CN106905599B - Light high-elasticity EVA composite foam material and preparation method and application thereof - Google Patents
Light high-elasticity EVA composite foam material and preparation method and application thereof Download PDFInfo
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- 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
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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
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- 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
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- 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
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- 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
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
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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
- 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
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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
- 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
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- C08L2203/14—Applications used for foams
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2207/04—Thermoplastic elastomer
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Abstract
The application provides an EVA composite foam material, a preparation method and application thereof, the material is prepared by mixing and foaming materials, and the materials mainly comprise: 35 to 50 parts by mass of an ethylene-vinyl acetate copolymer; 15 to 35 parts by mass of a polyolefin thermoplastic elastomer; 10-20 parts by mass of ethylene propylene diene monomer; 10 to 20 parts by mass of a polyolefin block copolymer; 10-20 parts by mass of a rubber-plastic composite elastomer, wherein the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene block copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer; 1.5-3 parts by mass of an anti-shrinking agent; 0.5 to 5 parts by mass of an activator; 0.7 to 1.2 parts by mass of a crosslinking agent; 2.5 to 5.5 parts by mass of a foaming agent. Under the combined action of the components, the material is soft, comfortable, light and excellent in resilience performance, so that the performance requirements of the sports shoe sole are met.
Description
Technical Field
The application relates to the technical field of rubber and plastic composite materials, in particular to a light high-elasticity EVA composite foam material and a preparation method and application thereof, and especially relates to an EVA composite foam material for sports shoe soles and a preparation method thereof.
Background
With the rapid development of the market of the sports shoes, the wearing experience requirements of people on parts such as soles are higher and higher. Consumers often demand that shoes not only be light and comfortable to wear, but also have a cool, stylish, bright-colored appearance, and therefore, the performance requirements for sole materials are increasing. Among them, high elasticity, comfort and light weight are the main development trends.
EVA (ethylene-vinyl acetate copolymer) foam material is adopted to replace part of rubber to be directly used as the outsole of the sports shoe, and certain high-elasticity requirements can be met. However, the sole material has generally higher hardness and higher density, and the material has poorer performances such as cushioning, rebound and the like. The common EVA foaming material in the market at present is hard in texture, the resilience is about 40% generally, and the fatigue resistance is poor. After wearing for a period of time, the problems of poor resilience such as collapse can occur, meanwhile, the sole loses elasticity quickly, the cushioning performance becomes poor, and the wearing experience and the appearance structure of the shoe are seriously influenced.
Disclosure of Invention
In view of this, the application provides a light high-elastic EVA composite foam material, and a preparation method and an application thereof, and the EVA composite foam material provided by the application is soft and comfortable, has excellent buffering and resilience properties, and good resilience properties, and can meet the performance requirements of sports shoe soles.
The application provides a high-elastic EVA composite foaming material of light is prepared through mixing, foaming by the material, the material includes:
35 to 50 parts by mass of an ethylene-vinyl acetate copolymer;
15-35 parts by mass of a polyolefin thermoplastic elastomer, wherein the polyolefin thermoplastic elastomer is an ethylene-octene random copolymer prepared by metallocene catalysis;
10-20 parts by mass of ethylene propylene diene monomer;
10 to 20 parts by mass of a polyolefin block copolymer;
10-20 parts by mass of a rubber-plastic composite elastomer, wherein the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene block copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer;
1.5-3.0 parts by mass of an anti-shrinking agent;
0.5 to 5 parts by mass of an activator;
0.7 to 1.2 parts by mass of a crosslinking agent;
2.5-5.5 parts by mass of a foaming agent;
0-10 parts by mass of an additive, wherein the additive comprises one or more of a reactive assistant, a crosslinking assistant and a processing assistant.
Preferably, the ethylene-vinyl acetate copolymer has a vinyl acetate mass content of not less than 25% and an MI of greater than 3.5g/10 min.
Preferably, the crosslinking agent is 1, 4-bis-tert-butylperoxyisopropyl benzene.
