CN110229411B - EVA (ethylene-vinyl acetate) coarse-pore composite foam material and preparation method thereof - Google Patents

EVA (ethylene-vinyl acetate) coarse-pore composite foam material and preparation method thereof Download PDF

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CN110229411B
CN110229411B CN201910540109.7A CN201910540109A CN110229411B CN 110229411 B CN110229411 B CN 110229411B CN 201910540109 A CN201910540109 A CN 201910540109A CN 110229411 B CN110229411 B CN 110229411B
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coarse
eva
foam material
composite foam
foaming
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CN110229411A (en
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刘超
陈绍猛
张志国
叶健桦
苏加明
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Anta China Co Ltd
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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
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • 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
    • 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
    • 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
    • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses an EVA coarse-pore composite foaming material and a preparation method thereof, wherein the EVA coarse-pore composite foaming material is prepared by mixing, granulating and foaming materials; the material comprises: 40-60 parts of ethylene-vinyl acetate copolymer, 10-20 parts of graphene modified isotactic polybutylene, 10-15 parts of polyolefin thermoplastic elastomer, 10-20 parts of polyester elastomer, 0.4-0.8 part of active agent, 0.7-1.5 parts of cross-linking agent, 2.5-3.5 parts of foaming agent and 0.1-0.3 part of auxiliary agent; the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 26-40 percent; weighing quantitative isotactic polybutene-1, melting, adding 0.05-0.2 mass percent of graphene at the melting temperature of the isotactic polybutene-1 of 140-170 ℃, and mixing the isotactic polybutene-1 and the graphene to obtain graphene modified isotactic polybutene; the EVA coarse-pore composite foaming material has good coarse-pore foaming effect, improves the compression resistance and resilience, and improves the softness and the abrasion resistance. The preparation method is simple and easy to operate.

Description

EVA (ethylene-vinyl acetate) coarse-pore composite foam material and preparation method thereof
Technical Field
The invention relates to the field of materials for soles of sports shoes, in particular to an EVA (ethylene vinyl acetate) coarse-pore composite foam material and a preparation method thereof.
Background
With the rapid development of the market of sports shoes, people not only have higher and higher requirements on the wearing comfort of soles, but also pursue the novelty and the attractiveness of the appearance of the soles. The pores in the existing EVA coarse-pore composite foam material are transparent cellular and have larger diameters, so that the material is beneficial to light transmission refraction, and the embodied color is more full and bright; therefore, the shoe soles in the market are mostly made of the EVA coarse-pore composite foaming material to improve the ornamental value.
However, the existing EVA coarse-pore composite foam material has poor overall compression resistance due to the overlarge pore diameter of the formed pore foam; the sole made of the material is easy to collapse under pressure, and is not easy to recover after collapse, and the like, so that the attractive appearance of the sole is influenced, and the wearing comfort of a user is reduced. Therefore, it is required to improve and enhance the compression resistance and resilience of the EVA macroporous composite foam material.
Secondly, the EVA coarse-pore composite foaming material also has the problems of over-hard texture, poor elasticity, no abrasion resistance and the like, so that the sole made of the material is also not suitable for wearing and needs to be further improved.
Disclosure of Invention
The invention aims to overcome the defects or problems in the background art and provides an EVA (ethylene-vinyl acetate) coarse-pore composite foaming material which is mostly used for soles, has good foam forming effect of coarse-pore foaming, greatly improves compression resistance and resilience, and improves softness and abrasion resistance. Also provides a preparation method of the EVA coarse-pore composite foam material, and the preparation method is simple and easy to operate.
In order to achieve the purpose, the invention adopts the following technical scheme: an EVA coarse-pore composite foaming material is prepared by mixing, granulating and foaming materials; the material comprises: 40-60 parts of ethylene-vinyl acetate copolymer, 110-20 parts of graphene modified isotactic polybutylene, 10-15 parts of polyolefin thermoplastic elastomer, 10-20 parts of polyester elastomer, 0.4-0.8 part of active agent, 0.7-1.5 parts of cross-linking agent, 2.5-3.5 parts of foaming agent and 0.1-0.3 part of auxiliary agent; wherein the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 26-40%; the graphene modified isotactic polybutene-1 is prepared by mixing graphene and isotactic polybutene-1.
