WO2019085008A1 - 一种鞋底用高回弹组合物发泡材料及其制备方法 - Google Patents

一种鞋底用高回弹组合物发泡材料及其制备方法 Download PDF

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Publication number
WO2019085008A1
WO2019085008A1 PCT/CN2017/110801 CN2017110801W WO2019085008A1 WO 2019085008 A1 WO2019085008 A1 WO 2019085008A1 CN 2017110801 W CN2017110801 W CN 2017110801W WO 2019085008 A1 WO2019085008 A1 WO 2019085008A1
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Prior art keywords
parts
foaming
weight
eva
high resilience
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PCT/CN2017/110801
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English (en)
French (fr)
Inventor
王光阜
战振生
宋红玮
张生
王仁鸿
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美瑞新材料股份有限公司
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Publication of WO2019085008A1 publication Critical patent/WO2019085008A1/zh

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    • 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
    • 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
    • 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
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • 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
    • C08J9/08—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 carbon dioxide
    • 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
    • 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
    • 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
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/06—Polyurethanes from polyesters
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/08—Polyurethanes from polyethers

Definitions

  • the invention relates to a foaming material and a preparation method thereof, in particular to a high resilience composition foaming material for a sole and a preparation method thereof, and belongs to the technical field of lightweight materials.
  • EVA Ethylene Vinyl Acetate
  • Foamed EVA is the main material of the sole material, especially the sole material of sports shoes. It has the advantages of light weight, softness and comfortable wearing, but the EVA sole foaming material with high expansion ratio is foamed EVA material after being worn for a long time. The resilience loss is very large, and the permanent deformation is large, the mechanical properties are seriously degraded, and the wear resistance is poor, which seriously affects its application in the field of shoe materials. Therefore, the development of an EVA foam material for soles with excellent resilience and high expansion ratio has become a goal pursued by many universities and enterprises.
  • the invention aims at a deficiency of high foaming ratio EVA sole material, and provides a high resilience composition foaming material for a sole and a preparation method thereof.
  • a high resilience composition foaming material for a sole characterized in that, by weight, the following components are included:
  • thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy can be prepared by any of the following methods:
  • TPU raw material 100 parts by weight of the TPU raw material is premixed and added to the feed port of the twin-screw extruder, and 5 to 95 parts by weight of the ethylene-vinyl acetate copolymer and 0.1 to 10 parts by weight of the double active material are passed through the side.
  • the feed is injected into the twin-screw extruder without prior sequence, 0.1-5 parts by weight of the auxiliary agent is added to the TPU raw material or the mixture of the ethylene-vinyl acetate copolymer and the double active material;
  • the second method comprises the steps of: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of the double active material and 0.1-5 parts by weight of the auxiliary agent, and processing the mixture through an extruder. After granulation, it is obtained;
  • the third method comprises the steps of: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of the double active material and 0.1-5 parts by weight of the auxiliary agent, and processing the mixture through an open mill. After granulation, it is obtained;
  • Method 4 comprising the steps of: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of the double active material, and 0.1-5 parts by weight of the auxiliary agent, and processing the mixture through an internal mixer. After granulation, it is obtained;
  • the bis-active substance is a compound containing one or more of an acid anhydride group, a carboxyl group-COOH, a hydroxy-OH group, an amino-NH group or a -NH 2 group, an isocyanate group-NCO group, and an epoxy group. Includes initiator.
  • the EVA materials of the present invention are well known and are conventional grades used in the field of expanded footwear, such as available from DuPont.
  • the double active material is maleic anhydride, glycidyl methacrylate, propylene One of acid, methyl methacrylate, butyl acrylate, acrylamide, allyl polyethylene glycol, amino acid, epoxy resin.
  • the TPU raw material described in the first method comprises a polymer polyol, a chain extender and an isocyanate
  • the polymer polyol is a polyester polyol, a polyether polyol, a polycaprolactone polyol, a polycarbonate polyol a compounding of one or more of an alcohol, a hydroxyl terminated polybutadiene diol, wherein the chain extender is a small molecule diol or a diamine having 12 or less carbon atoms
  • the isocyanate is Is one of toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, hexamethylene diisocyanate HDI, dicyclohexylmethane diisocyanate H12MDI, isophorone diisocyanate IPDI, benzene dimethylene diisocyanate XDI Or a plurality of compounding methods, method 2, method 3, method 4, the hardness of the T
  • the ethylene-vinyl acetate copolymer in the thermoplastic polyurethane/ethylene-vinyl acetate alloy has a vinyl acetate content of 10 to 80% by weight, preferably, the content of vinyl acetate is 20 to 50% by weight, and most preferably the content of vinyl acetate is 25- 45%.
  • the foaming agent is a mixture of one or more of an exothermic foaming agent, an endothermic foaming agent, and foamed microspheres.
  • the foaming agent refers to azomethicone. Amide, azobisisobutyronitrile, hydrazine azodicarboxylate, 4,4'-oxobisbenzenesulfonyl hydrazide, p-toluenesulfonylhydrazide, sodium hydrogencarbonate, sodium citrate, ammonium hydrogencarbonate, expandable microspheres a mixture of one or more of the following, wherein the expandable microspheres are well known, for example, from AKZO Nobel Industries series.
  • the crosslinking agent is dicumyl peroxide, di-tert-butylperoxyisopropylbenzene, azobisisobutyronitrile, azoisobutylcyanocarboxamide, azodicyclohexylmethane, a mixture of one or more of dimethyl azobisisobutyrate.
  • the filler is a mixture of one or more of talc, calcium carbonate, clay, sulfate, and toner.
  • composition foaming material further comprises an antioxidant, a lubricant, a UV-resistant auxiliary agent, a co-crosslinking agent and a foaming accelerator, wherein the co-crosslinking agent contains two or more carbon-carbon double bonds.
