WO2013053189A1 - Mousse d'eva modifiée et son procédé de préparation et son utilisation - Google Patents

Mousse d'eva modifiée et son procédé de préparation et son utilisation Download PDF

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Publication number
WO2013053189A1
WO2013053189A1 PCT/CN2012/000596 CN2012000596W WO2013053189A1 WO 2013053189 A1 WO2013053189 A1 WO 2013053189A1 CN 2012000596 W CN2012000596 W CN 2012000596W WO 2013053189 A1 WO2013053189 A1 WO 2013053189A1
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Prior art keywords
foam
core
powder
acetate copolymer
agent
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Application number
PCT/CN2012/000596
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English (en)
Chinese (zh)
Inventor
郝新敏
甘舸
张建春
赵鹏程
黄杰
Original Assignee
李宁（中国）体育用品有限公司
中国人民解放军总后勤部军需装备研究所
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Publication of WO2013053189A1 publication Critical patent/WO2013053189A1/fr

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    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
    • A43B13/18—Resilient soles
    • A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0033—Use of organic additives containing sulfur
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • 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
    • 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
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

  • the invention relates to a modified EVA foam and a preparation method and application thereof. Background technique
  • the ethylene vinyl acetate copolymer (referred to as EVA) is a product obtained by plasticating and granulating EVA raw materials at a high temperature and then ejecting them through a pipe to a mold and then foaming them outside the mold.
  • the sole of a sports shoe is composed of a foamed midsole and a wear-resistant rubber outsole. Because of the good plasticity, elasticity, and processability of ethylene and vinyl acetate copolymer (EVA), the material density after foaming is small, and the mechanical properties. Good, easy to color and so on. At present, the midsole or insole of most sports shoes is made of EVA foam.
  • An object of the present invention is to provide a modified EVA foam and a preparation method and application thereof.
  • the modified EVA foam provided by the present invention comprises an ethylene vinyl acetate copolymer, a polyolefin elastomer (abbreviated as P0E), a lignocellulose powder, a foaming agent, a bridging agent, an active agent, and zinc oxide.
  • P0E polyolefin elastomer
  • the above modified EVA foam may also be composed only of the above components.
  • the ethylene vinyl acetate copolymer has a number average molecular weight of 400-4000, preferably 800-2000, and the ethylene ethyl acetate copolymer has a mass percentage of ethyl acetate (VA) of 10-21%. Preferably 16-19%; the polyolefin elastomer has a number average molecular weight of 400-4000, preferably 600-2000;
  • the lignocellulose powder is selected from at least one of a softwood plant stalk core powder, a hardwood plant stalk core powder, and a grass stalk core powder, preferably a hemp core, a hemp stalk core, At least one of a jute core, a linen core, a sisal core, a ramie core, and a bamboo, the lignocellulose powder having a particle diameter of 200 mesh to 1000 mesh, preferably 400 to 800 mesh, more preferably 500.
  • the blowing agent is at least one selected from the group consisting of azodicarbonamide, p-toluenesulfonylhydrazide and azodimethylamine, preferably azodicarbonamide;
  • the bridging agent is selected from at least one of dicumyl peroxide (DCP), sulfur and di-tert-butyl peroxide, preferably dicumyl peroxide;
  • DCP dicumyl peroxide
  • sulfur and di-tert-butyl peroxide preferably dicumyl peroxide
  • the active agent is selected from at least one of stearic acid, magnesium carbonate and calcium oxide, preferably stearic acid.
  • the ethylene ethyl acetate copolymer, the polyolefin elastomer, the lignocellulose powder, the The mass ratio of the blowing agent, the bridging agent, the active agent and the zinc oxide is 70: 30: 20-80: 3. 0-5. 0: 0. 4-1. 0: 1. 0 -3. 0: 0. 5-2. 5, preferably 70: 30: 40-70: 3. 5-4. 5: 0. 6-0. 8: 2-2. 5: 1-1. 5, More preferably 70: 30: 50: 4: 0. 6: 2: 1.
