CN109438821B - High-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof - Google Patents
High-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
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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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- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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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
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
The invention discloses a high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material which comprises the following components in parts by weight: 40-75 parts of ethylene-vinyl acetate copolymer, 0-30 parts of elastomer, 0.5-10 parts of compatilizer, 0-30 parts of rubber, 15-40 parts of graphene, 0-5 parts of wear-resisting agent, 0.4-1.2 parts of bridging agent, 0.6-2.0 parts of foaming agent, 0-2 parts of crosslinking aid, 0.6-2.0 parts of foaming promoter, 0-1.5 parts of lubricant and 0-10 parts of toner. The invention also discloses a preparation method of the high-thermal-conductivity graphene modified EVA foaming material. The high-thermal-conductivity graphene modified EVA foaming material disclosed by the invention has good thermal conductivity, ensures that heat of soles in products such as slippers and sports shoes can be effectively dissipated, can obviously shorten the molding time of secondary foaming of the EVA foaming material, and improves the manufacturing efficiency of EVA foaming products.
Description
Technical Field
The invention relates to the technical field of high polymer material foaming, in particular to a high-thermal-conductivity graphene modified EVA foaming material and a preparation method thereof.
Background
EVA, an Ethylene Vinyl Acetate copolymer, is prepared by copolymerizing Ethylene (english name is Ethylene) and Vinyl Acetate (english name is Vinyl Acetate), which is called Ethylene Vinyl Acetate, abbreviated as EVA, or E/VAC, wherein the content of Vinyl Acetate is generally 5% to 40%. Because the cost is low and compared with polyethylene, because EVA introduces vinyl acetate monomer in molecular chain, thus has reduced the degree of crystallinity, has improved flexibility, impact resistance, filler intermiscibility and heat sealing performance, therefore is applied to fields such as shoes industry, building materials industry, case and bag industry and toy industry extensively.
At present, EVA foaming materials applied to the field of shoe materials are mainly prepared by adding auxiliary agents such as elastomers, polyolefin, rubber, foaming agents, fillers, bridging agents, auxiliary crosslinking agents, foaming promoters, lubricants and the like into EVA and then foaming. Seen from the heat conduction path of finished shoes, the cloth on the upper surface can be outwards output from the gap in the upper surface due to the fact that the cloth leads to the heat radiated upwards by the foot due to the textile structure of the cloth, but because a large amount of air is filled in the EVA foaming material used for manufacturing the insole of the shoe, the heat of the sole is difficult to penetrate through the sole and is timely removed. In addition, to the secondary foaming design of EVA, because the foaming structure of EVA itself leads to the time of heating to EVA expanded material to prolong greatly in the post forming, post forming's machining efficiency is lower.
Aiming at the problems of the secondary forming process and the heat conducting property of the existing EVA foaming insole, the EVA foaming material which has the advantages of high heat conducting property, high hardness, high tearing strength and the like, short secondary forming time, high processing efficiency and the like is developed, and the EVA foaming material has important application value and practical significance.
Disclosure of Invention
The invention aims to provide a high-thermal-conductivity graphene modified EVA foaming material which has good thermal conductivity, ensures that heat of soles in products such as slippers and sports shoes can be effectively dissipated, can remarkably shorten the molding time of secondary foaming of the EVA foaming material, and improves the manufacturing efficiency of EVA foaming products.
The invention also aims to provide a preparation method of the high-thermal-conductivity graphene modified EVA foaming material.
In order to achieve the above purpose, the solution of the invention is:
the high-thermal-conductivity graphene modified EVA foam material comprises the following components in parts by weight: 40-75 parts of ethylene-vinyl acetate copolymer, 0-30 parts of elastomer, 0.5-10 parts of compatilizer, 0-30 parts of rubber, 15-40 parts of graphene, 0-5 parts of wear-resisting agent, 0.4-1.2 parts of bridging agent, 0.6-2.0 parts of foaming agent, 0-2 parts of crosslinking aid, 0.6-2.0 parts of foaming promoter, 0-1.5 parts of lubricant and 0-10 parts of toner, wherein the compatilizer is glycidyl methacrylate graft copolymer compatilizer.
