Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D35/00—Producing footwear
  • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
  • B29D35/122—Soles
• • A—HUMAN NECESSITIES
  • A43—FOOTWEAR
  • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
  • A43B13/00—Soles; Sole-and-heel integral units
  • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
  • A43B13/04—Plastics, rubber or vulcanised fibre
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/026—Crosslinking before of after foaming
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
  • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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  • C08J2423/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/04—Homopolymers or copolymers of ethene
  • C08J2423/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
  • C08J2433/12—Homopolymers or copolymers of methyl methacrylate

Definitions

• the disclosure is related to an injection molded shoe sole with improved resilience and reduced compression set.
• EVA ethylene vinyl acetate copolymer
• U.S. Patent Publication No. 2005/0081980 disclosed foam cushions made from blends of resins (such as EVA) and natural rubber or synthetic rubber (such as polyacrylate rubber, polybutadiene rubber, styrene-butadiene rubber, and etc.). However it is found that such blends still could not solve the above mentioned problems.
• resins such as EVA
• natural rubber or synthetic rubber such as polyacrylate rubber, polybutadiene rubber, styrene-butadiene rubber, and etc.
• the present disclosure is directed to an injection molded shoe sole having high resilience and low compression set.
• the injection molded shoe sole disclosed herein is made of a foam composition, wherein the foam composition comprises:
• thermoplastic ethylene copolymer (a) at least one thermoplastic ethylene copolymer
• thermoplastic ethylene copolymer (a) comprises copolymerized units of ethylene and 5-50 wt% of copolymerized units of at least one non-ethylene comonomer selected from vinyl acetates and alkyl (meth)acrylates, with all copolymerized units comprised in the thermoplastic ethylene copolymer totaling to 100 wt%,
• the at least one ethylene/alkyl acrylate copolymer rubber (b) comprises copolymerized units of ethylene and from above 50 wt% to 95 wt% of copolymerized units of at least one alkyl (meth)acrylate, with all copolymerized units comprised in the ethylene/alkyl acrylate copolymer rubber totaling to 100 wt%,
• thermoplastic ethylene copolymer (a) is present at a level of 20-93 wt% and the at least one ethylene/alkyl acrylate copolymer rubber (b) is present at a level of 7-80 wt%, and
• the at least one cross-linking agent (c) is present at a level of 0.5-5 wt% and the at least one foaming agent (d) is present at a level of 0.5-5 wt%.
• the at least one thermoplastic ethylene copolymer (a) comprises 20-45 wt% or 30-45 wt% of copolymerized units of the at least one non-ethylene comonomer, with all copolymerized units comprised in the thermoplastic ethylene copolymer totaling to 100 wt%.
• the at least one thermoplastic ethylene copolymer (a) may further comprises up to 35 wt%, or up to 25 wt%, or up to 20 wt% of copolymerized units of an additional monomer, with all copolymerized units comprised in the thermoplastic ethylene copolymer totaling to 100 wt%.
• the additional monomer comprised in the thermoplastic ethylene copolymer (a) is selected from the group consisting of (meth)acrylic acid, maleic anhydride, butyl acrylate, carbon monoxide, and combinations of two or more thereof.
• the at least one thermoplastic ethylene copolymer (a) is an ethylene/alkyl (meth)acrylate copolymer.
• the at least one thermoplastic ethylene copolymer (a) is an ethylene vinyl acetate copolymer.
• the at least one ethylene/alkyl acrylate copolymer rubber (b) further comprises up to 5 wt% of copolymerized units of an additional monomer, with all copolymerized units comprised in the ethylene/alkyl acrylate copolymer rubber totaling to 100 wt%.
• the additional monomer comprised in the ethylene/alkyl acrylate copolymer rubber (b) is selected from the group consisting of (meth)acrylate glycidyl esters, maleic acids, comonomers having one or more reactive groups selected from acids, hydroxyls, epoxys, isocyanates, amines, oxazolines, chloroacetates, and dienes, and combinations of two or more thereof.
• the at least one thermoplastic ethylene copolymer (a) is present at a level of 45-93 wt% and the at least one ethylene/alkyl acrylate copolymer rubber (b) is present at a level of 7-55 wt%, or, the at least one thermoplastic ethylene copolymer (a) is present at a level of 70-88 wt% and the at least one ethylene/alkyl acrylate copolymer rubber (b) is present at a level of 12-30 wt%.
