CN112625308A - Graphene antistatic medical sole composite material and preparation method thereof - Google Patents
Graphene antistatic medical sole composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 42
- 229920001971 elastomer Polymers 0.000 claims abstract description 38
- 239000005060 rubber Substances 0.000 claims abstract description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 32
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 32
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008117 stearic acid Substances 0.000 claims abstract description 32
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 239000004088 foaming agent Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 21
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 19
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 19
- 229920001194 natural rubber Polymers 0.000 claims abstract description 19
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 18
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 18
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 18
- 230000009965 odorless effect Effects 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 230000009967 tasteless effect Effects 0.000 claims abstract description 4
- 238000004073 vulcanization Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 3
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- -1 ethoxylated aliphatic alkylamine Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- 230000009193 crawling Effects 0.000 claims 1
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
- C08J9/0061—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08J2323/22—Copolymers of isobutene; butyl rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- 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
- C08J2423/22—Copolymers of isobutene; butyl rubber
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a graphene antistatic medical sole composite material and a preparation method thereof, wherein the graphene antistatic medical sole composite material comprises the following raw materials: butyl rubber, natural rubber, butadiene rubber, ethylene propylene diene monomer, white carbon black, graphene, antistatic powder, a flow aid, zinc oxide, zinc stearate, stearic acid, an odorless crosslinking agent and a foaming agent. The preparation method of the composite material comprises the following steps: heating graphene treated by a flow aid and stearic acid, sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer rubber, and mixing in a mixing roll to obtain mixed virgin rubber; and then adding the white carbon black, the antistatic powder, the zinc oxide, the zinc stearate, the tasteless cross-linking agent and the foaming agent into the mixed virgin rubber for mixing, vulcanizing and cross-linking again to obtain the graphene antistatic medical sole composite material.
Description
Technical Field
The invention belongs to the technical field of rubber-based composite materials, and particularly relates to a graphene antistatic medical sole composite material and a preparation method thereof.
Background
The rubber material is one of indispensable and alternative key materials in the fields of national economy and high technology at present, and is widely applied to the fields of aerospace, military, transportation, high-speed rail, electronic information, energy power, national major infrastructure construction and the like. In recent years, with the progress of science and technology, the requirements on rubber materials are higher and higher, and the novel rubber materials not only need to have the performances of high strength, high elasticity and the like, but also need to have the characteristics of high wear resistance, high oil resistance, high and low temperature resistance, long service life and the like. The graphene is sp2The hybridized and connected carbon atoms are tightly packed into a new material with a single-layer two-dimensional honeycomb lattice structure. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, can greatly improve the mechanical properties of rubber by being filled in a small amount when being used as a reinforcing material of the rubber, can show good electrical and thermal properties, and can be used as a very ideal medical nano material.
Therefore, the research on the graphene and rubber composite material is developed, and the method has great significance for improving the overall level of the rubber industry in China. However, in the actual production process, the dispersion of graphene in the rubber matrix is always a bottleneck troubling the graphene rubber composite material, and due to the surface tension and self-aggregation, the bonding force between rubber and graphene is very low, and the graphene is easy to separate, so that the performance of the composite material is greatly reduced, and the expected effect cannot be achieved.
The medical composite material has the characteristics of high technical content and high added value, and has great development potential. As a medical composite material, the following conditions need to be met: the plasticizer used is not easy to exude from the material; heavy metal compounds are not suitable to be selected as heat stabilizers; other additives and auxiliaries have no side effect or have side reaction with materials, and the precipitation of the auxiliaries is prevented or reduced when the additive is used for a long time. Meanwhile, the sole used as a medical sole also needs to have an antistatic function so as to avoid the influence on the treatment activities of medical staff caused by static electricity generated in the walking process and the ground.
In order to solve the above problems, it is necessary to develop a graphene antistatic medical sole composite material.