The rubber-modified polyvinyl acetate composite material comprises, by weight, 50-65 parts of an ethylene-vinyl acetate copolymer, 10-20 parts of an elastomer, 1-5 parts of a compatilizer, 10-20 parts of rubber, 20-35 parts of graphene, 0-2 parts of an abrasion-resistant agent, 0.6-1.0 part of a bridging agent, 0.8-1.5 parts of a foaming agent, 0-1 part of a cross-linking aid, 0.8-1.5 parts of a foaming promoter, 0-1.0 part of a lubricant and 0-5 parts of a toner.
The ethylene-vinyl acetate copolymer is one or a combination of several of ethylene-vinyl acetate copolymers with the vinyl acetate content of 1-50%; the elastomer is one or the combination of two of polyolefin elastomer and styrene thermoplastic elastomer.
The compatilizer is one or a combination of more of glycidyl methacrylate grafted PE, glycidyl methacrylate grafted EVA, glycidyl methacrylate grafted SEBS and glycidyl methacrylate grafted POE.
The rubber is one or a combination of more of natural rubber, chloroprene rubber, brominated butyl rubber, nitrile rubber, ethylene propylene diene monomer rubber, butadiene rubber and styrene butadiene rubber; the graphene is a graphene material with less than 100 layers; the wear-resisting agent is polysiloxane with the molecular weight of 1-100 ten thousand; the bridging agent is one or a combination of more of dicumyl peroxide, di-tert-butylperoxyisopropyl benzene, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and tert-amyl peroxy (2-ethylhexyl) carbonate; the foaming agent is one or a combination of more of azodicarbonamide, N' -dinitrosopentamethylenetetramine and sodium bicarbonate.
The auxiliary crosslinking agent is one or the combination of two of triallyl isocyanurate and trimethylolpropane triacrylate; the foaming promoter is one or the combination of two of zinc oxide and zinc carbonate; the lubricant is one or a combination of stearic acid, stearate, wax substances and a plasticizer.
A preparation method of a high-thermal-conductivity graphene modified EVA foam material comprises the following steps:
(1) uniformly mixing 40-75 parts of ethylene-vinyl acetate copolymer, 0-30 parts of elastomer, 0.5-10 parts of compatilizer, 0-30 parts of rubber and 15-40 parts of graphene, and extruding and granulating by using a double screw to obtain the graphene-containing EVA composition;
(2) adding 0-5 parts of wear-resisting agent, 0.4-1.2 parts of bridging agent, 0.6-2.0 parts of foaming agent, 0-2 parts of auxiliary crosslinking agent, 0.6-2.0 parts of foaming promoter, 0-1.5 parts of lubricant and 0-10 parts of toner into the EVA composition obtained in the step (1), uniformly mixing, mixing by a mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
In the step (1), the rotating speed of the screws for twin-screw extrusion granulation is 10-50 rmp, the extrusion temperature is 130-210 ℃, and the extrusion time is 5-20 min.
In the step (2), the mixing time is 2-30 min; the mixing temperature is 90-140 ℃.
After the technical scheme is adopted, the high-thermal-conductivity graphene modified EVA foam material and the preparation method thereof have the following beneficial effects:
1) due to the addition of the glycidyl methacrylate graft copolymer compatilizer, the graphene can be uniformly dispersed in the EVA foam material, and the graphene and the EVA matrix have stronger interfacial bonding strength through the chemical reaction of the functional groups on the surface of the graphene and the glycidyl methacrylate graft copolymer, and the roller sticking problem caused by the traditional addition of the maleic anhydride graft copolymer compatilizer is effectively solved;
2) the heat conductivity of the EVA foaming material is greatly improved by the added high-filling-amount graphene, so that the heat of soles in products such as slippers and sports shoes can be effectively dissipated, the secondary foaming molding time of the EVA foaming material can be remarkably shortened, and the manufacturing efficiency of EVA foaming products is improved.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
40 parts of ethylene-vinyl acetate copolymer with 16 percent of EVA content, 20 parts of ethylene octene copolymer, 10 parts of natural rubber, 1 part of glycidyl methacrylate grafted POE, 20 parts of graphene with less than 10 layers, 0.4 part of silicone oil with 60 ten thousand of molecular weight, 1.2 parts of di-tert-butylperoxyisopropyl benzene, 2.0 parts of azodicarbonamide, 1.3 parts of triallyl isocyanurate, 1.8 parts of zinc oxide, 0.5 part of stearic acid and 3.0 parts of toner.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 40 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 20 parts of ethylene octene copolymer, 10 parts of natural rubber, 1 parts of glycidyl methacrylate grafted POE and 20 parts of graphene with the number of layers smaller than 10, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 40rmp, the extrusion temperature is 130 ℃ and the extrusion time is 20min to obtain the EVA composition containing graphene;
(2) adding 0.4 part of silicone oil with the molecular weight of 60 ten thousand, 1.2 parts of di-tert-butylperoxyisopropyl benzene, 2.0 parts of azodicarbonamide, 1.3 parts of triallyl isocyanurate, 1.8 parts of zinc oxide, 0.5 part of stearic acid and 3.0 parts of toner into the EVA composition obtained in the step (1), uniformly mixing, mixing for 30min at 90 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Performance testing of EVA foams
The EVA foaming material obtained is subjected to performance test, and has the hardness of 43(Type C) and the density of 0.24g/cm3The tensile strength is 2.9MPa, the elongation at break is 250%, the compression distortion is 30%, the rebound resilience is 47%, the thermal conductivity is 0.35W/m.K, and the secondary foaming and setting time is 250 s.