  • the compound, the foaming accelerator is any one of zinc oxide and zinc stearate.
  • the invention also claims a method for preparing the above-mentioned high resilience composition foaming material, comprising the following steps:
  • the mixture obtained in the step 1) is put into the internal mixer and kneaded uniformly, the mixing time is controlled for 5-25 minutes, and the kneading temperature is 100-150 ° C to obtain the first-stage kneaded product;
  • the second-stage kneaded material obtained in step 3) is placed in the mold of the sole product, and then placed in a flat vulcanizing machine for molding foaming, the foaming temperature is 100-200 ° C, and foaming The time is 1-10 minutes, and then the mold is cooled to 10-50 ° C to obtain a foamed sole material of high resilience EVA composition; or the second-stage kneaded material obtained in step 3) is put into a foamed shoe which is shot once.
  • One shot foaming was carried out in the material equipment, and the injection temperature was controlled at 120-180 ° C to obtain a foamed sole material of a high resilience EVA composition.
  • the one-shot foamed shoe material apparatus described in the step 4) refers to an injection foam molding machine.
  • the high resilience composition foaming material provided by the invention and the preparation method thereof have the following beneficial effects:
  • the high resilience composition foaming material for soles according to the present invention uses a TPU/EVA alloy to act as a compatibilizer, forming an EVA/TPU interpenetrating network structure (IPN) in a conventional EVA foaming system.
  • the TPU component was introduced to solve the performance of the final composition foaming material due to poor compatibility. Falling problem;
  • a process for preparing a TPU alloy material comprising the steps of:
  • a process for preparing a TPU alloy material comprising the steps of:
  • a process for preparing a TPU alloy material comprising the steps of:
  • a process for preparing a TPU alloy material comprising the steps of:
  • a process for preparing a TPU alloy material comprising the steps of:
  • a process for preparing a TPU alloy material comprising the steps of:
  • a process for preparing a TPU alloy material comprising the steps of:
  • a process for preparing a TPU alloy material comprising the steps of:
  • TPU/EVA alloy materials obtained in Example 7 and Example 8 were applied to the high resilience composition.
  • the specific composition, preparation method and properties of the composition are as follows:
  • a high resilience composition foaming material for a sole comprising, by weight, the following components:
  • the preliminary mixed mixture in the step 1) is put into the internal mixer and kneaded uniformly, the kneading temperature is set to 100 ° C, and the mixture is kneaded for 10 minutes to obtain a first-stage kneaded product;
  • the second kneading the first-stage kneaded material obtained in the step 2) is put into an open mill for the second kneading, the refining temperature is set to 100 ° C, and the kneading is carried out for 5 minutes to obtain the second-stage kneading.
  • Foaming and setting the second kneaded material obtained in the above step 3) is placed in the mold of the sole product, and then the mold of the sole product is placed in a flat vulcanizing machine for foaming, and the foaming time is 1 minute.
  • the foaming temperature is 100 ° C, and then the mold is cooled to 10 ° C to obtain a high resilience EVA composition sole foaming material.
  • a high resilience composition foaming material for a sole comprising, by weight, the following components:
  • the preparation method of the above foaming material is as follows:
  • the second kneading the first-stage kneaded material obtained in the step 2) is put into an open mill for the second kneading, the refining temperature is set to 120 ° C, and the kneading is carried out for 10 minutes to obtain the second-stage kneading.
  • Foaming and setting the second kneaded material obtained in the above step 3) is put into an injection molding machine. One shot foaming was carried out, and the injection temperature was controlled at 150 ° C to obtain a foamed sole material of a high resilience EVA composition.
  • a high resilience composition foaming material for a sole comprising, by weight, the following components:
  • the preparation method of the above foaming material is as follows:
  • the preliminary mixed mixture in the step 1) is put into the internal mixer, the kneading temperature is set to 120 ° C, and the mixture is kneaded for 25 minutes to obtain a first-stage kneaded product;
  • the second kneading the first-stage kneaded material obtained in the step 2) is put into an open mill for the second kneading, the refining temperature is set to 110 ° C, and the kneading is carried out for 30 minutes to obtain the second-stage kneading.
  • Foaming and setting the second kneaded material obtained in the above step 3) is placed in the mold of the sole product, Then, the sole product mold is placed in a flat vulcanizing machine for foaming, the foaming time is 10 minutes, the foaming temperature is 130 ° C, and then the mold is cooled to 30 ° C to obtain a high resilience EVA composition sole foaming material. .
  • a high resilience composition foaming material for a sole comprising, by weight, the following components:
  • the preparation method of the above foaming material is as follows:
  • the preliminary mixed mixture in the step 1) is put into the internal mixer, the kneading temperature is set to 140 ° C, and the mixture is kneaded for 10 minutes to obtain a first-stage kneaded product;
  • the second kneading the first-stage kneaded material obtained in the step 2) is put into an open mill for the second kneading, the refining temperature is set to 120 ° C, and the kneading is carried out for 15 minutes to obtain the second-stage kneading.
  • Foaming and setting the second kneaded material obtained in the above step 3) is put into a rotary injection to be foamed into The machine performs one shot foaming, and the injection temperature is controlled at 150 ° C to finally obtain a high resilience EVA composition sole foam material.
  • a high resilience composition foaming material for a sole comprising, by weight, the following components:
  • the preparation method of the above foaming material is as follows:
  • the preliminary mixed mixture in the step 1) is put into the internal mixer, the kneading temperature is set to 100 ° C, and the mixture is kneaded for 10 minutes to obtain a first-stage kneaded product;
  • the second kneading the first-stage kneaded material obtained in the step 2) is put into an open mill for the second kneading, the refining temperature is set to 120 ° C, and the kneading is carried out for 20 minutes to obtain the second-stage kneading.
