM.

The polyolefin elastomer may have a density of less than <NUM>/cc when measured according to ASTM D792. In embodiments, the polyolefin elastomer may have a density of from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc when measured according to ASTM D792.

Reference will now be made to embodiments of the cross-linkable blend, which includes an E/X/Y polymer and an epoxy-containing polymer. The reaction mechanism of the cross-linkable blend is provided as follows:
<CHM>
<CHM>.

The E/X/Y polymer includes ethylene monomer, represented as E; a monomer, represented as X, selected from the group consisting of C<NUM> to C<NUM> unsaturated carboxylic acids, esters of C<NUM> to C<NUM> unsaturated carboxylic acids, and anhydrides of C<NUM> to C<NUM> unsaturated carboxylic acids; and an alkyl (meth)acrylate monomer, represented as Y. Examples of suitable unsaturated carboxylic acids having <NUM> to <NUM> carbon atoms may include acrylic acids, methacrylic acids, itaconic acids, maleic acids, fumaric acids, monomethyl maleic acids, and combinations of two or more of these acid comonomers. In some embodiments, the unsaturated carboxylic acids having <NUM> to <NUM> carbon atoms comprise acrylic acid and methacrylic acid. In other embodiments, the unsaturated carboxylic acids having <NUM> to <NUM> carbon atoms comprise acrylic acid. Alkyl (meth)acrylate monomers may include alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, <NUM>-ethylhexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, and dodecyl methacrylate.

The E/X/Y polymer includes from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, or from <NUM> wt. % to <NUM> wt. % of X, based on the total amount of monomers present in the E/X/Y polymer. Y is optionally present in the E/X/Y polymer in an amount of from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, or <NUM> wt. % to <NUM> wt. %, based on the total amount of monomers present in the E/X/Y polymer. The balance of the E/X/Y polymer is E. The comonomer content may be measured using any suitable technique, such as techniques based on nuclear magnetic resonance ("NMR") spectroscopy, and, for example, by <NUM>C NMR analysis as described in <CIT>.

The E/X/Y polymer may have a melt index, I<NUM>, of from about <NUM>/<NUM> to about <NUM>/<NUM>. The melt index, I<NUM>, is determined according to ASTM D1238 at <NUM>, <NUM>. All individual values and subranges of <NUM>/<NUM> to <NUM>/<NUM> are included and disclosed herein. For examples, in some embodiments, the precursor acid copolymer may have a melt index, I<NUM>, of from about <NUM>/<NUM> to about <NUM>/ <NUM>, from about <NUM>/<NUM> to about <NUM>/<NUM>, from about <NUM>/<NUM> to about <NUM>/<NUM>, from about <NUM>/<NUM> to about <NUM>/<NUM>, from about <NUM>/<NUM> to about <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, from <NUM>/<NUM> to <NUM>/<NUM>, or from <NUM>/<NUM> to <NUM>/<NUM>.

The E/X/Y polymer may be synthesized in a continuous process in which each of the reactive monomers and the solvent(s), if any, are continuously fed, together with initiator, into a stirred reactor. The choice of initiator is based on the anticipated reactor temperature range coupled with the decomposition temperature of the initiator, the criteria for this selection being well-understood in the industry. In general, during the synthesis by copolymerization of ethylene and acid comonomers to produce the E/X/Y polymer, the reaction temperature may be maintained at about <NUM> to about <NUM>, or about <NUM> to about <NUM>. The pressure in the reactor may be maintained at about <NUM> MPa to about <NUM> MPa, or about <NUM> MPa to <NUM> MPa.

The reactor may be, for example, an autoclave reactor, such as those described in <CIT>, which describes a type of autoclave reactor that is equipped with means for intensive agitation. The patent also describes a continuous process for the polymerization of ethylene under a "substantially constant environment. " This environment is maintained by keeping certain parameters, for example, pressure, temperature, initiator concentration, and the ratio of polymer product to unreacted ethylene, substantially constant during the polymerization reaction. Such conditions may be achieved in any of a variety of continuously stirred tank reactors, among them, for example, continuously stirred isothermal reactors and continuously stirred adiabatic reactors.

The reaction mixture, which contains the E/X/Y polymer, may be vigorously agitated and continuously removed from the autoclave. After the reaction mixture leaves the reaction vessel, the resulting E/X/Y polymer product may be separated from the volatile unreacted monomers and solvent(s), if any, by conventional procedures, such as by vaporizing the unpolymerized materials and solvent(s) under reduced pressure or at an elevated temperature.