Disclosure of Invention
Based on the prior art, the invention aims to provide the graphene antistatic medical sole composite material and the preparation method thereof, and the graphene antistatic medical sole composite material has the advantages of antistatic property, antibacterial property, high elasticity, good wear resistance, no toxicity, difficult deformation, easy cleaning and the like, so that the graphene antistatic medical sole composite material has a better using effect when being used as a medical sole.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the graphene antistatic medical sole composite material comprises the following raw materials in parts by weight: 25-35 parts of butyl rubber, 35-45 parts of natural rubber, 5-15 parts of butadiene rubber, 10-20 parts of ethylene propylene diene monomer, 3-8 parts of white carbon black, 0.5-10 parts of graphene, 4-8 parts of antistatic powder, 0.5-1.5 parts of a flow promoter, 5-10 parts of zinc oxide, 1-3 parts of zinc stearate, 0.4-2 parts of stearic acid, 0.5-2.5 parts of an odorless cross-linking agent and 2-5 parts of a foaming agent.
In order to better realize the invention, further, the basic composition of the composite material comprises the following raw materials in parts by weight: 30 parts of butyl rubber, 40 parts of natural rubber, 10 parts of butadiene rubber, 15 parts of ethylene propylene diene monomer, 5 parts of white carbon black, 5 parts of graphene, 5 parts of antistatic powder, 1.0 part of flow aid, 7 parts of zinc oxide, 2 parts of zinc stearate, 1 part of stearic acid, 1.5 parts of odorless cross-linking agent and 3 parts of foaming agent.
In order to better realize the invention, further, the antistatic powder is ethoxylated aliphatic alkylamine, and the flow assistant is one of tetramethylthiuram disulfide and tetramethylthiuram hexasulfide.
In order to better realize the invention, further, the odorless cross-linking agent is di-tert-butylperoxydiisopropylbenzene, and the foaming agent is one of azodicarbonamide, diphenyl sulfonyl hydrazide ether and p-toluene sulfonyl hydrazide.
The invention also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:
step 1, heating graphene treated by a flow aid and stearic acid, sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer rubber, and mixing in a mixing roll to obtain mixed virgin rubber;
and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, a tasteless cross-linking agent and a foaming agent into the mixed virgin rubber, and mixing, vulcanizing and crosslinking again to obtain the graphene antistatic medical sole composite material.
In order to better realize the method, the graphene treatment in the step 1 comprises the specific steps of mixing the flow aid, stearic acid and deionized water according to the weight ratio of 0.5-1.5: 0.4-2: 100, uniformly mixing, heating to 100-160 ℃, slowly and gradually adding the graphene, continuously stirring for 1-3 hours after adding, wherein the adding amount of the graphene is 0.5-10 mg/ml, and obtaining the graphene treated by the flow aid and stearic acid.
In order to better realize the invention, the mixing temperature in the step 1 is 120-180 ℃, and the mixing time is 3-6 h.
In order to better realize the invention, further, during vulcanization crosslinking in the step 2, hot pressing is firstly carried out on a plate vulcanizing machine for 20-30 min at 120-160 ℃ and under the pressure of 8-10 Mpa, and then secondary vulcanization is carried out in an oven under the vulcanization conditions of 175-185 ℃, 2-4 h, 195-205 ℃, 2-3 h, 215-225 ℃ and 1-2 h, so as to obtain the graphene antistatic medical sole composite material.
Advantageous effects
The invention has the following beneficial effects:
(1) the composite material contains graphene, which is used as a reinforcing material of rubber, can greatly improve the mechanical property of the rubber by filling a small amount of graphene, can show good electrical and thermal properties of the graphene, and is an ideal rubber nano material.
(2) The composite material has an antistatic effect, and the antistatic powder used in the invention is an internal mixing type antistatic agent, which is a type of antistatic agent added into rubber in the processing process of products. The antistatic agent molecule can endow the surface of a high polymer material with certain lubricity, reduce the friction coefficient, inhibit and reduce static charge generation, and has the characteristic of permanent antistatic.