• the at least one cross-linking agent (c) is present at a level of 1 -4 wt% or 1 .5-3 wt%.
• the at least one foaming agent (d) is present at a level of 1 -4 wt% or 1 .5-3 wt%.
• the foam composition further comprises up to 50 wt% or up to 25 wt% of one or more other additives, relative to the combined weight of (a) and (b).
• the one or more other additives are selected from the group consisting of foaming agent activators, fillers, antioxidant, pigments, stabilizers, and combinations of two or more thereof.
• a method for preparing a shoe sole comprising: (i) providing a foam composition and (ii) injection molding the foam composition to obtain the shoe sole, wherein the foam composition comprises: a) at least one thermoplastic ethylene copolymer;
• thermoplastic ethylene copolymer (a) comprises copolymerized units of ethylene and 5-50 wt% of copolymerized units of at least one non-ethylene comonomer selected from vinyl acetates and alkyl (meth)acrylates, with all copolymerized units comprised in the thermoplastic ethylene copolymer totaling to 100 wt%,
• the at least one ethylene/alkyl acrylate copolymer rubber (b) comprises copolymerized units of ethylene and from above 50 wt% to 95 wt% of copolymerized units of at least one alkyl (meth)acrylate, with all copolymerized units comprised in the ethylene/alkyl acrylate copolymer rubber totaling to 100 wt%,
• thermoplastic ethylene copolymer (a) is present at a level of 20-93 wt% and the at least one ethylene/alkyl acrylate copolymer rubber (b) is present at a level of 7-80 wt%, and
• the at least one cross-linking agent (c) is present at a level of 0.5-5 wt% and the at least one foaming agent (d) is present at a level of 0.5-5 wt%.
• the range includes any value that is within the two particular end points and any value that is equal to or about equal to any of the two end points.
• (meth)acrylic acid means methacrylic acid and/or acrylic acid.
• (meth)acrylate means methacrylate and/or acrylate.
• Thermoplastic compositions are polymeric materials that can flow when heated under pressure. The whole process can be repeated a number of times till degradation take place.
• thermoplastic materials usually can be measured by melt flow rate.
• flow properties can be measured by their intrinsic viscosities.
• an injection molded shoe sole made of a foam composition
• the foam composition comprises: (a) about 20-93 wt% of at least one thermoplastic ethylene copolymer and (b) about 7-80 wt% of at least one ethylene/alkyl acrylate copolymer rubber, based on the combined weight of (a) and (b).
• the foam composition disclosed herein further comprises, relative to the combined weight of (a) and (b), (c) about 0.5-5 wt% of at least one cross-linking agent, and (d) about 0.5-5 wt% of at least one foaming agent.
• thermoplastic ethylene copolymer means a thermoplastic copolymer derived from the copolymerization of ethylene monomer and at least one non-ethylene comonomer selected from vinyl acetates and alkyl (meth)acrylates. In accordance with the present disclosure, based on the total weight of the thermoplastic ethylene copolymer, about 5-50 wt%, or about 20-45 wt%, or about 30-45 wt% of copolymerized units of the at least one non-ethylene comonomer are present in the thermoplastic ethylene copolymer.
• the at least one thermoplastic ethylene copolymer comprised in the foam composition is selected from ethylene/vinyl acetate copolymers (EVA) comprising about 5-50 wt%, or about 20-45 wt%, or about 30 to 45 wt% of copolymerized units of vinyl acetates, based on the total weight of the EVA.
• EVA ethylene/vinyl acetate copolymers
• the EVA used herein may also comprise up to about 35 wt%, or up to about 25 wt%, or up to about 20 wt% of copolymerized units of one or more additional monomers.
• Such one or more additional comonomers may include, without limitation, (meth)acrylic acid, maleic anhydride, butyl acrylate, carbon monoxide, and combinations of two or more thereof.
• Suitable EVA also may be obtained commercially.