Preferably, the foaming agent is one or more of azodicarbonamide, expandable microspheres and sodium bicarbonate.
Preferably, the active agent is selected from one or more of stearic acid and zinc stearate.
Preferably, the preparation material of the rubber-plastic composite elastomer also comprises an antioxidant.
Preferably, the preparation material of the rubber-plastic composite elastomer also comprises hydrogenated petroleum heavy alkane fractions.
Preferably, the EVA composite foaming material is translucent.
The invention provides a preparation method of a light high-elasticity EVA composite foam material, which comprises the following steps:
1) weighing materials, wherein the materials comprise: 35 to 50 parts by mass of an ethylene-vinyl acetate copolymer; 15-35 parts by mass of a polyolefin thermoplastic elastomer, wherein the polyolefin thermoplastic elastomer is an ethylene-octene random copolymer prepared by metallocene catalysis; 10-20 parts by mass of ethylene propylene diene monomer; 10 to 20 parts by mass of a polyolefin block copolymer; 10-20 parts by mass of a rubber-plastic composite elastomer, wherein the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene block copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer; 1.5-3.0 parts by mass of an anti-shrinking agent; 0.5 to 5 parts by mass of an activator; 0.7 to 1.2 parts by mass of a crosslinking agent; 2.5-5.5 parts by mass of a foaming agent; 0-10 parts by mass of an additive, wherein the additive comprises one or more of a reactive assistant, a crosslinking assistant and a processing assistant;
2) mixing all the components weighed in the step 1) except the cross-linking agent and the foaming agent;
3) mixing the materials mixed in the step 2) with the cross-linking agent and the foaming agent weighed in the step 1);
4) granulating the mixture obtained by mixing in the step 3), and then foaming to obtain the EVA composite foaming material.
The invention also provides the application of the EVA composite foaming material in manufacturing soles of sports shoes.
Compared with the prior art, the EVA composite foaming material is mainly prepared by mixing and foaming components such as ethylene-vinyl acetate copolymer, polyolefin thermoplastic elastomer, ethylene propylene diene monomer, polyolefin block copolymer, rubber-plastic composite elastomer, anti-shrinkage agent, active agent, cross-linking agent, foaming agent, additive and the like according to a certain ratio; the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene segmented copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer. Under the combined action of the components, the EVA composite foam material provided by the application is soft, comfortable, light, excellent in buffering and resilience performance (the elasticity is greater than 60%), and good in recovery performance, so that the performance requirements of sports shoe soles are met.
In addition, the material of the invention can have semitransparent characteristic, thus being convenient for color matching and application.
Drawings
FIG. 1 is a light irradiation pattern of a conventional EVA foam and the foam obtained in example 1.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a high-elastic EVA composite foaming material of light is prepared through mixing, foaming by the material, the material includes:
35 to 50 parts by mass of an ethylene-vinyl acetate copolymer;
15-35 parts by mass of a polyolefin thermoplastic elastomer, wherein the polyolefin thermoplastic elastomer is an ethylene-octene random copolymer prepared by metallocene catalysis;
10-20 parts by mass of ethylene propylene diene monomer;
10 to 20 parts by mass of a polyolefin block copolymer;
10-20 parts by mass of a rubber-plastic composite elastomer, wherein the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene block copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer;
1.5-3.0 parts by mass of an anti-shrinking agent;
0.5 to 5 parts by mass of an activator;
0.7 to 1.2 parts by mass of a crosslinking agent;
2.5-5.5 parts by mass of a foaming agent;
0-10 parts by mass of an additive, wherein the additive comprises one or more of a reactive assistant, a crosslinking assistant and a processing assistant.
The application provides a EVA composite foaming material's quality is light, and is soft comfortable, and resilience performance is high, and low compression can be as the sports shoe sole.
