CN110229411A - A kind of EVA gross porosity composite foam material and preparation method - Google Patents
A kind of EVA gross porosity composite foam material and preparation method Download PDFInfo
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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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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/0066—Use of inorganic compounding ingredients
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- 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
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- 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
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- 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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- 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
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- 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
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- 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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Abstract
The invention discloses a kind of EVA gross porosity composite foam materials and preparation method thereof, are made by material through mixing, granulation and foaming；Material includes: ethylene-vinyl acetate copolymer 40-60 mass parts, the modified isotactic polybutene 10-20 mass parts of graphene, polyolefin thermoplastic elastomer 10-15 mass parts, polyester elastomer 10-20 mass parts, activating agent 0.4-0.8 mass parts, crosslinking agent 0.7-1.5 mass parts, foaming agent 2.5-3.5 mass parts and auxiliary agent 0.1-0.3 mass parts；Vinylacetate mass content is 26%-40% in ethylene-vinyl acetate copolymer；The preparation method of the EVA gross porosity composite foam material, quantitative isotactic PB Polybutene-1 is weighed to be melted, it is 0.05%-0.2% graphene that mass content is added when the melting temperature of isotactic PB Polybutene-1 is 140-170 DEG C, so that the two obtains the modified isotactic polybutene of graphene after being kneaded；Its gross porosity of EVA gross porosity composite foam material foams good at bubble effect, and improves resistance against compression energy and resilience performance, and pliability and resistance to consumption mill property are also improved.The preparation method is simple, easy to operate.
Description
Technical field
The present invention relates to athletic shoe sole Material Fields, and in particular to a kind of EVA gross porosity composite foam material and preparation
Method.
Background technique
With the fast development in sport footwear market, requirement of the people not only to sole wearing comfort is higher and higher, also chases after
Ask the novelty of sole appearance brilliant.Hole bubble in existing EVA gross porosity composite foam material is transparent cellular and is relatively large in diameter,
Conducive to light transparent refractive, then the color that can be embodied is more full bright-coloured；Therefore, sole on the market mostly uses the EVA gross porosity compound
Foamed material watches degree to promote its.
But the hole abscess diameter that existing EVA gross porosity composite foam material is formed due to it is excessive, leads to the resistance to of its entirety
Compression performance is poor；Then the sole as made from the material is easy to appear compression and collapses, and the defects of restoring to the original state is not easy after collapsing, i.e.,
The beauty for affecting sole forming, also reduces the wearing comfort of user.Therefore, it is necessary to improve the EVA gross porosity
The resistance against compression energy and resilience performance of composite foam material.
Secondly, that there is also quality is really up to the mark, elasticity is poor and the problems such as intolerant to abrasion for the EVA gross porosity composite foam material,
Then the sole as made from the material is equally unsuitable for wearing, and needs further to improve.
Summary of the invention
It is an object of the invention to overcome the problems, such as drawbacks described above present in background technique or, provide a kind of EVA gross porosity
Composite foam material, the EVA gross porosity composite foam material are chiefly used in sole, and gross porosity foams good at bubble effect, and significantly
Resistance against compression energy and resilience performance are improved, pliability and resistance to consumption mill property are also improved.Additionally provide the EVA gross porosity
The preparation method of composite foam material, the preparation method are simple, easy to operate.
To reach above-mentioned purpose, the present invention adopts the following technical scheme: a kind of EVA gross porosity composite foam material, by material
It is made through mixing, granulation and foaming；The material includes: that ethylene-vinyl acetate copolymer 40-60 mass parts, graphene change
Property isotactic polybutene 10-20 mass parts, polyolefin thermoplastic elastomer 10-15 mass parts, polyester elastomer 10-20 mass
Part, activating agent 0.4-0.8 mass parts, crosslinking agent 0.7-1.5 mass parts, foaming agent 2.5-3.5 mass parts and auxiliary agent 0.1-0.3 matter
Measure part；Wherein, vinylacetate mass content is 26%-40% in ethylene-vinyl acetate copolymer.
Preferably, the model of the ethylene-vinyl acetate copolymer be EVA7470M, EVA460, EVA462,
One or more of EVA265, EVA40L-03, EVA40W.
Preferably, the graphene mass content in the modified isotactic polybutene of the graphene is 0.05%-0.2%.
Preferably, the polyolefin thermoplastic elastomer is the ethylene octene random copolymer of metallocene preparation.
Preferably, model Engage8450, Engage8003 of the polyolefin thermoplastic elastomer,
One or more of Engage7467, Engage8150, Engage8180.
Preferably, one of model Royal DSM EL460, EL740, EM460, EM630 of the polyester elastic component
Or it is several.
Preferably, the activating agent is the one or more of stearic acid, fatty acid.
Preferably, the crosslinking agent is Isosorbide-5-Nitrae-dual-tert-butyl peroxy isopropyl base benzene.
Preferably, the foaming agent is gross porosity foaming agent.