  • the method for producing the foam provided by the present invention comprises the steps of: vulcanizing and molding the above components to obtain the foam.
  • the temperature is 165 to 175 ° C, preferably 168 to 175 ° C, more preferably 175 ° C, and the time is 5 to 15 minutes, preferably 6 to 10 minutes, more preferably 6 minutes.
  • the method for preparing the foam further includes the following steps: before the vulcanization step, the manner of mixing in the mixing step may be kneading, and may include the following steps.
  • the mixing time is 0. 2, the mixing time is 0. 2, the mixing time is 0. 2, the mixing time can be 0. 2 Hours), at the same time, the blowing agent, bridging agent, active agent and zinc oxide are mixed in another internal mixer (in this step, the temperature does not exceed 70 ° C, the mixing temperature is 100-110 ° C, The mixing time is 0.1 hour).
  • the use of the foam provided by the present invention in the preparation of a sole, and the sole based on the foam, are also within the scope of the present invention.
  • the sole is a midsole or a sole.
  • the modified foam EVA of the invention not only has light weight performance, but also has better durability, and the sole made of the shoe has light weight and good durability, and can be suitably used for durability. Outsole of shoes.
  • the invention adopts ethylene vinyl acetate copolymer (EVA), polyolefin elastomer (P0E) and lignocellulosic powder as main compound, and is prepared by kneading, granulating and injection vulcanization.
  • EVA ethylene vinyl acetate copolymer
  • P0E polyolefin elastomer
  • lignocellulosic powder as main compound, and is prepared by kneading, granulating and injection vulcanization.
  • the modified EVA foam has a specific gravity of less than 0.2, a light weight, a compression resistance of less than 50%, and can withstand wearing for a long period of time.
  • the midsole of the modified foam is light and durable. It has good performance and is suitable for all kinds of sports and casual shoes. It has important application value. detailed description
  • EVA7350 70 parts by weight of a commercial name of EVA7350, an ethylene vinyl acetate copolymer having a number average molecular weight of 800-2000 (in which the mass percentage of ethyl acetate (VA) is 18%), and 30 parts by weight POE8003, a polyolefin elastomer having a number average molecular weight of 600-2000 and 50 parts by weight of a heparin core powder having a particle size of 500 mesh are put into an internal mixer, and the temperature of the mill is not more than 70 during the kneading process. 2 ⁇ ; The mixing time is 0. 2 hours;
  • the modified EVA foam obtained in the preparation of Examples 2-7 was obtained by merely replacing the components in the same manner as in the above, in the same manner as in the above.
  • the modified foam EVA provided by the present invention not only has light weight performance, but also has better durability, and the sole made of the shoe has light weight and good durability. It can be applied to a shoe midsole with a high durability requirement.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Biochemistry (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne une mousse d'EVA modifiée, et son procédé de préparation et son utilisation. La mousse d'EVA modifiée comprend un copolymère éthylène-acétate de vinyle, un élastomère de polyoléfine, une poudre de lignocellulose, un moussant, un agent de réticulation, un activateur et de l'oxyde de zinc. Le rapport en masse entre le copolymère éthylène-acétate de vinyle, l'élastomère de polyoléfine, la poudre de lignocellulose, le moussant, l'agent de réticulation, l'activateur et l'oxyde de zinc est de 70:30:20-80:3,0-5,0:0,4-1.0:1,0-3,0:0,5-2,5. La mousse d'EVA modifiée a un poids spécifique inférieur à 0,2, une masse légère, une déformation par compression inférieure à 50 %, et peut résister à l'usure pendant une longue période. La semelle intérieure de chaussure fabriquée avec la mousse modifiée est légère, durable et convient à diverses semelles intérieures et à divers talons pour chaussures athlétiques et de loisirs, et présente une applicabilité importante.
PCT/CN2012/000596 2011-10-11 2012-05-02 Mousse d'eva modifiée et son procédé de préparation et son utilisation WO2013053189A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201110306439.3 2011-10-11
CN2011103064393A CN102504398B (zh) 2011-10-11 2011-10-11 改性eva发泡体及其制备方法与应用