Comparative example 1
1. Preparation of traditional EVA foaming material
An ethylene-vinyl acetate copolymer having an EVA content of 16%, an ethylene-octene copolymer (EVA) of 20 parts, a natural rubber of 10 parts, a silicone oil having a molecular weight of 60 ten thousand (0.4 part), di-t-butylperoxyisopropyl benzene of 1.2 parts, azodicarbonamide of 2.0 parts, triallyl isocyanurate of 1.3 parts, zinc oxide of 1.8 parts, stearic acid of 0.5 part, and a toner of 3.0 parts were uniformly mixed, and then kneaded at 90 ℃ for 30 minutes in a kneader, followed by granulation in a granulator to obtain an EVA composition. And (3) injecting the obtained EVA composition by an EVA injection machine, vulcanizing and foaming outside a mould to obtain the EVA foaming material.
2. Performance testing of conventional EVA foam materials
The EVA foaming material obtained is subjected to performance test, and has the hardness of 41(Type C) and the density of 0.24g/cm3The tensile strength is 2.6MPa, the elongation at break is 280%, the compression distortion is 31%, the rebound resilience is 47%, the thermal conductivity is 0.06W/m.K, and the secondary foaming and setting time is 480 s.
Comparative example 2
1. Components of graphene modified EVA (ethylene-vinyl acetate) foaming material
40 parts of ethylene-vinyl acetate copolymer with 16 percent of EVA content, 20 parts of ethylene octene copolymer, 10 parts of natural rubber, 1 part of glycidyl methacrylate grafted POE, 10 parts of graphene with less than 10 layers, 0.4 part of silicone oil with 60 ten thousand of molecular weight, 1.2 parts of di-tert-butylperoxyisopropyl benzene, 2.0 parts of azodicarbonamide, 1.3 parts of triallyl isocyanurate, 1.8 parts of zinc oxide, 0.5 part of stearic acid and 3.0 parts of toner.
2. Preparation of graphene modified EVA (ethylene-vinyl acetate) foaming material
(1) Uniformly mixing 40 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 20 parts of ethylene octene copolymer, 10 parts of natural rubber, 1 parts of glycidyl methacrylate grafted POE and 10 parts of graphene with the number of layers smaller than 10, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 40rmp, the extrusion temperature is 130 ℃ and the extrusion time is 20min to obtain the EVA composition containing graphene;
(2) adding 0.4 part of silicone oil with the molecular weight of 60 ten thousand, 1.2 parts of di-tert-butylperoxyisopropyl benzene, 2.0 parts of azodicarbonamide, 1.3 parts of triallyl isocyanurate, 1.8 parts of zinc oxide, 0.5 part of stearic acid and 3.0 parts of toner into the EVA composition obtained in the step (1), uniformly mixing, mixing for 30min at 90 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) injecting the EVA granules obtained in the step (2) by an EVA injection machine, vulcanizing and foaming outside a mould to obtain the graphene modified EVA foaming material.