Preferably, the auxiliary agent is triallyl isocyanurate.
Preferably, a kind of preparation method of EVA gross porosity composite foam material as described above, comprising the following steps: step
1: weighing quantitative isotactic PB Polybutene-1 and melted, matter is added when the melting temperature of isotactic PB Polybutene-1 is 140-170 DEG C
Amount content is 0.05%-0.2% graphene, so that the two obtains the modified isotactic polybutene of graphene after being kneaded；Mixing time is
25-40 minutes, temperature was 150-180 DEG C；Step 2: score weighs each component in the material by weight；Step 3: by step
The weighed other compositions in addition to crosslinking agent and foaming agent are kneaded in 2；Step 4: to the material after being kneaded in step 3
It is kneaded with crosslinking agent weighed in step 2 and foaming agent；Step 5: after being kneaded in step 4 obtained mixture according to
It is secondary to be granulated and foamed, obtain EVA mixed foaming material.
Preferably, the time being kneaded in the step 3 is 8-10 minutes, and temperature is 110-115 DEG C.
Preferably, the time being kneaded in the step 4 is 3-5 minutes, and temperature is 110-120 DEG C.
Preferably, the time foamed in the step 5 is 3-5 minutes, and temperature is 130-160 DEG C.
By the above-mentioned description of this invention it is found that compared with the existing technology, have following of the present invention the utility model has the advantages that
Vinylacetate (VA) mass content exists in the ethylene-vinyl acetate copolymer (EVA) used in the formula
Between 26%-40%；For VA as the soft segment in EVA strand, intramolecular chemical key inward turning is more free, can be formed
The random coil conformation irregularly crimped.The suitable VA mass content range can guarantee random coil conformation in polymer three
Being uniformly distributed in level structure is effectively reduced the crystallizing power of ethylene segment in polymer, protects polymer molecular chain as far as possible
Flexibility is held, to guarantee the pliability and high resiliency of composite material.
The modified isotactic polybutene of the graphene used in the formula, wherein the mass content of graphene is in 0.05%-0.2%
Between.The modified isotactic polybutene of the graphene is kneaded by graphene and isotactic PB Polybutene-1 to be made；Specifically, isotactic PB Polybutene-1
It is a kind of high molecular inert polymer, has good resistance against compression and abrasion performance；But due to isotactic PB Polybutene-1
Fusing point height when in crystal form II, mobility are poor, it is difficult to it directly applies in the conventional composite foamed system of EVA gross porosity, because
This need by the mixing with graphene it is compound after so that the mobility of isotactic PB Polybutene-1 has obtained significantly improving, ability
So that the two is kneaded the modified isotactic polybutene of graphene obtained and be suitable for the composite foamed system of EVA gross porosity, and due to flowing
Property promotion so that the distribution of cells in the EVA gross porosity composite foam material is more uniform, and its mechanical property and elasticity are also equal
It is improved；Wherein, graphene is not yet clear at present to the specific mechanism of modification of isotactic PB Polybutene-1.
Secondly as graphene has biggish specific surface area, then graphene, can be with after being kneaded with isotactic PB Polybutene-1
More physical crosslinking point is formed with reinforcing effect, further to improve the anti-of isotactic PB Polybutene-1 with isotactic PB Polybutene-1
Compressive Strength and tensile strength then use the compression resistant of the EVA gross porosity composite foam material of the modified isotactic polybutene of the graphene
Property and resilience performance obtained it is biggish improve, to compensate for since the abscess aperture of gross porosity foaming is excessive and cause not withstand pressure
The defect of contracting, and solve the EVA gross porosity composite foam material simultaneously due to being necessary to ensure that the transparent setting of abscess, and be not added with
Caused by reinforcing agent the problem of wear resistance decrease.
Polyolefin thermoplastic elastomer employed in the formula is the ethylene octene random copolymerization of metallocene catalysis preparation
Object, which there is relatively narrow relative molecular mass distribution and uniform short-chain branch to be distributed, so that the EVA gross porosity is composite foamed
Material has the advantages that density is low, resilience is good.
Polyester elastic component employed in the formula is also equally thermoplastic elastomer (TPE), compared to other elastic components
It says that performance is stablized, is not influenced vulnerable to ambient temperature, that is, ensure that the weatherability of the EVA gross porosity composite foam material；And the polyester
Property elastic component have good chemical resistance and creep resistance, i.e., so that the EVA gross porosity composite foam material effectively improve it is durable
Property has simultaneously widened workable environment.
Optimal friendship is constructed in the formula by using the activating agent of rational proportion, crosslinking agent, foaming agent and auxiliary agent etc.
Join foaming system, so that gross porosity foaming obtains preferable foaming effect, the hole bulb diameter of formation is larger, and transparency is high, to guarantee
The sole aesthetics made of the EVA gross porosity composite foam material gets a promotion；And then improve the composite foamed material of EVA gross porosity
Expect whole mechanical property and resilience performance.