The EVA composite foaming material is mainly prepared from ethylene-vinyl acetate copolymer, polyolefin thermoplastic elastomer, ethylene propylene diene monomer, polyolefin block copolymer, rubber-plastic composite elastomer, anti-shrinkage agent, active agent, cross-linking agent, foaming agent and other component materials through mixing and foaming. In the embodiment of the invention, the EVA composite foaming material has the density0.20 to 0.22g/cm3(ii) a The hardness can be 45-50 Asker C. In the embodiment of the invention, the EVA composite foaming material is semitransparent. Compared with the traditional foaming system, the foaming material does not use filler, zinc oxide, titanium dioxide and the like in the formula of the embodiment of the invention, so that the foaming material can show the original color of the material, further has the semitransparent characteristic and is convenient for color matching.
The material comprises 35-50 parts by mass of ethylene-vinyl acetate copolymer, and preferably 35-40 parts by mass. In the preferred embodiment of the present application, the ethylene-vinyl acetate copolymer may be one or more of EVA7470M, EVA460, EVA462, EVA265, EVA40L-03, and EVA 40W. In the examples of the present application, the ethylene-vinyl acetate copolymer (EVA) used in the formulation has a Vinyl Acetate (VA) content of not less than 25% by mass, preferably between 26% and 40%; the melt index MI is greater than 3.5g/10min (test Standard: ASTM.D-1238-2013 Standard test method for measuring the flow Rate of a thermoplastic melt with an extrusion plastomer). The VA is used as a flexible chain segment in an EVA molecular chain, the proper VA content can ensure the uniform distribution of random coil conformation in a polymer tertiary structure, the crystallization capacity of an ethylene chain segment in the polymer is effectively reduced, the polymer molecular chain is kept flexible as much as possible, and the softness of the composite material is ensured.
The material comprises 15-35 parts by mass of polyolefin thermoplastic elastomer, and preferably comprises 18-20 parts by mass of polyolefin thermoplastic elastomer. Elastomer generally refers to a material which can be recovered after an external force is removed, and at present, particularly in China, when elastomer is referred to, thermoplastic elastomer is generally referred to, and rubber is not included. Polyolefin Thermoplastic elastomers are Thermoplastic polyolefin elastomers, Thermoplastic Elastomer-olefin (TPE-O, TEO).
In the present invention, the polyolefin thermoplastic elastomer is an ethylene-octene random copolymer prepared by metallocene catalysis. The copolymer has narrow relative molecular mass distribution and uniform short chain branch distribution, ensures that the polymer has excellent physical and mechanical properties and excellent fluidity, can effectively improve the processability of a blend, and simultaneously ensures that a composite material has the advantages of low density, good rebound resilience and the like. In a preferred embodiment of the present invention, the polyolefin thermoplastic elastomer may be one or more of Engage8450, Engage8003, Engage7467, Engage8150 and Engage8180, such as DOW standard.
The EVA composite foam material comprises 10-20 parts by mass of ethylene propylene diene monomer, and preferably 10-15 parts by mass of ethylene propylene diene monomer. In the present application, the hardness of the ethylene propylene diene monomer is preferably 60 to 70A. In the embodiment of the application, the model number of the ethylene propylene diene monomer rubber can be one or more of IP3745, EPDM8800, EPDM3092 and EPDM 9500.
The material comprises 10-20 parts by mass of polyolefin block copolymer, and preferably comprises 15-20 parts by mass of polyolefin block copolymer. In the present application, the polyolefin block copolymer preferably has a hardness of 60A to 90A. In embodiments herein, the polyolefin block copolymer may be of one or more of type Infuse9100, Infuse9107, Infuse9500, and Infuse 9507. In a preferred embodiment of the present application, the ethylene propylene diene monomer has a hardness of 60A to 70A, and the polyolefin block copolymer has a hardness of 60A to 90A.
The ethylene propylene diene monomer rubber with the hardness range of 60-70A and the electrodeless substituent in the molecular structure is introduced, the cohesive energy of the molecules is low, the molecular chain can keep flexibility in a wider temperature range, and the ethylene propylene diene monomer rubber has the advantages of low density, good resilience performance and the like.