• Elvax® EVA resins available from E. I. du Pont de Nemours and Company, U.S.A. (hereafter "DuPont”); EvataneTM EVA copolymers available from Arkerma, Inc., France; EscoreneTM EVA resins available from Exxonmobil Chemical, U.S.A.; Evaflex® EVA resins available from DuPont-Mitsui Polychemicals Co. Ltd; or AtevaTM EVA resins available from Celanese, Canada may be used herein.
• copolymer comprised in the foam composition is selected from ethylene/alkyi (meth)acrylate copolymers.
• ethylene/alkyi (meth)acrylate copolymer is used to refer to copolymers comprising copolymerized units of ethylene and at least one alkyl (meth)acrylate.
• alkyl acrylates include methyl acrylate, ethyl acrylate and butyl acrylate.
• the ethylene/alkyi (meth)acrylate copolymers used herein include, without limitation,
• EMA ethylene/methyl acrylate copolymers
• EBA ethylene/butyl acrylate copolymers
• the amount of the alkyl (meth)acrylate comonomer incorporated into the ethylene/alkyi (meth)acrylate copolymer may be about 5-50 wt%, or about 20-45 wt%, or about 30-35 wt%, based on the total weight of the ethylene/alkyi (meth)acrylate copolymer.
• the alkyl group used herein may be a branched or non-branched alkyl group with 1 -10, or 1 -8, or 1 -4 carbons. In one
• methyl acrylate (the most polar alkyl acrylate comonomer) may be used to prepare an ethylene/methyl acrylate dipolymer.
• the ethylene/alkyi (meth)acrylate copolymers may also optionally include up to about 35 wt%, or up to about 25 wt%, or up to about 20 wt% at least one additional comonomer, such as those disclosed above in reference to EVA.
• Ethylene/alkyl (meth)acrylate copolymers can be prepared by processes well known in the polymer art using either autoclave or tubular reactors.
• the copolymerization can be run as a continuous process in an autoclave.
• ethylene, an alkyl (meth)acrylate such as methyl acrylate, and optionally a solvent such as methanol are fed continuously into a stirred vessel such as autoclave, together with an initiator.
• the rate of addition may depend on polymerization temperature, pressure, and concentration of methyl acrylate monomer in the reaction mixture needed to achieve the target composition of the copolymer.
• the product mixture can be continuously removed from the vessel. After the product mixture leaves the reaction vessel, the copolymer can be separated from the un-reacted monomers and solvent (if used) by conventional means, e.g., vaporizing the non-polymerized materials and solvent under reduced pressure and at an elevated temperature.
• the ethylene/alkyl (meth)acrylate copolymers used herein may be produced at high pressure and elevated temperature in a tubular reactor or the like, wherein the inherent consequences of dissimilar reaction kinetics for the respective ethylene and alkyl (meth)acrylate (e.g. methyl acrylate) comonomers is alleviated or partially compensated by the intentional introduction of the monomers along the reaction flow path within the tubular reactor.
• a tubular reactor such a tubular reactor
• copolymerization technique will produce a copolymer having a greater relative degree of heterogeneity along the polymer backbone (a more blocky distribution of comonomers), will tend to reduce the presence of long chain branching and will produce a copolymer characterized by a higher melting point than one produced at the same comonomer ratio in a high pressure stirred autoclave reactor.
• the ethylene/alkyl (meth)acrylate copolymers used herein are also available commercially.
• Exemplary ethylene/alkyl (meth)acrylate copolymers may include those available from DuPont under the trade name Elvaloy®; from Arkerma under the trade name LotrylTM; from ExxonMobil Chemicals under the trade name OptemaTM; or from Westlake Chemical Corp under the trade name EMACTM.
• Ethylene/alkyl (meth)acrylate copolymer rubbers also known as AEM rubbers, are derived from copolymerization of ethylene and from above 50 wt% to about 90 wt%, or from above 50 wt% to about 80 wt%, or from above 50 wt% to about 75 wt% of at least one alkyl (meth)acrylate, based on the total weight of the AEM rubber.
• the alkyl (meth)acrylate groups used herein may be selected from those disclosed above in reference to the thermoplastic ethylene/alkyl (meth)acrylate copolymers.
• the AEM rubbers used herein may optionally further comprise up to about 5 wt% of a functionalized comonomer, based on the total weight of the AEM rubber.
