CN116554535B - Graphene modified rubber-plastic foaming colloidal particle and preparation method thereof - Google Patents
Graphene modified rubber-plastic foaming colloidal particle and preparation method thereof Download PDFInfo
- Publication number
- CN116554535B CN116554535B CN202310381623.7A CN202310381623A CN116554535B CN 116554535 B CN116554535 B CN 116554535B CN 202310381623 A CN202310381623 A CN 202310381623A CN 116554535 B CN116554535 B CN 116554535B
- Authority
- CN
- China
- Prior art keywords
- graphene
- rubber
- polyurethane
- rubber powder
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 98
- 239000002245 particle Substances 0.000 title claims abstract description 33
- 229920003023 plastic Polymers 0.000 title claims abstract description 32
- 239000004033 plastic Substances 0.000 title claims abstract description 32
- 238000005187 foaming Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 100
- 239000005060 rubber Substances 0.000 claims abstract description 100
- 239000000843 powder Substances 0.000 claims abstract description 60
- 229920002635 polyurethane Polymers 0.000 claims abstract description 40
- 239000004814 polyurethane Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 21
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 18
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 18
- 229920001194 natural rubber Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002699 waste material Substances 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 19
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 19
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000004088 foaming agent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- -1 siloxane modified graphene Chemical class 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 239000002984 plastic foam Substances 0.000 claims 7
- 229920001821 foam rubber Polymers 0.000 claims 4
- 239000000693 micelle Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010077 mastication Methods 0.000 abstract description 7
- 230000018984 mastication Effects 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 238000003801 milling Methods 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- 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
- C08J9/16—Making expandable particles
-
- 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
- C08J9/04—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
- C08J9/12—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 physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- 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
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2203/08—Supercritical fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2407/00—Characterised by the use of natural rubber
-
- 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
- C08J2419/00—Characterised by the use of rubbers not provided for in groups C08J2407/00 - C08J2417/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a graphene modified rubber-plastic foaming colloidal particle and a preparation method thereof, and polyurethane/graphene coated rubber powder is prepared; adding EVA and natural rubber after mastication and polyurethane/graphene coated rubber powder into an internal mixer, banburying together, pouring out and open milling; mixing the thinned rubber-plastic base material with other raw materials; and (3) directly granulating the mixed rubber on a granulator to obtain graphene modified rubber-plastic foaming colloidal particles. The process can improve the compatibility of rubber powder, EVA and natural rubber, plays a role of carbon dioxide in the supercritical foaming process, realizes accelerated saturation and uniform foaming, and is beneficial to obtaining a light microporous foaming structure; the polyurethane is covalently grafted on the graphene, and a hybrid porous structure is formed between the graphene layers and between the polyurethane and rubber powder and rubber plastic materials around the rubber powder, so that the effects of preventing sulfur migration, adjusting co-vulcanization, enhancing interfacial co-sulfur density, greatly enhancing the mechanical property of the material and remarkably improving the rebound resilience of the material are achieved.
Description
Technical Field
The invention relates to the technical field of shoe materials, in particular to a graphene modified rubber plastic foaming colloidal particle and a preparation method thereof.
Background
The rubber product is a high molecular compound product with high elasticity, high stretchability and high insulativity, and is divided into natural rubber and synthetic rubber; EVA is the abbreviation of ethylene-vinyl acetate copolymer, and EVA products have the good elasticity like rubber, and also have flexibility, low temperature resistance, transparency, surface gloss and the like which are different from rubber, and the products made of EVA resin can still have better flexibility at-50 ℃, and the EVA products have outstanding characteristics of blending performance and coloring performance with fillers, and good processability of easy hot pressing, cutting, gluing and laminating, and are far superior to rubber.
Disposal of waste rubber is one of the serious problems facing people today. In order to meet the requirements of continuously improving the material performance, rubber is developed towards high strength, wear resistance, stability and ageing resistance, but the problem that the discarded rubber cannot be naturally degraded for a long time is caused, and a large amount of waste rubber causes black pollution which is more difficult to treat than plastic pollution. The rubber powder is a powdery substance obtained by crushing vulcanized waste rubber in a mechanical way, the surface of the rubber powder is inert, the rubber powder is a cross-linked structure-containing material composed of rubber, carbon black, a softener, a vulcanizing machine, a vulcanization accelerator and other materials, and the rubber powder is directly mixed into rubber or plastic.
