WO2013053189A1 - Modified eva foam and preparation method and use thereof - Google Patents

Modified eva foam and preparation method and use thereof 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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foam
core
powder
acetate copolymer
agent
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PCT/CN2012/000596
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French (fr)
Chinese (zh)
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郝新敏
甘舸
张建春
赵鹏程
黄杰
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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/en

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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)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

Disclosed are a modified EVA foam, and a preparation method and a use thereofThe modified EVA foam comprises ethylene vinyl acetate copolymer, polyolefin elastomer, lignocellulose powder, foamer, crosslinker, activator, and zinc oxide. The mass ratio of the ethylene vinyl acetate copolymer, the polyolefin elastomer, the lignocellulose powder, the foamer, the crosslinker, the activator, 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. The modified EVA foam has a specific weight of less than 0.2, a light mass, a compression deformation of less than 50％, and can withstand wear for a long time. The shoe insole made by the modified foam is lightweight, durable, and suitable for a variety of insoles and foot pads for shoes of athletic and leisure type, and has an important application value.

Description

改性 EVA发泡体及其制备: 与应用  Modified EVA foam and its preparation: and application
技术领域 Technical field
本发明涉及一种改性 EVA发泡体及其制备方法与应用。 背景技术  The invention relates to a modified EVA foam and a preparation method and application thereof. Background technique
射出乙烯醋酸乙酯共聚物 （简称 EVA) 是将 EVA原材料塑炼造粒高温熔融后， 通过管道射出到模具， 继而在模外发泡得到的产品。 一般运动鞋的鞋底是由发泡 中底和耐磨橡胶大底组成， 由于乙烯与醋酸乙烯共聚物（EVA)具有很好的可塑性、 弹性、 可加工性， 发泡后材料密度小、 力学性能好、 易着色等优点。 目前绝大多 数运动鞋的中底或鞋垫采用 EVA发泡材料。  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.
一般射出 EVA产品存在收縮和压縮变形严重等缺点， 对后续的生产和使用有 很大的障碍和局限， 因此， 需要一种新的改性 EVA发泡体。 发明内容  Generally, EVA products have shortcomings such as shrinkage and severe compression deformation, which have great obstacles and limitations for subsequent production and use. Therefore, a new modified EVA foam is needed. Summary of the invention
本发明的目的是提供一种改性 EVA发泡体及其制备方法与应用。  SUMMARY OF THE INVENTION An object of the present invention is to provide a modified EVA foam and a preparation method and application thereof.
本发明提供的改性 EVA发泡体，包括乙烯醋酸乙酯共聚物、聚烯烃弹性体（简 称 P0E)、 木质纤维素粉体、 发泡剂、 架桥剂、 活性剂和氧化锌。  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.
上述改性 EVA发泡体也可只由上述组分组成。  The above modified EVA foam may also be composed only of the above components.