(3) The cross-linking agent selected by the composite material is di-tert-butylperoxydiisopropylbenzene, no pungent odor is generated in the operation process and the prepared product, the rubber material is added during mixing, and under the condition of the same cross-linking effect, the addition amount is only 2/3 of DCP, so that the dosage is reduced, and the composite material is more environment-friendly; the foaming agent is one of azodicarbonamide, diphenyl sulfonyl hydrazide ether and p-toluene sulfonyl hydrazide, has stable property during storage, is non-toxic and non-combustible, has better compatibility with rubber during mixing, is decomposed to generate nitrogen gas to form closed holes or connected holes, has small shrinkage rate, is not easy to deform, and ensures that the holes are not easy to collapse; the auxiliary agent is not easy to exude in a finished product after being used, does not generate side reaction with other materials, is nontoxic and harmless after being used for a long time, and has no pollution and influence on hospital environment.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 25 parts of butyl rubber, 35 parts of natural rubber, 5 parts of butadiene rubber, 10 parts of ethylene propylene diene monomer, 3 parts of white carbon black, 1 part of graphene, 4 parts of antistatic powder, 0.5 part of flow aid, 5 parts of zinc oxide, 1 part of zinc stearate, 0.4 part of stearic acid, 0.5 part of tasteless cross-linking agent and 2 parts of foaming agent.
The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:
step 1, mixing a flow aid, stearic acid and deionized water according to a weight ratio of 0.5:0.4:100, heating to 110 ℃ after uniformly mixing, slowly and gradually adding graphene, stirring continuously, stirring for 3 hours after adding, wherein the adding amount of the graphene is 1mg/ml, obtaining the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixing mill at the mixing temperature of 120 ℃ for 6 hours to obtain mixed virgin rubber;
and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 30min at 120 ℃ and 8Mpa in a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 175-DEG C, 4h, 195 ℃, 3h, 215 ℃ and 2h to obtain the graphene antistatic medical sole composite material.
Example 2
The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 28 parts of butyl rubber, 38 parts of natural rubber, 8 parts of butadiene rubber, 12 parts of ethylene propylene diene monomer, 4 parts of white carbon black, 3 parts of graphene, 5 parts of antistatic powder, 0.8 part of a flow aid, 6 parts of zinc oxide, 2 parts of zinc stearate, 0.8 part of stearic acid, 1.0 part of an odorless cross-linking agent and 3 parts of a foaming agent.
The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:
step 1, mixing a flow aid, stearic acid and deionized water according to a weight ratio of 0.8:0.8:100, heating to 120 ℃ after uniformly mixing, slowly and gradually adding graphene, stirring continuously, stirring for 3 hours after adding, wherein the adding amount of the graphene is 3mg/ml, obtaining the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixing mill at the mixing temperature of 140 ℃ for 5 hours to obtain mixed virgin rubber;
and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 28min at the temperature of 130 ℃ and under the pressure of 8Mpa on a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 178 ℃, 4 hours, 200 ℃, 3 hours, 220 ℃ and 2 hours to obtain the graphene antistatic medical sole composite material.
Example 3
The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 30 parts of butyl rubber, 40 parts of natural rubber, 10 parts of butadiene rubber, 15 parts of ethylene propylene diene monomer, 5 parts of white carbon black, 5 parts of graphene, 5 parts of antistatic powder, 1.0 part of flow aid, 7 parts of zinc oxide, 2 parts of zinc stearate, 1 part of stearic acid, 1.5 parts of odorless cross-linking agent and 3 parts of foaming agent.
The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:
step 1, proportioning a flow aid, stearic acid and deionized water according to a weight ratio of 1.0:1.0:100, uniformly mixing, heating to 140 ℃, slowly and gradually adding graphene, stirring continuously, stirring for 2 hours continuously after adding, wherein the adding amount of the graphene is 5mg/ml, so as to obtain the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixing mill at the mixing temperature of 150 ℃ for 5 hours, so as to obtain mixed virgin rubber;
and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 25min at 140 ℃ and 10Mpa in a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 180 ℃, 3 hours, 200 ℃, 2.5 hours, 220 ℃ and 1.5 hours to obtain the graphene antistatic medical sole composite material.