In addition, a polyolefin copolymer with alternately arranged soft and hard segments is specially introduced into the formula of the embodiment of the application, the hardness range is preferably 60A-90A, the flexibility of a molecular chain can be greatly improved due to the special high molecular chain configuration, meanwhile, the cross-linking points in the blend are more and uniformly distributed, the molecular chains in the composite are ensured not to easily slide, and the elasticity of the composite material is greatly improved.
The EVA composite foam material comprises 10-20 parts by mass of rubber-plastic composite elastomer, preferably 12-20 parts by mass of the rubber-plastic composite elastomer. In the invention, the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene segmented copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer; the melt index of the elastomer may be 1.5g/10min (test standard: ASTM D-1238-2013). Wherein, the styrene-ethylene-butylene-styrene block copolymer (SEBS) can provide excellent resilience performance for the final foaming shoe material; the Linear Low Density Polyethylene (LLDPE) is used as a linear chain-forging polymer to generate a physical crosslinking effect in a foaming system, and the stability of the foaming system can be maintained, so that the problems of overlarge thermal shrinkage of the foaming system and the like are solved; styrene-maleic anhydride copolymer (SMA) is used as an excellent dispersing and compatibilizing material, and can effectively disperse the rubber-plastic composite elastomer in a foaming system.
In some embodiments of the present invention, the main components of the rubber-plastic composite elastomer include: SEBS (CAS: 66070-58-4); LLDPE (CAS: 25087-34-7); SMA (CAS: 9011-13-6). The preparation material of the rubber-plastic composite elastomer preferably also comprises an antioxidant; the antioxidant is an organic compound capable of inhibiting or delaying thermal oxidation of high polymers and other organic compounds in the air, and is generally used in an amount of 0.1 to 0.5 wt%. Hindered phenols such as antioxidant 1076; specifically, A.O having CAS numbers 2082-79-3 can be used. Preferably, the preparation material of the rubber-plastic composite elastomer also comprises hydrogenated petroleum heavy alkane fraction, and specifically, Oil with CAS number 64742-54-7 can be adopted.
The embodiment of the invention can adopt a specific rubber-plastic composite elastomer BER6058, and the main component of the BER6058 comprises styrene block copolymer, specifically SEBS, Oil, LLDPE, A.O and SMA. The special rubber-plastic composite elastomer adopted in the formula can be uniformly distributed in the whole composite material system, so that the foaming material has high elasticity and high plasticity, the elasticity of the composite material can be provided, and the good dimensional stability of the material can be kept in the die pressing and shaping process.
In the application, the preparation material of the EVA composite foaming material comprises 2.5-5.5 parts by mass of foaming agent, and preferably comprises 3-5 parts by mass. The foaming agent is preferably one or more of azodicarbonamide, expandable microsphere polymer and sodium bicarbonate (such as OBSH sodium bicarbonate foaming agent), more preferably a composite foaming agent of azodicarbonamide and sodium bicarbonate, and the mass ratio of the azodicarbonamide to the sodium bicarbonate in the composite foaming agent can be 2:1 or 3: 2.
In the application, the material comprises 0.5-5 parts by mass of an active agent. The active agents include, but are not limited to, fatty acids; fatty acid is widely used as a basic raw material of a surfactant, and is mainly used as a vulcanization activator in the rubber industry at home. In the present application, the active agent is preferably selected from one or more of stearic acid and zinc stearate, more preferably used in combination. In a preferred embodiment of the present application, the material comprises 0.4 to 0.6 parts by mass of stearic acid (St), preferably 0.5 parts; and 0.5 to 1.5 parts by mass of zinc stearate (ZnSt), preferably 0.6 to 0.8 part.
Among them, stearic acid plays an important role in the synthesis and processing of rubber: stearic acid is a widely used vulcanization activator in natural gums, synthetic rubbers and latexes, and also as a plasticizer and softener. Stearic acid may be added as an emulsifier during the production of synthetic rubber, as a foaming agent during the production of foamed rubber, and as a mold release agent for rubber products.