The cross-linkable blend includes from <NUM> wt. % to <NUM> wt. % of the E/X/Y polymer, based on the total weight of the cross-linkable blend. In embodiments, the cross-linkable blend may include from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, or <NUM> wt. % to <NUM> wt. % of the E/X/Y polymer, based on the total weight of the cross-linkable blend.

As stated previously herein, the cross-linkable blend further includes an epoxy-containing polymer. In embodiments, the X monomer of the E/X/Y polymer may be cross-linked with one or more epoxy groups of the epoxy-containing polymer. Accordingly, embodiments of the polymer compositions described herein may not require an additional curing agent to crosslink the cross-linkable blend. In embodiments, the cross-linkable blend may be a crosslinked-blend. In the cross-linked blend, the X monomer of the E/X/Y polymer may be cross-linked with one or more epoxy groups of the epoxy-containing polymer.

The epoxy-containing polymer includes copolymerized monomers of ethylene, a monomer containing one or more epoxy groups, and an alkyl meth(acrylate) monomer. Suitable monomers containing one or more epoxy groups may include glycidyl acrylate and glycidyl methacrylate (GMA). Without being bound by theory, it is believed that the epoxy monomer present in the monomer containing one or more epoxy groups, for example in GMA, cross-links with the E/X/Y polymer to yield the cross-linked foam. In some embodiments, it is believed that the cross-linking between the GMA and the E/X/Y polymer enables the foam to be sufficiently crosslinked foam without the need for a peroxide crosslinker.

The epoxy-containing polymer may include from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, or <NUM> wt. % to <NUM> wt. % of the monomer containing one or more epoxy groups, based on the total amount of monomers present in the epoxy-containing polymer. The epoxy-containing polymer may include from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. %, to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, or <NUM> wt. % to <NUM> wt. % of the alkyl meth(acrylate) monomer, based on the total amount of monomers present in the epoxy-containing polymer. The comonomer content may be measured using any suitable technique, such as techniques based on nuclear magnetic resonance ("NMR") spectroscopy, and, for example, by 13C NMR analysis as described in <CIT>.

The cross-linkable blend includes from <NUM> wt. % to <NUM> wt. % of the epoxy-containing polymer, based on the total weight of the cross-linkable blend. In embodiments, the cross-linkable blend may include from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, or <NUM> wt. % to <NUM> wt. % of the epoxy-containing polymer, based on the total weight of the cross-linkable blend.

The polymer composition of any preceding claim, further comprising a compatibilizer or any other suitable additive known in the art. Additives may include plasticizers, processing aides, flow enhancing additives, flow reducing additives (e.g., organic peroxides), lubricants, pigments, dyes, optical brighteners, flame retardants, impact modifiers, nucleating agents, antiblocking agents (e.g., silica), thermal stabilizers, hindered amine light stabilizers (HALS), UV absorbers, UV stabilizers, dispersants, surfactants, chelating agents, coupling agents, adhesives, primers, reinforcement additives (e.g., glass fiber), and fillers, and mixtures or combinations of two or more conventional additives.

Foaming agents may include hydrocarbons, fluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, and other halogenated compounds. Other suitable chemical foaming agents can include, for example, sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, dinitrosopentamethylenediamine, and sulfonyl hydrazides. Foaming agents such as water or carbon dioxide added as a gas or liquid, or generated in-situ by the reaction of water with polyisocyanate, may also be used. The foaming agents can be used in mixtures of two or more, and chemical and physical foaming agents can be used together to tailor expansion-decomposition temperature and foaming processes.

Embodiments of the polymer compositions described herein may further include free radical initiators or crosslinking agents, co-curing agents, activators, and any other type of additive typically used in similar compositions, including pigments, adhesion promoters, fillers, nucleating agents, rubbers, stabilizers, and processing aids.