Performance testing of EVA foams
The EVA foaming material obtained is subjected to performance test, and has the hardness of 43(Type C) and the density of 0.24g/cm3The tensile strength is 2.8MPa, the elongation at break is 280%, the compression distortion is 28%, the rebound rate is 52%, the thermal conductivity is 0.09W/m.K, and the secondary foaming and setting time is 460 s.
Comparing the performance test result of example 1 with the performance test results of comparative examples 1 and 2, it is found that when the addition amount of graphene exceeds a certain content (more than 10 parts), the obtained high thermal conductivity graphene modified EVA foam material has high thermal conductivity and short secondary molding time on the basis of maintaining good hardness and tensile strength.
Example 2
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
75 parts of ethylene-vinyl acetate copolymer with the EVA content of 50 percent, 2 parts of ethylene-butylene copolymer, 4 parts of chloroprene rubber, 0.5 part of glycidyl methacrylate grafted EVA, 15 parts of graphene with less than 30 layers, 0.4 part of silicone oil with the molecular weight of 100 ten thousand, 0.4 part of dicumyl peroxide, 0.6 part of N, N' -dinitrosopentamethylenetetramine, 1.0 part of triallyl isocyanurate, 0.6 part of zinc carbonate and 1.0 part of zinc stearate.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 75 parts of ethylene-vinyl acetate copolymer with the EVA content of 50%, 2 parts of ethylene-butylene copolymer, 4 parts of chloroprene rubber, 0.5 part of glycidyl methacrylate grafted EVA and 15 parts of graphene with the number of layers smaller than 30, and extruding and granulating by using double screws under the conditions that the rotating speed of a screw is 10rmp, the temperature is 210 ℃ and the extrusion time is 5min to obtain the EVA composition containing the graphene;
(2) adding 0.4 part of silicone oil with the molecular weight of 100 ten thousand, 0.4 part of dicumyl peroxide, 0.6 part of N, N' -dinitrosopentamethylenetetramine, 1.0 part of triallyl isocyanurate, 0.6 part of zinc carbonate and 1.0 part of zinc stearate into the EVA composition obtained in the step (1), uniformly mixing, mixing for 2min at the temperature of 140 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 3
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
30 parts of ethylene-vinyl acetate copolymer with the EVA content of 1%, 35 parts of ethylene-vinyl acetate copolymer with the EVA content of 50%, 5 parts of glycidyl methacrylate grafted SEBS, 23.5 parts of graphene with less than 100 layers, 2.0 parts of silicone oil with the molecular weight of 100 ten thousand, 1.0 part of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane, 1.5 parts of sodium bicarbonate, 1.5 parts of zinc oxide and 1.5 parts of zinc stearate.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 30 parts of ethylene-vinyl acetate copolymer with the EVA content of 1%, 35 parts of ethylene-vinyl acetate copolymer with the EVA content of 50%, 5 parts of glycidyl methacrylate grafted SEBS (styrene-ethylene-butadiene-styrene), and 23.5 parts of graphene with the number of layers less than 100, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 50rmp, the temperature is 150 ℃ and the extrusion time is 10min to obtain the EVA composition containing the graphene;
(2) adding 2.0 parts of silicone oil with the molecular weight of 100 ten thousand, 1.0 part of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane, 1.5 parts of sodium bicarbonate, 1.5 parts of zinc oxide and 1.5 parts of zinc stearate into the composition obtained in the step (1), uniformly mixing, mixing for 10min at 120 ℃ by using an internal mixer, and granulating by using a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 4
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
50 parts of ethylene-vinyl acetate copolymer with the EVA content of 16 percent, 5.6 parts of glycidyl methacrylate grafted EVA, 40 parts of graphene with less than 100 layers, 0.6 part of dicumyl peroxide, 1.3 parts of sodium bicarbonate, 0.6 part of azodicarbonamide, 1.5 parts of zinc oxide and 0.5 part of zinc carbonate.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 50 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 5.6 parts of glycidyl methacrylate grafted EVA and 40 parts of graphene with the number of layers less than 100, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 50rmp, the temperature is 150 ℃ and the extrusion time is 10min to obtain the EVA composition containing graphene;
(2) adding 0.6 part of dicumyl peroxide, 1.3 parts of sodium bicarbonate, 0.6 part of azodicarbonamide, 1.5 parts of zinc oxide and 0.5 part of zinc carbonate into the EVA composition obtained in the step (1), uniformly mixing, mixing for 10min at 120 ℃ by using an internal mixer, and granulating by using a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 5