The material comprises 0.7-1.2 parts by mass of a cross-linking agent, and preferably comprises 0.75-1.0 part by mass of the cross-linking agent. In the present application, the crosslinking agent is preferably 1, 4-bis-tert-butylperoxyisopropyl benzene.
The material comprises 1.5-3.0 parts by mass of an anti-shrinking agent, and preferably comprises 1.5-2.5 parts by mass of an anti-shrinking agent or an anti-shrinking auxiliary agent. The material comprises 0-10 parts by mass of an additive, wherein the additive comprises one or more of a reactive assistant, a crosslinking assistant and a processing assistant, preferably the crosslinking assistant and can comprise 0.1-0.2 part by mass of the crosslinking assistant. Specifically, in some embodiments of the present invention, the crosslinking assistant may be a commercially available product having a model number of PL301 to 50D; the antishrinking agent may be a commercially available product of type SD-03A.
According to the embodiment of the invention, the optimal cross-linked foaming system is constructed by using the activating agent, the cross-linking agent, the composite foaming agent, the additive and the like which are reasonably proportioned, the mechanical property and the resilience of the composite material are also ensured, and the material can form more closed-cell foams to the maximum extent, so that resilience and shock absorption are provided for the composite foaming material in the aspects of structure and material, and the density of the composite foaming material is greatly reduced. In addition, the invention can use sodium bicarbonate in the composite foaming agent, not only has foaming function, but also the decomposition product is the same as inorganic salt in the traditional system, which is beneficial to the heat transfer function of the system.
In addition, compared with the traditional foaming system, the formula of the invention can be free of filler, zinc oxide and titanium dioxide, so that the semitransparent light high-elasticity EVA composite foaming material for the sports shoe sole is obtained.
Correspondingly, the invention provides a preparation method of a light high-elasticity EVA composite foam material, which comprises the following steps:
1) weighing materials, wherein the materials comprise: 35 to 50 parts by mass of an ethylene-vinyl acetate copolymer; 15-35 parts by mass of a polyolefin thermoplastic elastomer, wherein the polyolefin thermoplastic elastomer is an ethylene-octene random copolymer prepared by metallocene catalysis; 10-20 parts by mass of ethylene propylene diene monomer; 10 to 20 parts by mass of a polyolefin block copolymer; 10-20 parts by mass of a rubber-plastic composite elastomer, wherein the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene block copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer; 1.5-3.0 parts by mass of an anti-shrinking agent; 0.5 to 5 parts by mass of an activator; 0.7 to 1.2 parts by mass of a crosslinking agent; 2.5-5.5 parts by mass of a foaming agent; 0-10 parts by mass of an additive, wherein the additive comprises one or more of a reactive assistant, a crosslinking assistant and a processing assistant;
2) mixing all the components weighed in the step 1) except the cross-linking agent and the foaming agent;
3) mixing the materials mixed in the step 2) with the cross-linking agent and the foaming agent weighed in the step 1);
4) granulating the mixture obtained by mixing in the step 3), and then foaming to obtain the EVA composite foaming material.
This application can prepare and obtain soft comfortable, and buffering, resilience performance are excellent, and the light, the EVA composite foam material that the resilience performance is good simultaneously, this material can satisfy the design demand of sports shoe sole, also can replace rubber directly to touch to earth and use. In addition, the method is simple to operate and suitable for industrial production.
The embodiment of the application is characterized in that the components of the materials are weighed according to a certain proportion, and the components of the materials are as described above. In addition, the sequence, manner and the like of weighing the components are not particularly limited in the present application.
In the embodiment of the application, all the weighed components except the cross-linking agent and the foaming agent are introduced into an internal mixer for mixing to obtain the mixed material. The mixing time is preferably 8 to 10 minutes; the temperature is preferably 110 to 115 ℃.
In the embodiment of the application, the cross-linking agent and the foaming agent are added into the uniformly mixed materials to be continuously mixed, so as to obtain a mixture. In the examples of the present application, the equipment for carrying out the mixing is an internal mixer. The mixing time is preferably 3 to 5 minutes; the temperature is preferably 115-120 ℃.