Free radical initiators or crosslinking agents can include, by way of example, organic peroxides such as dialkyl organic peroxides. Example organic peroxides suitable for use include <NUM>,<NUM>-di-t-butyl peroxy-<NUM>,<NUM>,<NUM>-trimethylcyclohexane, t-butyl-cumyl peroxide, dicumyl-peroxide, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-di(tertiary-butyl-peroxyl)hexane, <NUM>,<NUM>-bis(tertiary-butyl-peroxyl-isopropyl)benzene, or combinations of two or more thereof. Co-curing agents include trimethyl propane triacrylate (and similar compounds), N,N-m-phenylenedimaleimide, triallyl cyanurate, or combinations of two or more thereof. Activators can include activators for the blowing agent, and can include one or more metal oxides, metal salts, or organometallic complexes. Examples include ZnO, Zn stearate, MgO, or combinations of two or more thereof.

Embodiments of the polymer compositions may be produced by combining the components of the polymer composition under heat to form a melt. Combining the components may include mixing and blending the components using any technique known and used in the art, including Banbury, intensive mixers, two-roll mills, and extruders. Time, temperature, and shear rate can be regulated to ensure dispersion without premature crosslinking or foaming.

In some embodiments, combining the polyolefin elastomer, the E/X/Y polymer, and the epoxy-containing polymer may include melt-blending the polyolefin elastomer with the cross-linkable blend of the E/X/Y polymer and the epoxy-containing polymer. Melt-blending the polyolefin elastomer and the cross-linkable blend may occur at a temperature of from <NUM> to <NUM>. In embodiments, the melt-blended polyolefin elastomer and cross-linkable blend may then be cured at a temperature of rom <NUM> to <NUM>.

In some embodiments, combining the polyolefin elastomer, the E/X/Y polymer, and the epoxy-containing polymer may include melt-blending the polyolefin elastomer and the E/X/Y polymer to produce a blend, and subsequently melt-blending the epoxy-containing polymer with the blend. In embodiments, melt-blending the polyolefin elastomer and the E/X/Y polymer to produce a blend may occur at a temperature of from <NUM> to <NUM>. Subsequently melt-blending the epoxy-containing polymer with the blend may occur at a temperature of from <NUM> to <NUM>. The melt-blended epoxy-containing polymer with the blend may then be cured at a temperature of rom <NUM> to <NUM>.

Embodiments of the present disclosure may include an article comprising the polymer composition described herein. According to various embodiments, the polymer composition may be used to form a foam or molded article. For example, in embodiments, the polymer composition can be combined with additives used to control foam properties to form foams of various shapes. In some embodiments, the foam may be extruded, such as from a twin screw extruder, as is known to those of ordinary skill in the art.

Foaming agents (also referred to as blowing agents) used in the manufacture of foams can be physical foaming agents or chemical foaming agents. As used herein, "physical foaming agents" are low-boiling liquids, which volatilize under the curing conditions to form the blowing gas. Exemplary physical foaming agents include hydrocarbons, fluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, and other halogenated compounds. Other suitable chemical foaming agents can include, for example, sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, dinitrosopentamethylenediamine, and sulfonyl hydrazides. Foaming agents such as water or carbon dioxide added as a gas or liquid, or generated in-situ by the reaction of water with polyisocyanate, may also be used. The foaming agents can be used in mixtures of two or more, and chemical and physical foaming agents can be used together to tailor expansion-decomposition temperature and foaming processes.

Foams formed from embodiments of the polymer compositions described herein may further include a free radical initiator or crosslinking agents, co-curing agents, an activator, and any other type of additive typically used in similar compositions, including pigments, adhesion promoters, fillers, nucleating agents, rubbers, stabilizers, and processing aids. Activators can include activators for the blowing agent, and can include one or more metal oxides, metal salts, or organometallic complexes. Examples include ZnO, Zn stearate, MgO, or combinations of two or more thereof. Free radical initiators or crosslinking agents can include, by way of example, organic peroxides such as dialkyl organic peroxides. Example organic peroxides suitable for use include <NUM>,<NUM>-di-t-butyl peroxy-<NUM>,<NUM>,<NUM>-trimethylcyclohexane, t-butyl-cumyl peroxide, dicumyl-peroxide, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-di(tertiary-butyl-peroxyl)hexane, <NUM>,<NUM>-bis(tertiary-butyl-peroxyl-isopropyl)benzene, or combinations of two or more thereof. Co-curing agents include trimethyl propane triacrylate (and similar compounds), N,N-m-phenylenedimaleimide, triallyl cyanurate, or combinations of two or more thereof. Foams formed from embodiments of the polymer compositions described herein may further include from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, of the free radical initiator or crosslinking agents, based on the total weight of the polymer compositions used to produce embodiments of foams.