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WO2013053189A1 true WO2013053189A1 (fr) 2013-04-18

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Cited By (2)

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US20170066893A1 (en) * 2015-09-09 2017-03-09 Bloom Holdings LLC Algae-derived flexible foam, and method of manufacturing the same
WO2017087895A1 (fr) * 2015-11-19 2017-05-26 Bloom Holdings, Llc Mousse souple dérivée d'algues, et son procédé de fabrication

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CN102816374B (zh) * 2012-09-04 2014-03-12 苏州伟伦运动休闲用品有限公司 轻量化eva中底及其生产方法
CN102863644B (zh) * 2012-10-23 2013-12-11 南通市黄海电机有限公司 发泡橡胶的制备方法
CN103027436B (zh) * 2012-11-08 2015-07-01 际华三五一五皮革皮鞋有限公司 一种汉麻成型内底的制备方法
CN103146051A (zh) * 2013-02-04 2013-06-12 宝成工业股份有限公司 含改质天然纤维的生质高分子材料及其制造方法
CN103275405B (zh) * 2013-06-21 2016-01-20 福建省晋江市晋亿鞋材有限公司 一种改性eva微孔发泡鞋垫材料及其制备方法
CN103360674B (zh) * 2013-07-26 2015-10-14 福州大学 一种木粉复合发泡材料及其制备方法
CN104610563A (zh) * 2013-11-05 2015-05-13 晋江凯基高分子材料有限公司 一种烯烃嵌段共聚物材料发泡体的制备方法与应用
CN104774481A (zh) * 2014-01-09 2015-07-15 晋江凯基高分子材料有限公司 茂金属热可塑弹性体发泡体循环再利用的制备方法与应用
CN103910925B (zh) * 2014-04-21 2016-02-03 南京东亚橡塑制品有限公司 一种用作鞋底的无味eva材料及其制备方法
CN104277316B (zh) * 2014-08-07 2017-03-22 茂泰(福建)鞋材有限公司 一种防滑eva鞋底及其制备方法
CN104231415A (zh) * 2014-10-08 2014-12-24 金猴集团威海鞋业有限公司 一种汉麻杆粉改性eva发泡鞋材及其制备方法
TWI576384B (zh) * 2014-11-25 2017-04-01 鴻明環保科技股份有限公司 高植物源含量之乙烯-醋酸乙烯共聚物混合物發泡材料、其製造方法及應用
CN105462049A (zh) * 2015-12-23 2016-04-06 上海大学 汉麻秆芯粉体改性eva复合发泡材料及其制备方法
CN105623066A (zh) * 2016-02-25 2016-06-01 苏州市景荣科技有限公司 一种抑菌透气的发泡鞋垫材料的制造方法
CN105924761B (zh) * 2016-06-27 2018-09-04 湖北福力德鞋业有限责任公司 一种植物纤维粉体改性eva复合发泡材料及其制备方法
CN106117766B (zh) * 2016-06-27 2018-08-24 湖北福力德鞋业有限责任公司 一种高回弹耐老化eva发泡材料及其制备方法
CN106117765B (zh) * 2016-06-27 2019-09-27 中国人民解放军总后勤部军需装备研究所 一种复合鞋底及其制备方法
CN106108246B (zh) * 2016-06-27 2017-11-21 中国人民解放军总后勤部军需装备研究所 一种梯度功能的复合鞋垫及其制备方法
CN106174870A (zh) * 2016-07-26 2016-12-07 中央军委后勤保障部军需装备研究所 一种多密度轻质弹性鞋底及其制作方法
CN107118426A (zh) * 2017-06-12 2017-09-01 江苏天有贸易有限公司 Eva/橡胶共混物鞋底材配方及其制备方法

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