According to the embodiment of the application, the uniformly mixed materials can be poured into a granulator to be granulated, and then foaming and forming are carried out, so that the semitransparent light high-elasticity EVA composite foaming material can be obtained. The granulation and foaming are well known to those skilled in the art, and the present application is not particularly limited. In the embodiment of the invention, the granulation temperature is 80-90 ℃; the foaming temperature is 160-170 ℃.
The invention can include the second compression molding to obtain the corresponding finished product. In this regard, the present invention is not particularly limited; according to the requirements of customers, the method is carried out according to the conventional process in the field.
The technical scheme is simple to operate and is the same as the traditional production process. Moreover, the composite foam material sole prepared by the technical scheme has lighter weight and higher rebound shock absorption than a common EVA sole, is soft and comfortable, and can bring lasting comfortable experience to consumers.
In addition, the application also provides the application of the EVA composite foaming material in manufacturing the soles of the sports shoes. In this application, adopt the EVA composite foaming material preparation sports shoes sole, can make shoes not only wear lightly comfortable, durable moreover more.
For further illustration of the present application, the EVA composite foam material provided in the present application, the preparation method and application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present application.
In the following examples, the technical indexes of the rubber-plastic composite elastomer BER6058 are shown in Table 1:
TABLE 1 product specification of BER6058 used in the examples
| Performance of | Unit of | Test method | Numerical value |
| Hardness of | Shore A | ASTM D-2240 | 50 |
| Density of | g/cm3 | ASTM D-792 | 0.88 |
| Melt index | g/10min. | ASTM D-1238 | 1.5 |
| Tensile strength | kgf/cm2 | ASTM D-412 | ＞45 |
| Elongation at break | ％ | ASTM D-412 | ＞700 |
Example 1
The formula combination of the semitransparent light high-elasticity EVA composite foaming material for the soles of the sports shoes is as follows:
ethylene-vinyl acetate copolymer: 35 parts by mass;
polyolefin thermoplastic elastomer: 20 parts by mass;
ethylene propylene diene monomer: 10 parts by mass;
polyolefin block copolymer: 20 parts by mass;
rubber-plastic composite elastomer: 12 parts by mass;
anti-shrinkage agent: 1.5 parts by mass;
stearic acid St: 0.5 part by mass;
zinc stearate ZnSt: 0.6 part by mass;
crosslinking assistant agent: 0.1 part by mass;
a crosslinking agent: 1.0 part by mass;
a composite foaming agent: and 5 parts by mass.
Wherein the ethylene-vinyl acetate copolymer is EVA265, produced by Taiwan plastics corporation; the polyolefin thermoplastic elastomer is prepared from an Engage8180 model and an Engage8450 model in a mass ratio of 2:1, manufactured by DuPont company; the model of the ethylene propylene diene monomer is 3092PM, produced by Dow company; the polyolefin block copolymer is Infuse9107, produced by the Dow company; the rubber-plastic composite elastomer is BER6058, produced by Baixian science and technology; the cross-linking agent is 1, 4-di-tert-butyl peroxy isopropyl benzene; the foaming agent is azodicarbonamide and sodium bicarbonate 2:1 (mass ratio). The crosslinking assistant is PL301-50D and is produced by Komao rubber and Plastic company; the antishrinking agent was SD-03A, produced by Komao rubber and Plastic company.
The components except the cross-linking agent and the foaming agent are poured into an internal mixer for mixing for 10 minutes at the temperature of 110 ℃.
Adding 1, 4-di-tert-butylperoxyisopropyl benzene and a composite foaming agent into the uniformly mixed materials, continuously mixing for 5 minutes at the temperature of 115 ℃.
And pouring the uniformly mixed materials into a granulator for granulation at the temperature of 80 ℃, and then foaming and forming at the temperature of 170 ℃ to obtain the EVA composite foaming material.
