Polymer composition and foam containing the polymer composition

Abstract

Embodiments are directed to polymer compositions and foams comprising the polymer compositions. The polymer composition embodiments may include at least 55 wt. % of a polyolefin elastomer, the polyolefin elastomer having an ethylene content of greater than 50 wt. % and less than 80 wt. %, based on the total weight of the polymer composition, and a crosslinkable blend comprising: (i) 1 wt. % to 99 wt. % of an E / X / Y polymer, based on the total weight of the crosslinkable blend, and (ii) 1 wt. % to 99 wt. % of an epoxy-containing polymer, based on the total weight of the crosslinkable blend.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 007,034, filed April 8, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to polymer compositions, and more particularly to polymer compositions for use in foams. [Background technology]

[0003] Polymer compositions are utilized in foams for a variety of applications, including athletic shoes and automotive applications. Conventional foams may contain a base polymer such as ethyl vinyl acetate copolymer (EVA), polyolefin elastomer (POE), olefin block copolymer (OBC), or ethylene-propylene-diene-monomer copolymer (EPDM). Summary of the Invention

[0004] Conventional foams can be formed from polyolefin elastomers, which are typically continuous-phase materials with good melt processability. However, improved rheological, mechanical, and thermal properties are desired. Therefore, to add these properties, crosslinked thermoplastic materials are often utilized. However, these crosslinked thermoplastics may require crosslinking agents to achieve the desired final foam properties, and these crosslinking agents often contain peroxides, which are not environmentally friendly and require special handling for transportation and storage. Therefore, there is a need for polymer compositions that produce foams with improved elasticity and modulus properties, and the polymer compositions may include polyolefin elastomers but may not require additional crosslinking agents.

[0005] Embodiments of the present disclosure meet these needs by providing a polymer composition that may include at least 55 wt. % of a polyolefin elastomer, based on its total weight, having an ethylene content greater than 50 wt. % and less than 80 wt. %, and a crosslinkable blend. The crosslinkable blend may include (i) 1 wt. % to 99 wt. % of an E / X / Y polymer, based on the total weight of the crosslinkable blend, and (ii) 1 wt. % to 99 wt. % of an epoxy-containing polymer, based on the total weight of the crosslinkable blend. E may be an ethylene monomer; X may be a monomer selected from the group consisting of a C3-C8 unsaturated carboxylic acid, an ester of a C3-C8 unsaturated carboxylic acid, and an anhydride of a C3-C8 unsaturated carboxylic acid; and Y may be an alkyl (meth)acrylate monomer. X may be present in an amount of 2 wt. % to 30 wt. % of the total amount of monomers present in the E / X / Y polymer. Y may be present in an amount of 0 wt. % to 40 wt. % of the total amount of monomers present in the E / X / Y polymer. The epoxy-containing polymer may include copolymerizable monomers of ethylene, 3% to 15% by weight, based on the total amount of monomers present in the epoxy-containing polymer, of a monomer containing one or more epoxy groups, and 0% to 40% by weight, based on the total amount of monomers present in the epoxy-containing polymer, of an alkyl meth(acrylate) monomer.

[0006] These and other embodiments are described in more detail in the detailed description that follows. DETAILED DESCRIPTION OF THE INVENTION

[0007] Certain 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.

[0008] Unless stated to the contrary, implied from the context, or customary in the art, all parts and percentages are by weight, all temperatures are in degrees Celsius, and all test methods are current as of the filing date of this disclosure.

[0009] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Thus, the general term polymer generally encompasses the term "homopolymer," which refers to a polymer prepared from only one type of monomer, as well as the term "copolymer," which refers to a polymer prepared from two or more different types of monomers. As used herein, the term "interpolymer" refers to a polymer prepared by polymerization of at least two different types of monomers. Thus, the general term interpolymer includes copolymers or polymers prepared from two or more different types of monomers, such as terpolymers.

[0010] "Polyolefin," "polyolefin polymer," "polyolefin resin," and similar terms refer to polymers made from simple olefins (also called alkenes, having the general formula CnH2n) as monomers. Polyethylene is made by polymerizing ethylene with or without one or more comonomers, polypropylene is made by polymerizing propylene with or without one or more comonomers, etc. Thus, polyolefin includes interpolymers such as ethylene-alpha-olefin copolymers, propylene-alpha-olefin copolymers, etc.

[0011] "Polyethylene" or "ethylene-based polymer" refers to a polymer containing greater than 50 mole percent units derived from ethylene monomers. This includes ethylene-based homopolymers and copolymers (meaning the units are derived from two or more comonomers). Common forms of ethylene-based polymers known in the art include, but are not limited to, 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 (m-LLDPE), including both linear and substantially linear low-density resins, medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0012] As used herein, "elastomer" refers to a polymeric material that, after being stretched, substantially recovers its original shape.

[0013] "(Meth)acrylic acid" includes methacrylic acid and / or acrylic acid, and "(meth)acrylate" includes methacrylate and / or acrylate.

[0014] As used herein, the term "composition" refers to the mixture of materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0015] "Blend," "polymer blend," and like terms refer to a composition of two or more polymers. Such blends may or may not be miscible. Such blends may or may not be phase separated. Such blends 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. A blend is not a laminate, although one or more layers of a laminate may contain the blend. Such blends may be prepared as dry blends or may be formed in situ (e.g., in a reactor), as melt blends, or using other techniques known to those skilled in the art.

[0016] "Foam" and like terms mean a material formed by trapping many gas bubbles within a liquid or solid.

[0017] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless otherwise stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or listed.

[0018] Reference will now be made in detail to the polymer composition embodiments described further herein. In embodiments, the polymer composition may comprise a polyolefin elastomer and a crosslinkable blend comprising an E / X / Y polymer and an epoxy-containing polymer.