Embodiments of the polymer compositions described hereinabove may be utilized in foams, which may be produced by a number of methods, such as compression molding, injection molding, and hybrids of extrusion and molding. The process can include mixing the components of the polymer composition under heat to form a melt. The components may be mixed and blended using any of the methods described herein and any technique known and used in the art, including Banbury, intensive mixers, two-roll mills, and extruders. Time, temperature, and shear rate can be regulated to ensure dispersion without premature crosslinking or foaming.

After polymer composition, with any optional additives, has been mixed, shaping can be carried out. Sheeting rolls or calendar rolls can be used to make appropriately dimensioned sheets for foaming. An extruder may be used to shape the composition into pellets.

Foaming can be carried out in a compression mold at a temperature and time to complete the decomposition of peroxides and blowing agents. Pressures, molding temperature, and heating time can be controlled. Foaming can be carried out using injection molding equipment by using pellets made from the foam composition. The resulting foam can be further shaped to the dimension of finished products by any means known and used in the art, including thermoforming and compression molding.

In various embodiments, the resulting foams formed from embodiments of the polymer compositions described herein can be substantially closed cell and useful for a variety of articles, e.g., footwear applications including midsoles or insoles.

In embodiments, foams formed from embodiments of the polymer compositions described herein may have a density of approximately <NUM>/cc. In embodiments, foams formed from embodiments of the polymer compositions described herein may have a density of less than <NUM>/cc or <NUM>/cc.

The embodiments described herein may be further illustrated by the following examples.

Unless otherwise stated, the following test methods are used.

Density is determined according to ASTM D792 and reported in grams per cubic centimeter (or g/cc).

Melt indices I<NUM> (or I2) and I<NUM> (or I10) are determined according to ASTM D1238 at <NUM> at <NUM> and <NUM> loads, respectively. I<NUM> and I<NUM> are each reported in grams per ten minutes (or g/<NUM>).

The tensile strength, tensile modulus and elongation at break were measured according to ASTM D1708. Micro-tensile bars were punched out of the compression molded plaques with a thickness of <NUM>.

Dynamic oscillatory shear measurements are performed with the ARES system of TA Instruments (New Castle, Del. ) at <NUM> using <NUM> parallel plates at a gap of <NUM> and at a constant strain of <NUM>% under an inert nitrogen atmosphere. The frequency interval is from <NUM> to <NUM> radians/second at <NUM> points per decade logarithmically spaced. The stress response is analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G"), complex modulus (G*), tan δ, phase angle δ and complex viscosity (η*) are calculated. The complex modulus, G*, is a complex number with G' as its real and G" as its imaginary components, respectively (G*=G'+iG"). The magnitude of G* is reported as |G*|=(G'<NUM>+G"<NUM>)<NUM>/<NUM>. Both tan δ and the phase angle δ are related to the material's relative elasticity. Tan δ is the ratio of the loss modulus to the storage modulus, that is tan δ = G"/G', and the phase angle δ can be obtained from δ = tan-<NUM>(G"/G'). The complex viscosity η* is also a complex number with η' as its real and η" as its imaginary components. The magnitude of η* is reported as: <MAT>
where ω is the angular frequency in radians/second.

Mooney Viscosity (ML<NUM>+<NUM>) is determined according to ASTM D1646, with a one minute preheat time and a four minutes rotor operation time. The instrument was an Alpha Technologies Mooney Viscometer <NUM>.

The materials used to produce Samples <NUM>-<NUM> included INFUSE™ <NUM> (polyolefin elastomer), commercially available from The Dow Chemical Company; NORDEL™ <NUM> XFC EPDM (polyolefin elastomer), commercially available from The Dow Chemical Company; an epoxy-containing polymer (E/<NUM> wt. % GMA/<NUM> wt. % nBA, with melt index of <NUM>/<NUM>) and an E/X/Y polymer (E/<NUM> wt. % AA/<NUM> wt. % nBA, with melt index of <NUM>/<NUM>). The epoxy-containing polymer and the E/X/Y polymer of this Example were prepared by standard free-radical copolymerization methods, using high pressure, operating in a continuous manner. Monomers were fed into the reaction mixture in a proportion which relates to the monomer's reactivity, and the amount desired to be incorporated. In this way, uniform, near-random distribution of monomer units along the chain is achieved. Polymerization in this manner is well known, and is described in <CIT>). Other polymerization techniques are described in <CIT>) and <CIT>).