  • Foaming and setting the second kneaded material obtained in the above step 3) is put into a rotary injection molding machine for one injection foaming, and the injection temperature is controlled at 120 ° C to finally obtain a high resilience EVA composition sole. foaming material.
  • a high-rebound EVA composition foaming material for a sole comprising, by weight, the following components:
  • the preparation method of the above foaming material is as follows:
  • the preliminary mixed mixture in the step 1) is put into the internal mixer, the kneading temperature is set to 100 ° C, and the mixture is kneaded for 10 minutes to obtain a first-stage kneaded product;
  • the second kneading the first-stage kneaded material obtained in the step 2) is put into an open mill for the second kneading, the refining temperature is set to 120 ° C, and the kneading is carried out for 15 minutes to obtain the second-stage kneading.
  • Foaming and setting the second kneaded material obtained in the above step 3) is placed in the mold of the sole product, and then the mold of the sole product is placed in a flat vulcanizing machine for foaming, and the foaming time is 1 minute.
  • the foaming temperature was 200 ° C, and then the mold was cooled to 30 ° C to obtain a high resilience EVA composition sole foaming material.
  • Example 14 product Market EVA foam products density ASTM-D792 g/cm 3 0.24 0.25 hardness GB/T10807-2006 Shore 45 45 Tensile Strength ISO 1798-2008 MPa 3.0 1.5 Elongation at break ISO 1798-2008 % 450 300 Tear strength GB/T10808-2006 N/mm 6.0 4.2 Falling ball back elasticity GB/T6670-2008 % 62 50 Compression set GB/T6669-2008 % 18 35 Wear resistance DIN 53516 Mm 3 380 500
  • a high resilience composition foaming material for a sole comprising, by weight, the following components:
  • the preparation method of the above foaming material is as follows:
  • the preliminary mixed mixture in the step 1) is put into the internal mixer, the kneading temperature is set to 100 ° C, and the mixture is kneaded for 10 minutes to obtain a first-stage kneaded product;
  • Foaming and setting The second kneaded material obtained in the above step 3) is put into a rotary injection molding machine for one injection foaming, and the injection temperature is controlled at 180 ° C to finally obtain a high resilience EVA composition sole. foaming material.
  • the preliminary mixed mixture in the step 1) is put into the internal mixer, the kneading temperature is set to 100 ° C, and kneading is carried out for 5 minutes to obtain a first-stage kneaded product;