Preferably, the type of the ethylene-vinyl acetate copolymer is one or more of EVA7470M, EVA460, EVA462, EVA265, EVA40L-03 and EVA 40W.
Preferably, the graphene mass content in the graphene modified isotactic polybutene-1 is 0.05-0.2%.
Preferably, the polyolefin thermoplastic elastomer is a metallocene-produced ethylene octene random copolymer.
Preferably, the polyolefin thermoplastic elastomer is one or more of Engage8450, Engage8003, Engage7467, Engage8150 and Engage 8180.
Preferably, the polyester elastomer is one or more of Tesmann EL460, EL740, EM460 and EM 630.
Preferably, the active agent is stearic acid.
Preferably, the crosslinking agent is 1, 4-bis-tert-butylperoxyisopropyl benzene.
Preferably, the blowing agent is a coarse cell blowing agent.
Preferably, the adjuvant is triallylisocyanurate.
Preferably, the preparation method of the EVA coarse-pore composite foam material comprises the following steps: step 1: weighing quantitative isotactic polybutene-1, melting, adding 0.05-0.2% by mass of graphene at the melting temperature of the isotactic polybutene-1 of 140-170 ℃, and mixing the two to obtain graphene modified isotactic polybutene-1; the mixing time is 25-40 minutes, and the temperature is 150-; step 2: weighing the components in the material according to the weight parts; and step 3: mixing the components except the cross-linking agent and the foaming agent weighed in the step 2; and 4, step 4: mixing the materials mixed in the step 3 with the cross-linking agent and the foaming agent weighed in the step 2; and 5: and (4) sequentially granulating and foaming the mixture obtained after mixing in the step (4) to obtain the EVA mixed foaming material.
Preferably, the mixing time in the step 3 is 8-10 minutes, and the temperature is 110-115 ℃.
Preferably, the mixing time in the step 4 is 3-5 minutes, and the temperature is 110-120 ℃.
Preferably, the foaming time in the step 5 is 3-5 minutes, and the temperature is 130-160 ℃.
As can be seen from the above description of the present invention, the present invention has the following advantages over the prior art:
the mass content of Vinyl Acetate (VA) in the ethylene-vinyl acetate copolymer (EVA) adopted in the formula is between 26 and 40 percent; VA is used as a flexible chain segment in an EVA molecular chain, and the intramolecular chemical bond internal rotation of VA is more free, so that irregular coiled random coil conformation can be formed. The proper VA mass content range can ensure the uniform distribution of random coil conformation in a polymer tertiary structure, effectively reduce the crystallization capacity of an ethylene chain segment in the polymer, and ensure that a polymer molecular chain keeps flexibility as much as possible, thereby ensuring the softness and high elasticity of the composite material.
The graphene modified isotactic polybutene-1 adopted in the formula has the mass content of 0.05-0.2%. The graphene modified isotactic polybutene-1 is prepared by mixing graphene and isotactic polybutene-1; specifically, isotactic polybutene-1 is a high molecular weight inert polymer having good compression resistance and abrasion resistance; however, the isotactic polybutene-1 in the crystal form II has high melting point and poor fluidity, and is difficult to be directly applied to a conventional EVA coarse-pore composite foaming system, so that the fluidity of the isotactic polybutene-1 is greatly improved after the isotactic polybutene-1 is mixed and compounded with graphene, the graphene modified isotactic polybutene-1 prepared by mixing the isotactic polybutene-1 and the graphene is suitable for the EVA coarse-pore composite foaming system, the distribution of cells in the EVA coarse-pore composite foaming material is more uniform due to the improvement of the fluidity, and the mechanical property and the elasticity of the EVA coarse-pore composite foaming material are also improved; the specific modification mechanism of graphene to isotactic polybutene-1 is not clear at present.
Secondly, as the graphene has a larger specific surface area, the graphene can form more physical cross-linking points with the isotactic polybutene-1 after being mixed with the isotactic polybutene-1 to have a reinforcing effect, so as to further improve the compressive strength and the tensile strength of the isotactic polybutene-1, and the compression resistance and the resilience of the EVA coarse-pore composite foaming material adopting the graphene modified isotactic polybutene-1 are greatly improved, so as to make up for the defect that the EVA coarse-pore composite foaming material is not compressed due to overlarge pore diameter of coarse pores, and solve the problem that the wear resistance of the EVA coarse-pore composite foaming material is reduced due to the fact that transparent arrangement of the pores needs to be ensured and no reinforcing agent is added.