[0019]

[0023] Embodiments of the polymer composition may comprise at least 55 weight percent (wt%) of a polyolefin elastomer, based on the total weight of the polymer composition. In some embodiments, the polymer composition may comprise from about 55 wt% to about 99 wt%, from about 55 wt% to about 90 wt%, from about 55 wt% to about 80 wt%, from about 55 wt% to about 70 wt%, from about 55 wt% to about 60 wt%, from about 60 wt% to about 99 wt%, from about 60 wt% to about 90 wt%, from about 60 wt% to about 80 wt%, from about 60 wt% to about 70 wt%, from about 70 wt% to about 99 wt%, from about 70 wt% to about 90 wt%, from about 70 wt% to about 80 wt%, from about 80 wt% to about 99 wt%, from about 80 wt% to about 90 wt%, or from about 90 wt% to about 99 wt%, based on the total weight of the polymer composition.

[0020]

[0013] Embodiments of the polymer composition may comprise 1 wt% to 45 wt% of a crosslinkable blend, based on the total weight of the polymer composition, comprising an E / X / Y polymer and an epoxy-containing polymer. In some embodiments, the polymer composition may comprise 1 wt% to 40 wt%, 1 wt% to 30 wt%, 1 wt% to 20 wt%, 1 wt% to 10 wt%, 10 wt% to 45 wt%, 10 wt% to 40 wt%, 10 wt% to 30 wt%, 10 wt% to 20 wt%, 20 wt% to 45 wt%, 20 wt% to 40 wt%, 20 wt% to 30 wt%, 30 wt% to 45 wt%, 30 wt% to 40 wt%, or 40 wt% to 45 wt% of the crosslinkable blend, based on the total weight of the polymer composition.

[0021] Embodiments of the polymer composition may have a melt flow index (I2) of less than 5 grams per 10 minutes (g / 10 min) when measured at 190°C and 2.16 kg according to ASTM D1238. Without being bound by theory, a composition having an I2 greater than 5 may indicate that the polymer composition does not have sufficient crosslinking to produce a foam with desirable properties. Thus, in embodiments, the polymer composition may be crosslinked. In embodiments, the polymer composition may have a melt flow index (I2) of 0.1 g / 10 min to 5 g / 10 min, 0.1 g / 10 min to 4 g / 10 min, 0.1 g / 10 min to 3 g / 10 min, 0.1 g / 10 min to 2 g / 10 min, 0.1 g / 10 min to 1 g / 10 min, 1 g / 10 min to 5 g / 10 min, 1 g / 10 min to 4 g / 10 min, or The melt flow index (I2) may be from 1 g / 10 min to 3 g / 10 min, from 1 g / 10 min to 2 g / 10 min, from 2 g / 10 min to 5 g / 10 min, from 2 g / 10 min to 4 g / 10 min, from 2 g / 10 min to 3 g / 10 min, from 3 g / 10 min to 5 g / 10 min, from 3 g / 10 min to 4 g / 10 min, or from 4 g / 10 min to 5 g / 10 min.

[0022] Embodiments of the polymer composition have a Mooney viscosity (ML) of greater than 65. 1+4 ) and Mooney viscosity (ML 1+4 ) is measured according to ASTM D1646. In embodiments, the polymer composition has a Mooney viscosity (ML) of 65-100, 65-90, 65-80, 65-70, 70-100, 70-90, 70-80, 80-100, 80-90, or 90-100. 1+4 ) viscosity, and Mooney viscosity (ML 1+4 ) is measured according to ASTM D1646.

[0023] Reference will now be made in detail to polyolefin elastomer embodiments of the polymer compositions described herein. As previously described in this disclosure, "elastomer" refers to a material that substantially recovers its original shape after being stretched. For example, upon application of a stretching force, the elastomer can stretch in at least one direction, such as the cross machine direction, and upon release of the stretching force, contracts, returning to approximately its original dimensions. For example, an exemplary elastomer is an extensible material that has an elongated length at least 50% greater than its relaxed, unstretched length and recovers to within at least 50% of its elongated length upon release of the stretching force. A hypothetical example would be a 1-inch sample of material that can be stretched to at least 1.50 inches and recovers to a length not exceeding 1.25 inches upon release of the stretching force.

[0024] As used herein, polyolefin elastomers are those having C2 to C6 20 "CO" refers to a copolymer composed of at least 50% by weight of ethylene and / or propylene derived from units copolymerized with different alpha-olefin monomer units selected from alpha-olefins, such as ethylene, 1-butene, 1-hexane, 4-methyl-1-pentene, and / or 1-octene. Embodiments of the polymer compositions described herein may include a polyolefin elastomer having an ethylene content of greater than 50% to less than 80% by weight. In embodiments, the polyolefin elastomer may have an ethylene content of 50% to 70%, 50% to 60%, 60% to 80%, 60% to 70%, or 70% to 80% by weight. Embodiments of the polymer compositions described herein may include a polyolefin elastomer having a comonomer content of at least 20% by weight. In embodiments, the ratio of ethylene and / or propylene derived units to C2 to C6 20The weight ratio of different alpha-olefin monomer units selected from alpha-olefins can be 50:50 to 80:20, 50:50 to 70:30, 50:50 to 60:40, 60:40 to 80:20, 60:40 to 70:30, or 70:30 to 80:20. Polyolefin elastomers can be polymerized using constrained geometry catalysts, such as metallocene catalysts. Polyolefin elastomers can provide desirable properties, including electrical insulation, good long-term chemical stability, and high strength, toughness, and elasticity.