The preparation method of the EVA gross porosity composite foam material, it is easy to operate, it is easily operated；Graphene obtained is blended in it
Modified isotactic polybutene performance is stablized, and the resistance against compression of the EVA gross porosity composite foam material is effectively improved；The preparation method institute
EVA gross porosity composite foam material obtained both can guarantee the aesthetic effect of gross porosity foaming, and its pliability, resilience and wear-resisting resistance to
Consumption is improved, so that the sole made of the EVA gross porosity composite foam material has good suitable wearing property and beauty
The property seen.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below.Obviously, described implementation
Example is the preferred embodiment of the present invention, and is not to be seen as excluding other embodiments.Based on the embodiment of the present invention, this field
Those of ordinary skill under the premise of not making creative work every other embodiment obtained, belong to protection of the present invention
Range.
In claims of the present invention and specification, unless otherwise specifically limited, term " first ", " second " are such as used
Or " third " etc., it is provided to distinguish different objects, be not use to describe a particular order.
In claims of the present invention and specification, unless otherwise specifically limited, such as using term " affixed " or " fixed
Connection ", should broadly understood, i.e., between the two without any connection mode of displacement relation and relative rotation relationship, that is,
It says including being unremovably fixedly connected with, being removably secured connection, be linked together and fixed by other devices or element
Connection.
In claims of the present invention and specification, term " includes ", " having " and their deformation, meaning are such as used
Figure is " including but not limited to ".
In embodiments of the present invention, the EVA gross porosity composite foam material is made by material through mixing, granulation and foaming；Institute
State material include: ethylene-vinyl acetate copolymer 40-60 mass parts, the modified isotactic polybutene 10-20 mass parts of graphene,
Polyolefin thermoplastic elastomer 10-15 mass parts, activating agent 0.4-0.8 mass parts, are handed over polyester elastomer 10-20 mass parts
Join agent 0.7-1.5 mass parts, foaming agent 2.5-3.5 mass parts and auxiliary agent 0.1-0.3 mass parts.
In the present embodiment, the model of used ethylene-vinyl acetate copolymer be EVA7470M, EVA460,
One or more of EVA462, EVA265, EVA40L-03, EVA40W.Wherein, acetic acid in ethylene-vinyl acetate copolymer
Vinyl acetate mass content is 26%-40%；VA is as the soft segment in EVA strand, and intramolecular chemical key inward turning is more
Freely, the random coil conformation irregularly crimped can be formed, which can guarantee random coil
Conformation being uniformly distributed in polymer tertiary structure, is effectively reduced the crystallizing power of ethylene segment in polymer, makes polymer
Strand keeps flexible as far as possible, to guarantee the pliability and high resiliency of composite material.
The modified isotactic polybutene of used graphene, wherein the mass content of graphene is between 0.05%-0.2%.
The modified isotactic polybutene of the graphene is kneaded by graphene and isotactic PB Polybutene-1 to be made；Specifically, isotactic PB Polybutene-1 is one
The high molecular inert polymer of kind, has good resistance against compression and abrasion performance；But since isotactic PB Polybutene-1 is in
Fusing point height when crystal form II, mobility are poor, it is difficult to directly apply in the conventional composite foamed system of EVA gross porosity, therefore need
Will by the mixing with graphene it is compound after so that the mobility of isotactic PB Polybutene-1 has obtained significantly improving, can just make two
Person is kneaded the modified isotactic polybutene of graphene obtained and is suitable for the composite foamed system of EVA gross porosity, and due to mobility
It is promoted so that the distribution of cells in the EVA gross porosity composite foam material is more uniform, and its mechanical property and elasticity also obtain
It is promoted；Wherein, graphene is not yet clear at present to the specific mechanism of modification of isotactic PB Polybutene-1.
Secondly as graphene has biggish specific surface area, then graphene, can be with after being kneaded with isotactic PB Polybutene-1
More physical crosslinking point is formed with reinforcing effect, further to improve the anti-of isotactic PB Polybutene-1 with isotactic PB Polybutene-1
Compressive Strength and tensile strength then use the compression resistant of the EVA gross porosity composite foam material of the modified isotactic polybutene of the graphene
Property and resilience performance obtained it is biggish improve, to compensate for since the abscess aperture of gross porosity foaming is excessive and cause not withstand pressure
The defect of contracting, and solve the EVA gross porosity composite foam material simultaneously due to being necessary to ensure that the transparent setting of abscess, and be not added with
Caused by reinforcing agent the problem of wear resistance decrease.
Specifically, isotactic polybutene and graphene are common raw material, and isotactic polybutene is that Shandong east great achievement chemical industry has
Companies market is limited, also there are many commercially available models may be selected for graphene.