The polyolefin thermoplastic elastomer adopted in the formula is an ethylene-octene random copolymer prepared by metallocene catalysis, and the copolymer has narrower relative molecular mass distribution and uniform short branched chain distribution, so that the EVA coarse-pore composite foam material has the advantages of low density, good rebound resilience and the like.
The polyester elastomer adopted in the formula is also a thermoplastic elastomer, and compared with other elastic parts, the polyester elastomer is stable in performance and not easily influenced by external temperature, so that the weather resistance of the EVA coarse-pore composite foam material is ensured; and the polyester elastomer has good chemical resistance and creep resistance, i.e. the EVA coarse-pore composite foam material effectively improves the durability and widens the usable environment.
An optimal cross-linked foaming system is constructed by using an active agent, a cross-linking agent, a foaming agent, an auxiliary agent and the like which are reasonably proportioned in the formula, so that the coarse-pore foaming obtains a better foaming effect, and the formed pore foam has larger diameter and high transparency, so that the attractiveness of the sole made of the EVA coarse-pore composite foaming material is improved; further improving the overall mechanical property and resilience of the EVA coarse-pore composite foam material.
The preparation method of the EVA coarse-pore composite foam material is simple to operate and easy to operate; the graphene modified isotactic polybutylene-1 prepared by blending has stable performance, and the compression resistance of the EVA coarse-pore composite foam material is effectively improved; the EVA coarse-pore composite foam material prepared by the preparation method can ensure the beautiful effect of coarse-pore foaming, and the softness, resilience and wear resistance and abrasion resistance of the EVA coarse-pore composite foam material are improved, so that a sole made of the EVA coarse-pore composite foam material has good wearing property and attractive appearance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are presently preferred embodiments of the invention and are not to be taken as an exclusion of other embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the claims and the specification of the present invention, unless otherwise specifically limited, the terms "first", "second", or "third", etc., are used for distinguishing between different objects and not for describing a particular order.
In the claims and the specification of the present invention, unless otherwise specifically limited, the terms "fixedly connected" or "fixedly connected" are used in a broad sense, i.e., any connection mode without displacement relationship or relative rotation relationship therebetween, that is, non-detachably fixed connection, integration, and fixedly connected by other devices or elements.
In the claims and specification of the present invention, the terms "including", "comprising" and "having", and variations thereof, are intended to be inclusive or non-exclusive.
In the embodiment of the invention, the EVA coarse-pore composite foam material is prepared by mixing, granulating and foaming materials; the material comprises: 40-60 parts of ethylene-vinyl acetate copolymer, 110-20 parts of graphene modified isotactic polybutylene, 10-15 parts of polyolefin thermoplastic elastomer, 10-20 parts of polyester elastomer, 0.4-0.8 part of active agent, 0.7-1.5 parts of cross-linking agent, 2.5-3.5 parts of foaming agent and 0.1-0.3 part of auxiliary agent.
In this embodiment, the type of the ethylene-vinyl acetate copolymer is one or more of EVA7470M, EVA460, EVA462, EVA265, EVA40L-03, and EVA 40W. Wherein the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 26-40%; VA is used as a flexible chain segment in an EVA molecular chain, internal rotation of chemical bonds in the molecule is more free, irregular curled random coil conformation can be formed, the appropriate VA mass content range can ensure uniform distribution of the random coil conformation in a polymer tertiary structure, the crystallization capacity of an ethylene chain segment in a polymer is effectively reduced, the polymer molecular chain is kept flexible as much as possible, and therefore softness and high elasticity of the composite material are ensured.