To produce Samples <NUM>-<NUM>, the polyolefin elastomer was mixed with the E/X/Y polymer using Haake Bowl mixing at a temperature of <NUM>, then the epoxy-containing polymer was added, and the blend was cured. The amounts of each component used to produce the compositions of Samples <NUM>-<NUM> are provided in Table <NUM>.

Comparative Sample A was a polyolefin elastomer, INFUSE™ <NUM> (<NUM> wt. %), commercially available from The Dow Chemical Company.

Comparative Sample A was a polyolefin elastomer, NORDEL™ <NUM> XFC EPDM (<NUM> wt. %), commercially available from The Dow Chemical Company.

The materials used to produce Sample C were the INFUSE™ <NUM> (polyolefin elastomer), commercially available from The Dow Chemical Company; the epoxy-containing polymer of Example <NUM>; and the E/X/Y polymer of Example <NUM>. To produce Comparative Sample C, the polyolefin elastomer was mixed with the E/X/Y polymer using Haake Bowl mixing at a temperature of <NUM>, then the epoxy-containing polymer was added, and the blend was cured. The amounts of each component used to produce the compositions of Comparative Sample C are provided in Table <NUM>.

In Example <NUM>, the tensile properties (tensile modulus, ultimate tensile strength, and tensile elongation) were measured for Comparative Sample A and Samples <NUM>-<NUM>. The tensile testing and subsequent tensile properties analysis of the samples provided tensile strength and ultimate tensile strength data with correlation to ASTM D1708. The results of Example <NUM> are provided in Table <NUM>.

As shown in Table <NUM>, each of Samples <NUM>-<NUM> showed improved or comparable tensile properties when compared to Comparative Sample A. Therefore, it was observed that polymer compositions that included polyolefin elastomer, E/X/Y polymer, and epoxy-containing polymer (Samples <NUM>-<NUM>), provided for a blend that exhibits improved or comparable mechanical properties, when compared to a sample comprising <NUM>% polyolefin elastomer.

In Example <NUM>, the melt properties (I<NUM> and I<NUM>) were measured for Comparative Sample A and Samples <NUM>-<NUM>. The results of Example <NUM> are provided in Table <NUM>.

As shown in Table <NUM>, each of Samples <NUM>-<NUM> exhibited a melt index I<NUM> of less than <NUM>, showing that Samples <NUM>-<NUM> each had some cross-linking but were still thermoplastic. However, the melt index I<NUM> of Comparative Sample C, which included less than <NUM> wt. % of the polyolefin elastomer, could not be measured as there was no flow.

In Example <NUM>, the storage modulus at <NUM> rad/s, <NUM> rad/s, <NUM> rad/s, and <NUM> rad/s were measured for Comparative Sample A and Samples <NUM>-<NUM>. The results of Example <NUM> are provided in Table <NUM>.

As shown in Table <NUM>, each of Samples <NUM>-<NUM> exhibited a higher modulus than Comparative Sample A. A higher modulus indicates a more elastic material, which is desirable for foam materials. Accordingly, Samples <NUM>-<NUM> may have more desirable properties for use in foams, as compared to Comparative Sample A.

In Example <NUM>, the shear thinning properties were measured for Comparative Sample A and Samples <NUM>-<NUM>.

The shearing thinning data was obtained from DMS rheology. A constant temperature frequency sweep was performed using a TA Instruments "Advanced Rheometric Expansion System (ARES)," equipped with <NUM> (diameter) parallel plates, under a nitrogen purge. The sample was placed on the plate, and allowed to melt for five minutes at <NUM>. The plates were then closed to a gap of "<NUM>," the sample trimmed (extra sample that extends beyond the circumference of the "<NUM> diameter" plate was removed), and then the test was started. The method had an additional five minute delay built in, to allow for temperature equilibrium. The experiments were performed at <NUM> over a frequency range of <NUM> to <NUM> rad/s. Viscosity was calculated from these data. The results of Example <NUM> are provided in Table <NUM>.