Disclosure of Invention
The invention aims to provide a graphene modified rubber-plastic foaming colloidal particle and a preparation method thereof, which are used for improving the compatibility of rubber powder and a rubber-plastic base material and adjusting a vulcanization system to realize the enhancement of mechanical properties.
The technical scheme adopted by the invention is as follows:
the preparation method of the graphene modified rubber-plastic foaming colloidal particle specifically comprises the following steps:
s1, preparing polyurethane/graphene coated rubber powder;
s2, adding EVA and natural rubber after banburying and polyurethane/graphene coated rubber powder obtained in the step S1 into an internal mixer, banburying for 10-15 min, pouring out, and thinning for 2 times in an open mill, and discharging sheets;
s3, putting the thinned rubber and plastic base material into an internal mixer, and then adding active zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a foaming agent and a flow aid to carry out mixing for 15-20 min, wherein the temperature is controlled at 110-115 ℃ to obtain a rubber compound;
s4, directly feeding the mixed rubber into a granulator for granulation to obtain graphene modified rubber-plastic foaming colloidal particles.
Preferably, the preparation method of the polyurethane/graphene coated rubber powder comprises the following steps:
s11, dispersing graphene oxide GO in an ethanol aqueous solution, adding a silane coupling agent, uniformly stirring, heating to 60-65 ℃, and carrying out heat preservation and stirring for 5-6 hours to enable GO to react with the silane coupling agent; then washing and filtering to obtain siloxane modified graphene oxide;
s12, reacting the siloxane modified graphene oxide obtained in the step S1 with ammonia water at 185-200 ℃ by using a high-boiling point solvent for 6-8 hours, and then washing and filtering to obtain a graphene mixture containing siloxane and amino-functionalized graphene;
s13, ultrasonically dispersing the graphene mixture and the waste rubber powder in DMF (dimethyl formamide), then dropwise adding diisocyanate under the ultrasonic dispersion operation, and reacting for 4-6 hours after dropwise adding to enable the diisocyanate to be covalently grafted to amino on the surface of the graphene containing siloxane and amino functionalization;
s14, adding dihydric alcohol and a catalyst, reacting with diisocyanate groups on the surface of the graphene to generate polyurethane molecular chains, coating the waste rubber powder, and spray-drying to obtain polyurethane/graphene coated rubber powder.
Preferably, the washing in steps S11 and S12 is performed 3 times with absolute ethanol and deionized water.
Preferably, the silane coupling agent is KH550 or KH560.
Preferably, the mass ratio of the silane coupling agent to the GO is 15-20:1, and the mass ratio of the graphene oxide to the waste rubber powder is 1.2-1.5:1.
Preferably, the high boiling point solvent is ethylene glycol.
Preferably, the diisocyanate is MDI or TDI.
Preferably, the particle size of the waste rubber powder is 300-400 meshes.
Preferably, the weight parts of the raw materials are as follows: 40-55 parts of EVA (ethylene vinyl acetate), 15-20 parts of natural rubber, 20-30 parts of polyurethane/graphene coated rubber powder, 2-3 parts of active zinc oxide, 0.5-1 part of zinc stearate, 0.5-1 part of stearic acid, 2-3 parts of cross-linking agent, 2-3 parts of foaming agent and 1-2 parts of flow aid.
The invention also provides the graphene modified rubber-plastic foaming colloidal particle prepared by the preparation method.
The invention has the beneficial effects that:
according to the rubber particle, EVA, natural rubber and polyurethane/graphene coated rubber powder are used as rubber and plastic base materials, wherein the rubber powder is coated by graphene and polyurethane, and a siloxane group is grafted on the graphene, so that the compatibility of the rubber powder, EVA and natural rubber is improved, and the rubber particle plays a role of carbon dioxide in a supercritical foaming process, so that saturation is accelerated, uniform foaming is achieved, and a light microporous foaming structure is facilitated to be obtained; the polyurethane is covalently grafted on the graphene, diisocyanate reacts with amino groups on the edge of the benzene ring of the graphene and amino groups on siloxane functional groups, a hybrid porous structure is formed between graphene layers and between the polyurethane and rubber powder and rubber plastic materials around the rubber powder, so that the effects of preventing sulfur migration, regulating co-vulcanization, enhancing interfacial co-sulfur density, greatly enhancing the mechanical property of the materials and remarkably improving the rebound resilience of the materials are achieved.