Model Engage8450, Engage8003 of used polyolefin thermoplastic elastomer, Engage7467,
One or more of Engage8150, Engage8180.The polyolefin thermoplastic elastomer is that the ethylene of metallocene preparation is pungent
Olefinic random copolymer.There is the copolymer relatively narrow relative molecular mass distribution and uniform short-chain branch to be distributed, so that the EVA is thick
Hole composite foam material has the advantages that density is low, resilience is good.
One of model Royal DSM EL460, EL740, EM460, EM630 of used polyester elastic component or
It is several.The polyester elastic component equally also be thermoplastic elastomer (TPE), compared to for other elastic components performance stablize, not vulnerable to
Ambient temperature influences, that is, ensure that the weatherability of the EVA gross porosity composite foam material；And the polyester elastic component is with good
Chemical resistance and creep resistance, even if the EVA gross porosity composite foam material effectively improves durability and widened workable ring
Border.
Used activating agent is the one or more of stearic acid, fatty acid.
Used crosslinking agent is 1,4 bis tert butyl peroxy isopropyl benzene.
Used foaming agent is gross porosity foaming agent.
Used auxiliary agent is triallyl isocyanurate.
Optimal friendship is constructed in the formula by using the activating agent of rational proportion, crosslinking agent, foaming agent and auxiliary agent etc.
Join foaming system, so that gross porosity foaming obtains preferable foaming effect, to guarantee made of the EVA gross porosity composite foam material
Sole aesthetics gets a promotion；And then improve the mechanical property and resilience performance of the EVA gross porosity composite foam material entirety.
Correspondingly, the embodiment of the invention also provides the preparation methods of the EVA gross porosity composite foam material, including following step
It is rapid:
Step 1: weighing quantitative isotactic PB Polybutene-1 and melted, be 140- in the melting temperature of isotactic PB Polybutene-1
It is 0.05%-0.2% graphene that mass content is added at 170 DEG C, so that the two obtains the modified poly- fourth of isotactic of graphene after being kneaded
Alkene；Mixing time is 25-40 minutes, and temperature is 150-180 DEG C；
Step 2: score weighs each component in the material by weight；
Step 3: the other compositions in addition to crosslinking agent and foaming agent weighed in step 2 are kneaded；It is kneaded
Time is 8-15 minutes, and temperature is 100-110 DEG C.
Step 4: being kneaded to the material after being kneaded in step 3 with crosslinking agent weighed in step 2 and foaming agent；It is mixed
The time of refining is 3-5 minutes, and temperature is 110-120 DEG C.
Step 5: the mixture obtained after being kneaded in step 4 is successively granulated and is foamed, and EVA mixed foaming is obtained
Material；The time of foaming is 3-5 minutes, and temperature is 14-160 DEG C.
In the present embodiment, the preparation method of the EVA gross porosity composite foam material is easy to operate, easily operated；It is blended
The modified isotactic polybutene performance of graphene obtained is stablized, and the resistance against compression of the EVA gross porosity composite foam material is effectively improved
And resilience performance；EVA gross porosity composite foam material obtained by the preparation method both can guarantee the aesthetic effect of gross porosity foaming, and
Its pliability, resilience and wear-resisting resistance to consumption are improved, so that the shoes made of the EVA gross porosity composite foam material
Bottom has good suitable wearing property and aesthetics.
EVA gross porosity composite foam material prepared by the embodiment of the present invention can be used for making the sole of sport footwear, then is made
Sole is beautiful novel and comfortable and easy to wear, compression resistant stretch-proof environmental enrichment applicatory.
Specifically, the EVA gross porosity composite foam material is made by the following two kinds embodiment in the present invention, and respectively to its object
Rationality can be carried out detection, and testing result is as shown in Table 1.
Embodiment one:
In the embodiment of the present invention one, the proportion by weight of its contained material of the EVA gross porosity composite foam material is as follows:
Ethylene-vinyl acetate copolymer: 45 mass parts
Graphene is modified isotactic polybutene: 15 mass parts
Polyolefin thermoplastic elastomer: 15 mass parts
Polyester elastomer: 15 mass parts
Activating agent: 0.6 mass parts
Crosslinking agent: 1.2 mass parts
Foaming agent: 3.0 mass parts
Auxiliary agent: 0.3 mass parts
Wherein, the production of ethylene-vinyl acetate copolymer model 7470M, Tai Su company；Polybutene is that Shandong east is macro
Industry Chemical Co., Ltd. is commercially available；Graphene is commercially available；Polyolefin thermoplastic elastomer model Engage8180 and
Engage8450, its ratio be 2:1, E.I.Du Pont Company's productions；The model Royal DSM EL430 of polyester elastomer；Activating agent is
Stearic acid, fatty acid；Crosslinking agent is Isosorbide-5-Nitrae dual-tert-butyl peroxy isopropyl base benzene；Foaming agent is gross porosity foaming agent, the unrestrained chemical industry of Fujian brocade
Co., Ltd's production；Auxiliary agent is triallyl isocyanurate, the beautiful chemical production in sea.