As shown in Table <NUM>, each of Samples <NUM>-<NUM> exhibited a higher viscosity than Comparative Sample A. A higher viscosity may be desirable for foam manufacturing processes. Also samples <NUM>-<NUM> showed higher shear thinning characteristics (a higher shear thinning ratio (η<NUM>/ η<NUM>)), indicating these samples had improved processability. Accordingly, Samples <NUM>-<NUM> may have more desirable processability properties for use in foams, as compared to Comparative Sample A.

In Example <NUM>, the phase angles at <NUM>,<NUM> Pa, <NUM>,<NUM> Pa, <NUM>,<NUM> Pa, and <NUM>,<NUM> Pa were measured for Comparative Sample A and Samples <NUM>-<NUM>. The results of Example <NUM> are provided in Table <NUM>.

As shown in Table <NUM>, each of Samples <NUM>-<NUM> exhibited a lower phase angle than Comparative Sample A. A lower phase angle indicates a more elastic material, which is desirable for foam materials. Accordingly, Samples <NUM>-<NUM> may have more desirable properties for use in foams, as compared to Comparative Sample A.

In Example <NUM>, the tan delta at <NUM> rad/s, <NUM> rad/s, <NUM> rad/s, and <NUM> rad/s at <NUM> were measured for Comparative Sample A and Samples <NUM>-<NUM>.

The elasticity in solid was measured by the DMS analysis described herein at <NUM>, where film samples with about <NUM> thickness were prepared for the test.

As shown in Table <NUM>, each of Samples <NUM>-<NUM> exhibited lower tan delta, indicating higher elasticity in a solid when compared to Comparative Sample A.

In Example <NUM>, the Mooney viscosity, complex viscosity at <NUM> rad/s and <NUM> rad/s, rheology ratio, and phase angle were measured for Comparative Sample B and Samples <NUM>-<NUM>.

To test these properties, a constant temperature frequency sweep was performed using a TA Instruments "Advanced Rheometric Expansion System (ARES)," equipped with <NUM> (diameter) parallel plates, under a nitrogen purge. The sample was placed on the plate, and allowed to melt for five minutes at <NUM>. The plates were then closed to a gap of "<NUM>," the sample trimmed (extra sample that extends beyond the circumference of the "<NUM> diameter" plate was removed), and then the test was started. The method had an additional five minute delay built in, to allow for temperature equilibrium. The experiments were performed at <NUM> over a frequency range of <NUM> to <NUM> rad/s. The strain amplitude was constant at <NUM>%. The complex viscosity η*, tan (δ) or tan delta, viscosity at <NUM> rad/s (V0. <NUM>), the viscosity at <NUM> rad/s (V100), and the viscosity ratio (V0. <NUM>/V100) were calculated from these data. Mooney Viscosity (ML<NUM>+<NUM>) was determined according to ASTM D1646. The results of Example <NUM> are provided in Table <NUM>.

Claim 1:
A polymer composition comprising:
at least <NUM> wt.%, based on the total weight of the polymer composition, of a polyolefin elastomer having an ethylene content of from greater than <NUM> wt.% to less than <NUM> wt.%;
a cross-linkable blend comprising:
(i) from <NUM> wt.% to <NUM> wt.%, based on the total weight of the cross-linkable blend, of an E/X/Y polymer, wherein:
E is ethylene monomer;
X is a monomer selected from the group consisting of a C<NUM> to C<NUM> unsaturated carboxylic acids, esters of C<NUM> to C<NUM> unsaturated carboxylic acids, and anhydrides of C<NUM> to C<NUM> unsaturated carboxylic acids, wherein X is present in an amount of from about <NUM> wt.% to about <NUM> wt.%, based on the total amount of monomers present in the E/X/Y polymer; and
Y is an alkyl (meth)acrylate monomer, wherein Y is present in an amount of from <NUM> wt.% to <NUM> wt.%, based on the total amount of monomers present in the E/X/Y polymer; and
(ii) from <NUM> wt.% to <NUM> wt.%, based on the total weight of the cross-linkable blend, of an epoxy-containing polymer comprising:
copolymerized monomers of ethylene,
from about <NUM> wt.% to <NUM> wt.%, based on the total amount of monomers present in the epoxy-containing polymer, of a monomer containing one or more epoxy groups, and
from <NUM> wt.% to <NUM> wt.%, based on the total amount of monomers present in the epoxy-containing polymer, of an alkyl meth(acrylate) monomer.