  • Foaming and setting the second kneaded material obtained in the above step 3) is placed in the mold of the sole product, and the product mold is placed in a flat vulcanizing machine for foaming, and the foaming time is 1 minute, foaming The temperature was 100 ° C, and then the mold was cooled to 10 ° C to obtain an EVA composition sole foaming material.
  • Example 9 Comparative Example 1 density ASTM-D792 g/cm 3 0.2 0.24 hardness GB/T10807-2006 Shore 45 45 Tensile Strength ISO 1798-2008 MPa 5.0 0.8 Elongation at break ISO 1798-2008 % 500 220 Tear strength GB/T10808-2006 N/mm 8 3.5 Falling ball back elasticity GB/T6670-2008 % 60 52 Compression set GB/T6669-2008 % 25 48 Wear resistance DIN 53516 Mm 3 400 550

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

一种鞋底用高回弹组合物发泡材料及其制备方法，按重量份计，包括如下组份：乙烯-醋酸乙烯共聚物EVA 100份；热塑性聚氨酯/乙烯-醋酸乙烯共聚物合金1-70份；发泡剂0.1-10份；交联剂0.01-10份；填料0-20份。

Description

一种鞋底用高回弹组合物发泡材料及其制备方法 技术领域
本发明涉及一种发泡材料及其制备方法，尤其涉及一种鞋底用高回弹组合物发泡材料及其制备方法，属于轻量化材料技术领域。
背景技术
乙烯-醋酸乙烯共聚物是由乙烯(E)和乙酸乙烯(VA)共聚而制得，英文名EthyleneVinylAcetate，简称EVA。发泡EVA作为目前鞋底材料，尤其是运动鞋鞋底材料的主要材料，具有轻质，柔软，穿着舒适的优点，但是高发泡倍率的EVA鞋底发泡材料在长时间穿着后，发泡EVA材料的回弹性损失非常大，并且永久变形大，力学性能下降严重，且存在耐磨性差等问题，严重影响其在鞋材领域的应用。因而，开发一种具有优异回弹性，较高发泡倍率的鞋底用EVA发泡材料成为许多高校和企业所追求的目标。
发明内容
本发明针对高发泡倍率的EVA鞋底材料存在的不足，提供一种鞋底用高回弹组合物发泡材料及其制备方法。
本发明解决上述技术问题的技术方案如下：
一种鞋底用高回弹组合物发泡材料，其特征在于，按重量份计，包括如下组份：
Figure PCTCN2017110801-appb-000001
Figure PCTCN2017110801-appb-000002
其中，所述热塑性聚氨酯/乙烯-醋酸乙烯共聚物合金可采用如下任意一种方法进行制备：
方法一，见专利号201710058676X所公开的工艺方法，包括如下步骤:
1)将100重量份的TPU原料经预混后加入到双螺杆挤出机的进料口，将5-95重量份的乙烯-醋酸乙烯共聚物和0.1-10重量份的双活性物质通过侧喂料注入到双螺杆挤出机中，二者无先后顺序，0.1-5重量份的助剂加入到TPU原料中或乙烯-醋酸乙烯共聚物与双活性物质的混合物中；
2)控制双螺杆挤出机的反应区温度为50-250℃，进行造粒；
3)将步骤2)所得的造粒后的产品干燥，即得；
方法二，包括如下步骤：将100重量份的TPU、5-95重量份的EVA、0.1-10重量份的双活性物质和0.1-5重量份的助剂混合均匀，将混合物通过挤出机加工后进行造粒，即得；
方法三，包括如下步骤：将100重量份的TPU、5-95重量份的EVA、0.1-10重量份的双活性物质和0.1-5重量份的助剂混合均匀，将混合物通过开炼机加工后进行造粒，即得；
方法四，包括如下步骤：将100重量份的TPU、5-95重量份的EVA、0.1-10重量份的双活性物质和0.1-5重量份的助剂混合均匀，将混合物通过密炼机加工后进行造粒，即得；
所述双活性物质为含有酸酐基团、羧基-COOH、羟基-OH、氨基-NH或-NH2、异氰酸酯基-NCO、环氧基团中的一种或多种的化合物，所述助剂包括引发剂。
本发明中的EVA材料是众所周知的且是应用于发泡鞋材领域常规的牌号，例如可购自杜邦(DuPont)
Figure PCTCN2017110801-appb-000003
进一步，所述的双活性物质为马来酸酐、甲基丙烯酸缩水甘油酯、丙烯 酸、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸酰胺、烯丙基聚乙二醇、氨基酸、环氧树脂中的一种。
进一步，方法一中所述的TPU原料包括聚合物多元醇、扩链剂和异氰酸酯，所述聚合物多元醇为聚酯多元醇、聚醚多元醇、聚己内酯多元醇、聚碳酸酯多元醇、端羟基聚丁二烯二醇中的一种或多种的复配，所述的扩链剂为含12个以下碳原子的小分子二元醇或二元胺类，所述异氰酸酯为为甲苯二异氰酸酯TDI、二苯基甲烷二异氰酸酯MDI、六亚甲基二异氰酸酯HDI、二环己基甲烷二异氰酸酯H12MDI、异弗尔酮二异氰酸酯IPDI、苯二亚甲基二异氰酸酯XDI中的一种或多种的复配，方法二、方法三、方法四中所述TPU的硬度为40-95 Shore A，优选60-90 ShoreA,特别优选70-85 ShoreA，其是根据ASTM D2240测得；熔体流动速率为5-100g/10min,其根据ASTM-1238在200℃施加5Kg的重量测得。
进一步，热塑性聚氨酯/乙烯-醋酸乙烯合金中乙烯-醋酸乙烯共聚物的醋酸乙烯含量为10-80wt％，优选地，醋酸乙烯的含量为20-50wt％，最优选地醋酸乙烯的含量为25-45％。
进一步，所述发泡剂为放热型发泡剂、吸热型发泡剂、发泡微球中的一种或几种的混合物，优选地，所述发泡剂是指偶氮二甲酰胺，偶氮二异丁腈，偶氮二甲酸钡，4,4’-氧代双苯磺酰肼，对甲苯磺酰肼，碳酸氢钠，柠檬酸钠，碳酸氢铵，可膨胀微球中的一种或多种的混合物，其中，可膨胀微球是众所周知的例如购自AKZO Nobel Industries