In embodiment one, operated in accordance with the following steps:
Step 1: weigh quantitative isotactic PB Polybutene-1, and the melting temperature of isotactic PB Polybutene-1 be 140-170 DEG C at present
The graphene that mass content is 0.05%-0.2% is added, so that the two is kneaded the modified poly- fourth of isotactic of modified acquisition graphene
Alkene.Preferably, it is 25-40 minutes that the time, which is blended, and melting temperature is 150-180 DEG C.
Step 2: the above component is poured into progress first time mixing in mixer in addition to crosslinking agent and foaming agent.Preferably,
First time mixing time is 8-10 minutes, and melting temperature is 100-115 DEG C.
Step 3: to be kneaded in step 2 in uniform material be added crosslinking agent (Isosorbide-5-Nitrae dual-tert-butyl peroxy isopropyl base benzene) and
It is poured into after foaming agent (gross porosity foaming agent) in mixer and carries out second of mixing.Preferably, mixing time is 3-5 minutes, is kneaded
Temperature is 115-120 DEG C.
Step 4: uniform material will be kneaded in step 3 and poured into start to be granulated in pelletizer, then foaming, to obtain
The EVA gross porosity composite foam material.Preferably, foamed time is 3-5 minutes, and temperature is 130-160 DEG C.
Embodiment two:
In the embodiment of the present invention two, the proportion by weight of its contained material of the EVA gross porosity composite foam material is as follows:
Ethylene-vinyl acetate copolymer: 40 mass parts
Graphene is modified isotactic polybutene: 20 mass parts
Polyolefin thermoplastic elastomer: 10 mass parts
Polyester elastomer: 10 mass parts
Activating agent: 0.8 mass parts
Crosslinking agent: 1.5 mass parts
Foaming agent: 2.8 mass parts
Auxiliary agent: 0.2 mass parts
Wherein, the production of ethylene-vinyl acetate copolymer model 7470M, Tai Su company；Polybutene is that Shandong east is macro
Industry Chemical Co., Ltd. is commercially available；Graphene is commercially available；Polyolefin thermoplastic elastomer model Engage8180 and
Engage8450, its ratio be 1:1, E.I.Du Pont Company's productions；Model the Royal DSM EL430 and EL250 of polyester elastomer are mixed
Complex ratios are 1:1；Activating agent is stearic acid, fatty acid；Crosslinking agent is Isosorbide-5-Nitrae dual-tert-butyl peroxy isopropyl base benzene；Foaming agent is
Gross porosity foaming agent, the production of Fujian Jin Lang Chemical Co., Ltd.；Auxiliary agent is triallyl isocyanurate, the beautiful chemical production in sea.
In example 2, it is operated in accordance with the following steps:
Step 1: weigh quantitative isotactic PB Polybutene-1, and the melting temperature of isotactic PB Polybutene-1 be 140-170 DEG C at present
The graphene that mass content is 0.05%-0.2% is added, so that the two is kneaded the modified poly- fourth of isotactic of modified acquisition graphene
Alkene.Preferably, it is 25-40 minutes that the time, which is blended, and melting temperature is 150-180 DEG C.
Step 2: the above component is poured into progress first time mixing in mixer in addition to crosslinking agent and foaming agent.Preferably,
First time mixing time is 8-10 minutes, and melting temperature is 100-115 DEG C.
Step 3: carrying out the to being kneaded in uniform material to be added after crosslinking agent and foaming agent to pour into mixer in step 2
Secondary mixing.Preferably, second of mixing time is 3-5 minutes, and melting temperature is 115-120 DEG C.
Step 4: uniform material will be kneaded in step 3 and poured into start to be granulated in pelletizer, then foaming, to obtain
The EVA gross porosity composite foam material.Preferably, foamed time is 3-5 minutes, and temperature is 130-160 DEG C.
For above-described embodiment one, following comparative example one and comparative example two are provided, the specific control area of component is as follows:
Comparative example one: compared with the formula in embodiment one, using the material such as alkene conventionally used for improving resistance against compression
Block copolymer infuse9017, to replace the modified isotactic polybutene of the graphene in this formula；Other components and mass parts are not
Become.
Comparative example two: compared with the formula in embodiment one, using the material such as alkene conventionally used for improving resistance against compression
Block copolymer infuse9017, to replace the modified isotactic polybutene of the graphene in formula；Polyolefin thermoplastic elastomer
Mass fraction is adjusted to 30 mass parts by 15 mass parts, to replace the polyester elastomer in formula；Other components and mass parts
It is constant.