Example 4
The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 33 parts of butyl rubber, 33 parts of natural rubber, 13 parts of butadiene rubber, 18 parts of ethylene propylene diene monomer, 6 parts of white carbon black, 6 parts of graphene, 6 parts of antistatic powder, 1.2 parts of a flow aid, 8 parts of zinc oxide, 2 parts of zinc stearate, 1.5 parts of stearic acid, 2.0 parts of an odorless cross-linking agent and 4 parts of a foaming agent.
The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:
step 1, mixing a flow aid, stearic acid and deionized water according to a weight ratio of 1.2:1.5:100, heating to 150 ℃ after uniformly mixing, slowly and gradually adding graphene, stirring continuously, stirring for 2 hours after adding, wherein the adding amount of the graphene is 6mg/ml, so as to obtain the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixer at the mixing temperature of 170 ℃ for 4 hours, so as to obtain mixed virgin rubber;
and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 20min at the temperature of 150 ℃ and the pressure of 10Mpa on a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 183 ℃, 3 hours, 200 ℃, 2 hours, 220 ℃ and 1.5 hours to obtain the graphene antistatic medical sole composite material.
Example 5
The embodiment provides a graphene antistatic medical sole composite material, which comprises the following raw materials in parts by weight: 35 parts of butyl rubber, 45 parts of natural rubber, 15 parts of butadiene rubber, 20 parts of ethylene propylene diene monomer, 8 parts of white carbon black, 10 parts of graphene, 8 parts of antistatic powder, 1.5 parts of a flow aid, 10 parts of zinc oxide, 3 parts of zinc stearate, 2 parts of stearic acid, 2.5 parts of an odorless cross-linking agent and 5 parts of a foaming agent.
The embodiment also provides a preparation method of the graphene antistatic medical sole composite material, which comprises the following steps:
step 1, mixing a flow aid, stearic acid and deionized water according to a weight ratio of 1.5:2:100, heating to 160 ℃ after uniformly mixing, slowly and gradually adding graphene, stirring continuously, stirring for 1h after adding, wherein the adding amount of the graphene is 10mg/ml, so as to obtain the flow aid and the stearic acid-treated graphene, then sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer into the flow aid and the stearic acid-treated graphene, and mixing in a mixing mill at 180 ℃ for 3h, so as to obtain mixed virgin rubber;
and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, an odorless cross-linking agent and a foaming agent into the mixed virgin rubber, carrying out hot pressing on the mixed virgin rubber for 20min at 160 ℃ and 10Mpa in a flat vulcanizing machine, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 185 ℃, 2h, 205 ℃, 2h, 225 ℃ and 1h to obtain the graphene antistatic medical sole composite material.
The mechanical property of the graphene antistatic medical sole composite material prepared in the above examples 1 to 5 can be tested, and the test method is as follows:
(1) and (4) detecting the volume resistivity and the surface conductivity according to a GB/T1410-2006 solid insulating material volume resistivity and surface resistivity test method.
(2) Tear strength: according to GB 6039-85, the tear strength is defined as: stretching the sample in the direction parallel to the main shaft of the sample until the maximum force is generated during cracking, preparing the sample according to the methods of GB529 and GB530, and standing the vulcanized test piece (the thickness is 2.0 +/-0.3 mm) in the testing step (1) at the standard room temperature (not less than 6 hours and not more than 15 days); (2) when a sample is taken, the direction of the bisector of the tearing angle of the cutter is consistent with the rolling direction; (3) vertically clamping the sample on an upper clamp and a lower clamp, and fully and uniformly clamping the sample at equal positions; (4) the tester is started after the stretching speed is adjusted (the tester is operated in a clamping device at the speed of 500 +/-100 mm/min), and then a gradually increased traction force can be applied to the test sample until the test sample is stopped after being torn off.
(3) Tensile strength: the procedure was followed according to ASTM D-412.
(4) Modulus: the method is carried out according to HG/T3321-2012 standard.