其中， 所述乙烯醋酸乙酯共聚物的数均分子量为 400-4000， 优选 800-2000， 所述乙烯醋酸乙酯共聚物中醋酸乙酯 (VA)的质量百分含量为 10-21%,优选 16-19%; 所述聚烯烃弹性体的数均分子量为 400-4000， 优选 600-2000 ;  Wherein, 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;
所述木质纤维素粉体选自针叶材植物秆芯粉体、 阔叶材植物秆芯粉体和禾本 科植物秆芯粉体中的至少一种， 优选大麻杆芯、 汉麻秆芯、 黄麻杆芯、 亚麻杆芯、 剑麻杆芯、 苎麻杆芯和竹子中的至少一种， 所述木质纤维素粉体的粒径为 200 目 -1000目， 优选 400-800目， 更优选 500目；  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. Project
所述发泡剂选自偶氮二甲酰胺、对甲苯磺酰肼和偶氮二甲硫胺中的至少一种， 优选偶氮二甲酰胺；  The blowing agent is at least one selected from the group consisting of azodicarbonamide, p-toluenesulfonylhydrazide and azodimethylamine, preferably azodicarbonamide;
所述架桥剂选自过氧化二异丙苯 （DCP)、 硫磺和二叔丁基过氧化物中的至少 一种， 优选过氧化二异丙苯；  The bridging agent is selected from at least one of dicumyl peroxide (DCP), sulfur and di-tert-butyl peroxide, preferably dicumyl peroxide;
所述活性剂选自硬脂酸、 碳酸镁和氧化钙中的至少一种， 优选硬脂酸。  The active agent is selected from at least one of stearic acid, magnesium carbonate and calcium oxide, preferably stearic acid.
所述乙烯醋酸乙酯共聚物、 所述聚烯烃弹性体、 所述木质纤维素粉体、 所述 发泡剂、所述架桥剂、所述活性剂和所述氧化锌的质量比为 70 : 30: 20-80: 3. 0-5. 0： 0. 4-1. 0： 1. 0-3. 0： 0. 5-2. 5， 优选 70: 30： 40-70： 3. 5-4. 5: 0. 6-0. 8: 2-2. 5: 1-1. 5， 更优选 70: 30： 50： 4： 0. 6: 2： 1。 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.
本发明提供的制备所述发泡体的方法， 包括如下步骤： 将前述各组分混合后 进行硫化成型， 得到所述发泡体。  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.
该方法所述硫化步骤中，温度为 165-175°C， 优选 168-175°C， 更优选 175°C， 时间为 5〜15分钟， 优选 6-10分钟， 更优选 6分钟。  In the vulcanization step of the method, 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.
另外， 为了使各组分混合得更加均匀， 所述制备发泡体的方法， 还包括如下 步骤： 在所述硫化步骤之前， 所述混合步骤中混合的方式可为混炼， 可包括如下 步骤： 将 EVA、 乙烯醋酸乙酯共聚物、 P0E和木质纤维素粉体进行混炼（该步骤中， 温度不超过 70度， 混炼温度为 80-100°C， 混炼时间可为 0. 2小时）， 同时将发泡 剂、 架桥剂、 活性剂和氧化锌于另一密炼机中进行混炼 （该步骤中， 温度不超过 70°C， 混炼温度为 100-110°C， 混炼时间为 0. 1小时）。  In addition, in order to make the components more uniformly mixed, 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).
上述本发明提供的发泡体在制备鞋底中的应用，及以所述发泡体为底的鞋底， 也属于本发明的保护范围。 其中， 所述鞋底为鞋中底或鞋大底。  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. Wherein, the sole is a midsole or a sole.
本发明改性发泡体 EVA不仅具有较轻重量的性能， 而且还具有较佳的耐久性 能， 由其制成的鞋中底重量轻、 耐久性好， 可适用于用作耐久性能要求较高的鞋 大底。  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.
本发明采用乙烯醋酸乙酯共聚物（EVA)、 聚烯烃弹性体（P0E)和木质纤维素 粉体为主体胶料， 经混炼、造粒和射出硫化制成。该改性 EVA发泡体的比重在 0. 2 以下， 质量轻， 耐压縮歪在 50 %以下， 能经受长时间的穿着， 以该改性发泡体制 备的鞋中底轻质、 耐久性能佳， 适用于各种竞技类和休闲类的鞋中底， 具有重要 的应用价值。 具体实施方式  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. 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
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。 所述方法如无特别说明均为常规方法。 所述材料如无特别说明均能从公开商业途 径而得。 实施例 1、 制备改性 EVA发泡体  The invention is further illustrated by the following specific examples, but the invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The materials are available from publicly available sources unless otherwise stated. Example 1. Preparation of modified EVA foam