The adopted graphene modified isotactic polybutene-1 has the mass content of graphene between 0.05% and 0.2%. The graphene modified isotactic polybutene-1 is prepared by mixing graphene and isotactic polybutene-1; specifically, isotactic polybutene-1 is a high molecular weight inert polymer having good compression resistance and abrasion resistance; however, the isotactic polybutene-1 in the crystal form II has high melting point and poor fluidity, and is difficult to be directly applied to a conventional EVA coarse-pore composite foaming system, so that the fluidity of the isotactic polybutene-1 is greatly improved after the isotactic polybutene-1 is mixed and compounded with graphene, the graphene modified isotactic polybutene-1 prepared by mixing the isotactic polybutene-1 and the graphene is suitable for the EVA coarse-pore composite foaming system, the distribution of cells in the EVA coarse-pore composite foaming material is more uniform due to the improvement of the fluidity, and the mechanical property and the elasticity of the EVA coarse-pore composite foaming material are also improved; the specific modification mechanism of graphene to isotactic polybutene-1 is not clear at present.
Secondly, as the graphene has a larger specific surface area, the graphene can form more physical cross-linking points with the isotactic polybutene-1 after being mixed with the isotactic polybutene-1 to have a reinforcing effect, so as to further improve the compressive strength and the tensile strength of the isotactic polybutene-1, and the compression resistance and the resilience of the EVA coarse-pore composite foaming material adopting the graphene modified isotactic polybutene-1 are greatly improved, so as to make up for the defect that the EVA coarse-pore composite foaming material is not compressed due to overlarge pore diameter of coarse pores, and solve the problem that the wear resistance of the EVA coarse-pore composite foaming material is reduced due to the fact that transparent arrangement of the pores needs to be ensured and no reinforcing agent is added.
Specifically, isotactic polybutene and graphene are common raw materials, isotactic polybutene is sold by Shandong Oriental Macro chemical industry Co., Ltd, and graphene is available in various types.
The adopted polyolefin thermoplastic elastomer is one or more of gag 8450, gag 8003, gag 7467, gag 8150 and gag 8180. The polyolefin thermoplastic elastomer is metallocene-prepared ethylene octene random copolymer. The copolymer has narrower relative molecular mass distribution and uniform short chain branch distribution, so that the EVA coarse-pore composite foam material has the advantages of low density, good rebound resilience and the like.
The polyester elastomer is one or more of Tesmann EL460, EL740, EM460 and EM 630. The polyester elastomer is also a thermoplastic elastomer, and compared with other elastic parts, the polyester elastomer is stable in performance and not easily influenced by external temperature, so that the weather resistance of the EVA coarse-pore composite foam material is ensured; and the polyester elastomer has good chemical resistance and creep resistance, even if the EVA coarse-pore composite foam material effectively improves the durability and widens the usable environment.
The active agent used is stearic acid.
The crosslinking agent is 1, 4-di-tert-butylperoxyisopropyl benzene.
The foaming agent is a coarse-pore foaming agent.
The adopted auxiliary agent is triallyl isocyanurate.
In the formula, an optimal cross-linking foaming system is constructed by using an active agent, a cross-linking agent, a foaming agent, an auxiliary agent and the like which are reasonably proportioned, so that the coarse pore foaming obtains a better foaming effect, and the attractiveness of a sole made of the EVA coarse pore composite foaming material is improved; further improving the overall mechanical property and resilience of the EVA coarse-pore composite foam material.
Correspondingly, the embodiment of the invention also provides a preparation method of the EVA coarse-pore composite foam material, which comprises the following steps:
step 1: weighing quantitative isotactic polybutene-1, melting, adding 0.05-0.2% by mass of graphene at the melting temperature of the isotactic polybutene-1 of 140-170 ℃, and mixing the two to obtain graphene modified isotactic polybutene-1; the mixing time is 25-40 minutes, and the temperature is 150-;
step 2: weighing the components in the material according to the weight parts;
and step 3: mixing the components except the cross-linking agent and the foaming agent weighed in the step 2; the mixing time is 8-15 minutes, and the temperature is 100-110 ℃.
And 4, step 4: mixing the materials mixed in the step 3 with the cross-linking agent and the foaming agent weighed in the step 2; the mixing time is 3-5 minutes, and the temperature is 110-120 ℃.
And 5: sequentially granulating and foaming the mixture obtained after mixing in the step 4 to obtain an EVA (ethylene-vinyl acetate) mixed foaming material; the foaming time is 3-5 minutes, and the temperature is 14-160 ℃.