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
60 parts of ethylene-vinyl acetate copolymer with 16 percent of EVA content, 10 parts of ethylene octene block copolymer, 5 parts of SBS (styrene-butadiene block copolymer), 21 parts of graphene with less than 100 layers, 1 part of glycidyl methacrylate grafted PE (polyethylene), 0.4 part of dicumyl peroxide, 0.4 part of tert-amyl peroxy (2-ethylhexyl) carbonate, 0.6 part of sodium bicarbonate, 0.6 part of azodicarbonamide, 1.5 parts of zinc oxide and 0.5 part of zinc carbonate.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 60 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 10 parts of ethylene octene block copolymer, 5 parts of styrene-butadiene block copolymer SBS, 1 part of glycidyl methacrylate grafted PE and 21 parts of graphene with the number of layers less than 100, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 50rmp, the temperature is 150 ℃ and the extrusion time is 10min to obtain the EVA composition containing the graphene;
(2) adding 0.4 part of dicumyl peroxide, 0.4 part of (2-ethylhexyl) peroxyl tert-amyl carbonate, 0.6 part of sodium bicarbonate, 0.6 part of azodicarbonamide, 1.5 parts of zinc oxide and 0.5 part of zinc carbonate into the EVA composition obtained in the step (1), uniformly mixing, mixing for 10min at 120 ℃ by using an internal mixer, and granulating by using a granulator to obtain an EVA material;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 6
1. High-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
45 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 15 parts of ethylene propylene diene monomer, 15 parts of styrene butadiene rubber, 21 parts of graphene with less than 100 layers, 0.5 part of glycidyl methacrylate grafted EVA, 0.5 part of glycidyl methacrylate grafted POE, 0.5 part of dicumyl peroxide, 0.4 part of (2-ethylhexyl) tert-amyl peroxycarbonate, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.5 part of zinc oxide and 0.5 part of zinc carbonate.
2. Preparation of high-thermal-conductivity graphene modified EVA foaming composition
(1) Uniformly mixing 45 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 15 parts of ethylene propylene diene monomer, 15 parts of styrene butadiene rubber, 0.5 part of glycidyl methacrylate grafted EVA, 0.5 part of glycidyl methacrylate grafted POE and 21 parts of graphene with the number of layers less than 100, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 40rmp, the temperature is 160 ℃ and the extrusion time is 20min to obtain the EVA composition containing the graphene;
(2) adding 0.5 part of dicumyl peroxide, 0.4 part of (2-ethylhexyl) peroxyl tert-amyl carbonate, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.5 part of zinc oxide and 0.5 part of zinc carbonate into the EVA composition obtained in the step (1), uniformly mixing, mixing for 20min at 120 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 7
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
50.5 parts of ethylene-vinyl acetate copolymer with 16 percent of EVA content, 10 parts of SEBS, 25 parts of graphene with less than 100 layers, 2 parts of glycidyl methacrylate grafted POE, 0.5 part of dicumyl peroxide, 0.4 part of tert-amyl peroxy (2-ethylhexyl) carbonate, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.4 part of triallyl isocyanurate, 0.4 part of trimethylolpropane triacrylate, 0.4 part of zinc oxide, 0.4 part of zinc carbonate, 1.2 parts of paraffin and 10 parts of toner.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 50.5 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 10 parts of SEBS, 2 parts of glycidyl methacrylate grafted POE and 25 parts of graphene with the number of layers less than 100, and carrying out twin-screw extrusion granulation under the conditions that the rotating speed of a screw is 40rmp, the temperature is 160 ℃ and the extrusion time is 20min to obtain the EVA composition containing the graphene;
(2) adding 0.5 part of dicumyl peroxide, 0.4 part of tert-amyl peroxy (2-ethylhexyl) carbonate, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.4 part of triallyl isocyanurate, 0.4 part of trimethylolpropane triacrylate, 0.4 part of zinc oxide, 0.4 part of zinc carbonate, 1.2 parts of paraffin and 10 parts of toner into the EVA composition obtained in the step (1), uniformly mixing, mixing for 20min at 120 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 8
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