[0025] Embodiments of polyolefin elastomers utilized in the polymer compositions described herein may have a melt index, as measured in accordance with ASTM D 1238, of less than 25 g / 10 min, less than 15 g / 10 min, or less than 10 g / 10 min. Embodiments of polyolefin elastomers utilized in the polymer compositions described herein may have a melt index, as measured in accordance with ASTM D 1238, of from 1 g / 10 min to 25 g / 10 min, from 1 g / 10 min to 15 g / 10 min, from 1 g / 10 min to 10 g / 10 min, from 1 g / 10 min to 5 g / 10 min, from 5 g / 10 min to 25 g / 10 min, from 5 g / 10 min to 15 g / 10 min, from 5 g / 10 min to 10 g / 10 min, from 10 g / 10 min to 25 g / 10 min, from 10 g / 10 min to 15 g / 10 min, or from 15 g / 10 min to 25 g / 10 min.

[0026] An exemplary polyolefin elastomer is available from The Dow Chemical Company of Midland, Mich. under the product name INFUSE™ 9507. In embodiments, the polyolefin elastomer may include an ethylene-propylene-diene terpolymer (EPDM), specifically a terpolymer product of ethylene, propylene, and ENB. A further exemplary polyolefin elastomer is available from The Dow Chemical Company of Midland, Mich. under the product name NORDEL™ 6565XFC EPDM.

[0027] The polyolefin elastomer may have a density of less than 0.900 g / cc, as measured according to ASTM D 792. In embodiments, the polyolefin elastomer may have a density of from 0.800 g / cc to 0.900 g / cc, from 0.800 g / cc to 0.880 g / cc, from 0.800 g / cc to 0.860 g / cc, from 0.800 g / cc to 0.840 g / cc, from 0.800 g / cc to 0.820 g / cc, from 0.820 g / cc to 0.900 g / cc, from 0.820 g / cc to 0.880 g / cc, or from 0.820 g / cc to 0.880 g / cc. The density may be 0.860 g / cc, 0.820 g / cc to 0.840 g / cc, 0.840 g / cc to 0.900 g / cc, 0.840 g / cc to 0.880 g / cc, 0.840 g / cc to 0.860 g / cc, 0.860 g / cc to 0.900 g / cc, 0.860 g / cc to 0.880 g / cc, or 0.880 g / cc to 0.900 g / cc.

[0028] Reference is now made to an embodiment of the crosslinkable blend, which may include an E / X / Y polymer and an epoxy-containing polymer. The reaction mechanism of the crosslinkable blend is provided as follows: [ka]

[0029] In embodiments, the E / X / Y polymer may include an ethylene monomer represented by E; a monomer represented by X selected from the group consisting of a C3-C8 unsaturated carboxylic acid, an ester of a C3-C8 unsaturated carboxylic acid, and an anhydride of a C3-C8 unsaturated carboxylic acid; and an alkyl (meth)acrylate monomer represented by Y. Examples of suitable unsaturated carboxylic acids having 3 to 8 carbon atoms include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, and combinations of two or more of these acid comonomers. In some embodiments, the unsaturated carboxylic acid having 3 to 8 carbon atoms includes acrylic acid and methacrylic acid. In other embodiments, the unsaturated carboxylic acid having 3 to 8 carbon atoms includes acrylic acid. Alkyl (meth)acrylate monomers can include alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, and dodecyl methacrylate.

[0030] The E / X / Y polymer can comprise 2% to 30%, 2% to 20%, 2% to 10%, 10% to 30%, 10% to 20%, or 20% to 30% by weight of X, based on the total amount of monomers present in the E / X / Y polymer. In embodiments, Y may optionally be present in an E / X / Y polymer in an amount of 0% to 40% by weight, 0% to 30% by weight, 0% to 20% by weight, 0% to 10% by weight, 5% to 40% by weight, 5% to 30% by weight, 5% to 20% by weight, 5% to 10% by weight, 10% to 40% by weight, 10% to 30% by weight, 10% to 20% by weight, 20% to 40% by weight, 20% to 30% by weight, or 30% to 40% by weight, based on the total amount of monomers present in the E / X / Y polymer. The remainder of the E / X / Y polymer may be E. Comonomer content may be determined using any suitable technique, such as techniques based on nuclear magnetic resonance ("NMR") spectroscopy, as described, for example, in U.S. Pat. No. 7,498,282, incorporated herein by reference. 13 It can be measured by C NMR analysis.

[0031] The E / X / Y polymer may have a melt index, I2, of from about 1 g / 10 min to about 500 g / 10 min. Melt index, I2, is determined according to ASTM D1238 at 190° C. and 2.16 kg. All individual values ​​and subranges from 10 g / 10 min to 100 g / 10 min are included and disclosed herein. For example, in some embodiments, the precursor acid copolymer may have a melt index, I2, of about 10 g / 10 min to about 80 g / 10 min, about 10 g / 10 min to about 60 g / 10 min, about 10 g / 10 min to about 20 g / 10 min, about 20 g / 10 min to about 100 g / 10 min, about 20 g / 10 min to about 60 g / 10 min, about 20 g / 10 min to 40 g / 10 min, 40 g / 10 min to 100 g / 10 min, 40 g / 10 min to 80 g / 10 min, 40 g / 10 min to 60 g / 10 min, 60 g / 10 min to 100 g / 10 min, 60 g / 10 min to 80 g / 10 min, or 80 g / 10 min to 100 g / 10 min.