In the embodiment, the preparation method of the EVA coarse-pore composite foam material is simple to operate and easy to operate; the graphene modified isotactic polybutylene-1 prepared by blending has stable performance, and the compression resistance and resilience of the EVA coarse-pore composite foam material are effectively improved; the EVA coarse-pore composite foam material prepared by the preparation method can ensure the beautiful effect of coarse-pore foaming, and the softness, resilience and wear resistance and abrasion resistance of the EVA coarse-pore composite foam material are improved, so that a sole made of the EVA coarse-pore composite foam material has good wearing property and attractive appearance.
The EVA coarse-pore composite foam material prepared by the embodiment of the invention can be used for manufacturing soles of sports shoes, and the manufactured soles are beautiful and novel, comfortable to wear, compression resistant and stretch resistant and can be applied to various environments.
Specifically, the EVA macroporous composite foam material is prepared through the following two examples, and the physical properties thereof are respectively detected, and the detection results are shown in table 1.
The first embodiment is as follows:
in the first embodiment of the invention, the EVA coarse-pore composite foam material comprises the following materials in parts by mass:
ethylene-vinyl acetate copolymer: 45 parts by mass
Graphene-modified isotactic polybutene-1: 15 parts by mass
Polyolefin thermoplastic elastomer: 15 parts by mass
Polyester elastomer: 15 parts by mass
Active agent(s): 0.6 part by mass
A crosslinking agent: 1.2 parts by mass
Foaming agent: 3.0 parts by mass
Auxiliary agent: 0.3 part by mass
Wherein the ethylene-vinyl acetate copolymer is 7470M, produced by Taiwan plastics corporation; the polybutene is sold by Shandong Oriental Macro chemical industry Co., Ltd; graphene is commercially available; polyolefin thermoplastic elastomers, model number Engage8180 and Engage8450, in a ratio of 2: 1, manufactured by dupont; the type of the polyester elastomer is Tesmann EL 430; the active agent is stearic acid; the cross-linking agent is 1, 4-bis-tert-butylperoxy isopropyl benzene; the foaming agent is a coarse foaming agent and is produced by Fujian brocade chemical company Limited; the auxiliary agent is triallyl isocyanurate and produced by marie chemistry.
In the first embodiment, the following steps are carried out:
step 1: weighing quantitative isotactic polybutene-1, and adding 0.05-0.2% by mass of graphene at the melting temperature of the isotactic polybutene-1 of 140-170 ℃ to mix and modify the isotactic polybutene-1 and the graphene to obtain the graphene modified isotactic polybutene-1. Preferably, the blending time is 25-40 minutes and the mixing temperature is 150-180 ℃.
Step 2: the components except the cross-linking agent and the foaming agent are poured into an internal mixer for first mixing. Preferably, the first mixing time is 8-10 minutes, and the mixing temperature is 100-115 ℃.
And step 3: and (3) adding a crosslinking agent (1, 4-bis (tert-butylperoxyisopropyl) benzene) and a foaming agent (a coarse pore foaming agent) into the uniformly mixed material in the step (2), and then pouring into an internal mixer for secondary mixing. Preferably, the mixing time is 3-5 minutes, and the mixing temperature is 115-120 ℃.
And 4, step 4: and (4) pouring the uniformly mixed materials in the step (3) into a granulator to start granulation, and then carrying out foaming molding to obtain the EVA coarse-pore composite foaming material. Preferably, the foaming time is 3-5 minutes and the temperature is 130-.
Example two:
in the second embodiment of the invention, the EVA coarse-pore composite foam material comprises the following materials in parts by mass:
ethylene-vinyl acetate copolymer: 40 parts by mass
Graphene-modified isotactic polybutene-1: 20 parts by mass
Polyolefin thermoplastic elastomer: 10 parts by mass
Polyester elastomer: 10 parts by mass
Active agent(s): 0.8 part by mass
A crosslinking agent: 1.5 parts by mass
Foaming agent: 2.8 parts by mass
Auxiliary agent: 0.2 part by mass
Wherein the ethylene-vinyl acetate copolymer is 7470M, produced by Taiwan plastics corporation; the polybutene is sold by Shandong Oriental Macro chemical industry Co., Ltd; graphene is commercially available; polyolefin thermoplastic elastomers, model number Engage8180 and Engage8450, in a ratio of 1: 1, manufactured by dupont; the polyester elastomer is a mixture of Tesmann EL430 and EL250 in a ratio of 1: 1; the active agent is stearic acid; the cross-linking agent is 1, 4-bis-tert-butylperoxy isopropyl benzene; the foaming agent is a coarse foaming agent and is produced by Fujian brocade chemical company Limited; the auxiliary agent is triallyl isocyanurate and produced by marie chemistry.