Detailed Description
Example 1
The embodiment provides a graphene modified rubber and plastic foaming colloidal particle, which comprises the following raw materials in parts by weight: 50 parts of EVA, 15 parts of natural rubber, 25 parts of polyurethane/graphene coated rubber powder, 2.5 parts of active zinc oxide, 0.5 part of zinc stearate, 1 part of stearic acid, 2.5 parts of sulfur, 3 parts of foaming agent AC and 1.5 parts of flow aid wax. The natural rubber is a sizing material which is naturally stored for 72 hours after mastication, and the mastication method comprises the following steps: placing into an internal mixer for banburying for 20min, and controlling the temperature at 150 ℃.
The preparation method of the graphene modified rubber-plastic foaming colloidal particle specifically comprises the following steps: s1, preparing polyurethane/graphene coated rubber powder; s2, adding EVA and natural rubber subjected to banburying and polyurethane/graphene coated rubber powder obtained in the step S1 into an internal mixer, banburying for 15min, pouring out, and thinning for 2 times by using an open mill, and discharging sheets; s3, putting the thinned rubber and plastic base material into an internal mixer, and then adding active zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a foaming agent and a flow aid to carry out mixing for 20min, wherein the temperature is controlled at 115 ℃ to obtain a mixed rubber; s4, directly feeding the mixed rubber into a granulator for granulation to obtain graphene modified rubber-plastic foaming colloidal particles.
Wherein: the preparation method of the polyurethane/graphene coated rubber powder comprises the following steps:
s11, dispersing graphene oxide GO in an ethanol water solution, adding a silane coupling agent, uniformly stirring, heating to 60 ℃, and carrying out heat preservation and stirring for 6 hours to enable GO and KH550 to react, wherein the mass ratio of the silane coupling agent to the GO is 20:1; then washing for 3 times by adopting absolute ethyl alcohol and deionized water respectively, and then filtering to obtain siloxane modified graphene oxide;
s12, reacting the siloxane-modified graphene oxide obtained in the step S1 with ammonia water at 200 ℃ by using ethylene glycol for 6 hours, and then washing and filtering to obtain a graphene mixture containing siloxane and amino-functionalized graphene;
s13, ultrasonically dispersing the graphene mixture obtained in the step 2 and waste rubber powder with the particle size of 300-400 meshes in DMF (dimethyl formamide), wherein the mass ratio of the waste rubber powder to graphene oxide is 1:1.5, then dropwise adding MDI (methylene diphenyl oxide) under ultrasonic dispersion operation, and reacting for 5 hours after dropwise adding to enable diisocyanate to be covalently grafted to amino groups on the surface of the graphene containing siloxane and amino groups;
s14, adding dihydric alcohol and a catalyst, reacting with diisocyanate groups on the surface of the graphene to generate polyurethane molecular chains, coating the waste rubber powder, and spray-drying to obtain polyurethane/graphene coated rubber powder.
Example 2
The embodiment provides a graphene modified rubber and plastic foaming colloidal particle, which comprises the following raw materials in parts by weight: 455 parts of EVA, 15 parts of natural rubber, 20 parts of polyurethane/graphene coated rubber powder, 3 parts of active zinc oxide, 1 part of zinc stearate, 0.6 part of stearic acid, 2 parts of sulfur, 3 parts of foaming agent AC and 2 parts of flow aid wax. The natural rubber is a sizing material which is naturally stored for 72 hours after mastication, and the mastication method comprises the following steps: placing into an internal mixer for banburying for 20min, and controlling the temperature at 150 ℃.
The preparation method of the graphene modified rubber-plastic foaming colloidal particle specifically comprises the following steps: s1, preparing polyurethane/graphene coated rubber powder; s2, adding EVA and natural rubber subjected to banburying and polyurethane/graphene coated rubber powder obtained in the step S1 into an internal mixer, banburying for 15min, pouring out, and thinning for 2 times by using an open mill, and discharging sheets; s3, putting the thinned rubber and plastic base material into an internal mixer, and then adding active zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a foaming agent and a flow aid to carry out mixing for 20min, wherein the temperature is controlled at 112 ℃ to obtain the rubber compound; s4, directly feeding the mixed rubber into a granulator for granulation to obtain graphene modified rubber-plastic foaming colloidal particles.