[0032] The E / X / Y polymer can be synthesized in a continuous process in which the reactive monomers and, if present, the solvent are each continuously fed into a stirred reactor along with an initiator. The selection of the initiator is based on the expected reactor temperature range coupled with the decomposition temperature of the initiator, and this selection criteria are well understood in the art. Generally, during synthesis by copolymerization of ethylene with an acid comonomer to produce the E / X / Y polymer, the reactor temperature can be maintained at about 120°C to about 300°C, or about 140°C to about 260°C. The pressure in the reactor can be maintained at about 130 MPa to about 310 MPa, or about 165 MPa to 250 MPa.

[0033] The reactor may be, for example, an autoclave reactor such as that described in U.S. Pat. No. 2,897,183, which describes certain autoclave reactors equipped with means for vigorous agitation. This patent also describes a continuous process for polymerizing ethylene under a "substantially constant environment." This environment is maintained by keeping certain parameters, such as 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 continuous stirred tank reactors, including, for example, continuously stirred isothermal reactors and continuously stirred adiabatic reactors, among others.

[0034] The reaction mixture containing the E / X / Y polymer can be vigorously stirred and continuously removed from the autoclave. After the reaction mixture leaves the reaction vessel, the resulting E / X / Y polymer product can be separated from the volatile unreacted monomer and solvent, if present, by conventional procedures, such as by vaporizing the unpolymerized material and solvent under reduced pressure or at elevated temperature.

[0035] In embodiments, the crosslinkable blend may comprise 1% to 99% by weight of the E / X / Y polymer, based on the total weight of the crosslinkable blend. In embodiments, the crosslinkable blend may comprise 1% to 99% by weight, 1% to 90% by weight, 1% to 80% by weight, 1% to 70% by weight, 1% to 60% by weight, 1% to 50% by weight, 1% to 40% by weight, 1% to 30% by weight, 1% to 20% by weight, 1% to 10% by weight, 10% to 99% by weight, 10% to 90% by weight, 10% to 80% by weight, based on the total weight of the crosslinkable blend. Weight%, 10% to 70% by weight, 10% to 60% by weight, 10% to 50% by weight, 10% to 40% by weight, 10% to 30% by weight, 10% to 20% by weight, 20% to 99% by weight , 20% to 90% by weight, 20% to 80% by weight, 20% to 70% by weight, 20% to 60% by weight, 20% to 50% by weight, 20% to 40% by weight, 20% to 30% by weight, 30% by weight Amount%~99wt%, 30wt%~90wt%, 30wt%~80wt%, 30wt%~70wt%, 30wt%~60wt%, 30wt%~50wt%, 30wt%~40wt%, 40wt%~ 99% by weight, 40% to 90% by weight, 40% to 80% by weight, 40% to 70% by weight, 40% to 60% by weight, 40% to 50% by weight, 50% to 99% by weight, 50% to 90% by weight %, 50% to 80% by weight, 50% to 70% by weight, 50% to 60% by weight, 60% to 99% by weight, 60% to 90% by weight, 60% to 80% by weight, 60% to 70% by weight, 70% to 99% by weight, 70% to 90% by weight, 70% to 80% by weight, 80% to 99% by weight, 80% to 90% by weight, or 90% to 99% by weight of the E / X / Y polymer.

[0036] As previously described herein, the crosslinkable blend may further comprise an epoxy-containing polymer. In embodiments, the X monomer of the E / X / Y polymer may crosslink with one or more epoxy groups of the epoxy-containing polymer. Thus, embodiments of the polymer compositions described herein may not require an additional curing agent to crosslink the crosslinkable blend. In embodiments, the crosslinkable blend may be a crosslinked blend. In a crosslinked blend, the X monomer of the E / X / Y polymer may crosslink with one or more epoxy groups of the epoxy-containing polymer.

[0037] In embodiments, the epoxy-containing polymer may include a copolymerized monomer 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, e.g., GMA, present in the monomer containing one or more epoxy groups crosslinks with the E / X / Y polymer to produce a crosslinked foam. In some embodiments, it is believed that the crosslinking between the GMA and the E / X / Y polymer allows the foam to be sufficiently crosslinked without the need for a peroxide crosslinking agent.

[0038] The epoxy-containing polymer may comprise 3% to 15%, 3% to 10%, 3% to 5%, 5% to 15%, 5% to 10%, or 10% to 15% by weight of a 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 comprise 0% to 40%, 0% to 30%, 0% to 20%, 0% to 10%, 5% to 40%, 5% to 30%, 5% to 20%, 5% to 10%, 10% to 40%, 10% to 30%, 10% to 20%, 20% to 40%, 20% to 30%, or 30% to 40% by weight of an alkyl meth(acrylate) monomer, based on the total amount of monomers present in the epoxy-containing polymer. Comonomer content can be measured using any suitable technique, such as techniques based on nuclear magnetic resonance (“NMR”) spectroscopy, for example, by C NMR analysis as described in U.S. Pat. No. 7,498,282, incorporated herein by reference.