Figure PCTCN2017110801-appb-000004
系列。
进一步，所述交联剂为过氧化二异丙苯，双叔丁基过氧化异丙基苯，偶氮二异丁腈，偶氮异丁氰基甲酰胺，偶氮二环己基甲氰，偶氮二异丁酸二甲酯中的一种或几种的混合物。
进一步，所述填料为滑石粉，碳酸钙，陶土，硫酸盐，色粉中的一种或几种的混合物。
进一步，所述组合物发泡材料中还包括抗氧剂、润滑剂、耐UV助剂、助交联剂和发泡促进剂，所述助交联剂为含有2个及以上碳碳双键的化合物，所述发泡促进剂为氧化锌、硬脂酸锌中的任意一种。
本发明还要求保护上述高回弹性组合物发泡材料的制备方法，包括如下步骤：
1)按重量份计，称取EVA 100份、热塑性聚氨酯/乙烯-醋酸乙烯共聚物合金1-70份、发泡剂0.1-10份、交联剂0.01-10份、填料0-20份投入到高混机中进行初步的混合；
2)第一次混炼：将步骤1)所得的混合物投入密炼机内混炼均匀，控制混炼时间5-25分钟，混炼温度100-150℃，得到第一级混炼物；
3)第二次混炼：将步骤2)所得的第一级混炼物投入到开炼机中进行第二次混炼，控制混炼时间5-30分钟，混炼温度80-200℃，得到第二级混炼物；
4)发泡与定型：将步骤3)所得的第二级混炼物置于鞋底制品模具中，后将其置于平板硫化机中进行模压发泡，发泡温度为100-200℃，发泡时间为1-10分钟，然后将模具冷却至10-50℃，得到高回弹性EVA组合物发泡鞋底材料；或者将步骤3)所得的第二级混炼物投入到一次射出的发泡鞋材设备中进行一次射出发泡，射出温度控制在120-180℃，得到高回弹性EVA组合物发泡鞋底材料。
进一步，步骤4)中所述的一次射出的发泡鞋材设备是指注射发泡成型机。
与现有技术相比，本发明提供的高回弹性组合物发泡材料及其制备方法的有益效果如下：
1)本发明所述的鞋底用高回弹性组合物发泡材料，利用TPU/EVA合金起到了增容剂的作用，形成了EVA/TPU互穿网络结构(IPN)，在常规EVA发泡体系中引入了TPU组份，解决两者由于相容性差导致最终组合物发泡材料性能 下降的问题；
2)利用TPU优异的回弹性、耐磨性和机械性能，大大改善了发泡EVA鞋底材料的回弹性，压缩永久变形等性能；
3)工艺流程简单，可在现有模压EVA发泡鞋材设备或一次射出EVA发泡鞋材设备直接使用，无需设备改造或新工艺设备的研发与投资。
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
一、TPU/EVA合金材料的制备
实施例1：
一种制备TPU合金材料的工艺，包括如下步骤：
1)将分子量为2000g/mol的聚酯多元醇68份、BDO 6份、二苯基甲烷二异氰酸酯MDI 26份加入到双螺杆挤出机的进料口，将95份EVA、MAH(马来酸酐)10份和引发剂DCP(过氧化二异丙苯)5份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-200℃，降温区温度为90-110℃，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
实施例2：
一种制备TPU合金材料的工艺，包括如下步骤：
1)将分子量为1500g/mol的聚酯多元醇55份、BDO 7份、二苯基甲烷二异氰酸酯MDI 38份加入到双螺杆挤出机的进料口，将75份EVA、MAH(马来酸酐)5份和引发剂DCP(过氧化二异丙苯)0.2份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为50-250℃，降温区温度为90-110℃，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
实施例3：
一种制备TPU合金材料的工艺，包括如下步骤：
1)将70重量份的分子量为1800g/mol的聚醚多元醇与BDO 5份、甲苯二异氰酸酯TDI 25份加入到双螺杆挤出机的进料口，将65份EVA(三井化学的
Figure PCTCN2017110801-appb-000005
)、丙烯酸0.1份和引发剂DCP(过氧化二异丙苯)0.1份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-180℃，降温区温度为90-110℃，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
实施例4：
一种制备TPU合金材料的工艺，包括如下步骤：
1)将45重量份的分子量为1000g/mol的聚醚多元醇与BDO 8份、甲苯二异氰酸酯TDI 47份加入到双螺杆挤出机的进料口，将34份EVA、丙烯酸酰胺0.5份和引发剂DCP(过氧化二异丙苯)0.15份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
实施例5：
一种制备TPU合金材料的工艺，包括如下步骤：
1)将45重量份的分子量为1800g/mol的聚醚多元醇与BDO 8份、六亚甲基二异氰酸酯HDI 47份加入到双螺杆挤出机的进料口，将45份EVA、丙烯酸 酰胺1.5份和引发剂DCP(过氧化二异丙苯)0.25份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
实施例6：
一种制备TPU合金材料的工艺，包括如下步骤：
1)将45重量份的分子量为1800g/mol的聚醚多元醇与BDO 8份、六亚甲基二异氰酸酯HDI 47份加入到双螺杆挤出机的进料口，将5份EVA、甲基丙烯酸甲酯0.1份和引发剂DCP(过氧化二异丙苯)1份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
实施例7：
一种制备TPU合金材料的工艺，包括如下步骤：
1)将45重量份的分子量为1800g/mol的聚醚多元醇与BDO 8份、六亚甲基二异氰酸酯HDI 47份加入到双螺杆挤出机的进料口，将75份EVA、丙烯酸丁酯6份和引发剂DCP(过氧化二异丙苯)2份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
实施例8：
一种制备TPU合金材料的工艺，包括如下步骤：
1)将100重量份的聚醚型TPU弹性体
Figure PCTCN2017110801-appb-000006