将 70重量份的商品名为 EVA7350、 数均分子量为 800-2000的乙烯醋酸乙酯 共聚物 （其中醋酸乙酯 （VA ) 的质量百分含量为 18%)、 30 重量份的商品名为 POE8003,数均分子量为 600-2000的聚烯烃弹性体和 50重量份的粒径为 500目的 汉麻杆芯粉体投入密炼机中混炼， 混炼过程中， 开炼机温度不超过 70度， 混炼温 度为 80-100°C， 混炼时间为 0. 2小时； 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小时; The mixing time is 0. 2 hours;
同时将 4重量份的商品名为 AC3000的发泡剂偶氮二甲酰胺、 0. 6重量份的架 5 桥剂过氧化二异丙苯（DCP)、 2重量份的活性剂硬脂酸和 1重量份的氧化锌投入另 一密炼机中混炼， 混炼过程中， 开炼机温度不超过 70°C， 混炼温度为 100-110°C， 混炼时间为 0. 1小时；  At the same time, 4 parts by weight of the foaming agent azodicarbonamide of the trade name AC3000, 0.6 parts by weight of the bridged agent dicumyl peroxide (DCP), 2 parts by weight of the active agent stearic acid and 1小时; The mixing time is 0.1 hour; the mixing time is 0.1 hour; the mixing time is 0. 1 hour;
混炼完毕后将所有原料于 iio°c进行排料， 排料后在开炼机台继续薄通， 然 后造粒干燥后， 通过射出机注入模具后硫化， 硫化温度为 175°C， 时间为 6分钟， 0 硫化后于定型烘箱中成型后， 得到本发明的改性 EVA发泡体。  After the mixing is completed, all the raw materials are discharged at iio °c, and after discharging, the thinning is continued on the open mill, and then granulated and dried, and then vulcanized by injection into the mold through an injection machine, and the vulcanization temperature is 175 ° C, and the time is After 6 minutes, after vulcanization, it was molded in a shaping oven to obtain a modified EVA foam of the present invention.
按照与上完全相同的步骤， 仅将各组分按照表 1所列重量份数进行替换， 得 到实施例 2-7制备所得的改性 EVA发泡体。  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.
表 1、 实施例 1-7制备改性 EVA发泡体中各原料的重量份数列表  Table 1. Examples 1-7 Preparation of modified EVA foams List of parts by weight of each raw material
Figure imgf000004_0002
Figure imgf000004_0002
经测定， 实施例广 7制备所得改性 EVA发泡体的物性如表 2所示。 The physical properties of the modified EVA foam obtained by the preparation of Example 7 were as shown in Table 2.
5 表 2、 实施例广 7制备所得改性 EVA发泡体的物性列表
Figure imgf000004_0001
测试方 5 Table 2, the physical properties of the modified EVA foam obtained by the preparation of Example 7
Figure imgf000004_0001
Test party
GB/T533- 91 GB/T531- 99 GB/T528-92 GB/T528-92 GB/T529-99 ASTM D395 法  GB/T533- 91 GB/T531- 99 GB/T528-92 GB/T528-92 GB/T529-99 ASTM D395 method
1 0. 19 55 26 272 19. 5 48 1 0. 19 55 26 272 19. 5 48
2 0. 19 56 26 275 18 442 0. 19 56 26 275 18 44
3 0. 18 53 25 280 18. 5 453 0. 18 53 25 280 18. 5 45
4 0. 19 55 25 271 16 414 0. 19 55 25 271 16 41
5 0. 19 55 26 277 19 465 0. 19 55 26 277 19 46
6 0. 19 56 25 252 18. 5 446 0. 19 56 25 252 18. 5 44
7 0. 19 56 26 260 16. 2 43 另改性 EVA发泡体的物性标准如表 3所示。 7 0. 19 56 26 260 16. 2 43 The physical properties of the modified EVA foam are shown in Table 3.
表 3、 改性 EVA发泡体的物性标准
Figure imgf000005_0001
Table 3. Physical property standards of modified EVA foams
Figure imgf000005_0001
由表 2和表 3可知，本发明提供的改性发泡体 EVA不仅具有较轻重量的性能， 而且还具有较佳的耐久性能， 由其制成的鞋中底重量轻、 耐久性好， 可适用于用 5 作耐久性能要求较高的鞋中底。  It can be seen from Table 2 and Table 3 that 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.