Example 2
The formula combination of the soft high-elastic wear-resistant EVA composite foam material for the soles of the sports shoes is as follows:
ethylene-vinyl acetate copolymer: 35 parts by mass;
polyolefin thermoplastic elastomer: 18 parts by mass;
ethylene propylene diene monomer: 15 parts by mass;
polyolefin block copolymer: 15 parts by mass;
rubber-plastic composite elastomer: 20 parts by mass;
anti-shrinkage agent: 2.5 parts by mass;
stearic acid St: 0.5 part by mass;
zinc stearate ZnSt: 0.8 part by mass;
crosslinking assistant agent: 0.17 part by mass;
a crosslinking agent: 1.0 part by mass;
a composite foaming agent: 5.0 parts by mass;
wherein the ethylene-vinyl acetate copolymer has the models of 265 and 40W, and the mass ratio of 2:1, manufactured by dupont; the polyolefin thermoplastic elastomer is produced by DuPont, with the model number of Engage 7467; the model of the ethylene propylene diene monomer is IP3745, and is produced by the Dow company; the polyolefin block copolymer is Infuse9107, produced by the Dow company; the rubber-plastic composite elastomer is BER6058, produced by Baixian science and technology; the cross-linking agent is 1, 4-di-tert-butyl peroxy isopropyl benzene; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate, and the mass ratio is 3: 2. the crosslinking assistant is PL301-50D and is produced by Komao rubber and Plastic company; the antishrinking agent was SD-03A, produced by Komao rubber and Plastic company.
The components except the cross-linking agent and the foaming agent are poured into an internal mixer for mixing for 8 minutes at the temperature of 115 ℃.
Adding 1, 4-di-tert-butylperoxyisopropyl benzene and a composite foaming agent into the uniformly mixed materials, continuously mixing for 3 minutes at the temperature of 120 ℃.
And pouring the uniformly mixed materials into a granulator for granulation at 90 ℃, and then foaming and forming at 170 ℃ to obtain the EVA composite foaming material.
Example 3
The foamed products obtained in the above examples were subjected to physical property tests, and the following comparative tests were carried out: comparison 1: ethylene propylene diene monomer elastomer (EPDM9500) was substituted for BER6058 in the formulation of example 1; comparison 2: polyolefin elastomer (Engage8450) substituted BER6056 in the formulation of example 1; the other components were unchanged.
The test results are shown in Table 2, and Table 2 shows the performance test results of the products obtained in examples 1-2 and comparison. Detection conditions are as follows: the temperature is 23 +/-3 ℃, and the humidity is 65 +/-5%.
Table 2 results of Performance test of examples 1-2 and comparative products
Note: table 2 the data are obtained according to the national standard test methods.
As can be seen from the table, the ethylene propylene diene monomer rubber is adopted to replace BER6058, and under the condition that other results are close to each other, the thermal shrinkage problem of the foaming material cannot be solved, and meanwhile, the compression deformation is large; when the polyolefin elastomer is used for replacing BER6058, although the thermal shrinkage is better solved, the resilience of the foaming material has larger difference, and meanwhile, the compression deformation is poorer.
In addition, the transmittance of the white foam material obtained in example 1 was tested according to GB/T2410-. And (3) testing environmental conditions: the temperature is 23 +/-2 ℃, and the humidity is 50 +/-5%. The thickness of the sample is 10 mm; and a C light source is used.
The results showed that the white foam obtained in example 1 had a transmittance of 2.1%. Light irradiation comparison referring to fig. 1, fig. 1 is a light irradiation diagram of a conventional EVA foam and a foam obtained in example 1. In FIG. 1, the conventional EVA foam is shown on the left side, and the foam obtained in example 1 is shown on the right side. From the results, the transmittance of the foaming material is more than or equal to 2%, and the foaming material has semitransparent characteristic and is convenient for color matching and application.
The embodiment shows that the EVA composite foaming material prepared by the invention is soft and comfortable, has high resilience (the elasticity is more than 60 percent) and light weight, solves the problems of hard texture, poor elasticity and the like of the traditional wear-resistant EVA material, meets the national relevant physical property standard, and is beneficial to application.