M70、90份VA含量为40％的EVA、马来酸酐1.5份和引发剂DCP(过氧化二异丙苯)0.25份置于高混机中预混合；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，将步骤1)中所得的混合物经挤出机挤出，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
我们将实施例7和实施例8所得的TPU/EVA合金材料应用于高回弹性组合物中，组合物的具体组成、制备方法及性能如下：
二、鞋底用高回弹性组合物发泡材料
实施例9：
一种鞋底用高回弹组合物发泡材料，按重量份计，包括如下组份：
Figure PCTCN2017110801-appb-000007
上述发泡材料的制备过程如下：
1)称取相应重量的EVA，TPU/EVA合金，偶氮二甲酰胺(AC)，双叔丁基过氧化异丙基苯DCP投入高混机中进行初步的混合；
2)第一次混炼：将步骤1)中经过初步混合的混合物投入密炼机内混炼均匀，混炼温度设定为100℃，混炼10分钟，得到第一级混炼物；
3)第二次混炼：将步骤2)中所得的第一级混炼物投入开炼机进行第二次混炼，炼温度设定为100℃，混炼5分钟得到第二级混炼物；
4)发泡与定型：将上述步骤3)所得的第二次混炼物置于鞋底制品模具中，然后将鞋底制品模具置于平板硫化机中进行模发发泡，发泡时间为1分钟，发泡温度为100℃，然后将模具冷却至10℃，得到高回弹性EVA组合物鞋底 发泡材料。
通过上述步骤制备的组合物鞋底发泡材料与市场上现有EVA发泡产品的物性测试结果数据如表1所示。
表1
项目 测试标准 单位 实施例9产品 市场EVA发泡产品
密度 ASTM-D792 g/cm3 0.2 0.25
硬度 GB/T10807-2006 Shore 45 45
拉伸强度 ISO 1798-2008 MPa 5.0 1.5
断裂伸长率 ISO 1798-2008 ％ 500 300
撕裂强度 GB/T10808-2006 N/mm 8 4.2
回弹性 GB/T6670-2008 ％ 60 50
压缩永久变形 GB/T6669-2008 ％ 25 35
耐磨性 DIN 53516 Mm3 400 500
实施例10：
一种鞋底用高回弹组合物发泡材料，按重量份计，包括如下组份：
Figure PCTCN2017110801-appb-000008
上述发泡材料的制备方法如下：
1)称取相应重量的VA含量为20％的EVA，TPU/EVA合金，偶氮二甲酰胺，过氧化二异丙苯(DCP)投入高混机中进行初步的混合；
2)第一次混炼：将步骤1)中经过初步混合的混合物投入密炼机内混炼均匀，混炼温度设定为150℃，混炼15分钟，得到第一级混炼物；
3)第二次混炼：将步骤2)中所得的第一级混炼物投入开炼机进行第二次混炼，炼温度设定为120℃，混炼10分钟得到第二级混炼物；
4)发泡与定型：将上述步骤3)所得的第二次混炼物投入注射发泡成型机进 行一次射出发泡，射出温度控制在150℃，得到高回弹性EVA组合物发泡鞋底材料。
通过上述步骤制备的组合物发泡材料与市场上现有EVA发泡产品的物性测试结果数据如表2所示。
表2
项目 测试标准 单位 实施例10产品 市场EVA发泡产品
密度 ASTM-D792 g/cm3 0.21 0.25
硬度 GB/T10807-2006 Shore 45 45
拉伸强度 ISO 1798-2008 MPa 6 1.5
断裂伸长率 ISO 1798-2008 ％ 550 300
撕裂强度 GB/T10808-2006 N/mm 10.4 4.2
落球回弹性 GB/T6670-2008 ％ 58 50
压缩永久变形 GB/T6669-2008 ％ 20 35
耐磨性 DIN 53516 Mm3 380 500
实施例11：
一种鞋底用高回弹组合物发泡材料，按重量份计，包括如下组份：
Figure PCTCN2017110801-appb-000009
上述发泡材料的制备方法如下：
1)称取相应重量的VA含量为20％的EVA，TPU/EVA合金，碳酸氢钠，过氧化二异丙苯(DCP)投入高混机中进行初步的混合；
2)第一次混炼：将步骤1)中经过初步混合的混合物投入密炼机内，混炼温度设定为120℃，混炼25分钟，得到第一级混炼物；
3)第二次混炼：将步骤2)中所得的第一级混炼物投入开炼机进行第二次混炼，炼温度设定为110℃，混炼30分钟得到第二级混炼物；
4)发泡与定型：将上述步骤3)所得的第二次混炼物置于鞋底制品模具中， 然后将鞋底制品模具置于平板硫化机中进行模发发泡，发泡时间为10分钟，发泡温度为130℃，然后将模具冷却至30℃，得到高回弹性EVA组合物鞋底发泡材料。
通过上述步骤制备的组合物鞋底发泡材料与市场上现有EVA发泡产品的物性测试结果数据如表3所示。
表3
项目 测试标准 单位 实施例11产品 市场EVA发泡产品
密度 ASTM-D792 g/cm3 0.22 0.25
硬度 GB/T10807-2006 Shore 45 45
拉伸强度 ISO 1798-2008 MPa 5.5 1.5
断裂伸长率 ISO 1798-2008 ％ 510 300
撕裂强度 GB/T10808-2006 N/mm 8.8 4.2
落球回弹性 GB/T6670-2008 ％ 61 50
压缩永久变形 GB/T6669-2008 ％ 22 35
耐磨性 DIN 53516 Mm3 350 500
实施例12：
一种鞋底用高回弹组合物发泡材料，按重量份计，包括如下组份：
Figure PCTCN2017110801-appb-000010
上述发泡材料的制备方法如下：
1)称取相应重量的VA含量为25％的EVA，TPU/EVA合金，偶氮二甲酰胺(AC)，过氧化二异丙苯(DCP)投入高混机中进行初步的混合；
2)第一次混炼：将步骤1)中经过初步混合的混合物投入密炼机内，混炼温度设定为140℃，混炼10分钟，得到第一级混炼物；
3)第二次混炼：将步骤2)中所得的第一级混炼物投入开炼机进行第二次混炼，炼温度设定为120℃，混炼15分钟得到第二级混炼物；
4)发泡与定型：将上述步骤3)所得的第二次混炼物投入转盘式注射发泡成 型机进行一次射出发泡，射出温度控制在150℃，最终得到高回弹性EVA组合物鞋底发泡材料。
通过上述步骤制备的组合物发泡材料与市场上现有EVA发泡产品的物性测试结果数据如表4所示。
表4