Wherein: the preparation method of the polyurethane/graphene coated rubber powder comprises the following steps:
s11, dispersing graphene oxide GO in an ethanol water solution, adding a silane coupling agent, uniformly stirring, heating to 60 ℃, preserving heat, and stirring for 6 hours to enable GO and KH560 to react, wherein the mass ratio of the silane coupling agent to GO is 15:1; then washing for 3 times by adopting absolute ethyl alcohol and deionized water respectively, and then filtering to obtain siloxane modified graphene oxide;
s12, reacting the siloxane-modified graphene oxide obtained in the step S1 with ammonia water at 185 ℃ for 8 hours by using ethylene glycol, and then washing and filtering to obtain a graphene mixture containing siloxane and amino-functionalized graphene;
s13, ultrasonically dispersing the graphene mixture obtained in the step 2 and waste rubber powder with the particle size of 300-400 meshes in DMF (dimethyl formamide), wherein the mass ratio of the waste rubber powder to graphene oxide is 1:1.2, then dropwise adding TDI (toluene diisocyanate) under the ultrasonic dispersion operation, and reacting for 6 hours after dropwise adding to enable diisocyanate to be covalently grafted to amino groups on the surface of the graphene containing siloxane and amino groups;
s14, adding dihydric alcohol and a catalyst, reacting with diisocyanate groups on the surface of the graphene to generate polyurethane molecular chains, coating the waste rubber powder, and spray-drying to obtain polyurethane/graphene coated rubber powder.
Example 3
The embodiment provides a graphene modified rubber and plastic foaming colloidal particle, which comprises the following raw materials in parts by weight: 40 parts of EVA, 20 parts of natural rubber, 30 parts of polyurethane/graphene coated rubber powder, 2 parts of active zinc oxide, 0.5 part of zinc stearate, 0.5 part of stearic acid, 3 parts of sulfur, 2 parts of foaming agent AC and 1 part of flow aid wax. The natural rubber is a sizing material which is naturally stored for 72 hours after mastication, and the mastication method comprises the following steps: placing into an internal mixer for banburying for 20min, and controlling the temperature at 150 ℃.
The preparation method of the graphene modified rubber-plastic foaming colloidal particle specifically comprises the following steps: s1, preparing polyurethane/graphene coated rubber powder; s2, adding EVA and natural rubber subjected to banburying and polyurethane/graphene coated rubber powder obtained in the step S1 into an internal mixer, banburying for 10min, pouring out, and thinning for 2 times by using an open mill, and discharging sheets; s3, putting the thinned rubber and plastic base material into an internal mixer, and then adding active zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a foaming agent and a flow aid to carry out mixing for 20min, wherein the temperature is controlled at 110 ℃ to obtain a mixed rubber; s4, directly feeding the mixed rubber into a granulator for granulation to obtain graphene modified rubber-plastic foaming colloidal particles.
Wherein: the preparation method of the polyurethane/graphene coated rubber powder comprises the following steps:
s11, dispersing graphene oxide GO in an ethanol water solution, adding a silane coupling agent, uniformly stirring, heating to 60 ℃, and carrying out heat preservation and stirring for 6 hours to enable GO and KH550 to react, wherein the mass ratio of the silane coupling agent to the GO is 20:1; then washing for 3 times by adopting absolute ethyl alcohol and deionized water respectively, and then filtering to obtain siloxane modified graphene oxide;
s12, reacting the siloxane-modified graphene oxide obtained in the step S1 with ammonia water at 200 ℃ by using ethylene glycol for 6 hours, and then washing and filtering to obtain a graphene mixture containing siloxane and amino-functionalized graphene;
s13, ultrasonically dispersing the graphene mixture obtained in the step 2 and waste rubber powder with the particle size of 300-400 meshes in DMF (dimethyl formamide), wherein the mass ratio of the waste rubber powder to graphene oxide is 1:1.5, then dropwise adding MDI (methylene diphenyl oxide) under ultrasonic dispersion operation, and reacting for 6 hours after dropwise adding to enable diisocyanate to be covalently grafted to amino groups on the surface of the graphene containing siloxane and amino groups;
s14, adding dihydric alcohol and a catalyst, reacting with diisocyanate groups on the surface of the graphene to generate polyurethane molecular chains, coating the waste rubber powder, and spray-drying to obtain polyurethane/graphene coated rubber powder.
Comparative example 1
This comparative example 1 differs from example 1 described above only in that: the polyurethane/graphene coated rubber powder is not prepared and replaced by 10 parts of waste rubber powder and 15 parts of graphene.
Comparative example 2
This comparative example 2 differs from example 1 described above only in that: the polyurethane/graphene coated rubber powder is directly subjected to S12-S14 without the step S11.