Claims

权利要求 Rights request
1、 一种改性 EVA发泡体， 包括乙烯醋酸乙酯共聚物、 聚烯烃弹性体、 木质纤 维素粉体、 发泡剂、 架桥剂、 活性剂和氧化锌。 A modified EVA foam comprising ethylene vinyl acetate copolymer, polyolefin elastomer, lignocellulosic powder, foaming agent, bridging agent, active agent and zinc oxide.
2、 根据权利要求 1所述的发泡体， 其特征在于： 所述改性 EVA发泡体由所述 乙烯醋酸乙酯共聚物、 聚烯烃弹性体、 木质纤维素粉体、 发泡剂、 架桥剂、 活性 剂和氧化锌组成。  The foam according to claim 1, wherein the modified EVA foam is composed of the ethylene vinyl acetate copolymer, a polyolefin elastomer, a lignocellulose powder, a foaming agent, It is composed of a bridging agent, an active agent and zinc oxide.
3、 根据权利要求 1或 2所述的发泡体， 其特征在于： 所述乙烯醋酸乙酯共聚 物的数均分子量为 400-4000， 优选 800-2000， 所述乙烯醋酸乙酯共聚物中醋酸乙 酯的质量百分含量为 10-21%， 优选 16-19%;  The foam according to claim 1 or 2, wherein the ethylene vinyl acetate copolymer has a number average molecular weight of from 400 to 4,000, preferably from 800 to 2,000, in the ethylene ethyl acetate copolymer. The mass percentage of ethyl acetate is 10-21%, preferably 16-19%;
所述聚烯烃弹性体的数均分子量为 400-4000， 优选 600-2000;  The polyolefin elastomer has a number average molecular weight of 400-4000, preferably 600-2000;
所述木质纤维素粉体选自针叶材植物秆芯粉体、 阔叶材植物秆芯粉体和禾本 科植物秆芯粉体中的至少一种， 优选大麻杆芯、 汉麻秆芯、 黄麻杆芯、 亚麻杆芯、 剑麻杆芯、 苎麻杆芯和竹子中的至少一种， 所述木质纤维素粉体的粒径为 200 目 -1000目， 优选 400-800目， 更优选 500目；  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. Project
所述发泡剂选自偶氮二甲酰胺、对甲苯磺酰肼和偶氮二甲硫胺中的至少一种， 优选偶氮二甲酰胺；  The blowing agent is at least one selected from the group consisting of azodicarbonamide, p-toluenesulfonylhydrazide and azodimethylamine, preferably azodicarbonamide;
所述架桥剂选自过氧化二异丙苯、 硫磺和二叔丁基过氧化物中的至少一种， 优选过氧化二异丙苯；  The bridging agent is selected from at least one of dicumyl peroxide, sulfur and di-tert-butyl peroxide, preferably dicumyl peroxide;
所述活性剂选自硬脂酸、 碳酸镁和氧化钙中的至少一种， 优选硬脂酸。  The active agent is selected from at least one of stearic acid, magnesium carbonate and calcium oxide, preferably stearic acid.
4、 根据权利要求 1-3任一所述的发泡体， 其特征在于： 所述乙烯醋酸乙酯共 聚物、 所述聚烯烃弹性体、 所述木质纤维素粉体、 所述发泡剂、 所述架桥剂、 所 述活性剂和所述氧化锌的质量比为 70: 30： 20-80： 3. 0-5. 0: 0. 4-1. 0： 1. 0-3. 0: 0. 5-2. 5， 优选 70: 30： 40-70： 3. 5-4. 5 : 0. 6-0. 8: 2-2. 5: 1-1. 5， 更优选 70: 30： 50： 4： 0. 6： 2： 1。  The foam according to any one of claims 1 to 3, wherein: the ethylene vinyl acetate copolymer, the polyolefin elastomer, the lignocellulose powder, and the foaming agent The mass ratio of 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.
5、 根据权利要求 1-4任一所述的发泡体， 其特征在于： 所述发泡体是按照权 利要求 6或 Ί所述方法制备而得。  The foam according to any one of claims 1 to 4, wherein the foam is produced by the method according to claim 6 or Ί.
6、 一种制备权利要求 1-4任一所述发泡体的方法， 包括如下步骤： 将权利要 求 1-4任一所述组分混合后进行硫化成型， 得到所述发泡体。  A method of producing the foam according to any one of claims 1 to 4, comprising the steps of: mixing the components according to any one of claims 1 to 4 and vulcanizing molding to obtain the foam.
7、 根据权利要求 6 所述的方法， 其特征在于： 所述硫化步骤中， 温度为 7. The method according to claim 6, wherein: in the vulcanization step, the temperature is
165- 175°C， 优选 168- 175°C， 更优选 175°C， 时间为 5〜15分钟， 优选 6-10分钟， 更优选 6分钟。 165-175 ° C, preferably 168-175 ° C, more preferably 175 ° C, time is 5 to 15 minutes, preferably 6-10 minutes, more preferably 6 minutes.
8、 权利要求 1-4任一所述发泡体在制备鞋底或鞋垫中的应用。 8. Use of a foam according to any of claims 1-4 in the preparation of a sole or insole.
9、 以权利要求 1-4任一所述发泡体为底的鞋底。  9. A foam sole-based sole according to any of claims 1-4.
10、 根据权利要求 8所述的应用或权利要求 9所述的鞋底， 其特征在于： 所 述鞋底为鞋中底或鞋大底。  10. A sole according to claim 8 or a sole according to claim 9, wherein: the sole is a midsole or a outsole.
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