项目 测试标准 单位 实施例12产品 市场EVA发泡产品
密度 ASTM-D792 g/cm3 0.22 0.25
硬度 GB/T10807-2006 Shore 45 45
拉伸强度 ISO 1798-2008 MPa 9.2 1.5
断裂伸长率 ISO 1798-2008 ％ 480 300
撕裂强度 GB/T10808-2006 N/mm 10.4 4.2
落球回弹性 GB/T6670-2008 ％ 62 50
压缩永久变形 GB/T6669-2008 ％ 18 35
耐磨性 DIN 53516 Mm3 400 500
实施例13：
一种鞋底用高回弹组合物发泡材料，按重量份计，包括如下组份：
Figure PCTCN2017110801-appb-000011
上述发泡材料的制备方法如下：
1)称取相应重量的VA含量为25％的EVA，TPU/EVA合金，对甲苯磺酰肼，双叔丁基过氧化异丙基苯和碳酸钙投入高混机中进行初步的混合；
2)第一次混炼：将步骤1)中经过初步混合的混合物投入密炼机内，混炼温度设定为100℃，混炼10分钟，得到第一级混炼物；
3)第二次混炼：将步骤2)中所得的第一级混炼物投入开炼机进行第二次混炼，炼温度设定为120℃，混炼20分钟得到第二级混炼物；
4)发泡与定型：将上述步骤3)所得的第二次混炼物投入转盘式注射发泡成型机进行一次射出发泡，射出温度控制在120℃，最终得到高回弹性EVA组合物鞋底发泡材料。
通过上述步骤制备的组合物发泡材料与市场上现有EVA发泡产品的物性测试结果数据如表5所示。
表5
项目 测试标准 单位 实施例13产品 市场EVA发泡产品
密度 ASTM-D792 g/cm3 0.23 0.25
硬度 GB/T10807-2006 Shore 45 45
拉伸强度 ISO 1798-2008 MPa 3.8 1.5
断裂伸长率 ISO 1798-2008 ％ 500 300
撕裂强度 GB/T10808-2006 N/mm 6.0 4.2
落球回弹性 GB/T6670-2008 ％ 62 50
压缩永久变形 GB/T6669-2008 ％ 20 35
耐磨性 DIN 53516 Mm3 410 500
实施例14：
一种鞋底用高回弹EVA组合物发泡材料，按重量份计，包括如下组份：
Figure PCTCN2017110801-appb-000012
上述发泡材料的制备方法如下：
1)称取相应重量的VA含量为25％的EVA，TPU/EVA合金，柠檬酸钠，双叔丁基过氧化异丙基苯和钛白粉投入高混机中进行初步的混合；
2)第一次混炼：将步骤1)中经过初步混合的混合物投入密炼机内，混炼温度设定为100℃，混炼10分钟，得到第一级混炼物；
3)第二次混炼：将步骤2)中所得的第一级混炼物投入开炼机进行第二次混炼，炼温度设定为120℃，混炼15分钟得到第二级混炼物；
4)发泡与定型：将上述步骤3)所得的第二次混炼物置于鞋底制品模具中，然后将鞋底制品模具置于平板硫化机中进行模发发泡，发泡时间为1分钟，发泡温度为200℃，然后将模具冷却至30℃，得到高回弹性EVA组合物鞋底发泡材料。
通过上述步骤制备的组合物发泡材料与市场上现有EVA发泡产品的物性测试结果数据如表6所示。
表6
项目 测试标准 单位 实施例14产品 市场EVA发泡产品
密度 ASTM-D792 g/cm3 0.24 0.25
硬度 GB/T10807-2006 Shore 45 45
拉伸强度 ISO 1798-2008 MPa 3.0 1.5
断裂伸长率 ISO 1798-2008 ％ 450 300
撕裂强度 GB/T10808-2006 N/mm 6.0 4.2
落球回弹性 GB/T6670-2008 ％ 62 50
压缩永久变形 GB/T6669-2008 ％ 18 35
耐磨性 DIN 53516 Mm3 380 500
实施例15：
一种鞋底用高回弹组合物发泡材料，按重量份计，包括如下组份：
Figure PCTCN2017110801-appb-000013
上述发泡材料的制备方法如下：
1)称取相应重量的VA含量为25％的EVA，TPU/EVA合金，偶氮二钾酸钡，双叔丁基过氧化异丙基苯和陶土投入高混机中进行初步的混合；
2)第一次混炼：将步骤1)中经过初步混合的混合物投入密炼机内，混炼温度设定为100℃，混炼10分钟，得到第一级混炼物；
3)第二次混炼：将步骤2)中所得的第一级混炼物投入开炼机进行第二次混炼，混炼温度设定为120℃，混炼25分钟得到第二级混炼物；
4)发泡与定型：将上述步骤3)所得的第二次混炼物投入转盘式注射发泡成型机进行一次射出发泡，射出温度控制在180℃，最终得到高回弹性EVA组合物鞋底发泡材料。
通过上述步骤制备的组合物发泡材料与市场上现有EVA发泡产品的物性测试结果数据如表7所示。
表7
项目 测试标准 单位 实施例15产品 市场EVA发泡产品
密度 ASTM-D792 g/cm3 0.18 0.25
硬度 GB/T10807-2006 Shore 45 45
拉伸强度 ISO 1798-2008 MPa 2.8 1.5
断裂伸长率 ISO 1798-2008 ％ 420 300
撕裂强度 GB/T10808-2006 N/mm 5.5 4.2
落球回弹性 GB/T6670-2008 ％ 62 50
压缩永久变形 GB/T6669-2008 ％ 20 35
耐磨性 DIN 53516 Mm3 380 500
对比例1：
1)称取100重量份VA含量为10％的EVA，1重量份TPU，1重量份偶氮二甲酰胺AC，投入高混机中进行初步的混合；
2)第一次混炼：将步骤1)中经过初步混合的混合物投入密炼机内，混炼温度设定为100℃，混炼5分钟，得到第一级混炼物；
3)第二次混炼：将步骤2)中得到的第一级混炼物投入开炼机进行第二次混炼，混炼温度设定为100℃，混炼5分钟得到第二级混炼物；
4)发泡与定型：将上述步骤3)所得的第二次混炼物置于鞋底制品模具中，将制品模具置于平板硫化机中进行模发发泡，发泡时间为1分钟，发泡温度为100℃，然后将模具冷却至10℃，得到EVA组合物鞋底发泡材料。
将对比例1所得组合物发泡材料与实施例9所得产品的物性测试数据进行比较，结果如表8所示：
表8
项目 测试标准 单位 实施例9 对比实施例1
密度 ASTM-D792 g/cm3 0.2 0.24
硬度 GB/T10807-2006 Shore 45 45