In example two, the procedure was followed:
step 1: weighing quantitative isotactic polybutene-1, and adding 0.05-0.2% by mass of graphene at the melting temperature of the isotactic polybutene-1 of 140-170 ℃ to mix and modify the isotactic polybutene-1 and the graphene to obtain the graphene modified isotactic polybutene-1. Preferably, the blending time is 25-40 minutes and the mixing temperature is 150-180 ℃.
Step 2: the components except the cross-linking agent and the foaming agent are poured into an internal mixer for first mixing. Preferably, the first mixing time is 8-10 minutes, and the mixing temperature is 100-115 ℃.
And step 3: and (3) adding a cross-linking agent and a foaming agent into the uniformly mixed material in the step (2), and then pouring into an internal mixer for secondary mixing. Preferably, the second mixing time is 3-5 minutes, and the mixing temperature is 115-120 ℃.
And 4, step 4: and (4) pouring the uniformly mixed materials in the step (3) into a granulator to start granulation, and then carrying out foaming molding to obtain the EVA coarse-pore composite foaming material. Preferably, the foaming time is 3-5 minutes and the temperature is 130-.
For the first example, the following first and second comparative examples are provided, with the component specific controls distinguished as follows:
comparative example one: compared with the formula in the first embodiment, the material which is conventionally used for improving the compression resistance, such as olefin block copolymer infuse9017, is adopted to replace the graphene modified isotactic polybutene-1 in the formula; other components and parts by mass are unchanged.
Comparative example two: compared with the formula in the first embodiment, the material which is conventionally used for improving the compression resistance, such as olefin block copolymer infuse9017, is adopted to replace the graphene modified isotactic polybutene-1 in the formula; the mass fraction of the polyolefin thermoplastic elastomer is adjusted from 15 parts by mass to 30 parts by mass so as to replace the polyester elastomer in the formula; other components and parts by mass are unchanged.
In the first comparative example of the invention, the EVA coarse-pore composite foam material comprises the following materials in parts by mass:
ethylene-vinyl acetate copolymer: 45 parts by mass
Polyolefin block copolymer: 15 parts by mass
Polyolefin thermoplastic elastomer: 15 parts by mass
Polyester elastomer: 15 parts by mass
Active agent(s): 0.6 part by mass
A crosslinking agent: 1.2 parts by mass
Foaming agent: 3.0 parts by mass
Auxiliary agent: 0.3 part by mass
Wherein the ethylene-vinyl acetate copolymer is 7470M, produced by Taiwan plastics corporation; olefin block copolymer infuse9017, manufactured by dow corporation; polyolefin thermoplastic elastomers, model number Engage8180 and Engage8450, in a ratio of 2: 1, manufactured by dupont; the type of the polyester elastomer is Tesmann EL 430; the active agent is stearic acid; the cross-linking agent is 1, 4-bis-tert-butylperoxy isopropyl benzene; the foaming agent is a coarse foaming agent and is produced by Fujian brocade chemical company Limited; the auxiliary agent is triallyl isocyanurate and produced by marie chemistry. The foaming process conditions of the comparative example one are the same as those of the example one, and the description will not be repeated.
In the second comparative example of the invention, the EVA coarse-pore composite foam material comprises the following materials in parts by mass:
ethylene-vinyl acetate copolymer: 45 parts by mass
Polyolefin block copolymer: 15 parts by mass
Polyolefin thermoplastic elastomer: 30 parts by mass
Active agent(s): 0.6 part by mass
A crosslinking agent: 1.2 parts by mass
Foaming agent: 3.0 parts by mass
Auxiliary agent: 0.3 part by mass
Wherein the ethylene-vinyl acetate copolymer is 7470M, produced by Taiwan plastics corporation; olefin block copolymer infuse9017, manufactured by dow corporation; polyolefin thermoplastic elastomers, model number Engage8180 and Engage8450, in a ratio of 2: 1, manufactured by dupont; the type of the polyester elastomer is Tesmann EL 430; the active agent is stearic acid; the cross-linking agent is 1, 4-bis-tert-butylperoxy isopropyl benzene; the foaming agent is a coarse foaming agent and is produced by Fujian brocade chemical company Limited; the auxiliary agent is triallyl isocyanurate and produced by marie chemistry. The foaming process conditions of the comparative example one are the same as those of the example one, and the description will not be repeated.