In comparative example one of the present invention, the proportion by weight of its contained material of the EVA gross porosity composite foam material is as follows:
Ethylene-vinyl acetate copolymer: 45 mass parts
Polyolefin block copolymer: 15 mass parts
Polyolefin thermoplastic elastomer: 15 mass parts
Polyester elastomer: 15 mass parts
Activating agent: 0.6 mass parts
Crosslinking agent: 1.2 mass parts
Foaming agent: 3.0 mass parts
Auxiliary agent: 0.3 mass parts
Wherein, the production of ethylene-vinyl acetate copolymer model 7470M, Tai Su company；Olefin block copolymers
Infuse9017, the Dow Chemical Company's production；Polyolefin thermoplastic elastomer model Engage8180 and Engage8450, ratio
For 2:1, E.I.Du Pont Company's production；The model Royal DSM EL430 of polyester elastomer；Activating agent is stearic acid, fatty acid；Crosslinking
Agent is Isosorbide-5-Nitrae dual-tert-butyl peroxy isopropyl base benzene；Foaming agent is gross porosity foaming agent, the production of Fujian Jin Lang Chemical Co., Ltd.；Auxiliary agent
For triallyl isocyanurate, the beautiful chemical production in sea.The foaming process conditions of the comparative example one are the same as example 1, and are not made
Repeated explanation.
In comparative example two of the present invention, the proportion by weight of its contained material of the EVA gross porosity composite foam material is as follows:
Ethylene-vinyl acetate copolymer: 45 mass parts
Polyolefin block copolymer: 15 mass parts
Polyolefin thermoplastic elastomer: 30 mass parts
Activating agent: 0.6 mass parts
Crosslinking agent: 1.2 mass parts
Foaming agent: 3.0 mass parts
Auxiliary agent: 0.3 mass parts
Wherein, the production of ethylene-vinyl acetate copolymer model 7470M, Tai Su company；Olefin block copolymers
Infuse9017, the Dow Chemical Company's production；Polyolefin thermoplastic elastomer model Engage8180 and Engage8450, ratio
For 2:1, E.I.Du Pont Company's production；The model Royal DSM EL430 of polyester elastomer；Activating agent is stearic acid, fatty acid；Crosslinking
Agent is Isosorbide-5-Nitrae dual-tert-butyl peroxy isopropyl base benzene；Foaming agent is gross porosity foaming agent, the production of Fujian Jin Lang Chemical Co., Ltd.；Auxiliary agent
For triallyl isocyanurate, the beautiful chemical production in sea.The foaming process conditions of the comparative example one are the same as example 1, and are not made
Repeated explanation.
It is compound with EVA gross porosity obtained by above-described embodiment one and embodiment two and comparative example one and comparative example two respectively
Foamed material carries out quantitative measurement, and test result is referring to table 1.
Table 1 shows the physical properties feelings of EVA gross porosity composite foam material obtained by each embodiment and comparative example
Condition.Wherein, specific testing conditions are 23 ± 3 DEG C of temperature, humidity 65 ± 5%.
The quantitative measurement result of product obtained by 1 embodiment one of table, embodiment two and comparative example one, comparative example two
Note: 1 data of table are the data obtained by national standard test method.
The results show that compression measured by EVA gross porosity composite foam material obtained by embodiment one and embodiment two becomes
Form quotient is respectively 42% and 39%, and measured resilience is respectively 57% and 59%；And EVA obtained in comparative example one is thick
Compression deformation rate measured by the composite foam material of hole is 45%, and measured resilience is 51%；That is embodiment one and implementation
The compression deformation rate of the EVA gross porosity composite foam material of example two is low compared to comparative example one, and resilience performance is compared to comparative example
One is high.
It follows that the modified isotactic polybutene of added graphene improves really in embodiment one and embodiment two
The resistance against compression energy and resilience performance of EVA gross porosity composite foam material entirety, and do not influence EVA gross porosity composite foam material simultaneously
Other performances.It ensure that and use the sole of EVA gross porosity composite foam material made from embodiment one and embodiment two can be with
Long-time compression resistant is not easy to collapse and rebound degree is high, while improving its aesthetics and suitable wearing property.
Compression deformation rate measured by EVA gross porosity composite foam material obtained by embodiment one and embodiment two is respectively
42% and 39%, measured resilience is respectively 57% and 59%；And EVA gross porosity obtained in comparative example two is composite foamed
Compression deformation rate measured by material is 47%, and measured resilience is 43%；That is the EVA of embodiment one and embodiment two is thick
The compressed shape variability of hole composite foam material is low compared to comparative example one, and resilience performance is high compared to comparative example one.
It is i.e. provable, it is modified that graphene is not only in the EVA gross porosity composite foam material in embodiment one and embodiment two
Isotactic polybutene improves the resistance against compression energy and resilience performance of material entirety, and polyester elastomer is equally to material entirety
Resistance against compression can have with resilience performance to be significantly affected, wherein the improvement to resilience performance is more significant.That is one He of the present embodiment
The resilience performance of EVA gross porosity composite foam material in embodiment two is excellent, its damping effect that sole is made has been effectively ensured.