40 parts of ethylene-vinyl acetate copolymer with 16 percent of EVA content, 10 parts of chloroprene rubber, 5 parts of brominated butyl rubber, 5 parts of nitrile rubber, 0.6 part of glycidyl methacrylate grafted POE, 25 parts of graphene with less than 100 layers, 0.8 part of di-tert-butylperoxyisopropyl benzene, 5 parts of silicone oil with the molecular weight of 100 ten thousand, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.4 part of triallyl isocyanurate, 0.4 part of trimethylolpropane triacrylate, 0.4 part of zinc oxide, 0.4 part of zinc carbonate, 1.2 parts of paraffin and 5 parts of toner.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 40 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 10 parts of chloroprene rubber, 5 parts of brominated butyl rubber, 5 parts of nitrile rubber, 0.6 part of glycidyl methacrylate grafted POE and 25 parts of graphene with the number of layers less than 100, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 40rmp, the temperature is 160 ℃ and the extrusion time is 20min to obtain the EVA composition containing the graphene;
(2) adding 0.8 part of di-tert-butylperoxyisopropyl benzene, 5 parts of silicone oil with the molecular weight of 100 ten thousand, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.4 part of triallyl isocyanurate, 0.4 part of trimethylolpropane triacrylate, 0.4 part of zinc oxide, 0.4 part of zinc carbonate, 1.2 parts of paraffin and 5 parts of toner into the composition obtained in the step (1), uniformly mixing, mixing for 20min at 120 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 9
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
40 parts of ethylene-vinyl acetate copolymer with the EVA content of 26 percent, 30 parts of polyolefin elastomer, 0.6 part of glycidyl methacrylate grafted EVA, 20 parts of graphene with less than 100 layers, 0.4 part of di-tert-butylperoxyisopropyl benzene, 5 parts of silicone oil with the molecular weight of 100 ten thousand, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.4 part of triallyl isocyanurate, 0.4 part of trimethylolpropane triacrylate, 0.4 part of zinc oxide, 0.4 part of zinc carbonate and 1.2 parts of paraffin.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 40 parts of ethylene-vinyl acetate copolymer with the EVA content of 26%, 30 parts of polyolefin elastomer, 0.6 part of glycidyl methacrylate grafted EVA and 20 parts of graphene with the number of layers being less than 100, and then carrying out twin-screw extrusion granulation under the conditions that the rotating speed of a screw is 40rmp, the temperature is 160 ℃ and the extrusion time is 20min to obtain the EVA composition containing graphene;
(2) adding 0.4 part of di-tert-butylperoxyisopropyl benzene, 5 parts of silicone oil with the molecular weight of 100 ten thousand, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.4 part of triallyl isocyanurate, 0.4 part of trimethylolpropane triacrylate, 0.4 part of zinc oxide, 0.4 part of zinc carbonate and 1.2 parts of paraffin into the EVA composition obtained in the step (1), uniformly mixing, mixing for 20min at 120 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 10
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
40 parts of ethylene-vinyl acetate copolymer with the EVA content of 26 percent, 10 parts of polyolefin elastomer, 5 parts of glycidyl methacrylate grafted POE, 35 parts of graphene with less than 100 layers, 0.4 part of di-tert-butylperoxyisopropyl benzene, 6 parts of silicone oil with the molecular weight of 100 ten thousand, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.4 part of triallyl isocyanurate, 0.4 part of trimethylolpropane triacrylate, 0.4 part of zinc oxide, 0.4 part of zinc carbonate and 1.2 parts of paraffin.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 40 parts of ethylene-vinyl acetate copolymer with the EVA content of 26%, 10 parts of polyolefin elastomer, 5 parts of glycidyl methacrylate grafted POE and 35 parts of graphene with the number of layers less than 100, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 40rmp, the temperature is 160 ℃ and the extrusion time is 20min to obtain the EVA composition containing the graphene;
(2) adding 0.4 part of di-tert-butylperoxyisopropyl benzene, 6 parts of silicone oil with the molecular weight of 100 ten thousand, 0.6 part of sodium bicarbonate, 0.2 part of azodicarbonamide, 0.4 part of triallyl isocyanurate, 0.4 part of trimethylolpropane triacrylate, 0.4 part of zinc oxide, 0.4 part of zinc carbonate and 1.2 parts of paraffin into the EVA composition obtained in the step (1), uniformly mixing, mixing for 20min at 120 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
Example 11
1. Components of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
51 parts of ethylene-vinyl acetate copolymer with the EVA content of 26 percent, 11 parts of polyolefin elastomer, 2 parts of glycidyl methacrylate grafted EVA, 11 parts of chloroprene rubber, 21 parts of graphene with less than 100 layers, 0.7 part of bis-tert-butylperoxyisopropyl benzene, 0.2 part of silicone oil with the molecular weight of 100 ten thousand, 1.0 part of azodicarbonamide, 0.4 part of trimethylolpropane triacrylate, 1.0 part of zinc oxide, 0.5 part of paraffin and 0.2 part of toner.