The soles of the shoes were produced in the same supercritical foaming process as in examples 1-3 and comparative examples 1-2, the supercritical gas was supercritical carbon dioxide, the mold temperature was 150℃and the carbon dioxide pressure was 12.5MPa, and physical properties were measured, and the measurement results are shown in Table 1.
While the basic principles and main features of the invention and advantages of the invention have been shown and described, it will be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are described in the foregoing description merely illustrate the principles of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the graphene modified rubber-plastic foaming colloidal particle is characterized by comprising the following steps of:
s1, preparing polyurethane/graphene coated rubber powder;
s2, adding EVA and natural rubber after banburying and polyurethane/graphene coated rubber powder obtained in the step S1 into an internal mixer, banburying for 10-15 min, pouring out, and thinning for 2 times in an open mill, and discharging sheets;
s3, putting the thinned rubber and plastic base material into an internal mixer, and then adding active zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a foaming agent and a flow aid to carry out mixing for 15-20 min, wherein the temperature is controlled at 110-115 ℃ to obtain a rubber compound;
s4, directly granulating the mixed rubber compound on a granulator to obtain graphene modified rubber plastic foaming colloidal particles;
the weight portions of the raw materials are as follows: 40-55 parts of EVA (ethylene vinyl acetate), 15-20 parts of natural rubber, 20-30 parts of polyurethane/graphene coated rubber powder, 2-3 parts of active zinc oxide, 0.5-1 part of zinc stearate, 0.5-1 part of stearic acid, 2-3 parts of cross-linking agent, 2-3 parts of foaming agent and 1-2 parts of flow aid;
the preparation method of the polyurethane/graphene coated rubber powder comprises the following steps:
s11, dispersing graphene oxide GO in an ethanol aqueous solution, adding a silane coupling agent, uniformly stirring, heating to 60-65 ℃, and carrying out heat preservation and stirring for 5-6 hours to enable GO to react with the silane coupling agent; then washing and filtering to obtain siloxane modified graphene oxide;
s12, reacting the siloxane modified graphene oxide obtained in the step S1 with ammonia water at 185-200 ℃ by using a high-boiling point solvent for 6-8 hours, and then washing and filtering to obtain a graphene mixture containing siloxane and amino-functionalized graphene;
s13, ultrasonically dispersing the graphene mixture and the waste rubber powder in DMF (dimethyl formamide), then dropwise adding diisocyanate under the ultrasonic dispersion operation, and reacting for 4-6 hours after dropwise adding to enable the diisocyanate to be covalently grafted to amino on the surface of the graphene containing siloxane and amino functionalization;
s14, adding dihydric alcohol and a catalyst, reacting with diisocyanate groups on the surface of the graphene to generate polyurethane molecular chains, coating the waste rubber powder, and spray-drying to obtain polyurethane/graphene coated rubber powder.
2. The method for preparing the graphene modified rubber and plastic foam rubber particles according to claim 1, wherein the washing in the steps S11 and S12 is carried out 3 times by adopting absolute ethyl alcohol and deionized water.
3. The method for preparing graphene modified rubber and plastic foam rubber particles according to claim 1, wherein the silane coupling agent is KH550 or KH560.
4. The preparation method of the graphene modified rubber-plastic foam colloidal particle according to claim 1, wherein the mass ratio of the silane coupling agent to GO is 15-20:1, and the mass ratio of the graphene oxide to the waste rubber powder is 1.2-1.5:1.
5. The method for preparing graphene-modified rubber-plastic foam colloidal particles according to claim 1, wherein the high-boiling solvent is ethylene glycol.
6. The method for preparing graphene modified rubber and plastic foam rubber particles according to claim 1, wherein the diisocyanate is MDI or TDI.
7. The method for preparing graphene modified rubber-plastic foam rubber particles according to claim 1, wherein the particle size of the waste rubber powder is 300-400 meshes.