[0039] In embodiments, the crosslinkable blend may comprise 1 wt% to 99 wt% of the epoxy-containing polymer, based on the total weight of the crosslinkable blend. In embodiments, the crosslinkable blend may comprise 1 wt% to 99 wt%, 1 wt% to 90 wt%, 1 wt% to 80 wt%, 1 wt% to 70 wt%, 1 wt% to 60 wt%, 1 wt% to 50 wt%, 1 wt% to 40 wt%, 1 wt% to 30 wt%, 1 wt% to 20 wt%, 1 wt% to 10 wt%, 10 wt% to 99 wt%, 10 wt% to 90 wt%, 10 wt% to 80 wt%, based on the total weight of the crosslinkable blend. Weight%, 10% to 70% by weight, 10% to 60% by weight, 10% to 50% by weight, 10% to 40% by weight, 10% to 30% by weight, 10% to 20% by weight, 20% to 99% by weight , 20% to 90% by weight, 20% to 80% by weight, 20% to 70% by weight, 20% to 60% by weight, 20% to 50% by weight, 20% to 40% by weight, 20% to 30% by weight, 30% by weight Amount%~99wt%, 30wt%~90wt%, 30wt%~80wt%, 30wt%~70wt%, 30wt%~60wt%, 30wt%~50wt%, 30wt%~40wt%, 40wt%~ 99% by weight, 40% to 90% by weight, 40% to 80% by weight, 40% to 70% by weight, 40% to 60% by weight, 40% to 50% by weight, 50% to 99% by weight, 50% to 90% by weight %, 50% to 80% by weight, 50% to 70% by weight, 50% to 60% by weight, 60% to 99% by weight, 60% to 90% by weight, 60% to 80% by weight, 60% to 70% by weight, 70% to 99% by weight, 70% to 90% by weight, 70% to 80% by weight, 80% to 99% by weight, 80% to 90% by weight, or 90% to 99% by weight of the epoxy-containing polymer.

[0040] 10. The polymer composition of claim 9, further comprising a compatibilizer or any other suitable additive known in the art, which may include plasticizers, processing aids, 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), heat stabilizers, hindered amine light stabilizers (HALS), UV absorbers, UV stabilizers, dispersants, surfactants, chelating agents, coupling agents, adhesives, primers, reinforcing additives (e.g., glass fibers), fillers, and the like, as well as mixtures or combinations of two or more conventional additives.

[0041] Blowing agents can include hydrocarbons, fluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, and other halogenated compounds. Other suitable chemical blowing agents can include, for example, sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, dinitrosopentamethylenediamine, and sulfonylhydrazide. Blowing agents such as water or carbon dioxide, added as a gas or liquid or generated in situ by the reaction of water with polyisocyanate, can also be used. Blowing agents can be used in mixtures of two or more, and chemical and physical blowing agents can be used together to adjust the expansion decomposition temperature and foaming process.

[0042] Embodiments of the polymer compositions described herein may further include free radical initiators or crosslinkers, co-curatives, activators, and any other types of additives typically used in similar compositions, including, but not limited to, pigments, adhesion promoters, fillers, nucleating agents, rubbers, stabilizers, and processing aids.

[0043] The free radical initiator or crosslinking agent can include, by way of example and not limitation, an organic peroxide such as a dialkyl organic peroxide. Examples of organic peroxides suitable for use include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tertiary-butyl-peroxyl)hexane, 1,3-bis(tertiary-butyl-peroxyl-isopropyl)benzene, or a combination of two or more thereof. Co-curing agents include trimethylpropane triacrylate (and similar compounds), N,Nm-phenylenedimaleimide, triallyl cyanurate, or a combination of two or more thereof. The activator can include an activator for a foaming agent and can include one or more metal oxides, metal salts, or organometallic complexes. Examples include ZnO, Zn stearate, MgO, or a combination of two or more thereof.

[0044] Embodiments of the polymer composition can be produced by combining the components of the polymer composition under heat to form a melt. Combining the components can include mixing and blending the components using any technique known and used in the art, including a Banbury, an intensive mixer, a two-roll mill, and an extruder. Time, temperature, and shear rate can be adjusted to ensure dispersion without premature crosslinking or foaming.

[0045] In some embodiments, combining the polyolefin elastomer, the E / X / Y polymer, and the epoxy-containing polymer can include melt-blending the polyolefin elastomer with a crosslinkable blend of the E / X / Y polymer and the epoxy-containing polymer. Melt-blending of the polyolefin elastomer and the crosslinkable blend can occur at a temperature of 100°C to 150°C. In embodiments, the melt-blended polyolefin elastomer and the crosslinkable blend can then be cured at a temperature of 180°C to 240°C.

[0046] 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 E / X / Y polymer to form a blend, and subsequently melt-blending the blend with the epoxy-containing polymer. In embodiments, melt-blending the polyolefin elastomer with the E / X / Y polymer to form a blend may occur at a temperature of from 180°C to 240°C. Subsequent melt-blending of the blend with the epoxy-containing polymer may occur at a temperature of from 180°C to 240°C. The blend and the melt-blended epoxy-containing polymer may then be cured at a temperature of from 180°C to 240°C.

[0047] Embodiments of the present disclosure may include articles comprising the polymer compositions described herein. According to various embodiments, the polymer compositions may be used to form foams or molded articles. For example, in embodiments, the polymer compositions may be combined with additives used to control the foam properties to form foams of various shapes. In some embodiments, the foams may be extruded, such as from a twin-screw extruder, as known to those skilled in the art.

[0048] The blowing agents (also called foaming agents) used to produce foams can be physical or chemical blowing agents. As used herein, a "physical blowing agent" is a low-boiling liquid that volatilizes under curing conditions to form a foaming gas. Exemplary physical blowing agents include hydrocarbons, fluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, and other halogenated compounds. Other suitable chemical blowing agents may include, for example, sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, dinitrosopentamethylenediamine, and sulfonylhydrazides. Blowing agents such as water or carbon dioxide, added as gases or liquids or generated in situ by the reaction of water with polyisocyanates, can also be used. Blowing agents can be used in mixtures of two or more, and chemical and physical blowing agents can be used together to adjust the expansion decomposition temperature and foaming process.