2. Preparation of high-thermal-conductivity graphene modified EVA (ethylene-vinyl acetate) foam material
(1) Uniformly mixing 51 parts of ethylene-vinyl acetate copolymer with the EVA content of 26%, 11 parts of polyolefin elastomer, 2 parts of glycidyl methacrylate grafted EVA, 11 parts of chloroprene rubber and 21 parts of graphene with the number of layers less than 100, and then extruding and granulating by using double screws under the conditions that the rotating speed of a screw is 40rmp, the temperature is 160 ℃ and the extrusion time is 20min to obtain the EVA composition containing the graphene;
(2) adding 0.7 part of di-tert-butylperoxyisopropyl benzene, 0.2 part of silicone oil with the molecular weight of 100 ten thousand, 1.0 part of azodicarbonamide, 0.4 part of trimethylolpropane triacrylate, 1.0 part of zinc oxide, 0.5 part of paraffin and 0.2 part of toner into the EVA composition obtained in the step (1), uniformly mixing, mixing for 20min at 120 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the high-thermal-conductivity graphene modified EVA foaming material.
The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (1)
1. A preparation method for shortening the forming time of secondary foaming of an EVA foaming material is characterized by comprising the following steps: the EVA foaming material comprises the following components in parts by weight: 40 parts of ethylene-vinyl acetate copolymer with 16 percent of EVA content, 20 parts of ethylene octene copolymer, 10 parts of natural rubber, 1 part of glycidyl methacrylate grafted POE, 20 parts of graphene with less than 10 layers, 0.4 part of silicone oil with 60 ten thousand of molecular weight, 1.2 parts of di-tert-butylperoxyisopropyl benzene, 2.0 parts of azodicarbonamide, 1.3 parts of triallyl isocyanurate, 1.8 parts of zinc oxide, 0.5 part of stearic acid and 3.0 parts of toner;
the preparation method comprises the following steps:
(1) uniformly mixing 40 parts of ethylene-vinyl acetate copolymer with the EVA content of 16%, 20 parts of ethylene octene copolymer, 10 parts of natural rubber, 1 part of glycidyl methacrylate grafted POE and 20 parts of graphene with the number of layers less than 10, and carrying out twin-screw extrusion granulation under the conditions that the screw rotation speed is 40rpm, the extrusion temperature is 130 ℃ and the extrusion time is 20min to obtain the EVA composition containing graphene;
(2) adding 0.4 part of silicone oil with the molecular weight of 60 ten thousand, 1.2 parts of di-tert-butylperoxyisopropyl benzene, 2.0 parts of azodicarbonamide, 1.3 parts of triallyl isocyanurate, 1.8 parts of zinc oxide, 0.5 part of stearic acid and 3.0 parts of toner into the EVA composition obtained in the step (1), uniformly mixing, mixing for 30min at 90 ℃ by an internal mixer, and granulating by a granulator to obtain EVA granules;
(3) and (3) carrying out injection, vulcanization and foaming outside the die on the EVA granules obtained in the step (2) by using an EVA injection machine to obtain the EVA foaming material.
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| CN110054832A (en) * | 2019-05-08 | 2019-07-26 | 福建五持恒科技发展有限公司 | Ultralight graphene rubber pange insole and preparation method thereof |
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| CN111286110B (en) * | 2020-02-18 | 2022-09-23 | 安踏（中国）有限公司 | High-comfort shock-absorption foaming midsole material, preparation method thereof and sports shoes |
| CN111909416A (en) * | 2020-08-29 | 2020-11-10 | 福建省灿辉环保科技有限公司 | Efficient EVA foaming fast curing agent and preparation method thereof |
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