拉伸强度 ISO 1798-2008 MPa 5.0 0.8
断裂伸长率 ISO 1798-2008 ％ 500 220
撕裂强度 GB/T10808-2006 N/mm 8 3.5
落球回弹性 GB/T6670-2008 ％ 60 52
压缩永久变形 GB/T6669-2008 ％ 25 48
耐磨性 DIN 53516 Mm3 400 550
从表1-表8中的数据可以看出，采用本发明技术方案所制备的产品性能明显优于EVA与TPU直接混合发泡或现有常规EVA发泡体系所制备的产品性能；另一面本发明利用TPU优异的耐磨性，机械性能，大大改善了现有发泡EVA材料的回弹性，压缩永久变形等性能，并且简化工艺流程，无需进行设备改造或设备研发、投资，生产成本降低。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种鞋底用高回弹组合物发泡材料，其特征在于，按重量份计，包括如下组份：
    Figure PCTCN2017110801-appb-100001
    其中，所述热塑性聚氨酯/乙烯-醋酸乙烯共聚物合金可采用如下四种方法之一进行制备,方法一，包括如下步骤:
    1)将100重量份的TPU原料经预混后加入到双螺杆挤出机的进料口，将5-95重量份的乙烯-醋酸乙烯共聚物和0.1-10重量份的双活性物质通过侧喂料注入到挤出机中，二者无先后顺序，0.1-5重量份的助剂加入到TPU原料中或乙烯-醋酸乙烯共聚物与双活性物质的混合物中；
    2)控制挤出机的反应区温度为50-250℃，挤出后的物料经造粒，干燥，即得；
    方法二，包括如下步骤：将100重量份的TPU、5-95重量份的EVA、0.1-10重量份的双活性物质和0.1-5重量份的助剂混合均匀，将混合物通过挤出机加工后进行造粒，即得；
    方法三，包括如下步骤：将100重量份的TPU、5-95重量份的EVA、0.1-10重量份的双活性物质和0.1-5重量份的助剂混合均匀，将混合物通过开炼机加工后进行造粒，即得；
    方法四，包括如下步骤：将100重量份的TPU、5-95重量份的EVA、0.1-10重量份的双活性物质和0.1-5重量份的助剂混合均匀，将混合物通过密炼机 加工后进行造粒，即得；
    所述双活性物质为含有酸酐基团、羧基-COOH、羟基-OH、氨基-NH或-NH2、异氰酸酯基-NCO、环氧基团中的一种或多种的化合物，所述助剂包括引发剂。
  2. 根据权利要求1所述的鞋底用高回弹组合物发泡材料，其特征在于，所述的双活性物质为马来酸酐、甲基丙烯酸缩水甘油酯、丙烯酸、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸酰胺、烯丙基聚乙二醇、氨基酸、环氧树脂中的一种。
  3. 根据权利要求1或2所述的鞋底用高回弹组合物发泡材料，其特征在于，方法一中所述的TPU原料包括聚合物多元醇、扩链剂和异氰酸酯，所述聚合物多元醇为聚酯多元醇、聚醚多元醇、聚己内酯多元醇、聚碳酸酯多元醇、端羟基聚丁二烯二醇中的一种或多种的复配，所述的扩链剂为含12个以下碳原子的小分子二元醇或二元胺类，所述异氰酸酯为为甲苯二异氰酸酯TDI、二苯基甲烷二异氰酸酯MDI、六亚甲基二异氰酸酯HDI、二环己基甲烷二异氰酸酯H12MDI、异弗尔酮二异氰酸酯IPDI、苯二亚甲基二异氰酸酯XDI中的一种或多种的复配，方法二、方法三、方法四中所述TPU的硬度为40-95 Shore A，熔体流动速率为5-100g/10min,其根据ASTM-1238在200℃施加5Kg的重量测得。
  4. 根据权利要求1或2所述的鞋底用高回弹组合物发泡材料，其特征在于，所述热塑性聚氨酯/乙烯-醋酸乙烯合金中乙烯-醋酸乙烯共聚物的醋酸乙烯含量为10-80wt％，优选地，醋酸乙烯的含量为20-50wt％，最优选地醋酸乙烯的含量为25-45％。
  5. 根据权利要求1或2所述的鞋底用高回弹组合物发泡材料，其特征在于，所述发泡剂为放热型发泡剂、吸热型发泡剂、发泡微球中的一种或几种的混合物，优选地，所述发泡剂是指偶氮二甲酰胺，偶氮二异丁腈，偶氮二甲酸钡，4,4’-氧代双苯磺酰肼，对甲苯磺酰肼，碳酸氢钠，柠檬酸钠， 碳酸氢铵，可膨胀微球中的一种或多种的混合物。
  6. 根据权利要求1或2所述的鞋底用高回弹组合物发泡材料，其特征在于，所述交联剂为过氧化二异丙苯，双叔丁基过氧化异丙基苯，偶氮二异丁腈，偶氮异丁氰基甲酰胺，偶氮二环己基甲氰，偶氮二异丁酸二甲酯中的一种或几种的混合物。
  7. 根据权利要求1或2所述的鞋底用高回弹EVA组合物发泡材料，其特征在于，所述填料为滑石粉，碳酸钙，陶土，硫酸盐，色粉中的一种或几种的混合物。
  8. 根据权利要求1或2所述的鞋底用高回弹组合物发泡材料，其特征在于，所述组合物发泡材料中还包括抗氧剂、润滑剂、耐UV助剂、助交联剂和发泡促进剂，所述助交联剂为含有2个及以上碳碳双键的化合物，所述发泡促进剂为氧化锌、硬脂酸锌中的任意一种。
  9. 权利要求1-8中任一项所述的鞋底用高回弹组合物发泡材料的制备方法，其特征在于，包括如下步骤：
    1)按重量份计，称取EVA100份、热塑性聚氨酯/乙烯-醋酸乙烯共聚物合金1-70份、发泡剂0.1-10份、交联剂0.01-10份、填料0-20份投入到高混机中进行初步的混合；
    2)第一次混炼：将步骤1)所得的混合物投入密炼机内混炼均匀，控制混炼时间5-25分钟，混炼温度100-150℃，得到第一级混炼物；
    3)第二次混炼：将步骤2)所得的第一级混炼物投入到开炼机中进行第二次混炼，控制混炼时间5-30分钟，混炼温度80-200℃，得到第二级混炼物；
    4)发泡与定型：将步骤3)所得的第二级混炼物置于鞋底制品模具中，后将其置于平板硫化机中进行模压发泡，发泡温度为100-200℃，发泡时间为1-10分钟，然后将模具冷却至10-50℃，得到高回弹性EVA组合物发泡鞋底材料；或者将步骤3)所得的第二级混炼物投入到一次射出的发泡鞋材设备中进行 一次射出发泡，射出温度控制在120-180℃，得到高回弹性EVA组合物发泡鞋底材料。
  10. 根据权利要求9所述的制备方法，其特征在于，步骤4)中所述的一次射出的发泡鞋材设备是指注射发泡成型机。
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