[0049] Foams formed from embodiments of the polymer compositions described herein may further include free radical initiators or crosslinkers, co-curing agents, activators, and any other types of additives typically used in similar compositions, including, but not limited to, pigments, adhesion promoters, fillers, nucleating agents, rubbers, stabilizers, and processing aids. Activators can include activators for foaming agents 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 crosslinkers can include, by way of example and not limitation, organic peroxides such as dialkyl organic peroxides. Examples of organic peroxides suitable for use include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl-cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl-peroxyl)hexane, 1,3-bis(tert-butyl-peroxyl-isopropyl)benzene, or combinations of two or more thereof. Co-curing agents include trimethylpropane triacrylate (and similar compounds), N,Nm-phenylenedimaleimide, triallyl cyanurate, or combinations of two or more thereof. Foams formed from embodiments of the polymer compositions described herein may further comprise 0% to 10%, 0% to 8%, 0% to 6%, 0% to 4%, 0% to 2%, 2% to 10%, 2% to 8%, 2% to 6%, 2% to 4%, 4% to 10%, 4% to 8%, 4% to 6%, 6% to 10%, 6% to 8%, 8% to 10% by weight of a free radical initiator or crosslinker, based on the total weight of the polymer composition used to produce the foam embodiment.

[0050] The polymer composition embodiments described herein above may be utilized in foams, which may be produced by a number of methods, such as compression molding, injection molding, or a hybrid of extrusion and molding. This process may involve 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, as well as any techniques known and used in the art, including Banbury mixers, intensive mixers, two-roll mills, and extruders. Time, temperature, and shear rate may be adjusted to ensure dispersion without premature crosslinking or foaming.

[0051] After the polymer composition has been mixed with any additives, it can be molded. Sheeting or calendaring rolls can be used to create appropriately sized sheets for foaming. Extruders can be used to mold the composition into pellets.

[0052] Foaming can be carried out in a compression mold at a temperature and time to complete the decomposition of the peroxide and foaming agent. Pressure, 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 formed to the dimensions of the final product by any means known and used in the art, including thermoforming and compression molding.

[0053] In various embodiments, the resulting foams formed from embodiments of the polymer compositions described herein are substantially closed-cell and may be useful in a variety of articles, for example, footwear applications, including midsoles or insoles.

[0054] In embodiments, foams formed from embodiments of the polymer compositions described herein may have a density of about 0.2 g / cc, hi embodiments, foams formed from embodiments of the polymer compositions described herein may have a density of less than 0.2 g / cc or 0.15 g / cc.

[0055] The embodiments described herein may be further illustrated by the following non-limiting examples. Test Method

[0056] Unless otherwise specified, the following test methods are used:

[0057] density

[0058] Density was determined according to ASTM D792 and is reported in grams per cubic centimeter (or g / cc).

[0059] Melt Index

[0060] "Melt index": I2 (or I2) and I 10 (or I10) are determined according to ASTM D1238 at 190°C with a 2.16 kg load and a 10 kg load, respectively. 10 are each reported in grams per 10 minutes (or g / 10 min).

[0061] Tensile properties

[0062] Tensile strength, tensile modulus, and elongation at break were measured according to ASTM D 1708. Micro-tensile bars were punched from compression-molded plaques with a thickness of 1.5 mm.

[0063] Dynamic Mechanical Spectroscopy (DMS)

[0064] Dynamic oscillatory shear measurements are performed using a TA Instruments (New Castle, Del.) ARES system at 190°C under an inert nitrogen atmosphere at a constant strain of 10% using 25 mm parallel plates with a 2.0 mm gap. The frequency interval is logarithmically spaced from 0.03 to 300 rad / s at 5 points per decade. The stress response is analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G''), and complex modulus (G *), tan δ, phase angle δ, and complex viscosity (η * ) is calculated. * is G' as its real component and G'' as its imaginary component, respectively (G * =G'+iG'') is a complex number. * The magnitude of |G * |=(G' 2 +G'' 2 ) 1 / 2 Both tan δ and phase angle δ are related to the relative elasticity of a material. Tan δ is the ratio of loss modulus to storage modulus, tan δ = G'' / G', and phase angle δ is δ = tan -1 (G'' / G') * Also, η' is a complex number with its real number and η'' as its imaginary component. * The magnitude of is reported as

number

[0065] where ω is the angular frequency in radians / second.

[0066] Mooney Viscosity

[0067] Mooney viscosity (ML 1+4 ) is determined according to ASTM D1646 with a 1 minute preheat time and a 4 minute rotor operation time. The instrument was an Alpha Technologies Mooney Viscometer 2000. [Example]

[0068] Example 1 - Samples 1 to 5

[0069] The materials used to produce Samples 1-5 included INFUSE™ 9507 (a polyolefin elastomer) commercially available from The Dow Chemical Company, NORDEL™ 6565XFC EPDM (a polyolefin elastomer) commercially available from The Dow Chemical Company, an epoxy-containing polymer (E / 5.25 wt%-GMA / 28 wt% nBA, with a melt index of 12 g / 10 min), and an E / X / Y polymer (E / 6.2 wt%-AA / 28 wt% nBA, with a melt index of 60 g / 10 min). The epoxy-containing polymer and E / X / Y polymer in this example were prepared by a standard free-radical copolymerization method operating in a continuous mode using high pressure. Monomers were fed into the reaction mixture in proportions related to the reactivity of the monomers and the amount desired for incorporation. In this way, a uniform, nearly random distribution of the monomer units along the chain was achieved. Polymerization in this manner is well known and is described in U.S. Patent No. 4,351,931 (Armitage), which is incorporated herein by reference. Other polymerization techniques are described in U.S. Patent No. 5,028,674 (Hatch et al.) and U.S. Patent No. 5,057,593 (Statz), both of which are incorporated herein by reference.