The test results were as follows:
TABLE 1 test results
| Test results | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Volume resistivity Ω · m | 1015 | 1015 | 1015 | 1015 | 1015 |
| Surface resistivity omega | 1015 | 1015 | 1015 | 1015 | 1015 |
| Tear Strength kN/m | 98 | 110 | 118 | 113 | 108 |
| Tensile strength Mpa | 33 | 34 | 38 | 37 | 35 |
| Modulus Mpa | 2.7 | 3.1 | 3.3 | 3.0 | 2.8 |
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The graphene antistatic medical sole composite material is characterized by comprising the following raw materials in parts by weight: 25-35 parts of butyl rubber, 35-45 parts of natural rubber, 5-15 parts of butadiene rubber, 10-20 parts of ethylene propylene diene monomer, 3-8 parts of white carbon black, 0.5-10 parts of graphene, 4-8 parts of antistatic powder, 0.5-1.5 parts of a flow promoter, 5-10 parts of zinc oxide, 1-3 parts of zinc stearate, 0.4-2 parts of stearic acid, 0.5-2.5 parts of an odorless cross-linking agent and 2-5 parts of a foaming agent.
2. The graphene antistatic medical sole composite material as claimed in claim 1, is characterized in that the basic composition of the composite material comprises the following raw materials in parts by weight: 30 parts of butyl rubber, 40 parts of natural rubber, 10 parts of butadiene rubber, 15 parts of ethylene propylene diene monomer, 5 parts of white carbon black, 5 parts of graphene, 5 parts of antistatic powder, 1.0 part of flow aid, 7 parts of zinc oxide, 2 parts of zinc stearate, 1 part of stearic acid, 1.5 parts of odorless cross-linking agent and 3 parts of foaming agent.
3. The graphene antistatic medical sole composite material according to claim 1, wherein the antistatic powder is ethoxylated aliphatic alkylamine, and the flow aid is one of tetramethylthiuram disulfide and tetramethylthiuram hexasulfide.
4. The graphene natural rubber antibacterial crawling composite material for children as claimed in claim 1, wherein the odorless cross-linking agent is di-tert-butylperoxydiisopropylbenzene, and the foaming agent is one of azodicarbonamide, diphenyl sulfonyl hydrazide ether and p-toluenesulfonyl hydrazide.
5. The graphene antistatic medical sole composite material as claimed in claim 1 or 2, comprising the following steps:
step 1, heating graphene treated by a flow aid and stearic acid, sequentially adding butyl rubber, natural rubber, butadiene rubber and ethylene propylene diene monomer rubber, and mixing in a mixing roll to obtain mixed virgin rubber;
and 2, adding white carbon black, antistatic powder, zinc oxide, zinc stearate, a tasteless cross-linking agent and a foaming agent into the mixed virgin rubber, and mixing, vulcanizing and crosslinking again to obtain the graphene antistatic medical sole composite material.
6. The preparation method of the graphene antistatic medical sole composite material according to claim 5, wherein the graphene treatment in the step 1 specifically comprises the steps of mixing the flow aid, stearic acid and deionized water according to a weight ratio of 0.5-1.5: 0.4-2: 100, heating to 100-160 ℃ after uniform mixing, slowly and gradually adding the graphene, continuously stirring, and continuously stirring for 1-3 hours after adding, wherein the adding amount of the graphene is 0.5-10 mg/ml, so as to obtain the graphene treated by the flow aid and stearic acid.
7. The preparation method of the graphene antistatic medical sole composite material according to claim 5, wherein in the step 1, the mixing temperature is 120-180 ℃, and the mixing time is 3-6 hours.
8. The preparation method of the graphene antistatic medical sole composite material according to claim 5, wherein during vulcanization crosslinking in step 2, the graphene antistatic medical sole composite material is obtained by hot pressing on a flat vulcanizing machine at 120-160 ℃ and under the pressure of 8-10 MPa for 20-30 min, and then carrying out secondary vulcanization in an oven under the vulcanization conditions of 175-185 ℃, 2-4 h, 195-205 ℃, 2-3 h, 215-225 ℃ and 1-2 h.
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