The difference of DIN abrasion performance value measured by EVA gross porosity composite foam material obtained by embodiment one and embodiment two
For 252mm3And 236mm3；And DIN measured by EVA gross porosity composite foam material obtained in comparative example one and comparative example two
Abrasion performance value is respectively 337mm3And 366mm3；That is the DIN of the EVA gross porosity composite foam material of embodiment one and embodiment two is resistance to
Wearing valve is obvious relatively low compared to comparative example one and comparative example two.
It follows that the modified isotactic polybutene of added graphene improves really in embodiment one and embodiment two
The abrasion performance of EVA gross porosity composite foam material entirety, and do not influence other performances of EVA gross porosity composite foam material simultaneously.I.e.
It ensure that durable using the sole of EVA gross porosity composite foam material made from embodiment one and embodiment two.
By the test data of above embodiments one and embodiment two it is found that the composite foamed material of EVA gross porosity produced by the present invention
The hardness of material is less than 55Asker C, and soft, the high and low compression deformation rate of resilience performance, abrasion resisting ability are strong, improve
Traditional EVA gross porosity composite foam material quality is hard, resilience performance is poor, intolerant to compression, intolerant to abrasion the problems such as, meet national phase
Close physical property standard.
In summary it analyzes, technical solution disclosed by the invention solves whole technical problems listed by specification, realizes
Corresponding technical effect.Its gross porosity of provided EVA gross porosity composite foam material foams good at bubble effect, and significantly mentions
High resistance against compression energy and resilience performance, pliability and resistance to consumption grind property and are also improved.It is multiple to additionally provide the EVA gross porosity
The preparation method of foamed material is closed, the preparation method is simple, easy to operate.
The description of description above and embodiment is used to explain the present invention protection scope, but does not constitute and protect to the present invention
Protect the restriction of range.Through the invention or the enlightenment of above-described embodiment, those of ordinary skill in the art combine common knowledge, ability
The ordinary technical knowledge and/or the prior art in domain, it is available right by logical analysis, reasoning or limited test
Modification, equivalent replacement or the other improvements of the embodiment of the present invention or in which a part of technical characteristic, should be included in of the invention
Within protection scope.
Claims (14)
1. a kind of EVA gross porosity composite foam material, it is characterized in that: being made by material through mixing, granulation and foaming；The material packet
It includes: the modified isotactic polybutene 10-20 mass parts of ethylene-vinyl acetate copolymer 40-60 mass parts, graphene, polyolefin heat
Thermoplastic elastic 10-15 mass parts, polyester elastomer 10-20 mass parts, activating agent 0.4-0.8 mass parts, crosslinking agent 0.7-
1.5 mass parts, foaming agent 2.5-3.5 mass parts and auxiliary agent 0.1-0.3 mass parts；Wherein, in ethylene-vinyl acetate copolymer
Vinylacetate mass content is 26%-40%.
2. a kind of EVA gross porosity composite foam material as described in claim 1, it is characterised in that: the ethylene-vinyl acetate
The model of copolymer is one or more of EVA7470M, EVA460, EVA462, EVA265, EVA40L-03, EVA40W.
3. a kind of EVA gross porosity composite foam material as described in claim 1, it is characterised in that: the modified isotactic of the graphene
Graphene mass content in polybutene is 0.05%-0.2%.
4. a kind of EVA gross porosity composite foam material as described in claim 1, it is characterised in that: the polylefin thermoplatic bullet
Property body be metallocene preparation ethylene octene random copolymer.
5. a kind of EVA gross porosity composite foam material as claimed in claim 4, it is characterised in that: the polylefin thermoplatic bullet
One of model Engage8450, Engage8003, Engage7467, Engage8150, Engage8180 of property body or
It is several.
6. a kind of EVA gross porosity composite foam material as described in claim 1, it is characterised in that: the polyester elastic component
One of model Royal DSM EL460, EL740, EM460, EM630 are several.
7. a kind of EVA gross porosity composite foam material as claimed in claim 6, it is characterised in that: the activating agent be stearic acid,
The one or more of fatty acid.
8. a kind of EVA gross porosity composite foam material as described in claim 1, it is characterised in that: the crosslinking agent is that Isosorbide-5-Nitrae-is bis-
Tert-butylperoxyiso-propyl benzene.
9. a kind of EVA gross porosity composite foam material as described in claim 1, it is characterised in that: the foaming agent is gross porosity hair
Infusion.
10. a kind of EVA gross porosity composite foam material as described in claim 1, it is characterised in that: the auxiliary agent is triallyl
Chlorinated isocyanurates.
11. such as a kind of described in any item preparation methods of EVA gross porosity composite foam material of claim 1-10, feature exists
In: the following steps are included:
Step 1: weighing quantitative isotactic PB Polybutene-1 and melted, be 140-170 DEG C in the melting temperature of isotactic PB Polybutene-1
When mass content is added is 0.05%-0.2% graphene so that the two obtains the modified isotactic polybutene of graphene after being kneaded；It is mixed
Refining the time is 25-40 minutes, and temperature is 150-180 DEG C；
Step 2: score weighs each component in the material by weight；
Step 3: the other compositions in addition to crosslinking agent and foaming agent weighed in step 2 are kneaded；
Step 4: being kneaded to the material after being kneaded in step 3 with crosslinking agent weighed in step 2 and foaming agent；
Step 5: the mixture obtained after being kneaded in step 4 is successively granulated and is foamed, and EVA mixed foaming material is obtained
Material.