• the optional functionalized comonomers used herein include, without limitation,
• (meth)acrylate glycidyl esters such as glycidyl methacrylate
• maleic acids and other comonomers having one or more reactive groups including acid, hydroxyl, epoxy, isocyanates, amine, oxazoline, chloroacetate, or diene functionality.
• the AEM rubbers used herein are made by copolymerizing ethylene and more than one (e.g., two) alkyl (meth)acrylate monomers. Examples are AEM rubbers made by polymerizing ethylene, methyl acrylate, and a second acrylate (such as butyl acrylate).
• the AEM rubbers used herein are also available commercially.
• Exemplary AEM rubbers may include those available from DuPont under the trade name Vamac®.
• thermoplastic ethylene copolymer comprised in the foam composition disclosed herein may be a blend of two or more thermoplastic ethylene copolymers. It is also conceivable that the AEM rubber comprised in the foam composition also may be a blend of two or more AEM rubbers.
• the foam composition disclosed herein based on the combined weight of the thermoplastic ethylene
• thermoplastic ethylene compolymer(s) may be present at a level of about 20-93 wt% and the AEM rubber(s) may be present at a level of about 7-80 wt%.
• thermoplastic ethylene compolymer(s) may be present at a level of about 45-93 wt% and the AEM rubber(s) may be present at a level of about 7-55 wt%.
• thermoplastic ethylene compolymer(s) may be present at a level of about 70-88 wt% and the AEM rubber(s) may be present at a level of about 12-30 wt%.
• the cross-linking agents used herein may be any suitable peroxide.
• peroxide refers to an organic compound that includes one or more peroxide, i.e., O--O, linkages. Suitable peroxides are disclosed, e.g., in Aldrich Catalogue of Fine Chemicals. Heating the peroxide causes it to generate radicals which react with the components of the composition to cause covalent cross-links in the mixture. By regulating the amounts and types of organic peroxide present in the composition, the relative rates of radical generation, abstraction, and cross-linking steps can be controlled.
• peroxide cross-linking agents that are suitable herein include, without limitation, methylethyl ketone peroxide; dicumyl peroxide;
• cross-linking agents used herein are also available commercially.
• Exemplary cross-linking agents may include those available from AkzoNobel Corporate, the Netherlands, under the trade name PerkadoxTM; or from
• DCP cross-linking agents may be obtained from Shanghai Fangruida
• the at least one cross-linking agent may be present in the foam composition at a level of about 0.5-5 wt%, or about 1 -4 wt%, or about 1 .5-3 wt%, relative to the combined weight of the thermoplastic ethylene copolymer(s) and the AEM rubber(s).
• the foaming agent that can be used in the present invention may be a thermally decomposable foaming agent having a decomposition temperature that is equal to or higher than the melting temperature of the foam composition used herein.
• Foaming agents useful herein may be organic or inorganic foaming agents. Exemplary organic foaming agents include, without limitation, azobisformamide; azobisisobutyronitrile; diazoaminobenzene;
• benzene-1 ,3-disulfonyl hydrazide diphenylsulfon-3-3, disulfonyl hydrazide; 4,4'-oxybis benzene sulfonyl hydrazide; p-toluene sulfonyl semicarbizide; barium azodicarboxylate; butylamine nitrile; nitroureas; trihydrazino triazine; phenyl-methyl-uranthan; p-sulfonhydrazide; and combinations of two or more thereof, while exemplary inorganic foaming agents include, without limitation, ammonium bicarbonate, sodium bicarbonate, and combinations thereof.
• foaming agents used herein are also available commercially.
• Exemplary foaming agents may include those available from Hangzhou Hi-Tech Fine Chemical Co. Ltd. China under the product name AC3000.
• the at least one foaming agent may be present in the foam composition at a level of about 0.5-5 wt%, or about 1 -4 wt%, or about 1 .5-3 wt%, relative to the combined weight of the
• the foam composition disclosed herein may optionally further comprise one or more any other suitable additives.
• suitable additives include, without limitation, foaming agent activators, fillers, antioxidant, pigments, stabilizers.
• the total amount of such one or more other suitable additives may be present in the foam composition at a level of up to about 50 wt% or about 25 wt%, relative to the combined weight of the thermoplastic ethylene copolymer(s) and the AEM rubber(s).