[0070] To produce Samples 1-5, the polyolefin elastomer was mixed with the E / X / Y polymer using a Haake Bowl mixer at a temperature of 220° C., after which the epoxy-containing polymer was added and the blend cured. The amount of each component used to produce the compositions of Samples 1-5 is provided in Table 1. [Table 1]

[0071] Example 2 - Comparative Sample A

[0072] Comparative Sample A was INFUSE™ 9507 (100 wt %), a polyolefin elastomer commercially available from The Dow Chemical Company.

[0073] Example 3 - Comparative Sample B

[0074] Comparative Sample A was a polyolefin elastomer, NORDEL™ 6565XFC EPDM (100 wt %), commercially available from The Dow Chemical Company.

[0075] Example 4 - Comparative Sample C

[0076] The materials used to produce Sample C were INFUSE™ 9507 (a polyolefin elastomer) commercially available from The Dow Chemical Company, the epoxy-containing polymer of Example 1, and the E / X / Y polymer of Example 1. To produce Comparative Sample C, the polyolefin elastomer was mixed with the E / X / Y polymer using a Haake Bowl mixer at a temperature of 220° C., after which the epoxy-containing polymer was added and the blend was cured. The amount of each component used to produce the composition of Comparative Sample C is shown in Table 2. [Table 2]

[0077] Example 5 - Mechanical properties of Comparative Sample A and Samples 1-3

[0078] In Example 5, tensile properties (tensile modulus, ultimate tensile strength, and tensile elongation) were measured for Comparative Sample A and Samples 1-3. Tensile testing of the samples and subsequent tensile property analysis provided tensile strength and ultimate tensile strength data that correlates with ASTM D1708. The results for Example 3 are shown in Table 3. [Table 3]

[0079] As shown in Table 3, each of Samples 1-3 exhibited improved or equivalent tensile properties compared to Comparative Sample A. Thus, it was observed that the polymer compositions comprising polyolefin elastomer, E / X / Y polymer, and epoxy-containing polymer (Samples 1-3) resulted in blends that exhibited improved or equivalent mechanical properties compared to the samples comprising 100% polyolefin elastomer.

[0080] Example 6 - Melting properties of Comparative Sample A and Samples 1-3

[0081] In Example 6, the melting properties (I2 and I3) of Comparative Sample A and Samples 1 to 3 were measured. 10 The results of Example 6 are shown in Table 4. [Table 4]

[0082] As shown in Table 4, each of Samples 1-3 exhibited a melt index I2 of less than 5, indicating that each of Samples 1-3 had some crosslinking but was still thermoplastic. However, the melt index I2 of Comparative Sample C, which contained less than 55 wt% polyolefin elastomer, could not be measured due to a lack of flow.

[0083] Example 7 - Storage modulus of comparative sample A and samples 1 to 3

[0084] In Example 7, the storage moduli were measured at 0.1 radian / sec, 1 radian / sec, 10 radian / sec, and 100 radian / sec for Comparative Sample A and Samples 1 to 3. The results for Example 7 are shown in Table 5. [Table 5]

[0085] As shown in Table 5, each of Samples 1-3 exhibited a higher modulus than Comparative Sample A. A higher modulus indicates a material is more resilient, which is desirable for a foam material. Thus, Samples 1-3 may have more desirable properties for use in a foam than Comparative Sample A.

[0086] Example 8 - Shear thinning of Comparative Sample A and Samples 1 to 3

[0087] In Example 8, the shear thinning properties of Comparative Sample A and Samples 1 to 3 were measured.

[0088] Shear thinning data was obtained from DMS Rheology. Constant temperature frequency sweeps were performed using a TA Instruments Advanced Rheometric Expansion System (ARES) equipped with 25 mm diameter parallel plates under a nitrogen purge. The sample was placed on the plates and melted at 190°C for 5 minutes. The plates were then closed to a 2 mm gap, the sample was trimmed (removing excess sample extending beyond the circumference of the 25 mm diameter plates), and the test was then initiated. The method incorporated an additional 5 minute delay to allow for temperature equilibration. The experiment was performed at 190°C over a frequency range of 0.1 to 100 rad / s. Viscosity was calculated from these data. The results for Example 8 are shown in Table 6. [Table 6]

[0089] As shown in Table 6, each of Samples 1-3 exhibited a higher viscosity than Comparative Sample A. Higher viscosity may be desirable in foam manufacturing processes. Samples 1-3 also exhibited higher shear thinning properties (higher shear thinning ratios (η 0.1 / η 100 ), indicating that these samples had improved processability. Thus, Samples 1-3 may have more desirable processability properties for use in foams compared to Comparative Sample A.

[0090] Example 9 - Melt Elasticity of Comparative Sample A and Samples 1-3

[0091] In Example 9, the phase angles at 5,000 Pa, 8,000 Pa, 12,000 Pa, and 18,000 Pa were measured for Comparative Sample A and Samples 1 to 3. The results of Example 9 are shown in Table 7. [Table 7]

[0092] As shown in Table 7, each of Samples 1-3 exhibited a lower phase angle than Comparative Sample A. A lower phase angle indicates a material with greater resilience, which is desirable for a foam material. Therefore, Samples 1-3 may have more desirable properties for use in a foam than Comparative Sample A.

[0093] Example 10 - Elasticity of Comparative Sample A and Samples 2-3 in Solid State

[0094] In Example 10, the tan delta of Comparative Sample A and Samples 2-3 was measured at 25° C. and at 0.1 radian / sec, 1 radian / sec, 10 radian / sec, and 100 radian / sec.

[0095] Solid state elasticity was measured at 25° C. by DMS analysis as described herein, and film samples approximately 0.5 mm thick were prepared for testing. [Table 8]

[0096] As shown in Table 7, each of Samples 2-3 exhibited lower tan delta and higher elasticity at the solid when compared to Comparative Sample A.