The EVA coarse-cell composite foam materials prepared in the first and second examples and the first and second comparative examples are subjected to physical property tests, and the test results are shown in Table 1.
Table 1 shows the physical properties of the EVA coarse-cell composite foam materials prepared in the examples and the comparative examples. Wherein, the specific detection conditions are that the temperature is 23 +/-3 ℃ and the humidity is 65 +/-5%.
TABLE 1 results of physical Properties test of products obtained in example one and example two and comparative example one and comparative example two
Figure GDA0003359301340000081
Figure GDA0003359301340000091
Note that the data in Table 1 are obtained according to the national standard test method.
The results show that the EVA coarse-cell composite foam materials prepared in the first and second examples respectively have the compression deformation rates of 42% and 39%, and the rebound resilience of 57% and 59%; the compression deformation rate of the EVA coarse-pore composite foam material prepared in the comparative example A is 45%, and the rebound resilience is 51%; namely, the compression deformation rate of the EVA coarse-cell composite foamed material of example one and example two is low compared to that of comparative example one, and the resilience performance is high compared to that of comparative example one.
Therefore, the graphene modified isotactic polybutylene-1 added in the first embodiment and the second embodiment indeed improves the compression resistance and the resilience of the whole EVA coarse-pore composite foam material, and does not affect other performances of the EVA coarse-pore composite foam material. The shoe sole made of the EVA coarse-pore composite foam material prepared in the first embodiment and the second embodiment can be compressed for a long time, is not easy to collapse, has high rebound rate, and improves the attractiveness and the wearing property of the shoe sole.
The EVA coarse-pore composite foam materials prepared in the first embodiment and the second embodiment respectively have compression deformation rates of 42% and 39%, and rebound resilience of 57% and 59%; the compression deformation rate of the EVA coarse-pore composite foam material prepared in the comparative example is 47%, and the rebound resilience is 43%; namely, the compression deformation rate of the EVA coarse-pore composite foam material of the first embodiment and the second embodiment is lower than that of the first embodiment, and the resilience performance is higher than that of the first embodiment.
Namely, it can be proved that in the EVA coarse-cell composite foam materials in the first and second embodiments, not only the graphene modified isotactic polybutene-1 improves the compression resistance and resilience of the whole material, but also the polyester elastomer has an obvious influence on the compression resistance and resilience of the whole material, wherein the improvement on the resilience is more significant. Namely, the EVA coarse-pore composite foam material in the first embodiment and the second embodiment has excellent resilience, and effectively ensures the damping effect of the sole made of the EVA coarse-pore composite foam material.
The DIN abrasion resistance values of the EVA coarse-pore composite foaming materials prepared in the first embodiment and the second embodiment are respectively 252mm3And 236mm3(ii) a The DIN abrasion resistance values of the EVA coarse-pore composite foaming materials prepared in the comparative example I and the comparative example II are 337mm respectively3And 366mm3(ii) a Namely, the DIN abrasion resistance value of the EVA coarse-pore composite foaming materials of the example I and the example II is obviously lower than that of the comparative example I and the comparative example II.
Therefore, the graphene modified isotactic polybutylene-1 added in the first embodiment and the second embodiment indeed improves the overall wear resistance of the EVA coarse-pore composite foam material, and does not affect other performances of the EVA coarse-pore composite foam material. Namely, the durability of the soles made of the EVA coarse-pore composite foaming materials prepared in the first embodiment and the second embodiment is ensured.
According to the test data of the first embodiment and the second embodiment, the hardness of the EVA coarse-pore composite foam material prepared by the invention is less than 55Asker C, the EVA coarse-pore composite foam material is soft in texture, high in resilience, low in compression deformation rate and strong in abrasion resistance, the problems of hard texture, poor resilience, no compression resistance, no abrasion resistance and the like of the traditional EVA coarse-pore composite foam material are solved, and the EVA coarse-pore composite foam material meets the national relevant physical performance standard.