• the shoe sole disclosed herein are made from the foam composition disclosed herein by injection molding.
• all components of the foam composition may be first melt blended into an essentially homogeneous composition.
• the ingredients may be mixed and blended by any means known in the art such as Brabender mixer. Those skilled in the art should know how to adjust mixing conditions, such as temperature, shear rate, duration, etc. to ensure homogenization.
• the mixing temperature may be kept at about 60-90°C and the mixing time at about 8-15 min.
• the homogeneous compositions as such obtained may then be pelletized with any suitable shaping machine, such as single screw pelletizers, and the resulting pellets are then injection molded into articles using any suitable molding machine.
• any suitable shaping machine such as single screw pelletizers
• the method of injection molding useful herein is not particularly limited, and any known injection molding method may be employed.
• the foam composition as pelletized is melted by heating, then pressed by a plunger or screw so that it may be poured into a mold until the mold is filled with the composition, and a molded shoe sole is obtained by solidifying or curing the resin composition in the mold.
• usable injection molding methods include the method in which the foam composition is injection molded on an in-line screw system to obtain the injection molded shoe sole disclosed herein.
• AEM Ethylene/methyl acrylate copolymer rubber (with 65 wt% of methyl acrylate) obtained from DuPont under the trade name Vamac®;
• EVM Ethylene/vinyl acetate copolymer rubber (with 70 wt% of vinyl acetate) obtained from Lanxess AG, Germany, under the trade name LevaprenTM 700.
• ECP-1 Ethylene/methyl acrylate copolymer (with 30 wt% of methyl acrylate) obtained from DuPont under the trade name Elvaloy® AC1330;
• ECP-2 Ethylene/vinyl acetate (with 40 wt% of vinyl acetate) obtained from DuPont under the trade name Elvax® 40L-03.
• TiO? Titanium dioxide obtained from DuPont under the trade name Ti-pure® R101 ;
• ZnO Zinc oxide obtained from Guangdong Guanghua Sci-Tech co. Ltd., China;
• Compression set tests were conducted according to the standard ASTM-D-395-B. 50% deformation was employed onto the testing sample before placing the apparatus into an oven at 50°C for 6 hr. For each sample, 3 specimens were prepared and tested to obtain an average compression set reading.
• Hardness tests were conducted according to the Type C hardness test outlined in standard JIS K 7312 (1996), with the sample thickness at 12 mm. For each sample, 3 specimens were prepared and tested to obtain an average hardness reading.
• resin pellets were prepared as follows. First, all components comprised in each example (listed in Table 1 ) were mixed in a Brabender mixer set at about 80°C-90°C for about 10 min or until homogeneous resin compositions were obtained. Thereafter, the resin compositions in each example were pelletized using a single screw pelletizer at 100°C. The pellets were examined visually to obtain each sample's processability rating.
• the pellets as such obtained were fed into the feeder of an injection molding machine (KS-0901 ULYL from King Steel Machinery Co., Ltd., Taiwan and further mixed under screw shear at different zones set at 60rpm/88-88-88-85°C.
• the mixtures coming out of the nozzles were then ejected to and maintained in the mold (with the mold temperature set at 175°C) for 400s, followed by going through a step-by-step cooling tunnel (60-50-40-30°C) for 5min, to obtain the final foam product.
• the foam products were then subjected to resilience, compression set, hardness, and density tests.
• thermoplastic ethylene copolymers CE1 and CE4
• the processability thereof was excellent, it would still be desirable to have further improved resilience further reduced compression set.
• thermoplastic ethylene copolymer with about 7-80 wt% of AEM rubbers (E1 -E7), the resilience thereof was improved and the compression set thereof was reduced while the processability thereof remains from acceptable to excellent).
• the pellets (except the ones in CE13) were molded into foam products similarly as those described above in reference to CE1 .
• the foam products were then subjected to resilience, compression set, hardness, and density tests.
• thermoplastic ethylene copolymers with EVM rubbers, although processability remains acceptable to excellent and the compression set got reduced, the resilience thereof could not be improved consistently.
• thermoplastic ethylene copolymers with ACM rubbers although processability remains acceptable to excellent, the compression set thereof could not be reduced consistently and the resilience thereof could not be improved consistently.

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