[0097] Example 11 - Viscosity of Comparative Sample B and Samples 4-5

[0098] In Example 11, Mooney viscosity, complex viscosity at 0.1 rad / sec and 100 rad / sec, rheological ratio, and phase angle were measured for Comparative Sample B and Samples 2-3.

[0099] Constant temperature frequency sweeps were performed using a TA Instruments Advanced Rheometric Expansion System (ARES) equipped with 25 mm diameter parallel plates under a nitrogen purge. The sample was placed on the plates and melted at 125 °C for 5 minutes. The plates were then closed to a 2 mm separation, the sample was trimmed (removing excess sample extending beyond the circumference of the 25 mm diameter plates), and then the test was initiated. The method incorporated an additional 5 minute delay to allow for temperature equilibration. The experiment was performed at 125 °C over a frequency range of 0.1 to 100 rad / s. The strain amplitude was constant at 10%. The complex viscosity η * The Mooney viscosity (ML), tan (δ) or tan delta, viscosity at 0.1 rad / sec (V), viscosity at 100 rad / sec (V), and viscosity ratio (V / V) were calculated from these data. 1+4 ) was determined according to ASTM D1646. The results for Example 11 are shown in Table 9. [Table 9]

[0100] As shown in Table 9, each of Samples 4-5 exhibited improved Mooney viscosity, shear thinning, and melt elasticity (reduced phase angle) properties when compared to Comparative Sample B.

[0101] The dimensions and values ​​disclosed herein should not be understood to be strictly limited to the exact numerical values ​​recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."

[0102] All documents cited herein, including any cross-referenced or related patents or applications, if any, and any patent application or patent to which this application claims priority or benefit, are hereby incorporated by reference in their entirety, unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any embodiment disclosed or claimed herein, or that it alone or in combination with any other reference or references teaches, suggests, or discloses any such embodiment. Furthermore, to the extent that the meaning or definition of any term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

Claims

1. 1. A polymer composition comprising: at least 55 wt. % of a polyolefin elastomer, the polyolefin elastomer having an ethylene content of greater than 50 wt. % and less than 80 wt. %, based on the total weight of the polymer composition; A crosslinkable blend comprising: (i) 1 wt % to 99 wt % of an E / X / Y polymer, based on the total weight of the crosslinkable blend; E is an ethylene monomer; X is C ３ ~C ８ Unsaturated carboxylic acids, C ３ ~C ８ Esters of unsaturated carboxylic acids, and C ３ ~C ８ a monomer selected from the group consisting of anhydrides of unsaturated carboxylic acids, wherein X is present in an amount of 2% to 30% by weight, based on the total amount of monomers present in the E / X / Y polymer; an E / X / Y polymer, wherein Y is an alkyl (meth)acrylate monomer, and Y is present in an amount of 0% to 40% by weight, based on the total amount of said monomers present in said E / X / Y polymer; (ii) 1 wt % to 99 wt % of an epoxy-containing polymer, based on the total weight of the crosslinkable blend; Copolymerization monomer of ethylene, 3% to 15% by weight of a monomer containing one or more epoxy groups, based on the total amount of said monomers present in said epoxy-containing polymer; and and an epoxy-containing polymer comprising 0% to 40% by weight of an alkyl meth(acrylate) monomer, based on the total amount of said monomers present in said epoxy-containing polymer.

2. 10. The polymer composition of claim 1, wherein the polyolefin elastomer comprises an ethylene-based polymer having a density less than 0.900 g / cc as measured according to ASTM D792.

3. 3. The polymer composition of claim 1 or 2, wherein the polyolefin elastomer comprises less than 80 wt. % ethylene monomer units, based on the total weight of the polyolefin elastomer.

4. The polymer composition has a melt flow index (I) of less than 5 grams per 10 minutes (g / 10 min) when measured at 190° C. and 2.16 kg according to ASTM D1238. ２ The polymer composition according to any one of claims 1 to 3, wherein

5. The polymer composition of any one of claims 1 to 4, wherein the E / X / Y polymer comprises 5% to 30% by weight of alkyl meth(acrylate) monomer.

6. The polymer composition of any one of claims 1 to 5, wherein the epoxy-containing polymer comprises 5% to 30% by weight of alkyl meth(acrylate) monomer.

7. 7. The polymer composition of any one of claims 1 to 6, wherein the X monomer of the E / X / Y polymer is crosslinked with the one or more epoxy groups of the epoxy-containing polymer.

8. The polymer composition of any one of claims 1 to 7, comprising 1 wt% to 45 wt% of said crosslinkable blend, based on the total weight of said polymer composition.

9. The polymer composition of any one of claims 1 to 8, comprising 55 wt% to 99 wt% of said polyolefin elastomer, based on the total weight of said polymer composition.

10. The polymer composition of any one of claims 1 to 9, wherein the crosslinkable blend is crosslinked.

11. A method for producing a polymer composition according to any one of claims 1 to 10, said method comprising: combining said polyolefin elastomer, said E / X / Y polymer, and said epoxy-containing polymer to form said polymer composition.

12. combining the polyolefin elastomer, the E / X / Y polymer, and the epoxy-containing polymer, 12. The method of claim 11, comprising melt blending the polyolefin elastomer with the crosslinkable blend of the E / X / Y polymer and the epoxy-containing polymer.

13. combining the polyolefin elastomer, the E / X / Y polymer, and the epoxy-containing polymer, melt blending said polyolefin elastomer with said E / X / Y polymer to form a blend; 12. The method of claim 11, further comprising: subsequently melt-blending the epoxy-containing polymer with the blend.

14. An article comprising the polymer composition of any one of claims 1 to 10.

15. The article of claim 14, wherein the article is a foam.

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