By combining the above analysis, the technical scheme disclosed by the invention solves all the technical problems listed in the specification, and realizes the corresponding technical effects. The EVA coarse-pore composite foam material has good coarse-pore foaming effect, greatly improves the compression resistance and resilience, and improves the softness and the abrasion resistance. Also provides a preparation method of the EVA coarse-pore composite foam material, and the preparation method is simple and easy to operate.
The description of the above specification and examples is intended to be illustrative of the scope of the present invention and is not intended to be limiting. Modifications, equivalents and other improvements which may occur to those skilled in the art and which may be made to the embodiments of the invention or portions thereof through a reasonable analysis, inference or limited experimentation, in light of the common general knowledge, the common general knowledge in the art and/or the prior art, are intended to be within the scope of the invention.

Claims (13)

1. An EVA coarse-pore composite foam material is characterized in that: the material is prepared by mixing, granulating and foaming; the material comprises: 40-60 parts of ethylene-vinyl acetate copolymer, 110-20 parts of graphene modified isotactic polybutylene, 10-15 parts of polyolefin thermoplastic elastomer, 10-20 parts of polyester elastomer, 0.4-0.8 part of active agent, 0.7-1.5 parts of cross-linking agent, 2.5-3.5 parts of foaming agent and 0.1-0.3 part of auxiliary agent; wherein the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 26-40%; the graphene modified isotactic polybutene-1 is prepared by mixing graphene and isotactic polybutene-1; the graphene mass content of the graphene modified isotactic polybutene-1 is 0.05-0.2%.
2. The EVA coarse-cell composite foam material of claim 1, wherein: the ethylene-vinyl acetate copolymer is one or more of EVA7470M, EVA460, EVA462, EVA265, EVA40L-03 and EVA 40W.
3. The EVA coarse-cell composite foam material of claim 1, wherein: the polyolefin thermoplastic elastomer is metallocene-prepared ethylene octene random copolymer.
4. The EVA coarse-cell composite foam material of claim 3, wherein: the polyolefin thermoplastic elastomer is one or more of gag 8450, gag 8003, gag 7467, gag 8150 and gag 8180.
5. The EVA coarse-cell composite foam material of claim 1, wherein: the polyester elastomer is one or more of Tesmann EL460, EL740, EM460 and EM 630.
6. The EVA coarse-cell composite foam material of claim 5, wherein: the active agent is stearic acid.
7. The EVA coarse-cell composite foam material of claim 1, wherein: the cross-linking agent is 1, 4-bis (tert-butylperoxyisopropyl) benzene.
8. The EVA coarse-cell composite foam material of claim 1, wherein: the foaming agent is a coarse pore foaming agent.
9. The EVA coarse-cell composite foam material of claim 1, wherein: the auxiliary agent is triallyl isocyanurate.
10. The method for preparing EVA coarse-cell composite foam material according to any one of claims 1-9, wherein: the method comprises the following steps:
step 1: weighing quantitative isotactic polybutene-1, melting, adding 0.05-0.2% by mass of graphene at the melting temperature of the isotactic polybutene-1 of 140-170 ℃, and mixing the two to obtain graphene modified isotactic polybutene-1; the mixing time is 25-40 minutes, and the temperature is 150-;
step 2: weighing the components in the material according to the weight parts;
and step 3: mixing the components except the cross-linking agent and the foaming agent weighed in the step 2;
and 4, step 4: mixing the materials mixed in the step 3 with the cross-linking agent and the foaming agent weighed in the step 2;
and 5: and (4) sequentially granulating and foaming the mixture obtained after mixing in the step (4) to obtain the EVA mixed foaming material.
11. The preparation method of the EVA coarse-pore composite foam material of claim 10, which comprises the following steps: the mixing time in the step 3 is 8-10 minutes, and the temperature is 110-115 ℃.
12. The preparation method of the EVA coarse-pore composite foam material of claim 10, which comprises the following steps: the mixing time in the step 4 is 3-5 minutes, and the temperature is 110-120 ℃.
13. The preparation method of the EVA coarse-pore composite foam material of claim 10, which comprises the following steps: the foaming time in the step 5 is 3-5 minutes, and the temperature is 130-160 ℃.
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