12. a kind of preparation method of EVA gross porosity composite foam material as claimed in claim 11, it is characterised in that: the step
The time being kneaded in rapid 3 is 8-10 minutes, and temperature is 110-115 DEG C.
13. a kind of preparation method of EVA gross porosity composite foam material as claimed in claim 11, it is characterised in that: the step
The time being kneaded in rapid 4 is 3-5 minutes, and temperature is 110-120 DEG C.
14. a kind of preparation method of EVA gross porosity composite foam material as claimed in claim 11, it is characterised in that: the step
The time foamed in rapid 5 is 3-5 minutes, and temperature is 130-160 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040290A (en) * | 2019-12-27 | 2020-04-21 | 安踏（中国）有限公司 | High-cushioning composite foam material and preparation method thereof |
| CN111138750A (en) * | 2019-12-27 | 2020-05-12 | 安踏（中国）有限公司 | Anti-slip wear-resistant composite material and preparation method thereof |
| CN111534081A (en) * | 2020-06-02 | 2020-08-14 | 安踏（中国）有限公司 | Insole material with natural light transmission and preparation method thereof |
| CN112778621A (en) * | 2020-12-31 | 2021-05-11 | 安踏（中国）有限公司 | Composition for preparing high-elasticity memory EVA composite foaming material for sneaker sole and preparation method |
| CN114921018A (en) * | 2022-03-17 | 2022-08-19 | 三六一度(中国)有限公司 | Ultralight wear-resistant sole material, preparation method thereof and shoes |
| WO2022184597A1 (en) * | 2021-03-02 | 2022-09-09 | Inoveight Limited | A shoe sole formed from a polymeric foam compound with enhanced perfomance characteristics |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383567A (en) * | 2017-03-15 | 2017-11-24 | 墨烯材料科技有限公司 | High-elastic soft composite foam material of a kind of graphene/polymer lightweight and preparation method thereof |
| KR101814003B1 (en) * | 2016-08-26 | 2018-01-02 | 주식회사 미래텍 | Automotive interior foam composition using an olefin block copolymer and method for manufacturing a foam using the same |
| CN109021374A (en) * | 2018-07-14 | 2018-12-18 | 福州大学 | A kind of weather-proof anti-skidding EVA foamed material that graphene oxide-polyisobutene is modified |
-
2019
- 2019-06-21 CN CN201910540109.7A patent/CN110229411B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101814003B1 (en) * | 2016-08-26 | 2018-01-02 | 주식회사 미래텍 | Automotive interior foam composition using an olefin block copolymer and method for manufacturing a foam using the same |
| CN107383567A (en) * | 2017-03-15 | 2017-11-24 | 墨烯材料科技有限公司 | High-elastic soft composite foam material of a kind of graphene/polymer lightweight and preparation method thereof |
| CN109021374A (en) * | 2018-07-14 | 2018-12-18 | 福州大学 | A kind of weather-proof anti-skidding EVA foamed material that graphene oxide-polyisobutene is modified |
Non-Patent Citations (1)
| Title |
|---|
| 段成龙 等: "聚丁烯-1复合材料研究概况", 《合成材料老化与应用》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040290A (en) * | 2019-12-27 | 2020-04-21 | 安踏（中国）有限公司 | High-cushioning composite foam material and preparation method thereof |
| CN111138750A (en) * | 2019-12-27 | 2020-05-12 | 安踏（中国）有限公司 | Anti-slip wear-resistant composite material and preparation method thereof |
| CN111534081A (en) * | 2020-06-02 | 2020-08-14 | 安踏（中国）有限公司 | Insole material with natural light transmission and preparation method thereof |
| CN111534081B (en) * | 2020-06-02 | 2021-12-24 | 安踏（中国）有限公司 | Insole material with natural light transmission and preparation method thereof |
| CN112778621A (en) * | 2020-12-31 | 2021-05-11 | 安踏（中国）有限公司 | Composition for preparing high-elasticity memory EVA composite foaming material for sneaker sole and preparation method |
| CN112778621B (en) * | 2020-12-31 | 2023-01-10 | 安踏（中国）有限公司 | Composition for preparing high-elasticity memory EVA composite foaming material for sneaker sole and preparation method |
| WO2022184597A1 (en) * | 2021-03-02 | 2022-09-09 | Inoveight Limited | A shoe sole formed from a polymeric foam compound with enhanced perfomance characteristics |
| CN114921018A (en) * | 2022-03-17 | 2022-08-19 | 三六一度(中国)有限公司 | Ultralight wear-resistant sole material, preparation method thereof and shoes |
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