The invention provides a soft high-elastic wear-resistant rubber-plastic composite foaming material for sports shoe soles and a preparation method thereof. While the embodiments of the present invention have been described with reference to specific examples, the description of the embodiments is only for the purpose of facilitating understanding of the method and the core concept of the present invention, and it should be noted that, for those skilled in the art, various modifications and changes can be made without departing from the principle of the present invention, and these modifications and changes fall within the protection scope of the appended claims.
Claims (10)
1. A light high-elastic EVA composite foam material is prepared by mixing and foaming materials, wherein the materials comprise:
35 to 50 parts by mass of an ethylene-vinyl acetate copolymer;
15-35 parts by mass of a polyolefin thermoplastic elastomer, wherein the polyolefin thermoplastic elastomer is an ethylene-octene random copolymer prepared by metallocene catalysis;
10-20 parts by mass of ethylene propylene diene monomer;
10 to 20 parts by mass of a polyolefin block copolymer;
10-20 parts by mass of a rubber-plastic composite elastomer, wherein the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene block copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer;
1.5-3 parts by mass of an anti-shrinking agent;
0.5 to 5 parts by mass of an activator;
0.7 to 1.2 parts by mass of a crosslinking agent;
2.5-5.5 parts by mass of a foaming agent;
0-10 parts by mass of an additive, wherein the additive comprises one or more of a reactive assistant, a crosslinking assistant and a processing assistant.
2. The EVA composite foam material as claimed in claim 1, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of not less than 25% by mass and an MI of more than 3.5g/10min according to ASTM D-1238-2013.
3. The light-weight high-elasticity EVA composite foam material of claim 1, wherein the crosslinking agent is 1, 4-di-tert-butylperoxyisopropyl benzene.
4. The light-weight high-elasticity EVA composite foam material of claim 1, wherein the foaming agent is one or more of azodicarbonamide, expandable microspheres and sodium bicarbonate.
5. The light-weight high-elasticity EVA composite foam material of claim 1, wherein the active agent is one or more selected from stearic acid and zinc stearate.
6. The light-weight high-elasticity EVA composite foam material as claimed in any one of claims 1 to 5, wherein the preparation material of the rubber-plastic composite elastomer further comprises an antioxidant.
7. The light-weight high-elasticity EVA composite foam material of claim 6, wherein the preparation material of the rubber-plastic composite elastomer further comprises hydrogenated petroleum heavy alkane fraction.
8. The EVA composite foam material of claim 1, which is translucent.
9. A preparation method of a light high-elastic EVA composite foam material comprises the following steps:
1) weighing materials, wherein the materials comprise: 35 to 50 parts by mass of an ethylene-vinyl acetate copolymer; 15-35 parts by mass of a polyolefin thermoplastic elastomer, wherein the polyolefin thermoplastic elastomer is an ethylene-octene random copolymer prepared by metallocene catalysis; 10-20 parts by mass of ethylene propylene diene monomer; 10 to 20 parts by mass of a polyolefin block copolymer; 10-20 parts by mass of a rubber-plastic composite elastomer, wherein the rubber-plastic composite elastomer is prepared by mixing styrene-ethylene-butylene-styrene block copolymer, linear low-density polyethylene and styrene-maleic anhydride copolymer; 1.5-3.0 parts by mass of an anti-shrinking agent; 0.5 to 5 parts by mass of an activator; 0.7 to 1.2 parts by mass of a crosslinking agent; 2.5-5.5 parts by mass of a foaming agent; 0-10 parts by mass of an additive, wherein the additive comprises one or more of a reactive assistant, a crosslinking assistant and a processing assistant;
2) mixing all the components weighed in the step 1) except the cross-linking agent and the foaming agent;
3) mixing the materials mixed in the step 2) with the cross-linking agent and the foaming agent weighed in the step 1);
4) granulating the mixture obtained by mixing in the step 3), and then foaming to obtain the EVA composite foaming material.
10. Use of the EVA composite foam material according to any one of claims 1 to 8 or the EVA composite foam material prepared by the preparation method according to claim 9 in manufacturing soles of sports shoes.
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