8. A graphene-modified rubber-plastic foam micelle prepared by the preparation method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310381623.7A CN116554535B (en) | 2023-04-11 | 2023-04-11 | Graphene modified rubber-plastic foaming colloidal particle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310381623.7A CN116554535B (en) | 2023-04-11 | 2023-04-11 | Graphene modified rubber-plastic foaming colloidal particle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116554535A CN116554535A (en) | 2023-08-08 |
| CN116554535B true CN116554535B (en) | 2024-04-05 |
Family
ID=87493638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310381623.7A Active CN116554535B (en) | 2023-04-11 | 2023-04-11 | Graphene modified rubber-plastic foaming colloidal particle and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116554535B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880226A (en) * | 2019-03-13 | 2019-06-14 | 福建五持恒科技发展有限公司 | Sole graphene regeneration rubber-plastic foaming micelle and preparation method thereof |
| CN110511452A (en) * | 2019-10-14 | 2019-11-29 | 福建五持恒科技发展有限公司 | Graphene natural rubber macromolecule control bacterium mixed foaming material and preparation method thereof |
| CN111500052A (en) * | 2020-05-15 | 2020-08-07 | 鲍维江 | Tear-resistant light polyurethane shoe material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9574069B2 (en) * | 2014-04-30 | 2017-02-21 | Lehigh Technologies, Inc. | Chemically functionalized renewed rubber composition |
-
2023
- 2023-04-11 CN CN202310381623.7A patent/CN116554535B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880226A (en) * | 2019-03-13 | 2019-06-14 | 福建五持恒科技发展有限公司 | Sole graphene regeneration rubber-plastic foaming micelle and preparation method thereof |
| CN110511452A (en) * | 2019-10-14 | 2019-11-29 | 福建五持恒科技发展有限公司 | Graphene natural rubber macromolecule control bacterium mixed foaming material and preparation method thereof |
| CN111500052A (en) * | 2020-05-15 | 2020-08-07 | 鲍维江 | Tear-resistant light polyurethane shoe material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116554535A (en) | 2023-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109880226B (en) | Graphene regenerated rubber-plastic foamed colloidal particle for shoe sole and preparation method thereof | |
| CN107674292A (en) | A kind of preparation method of the expanded material of doped graphene | |
| CA3043354C (en) | A method for preparing high shrinkage stability styrene butadiene rubber-based nanocomposite foams | |
| CN102558637B (en) | Organic peroxide master batches and preparation method thereof | |
| CN113527790A (en) | Anti-static irradiation crosslinked polyethylene foam material and preparation method thereof | |
| CN109054343B (en) | Blended vulcanized rubber and preparation method thereof | |
| CN112250924A (en) | Formula and production process of environment-friendly recycled high-wear-resistance rubber and plastic material | |
| CN113845716B (en) | Modified EVA (ethylene-vinyl acetate copolymer), preparation method thereof and wide-temperature-range high-performance EVA composite foam material | |
| CN116554535B (en) | Graphene modified rubber-plastic foaming colloidal particle and preparation method thereof | |
| CN114350036B (en) | High-weather-resistance anti-slip foaming sole and preparation method thereof | |
| CN106751095A (en) | Isomerism containing L POSS crosslinking agents is modified to reclaim PS and preparation method thereof | |
| CN107400493A (en) | Degradable Adhesive composition and its production and use | |
| CN103073786A (en) | Polypropylene-use matting agent masterbatch, and preparation method and application thereof | |
| CN109504104A (en) | A kind of thermoplastic elastomer blending material of high adherence and preparation method thereof | |
| CN105218938A (en) | A kind of high jump pad EVA matrix material and preparation method thereof | |
| CN107541004B (en) | Load-resistant and fatigue-resistant TPE (thermoplastic elastomer) and preparation method thereof | |
| CN115449118B (en) | Light wear-resistant polyurethane sole and preparation method thereof | |
| CN111320790A (en) | Rubber composite material and ultralight high-elastic sole | |
| CN113698692A (en) | Silane cross-linked LLDPE material and preparation method and application thereof | |
| CN112063036A (en) | Protein filler composite EVA (ethylene-vinyl acetate copolymer) foamed shoe material and preparation method thereof | |
| CN113248839B (en) | Reinforced TPV (thermoplastic vulcanizate) material for MDI (diphenylmethane diisocyanate) foaming bonding and preparation method thereof | |
| CN112961427B (en) | Wear-resistant agent for shoes and preparation method and application thereof | |
| Kuriakose et al. | Tear and wear resistance of silica filled thermoplastic polypropylene—natural rubber blend | |
| CN114933760A (en) | EVA (ethylene-vinyl acetate copolymer) foamed sole, wear-resistant and anti-skid composition for EVA foamed sole and preparation method of composition | |
| CN106810832A (en) | Modified polyethylene terephthalate of isomerism containing condensed cyclic structure crosslinking agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |