CN113980291A - Preparation method of eucommia ulmoides latex, eucommia ulmoides gum base composite material and preparation method - Google Patents
Preparation method of eucommia ulmoides latex, eucommia ulmoides gum base composite material and preparation method Download PDFInfo
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- CN113980291A CN113980291A CN202111359147.6A CN202111359147A CN113980291A CN 113980291 A CN113980291 A CN 113980291A CN 202111359147 A CN202111359147 A CN 202111359147A CN 113980291 A CN113980291 A CN 113980291A
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- latex
- eucommia ulmoides
- eucommia
- water
- composite material
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- 229920000126 latex Polymers 0.000 title claims abstract description 149
- 239000004816 latex Substances 0.000 title claims abstract description 144
- 241000208689 Eucommia ulmoides Species 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229920001971 elastomer Polymers 0.000 claims abstract description 42
- 239000005060 rubber Substances 0.000 claims abstract description 42
- 241000208688 Eucommia Species 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 33
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- -1 polyoxyethylene dodecyl ether Polymers 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 15
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 13
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 11
- 239000002174 Styrene-butadiene Substances 0.000 claims description 10
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- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 239000011115 styrene butadiene Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 8
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 8
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 8
- 238000005189 flocculation Methods 0.000 claims description 7
- 230000016615 flocculation Effects 0.000 claims description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- QRIPJHVJKXPQBX-UHFFFAOYSA-N 1-dodecylsulfanyldodecane;sodium Chemical compound [Na].CCCCCCCCCCCCSCCCCCCCCCCCC QRIPJHVJKXPQBX-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 4
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 claims description 4
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 3
- 230000003311 flocculating effect Effects 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229940096992 potassium oleate Drugs 0.000 claims description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 23
- 239000002245 particle Substances 0.000 abstract description 16
- 239000012071 phase Substances 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000899 Gutta-Percha Substances 0.000 description 24
- 240000000342 Palaquium gutta Species 0.000 description 24
- 229920000588 gutta-percha Polymers 0.000 description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 244000043261 Hevea brasiliensis Species 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229920003052 natural elastomer Polymers 0.000 description 13
- 229920001194 natural rubber Polymers 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 235000021355 Stearic acid Nutrition 0.000 description 11
- 230000003712 anti-aging effect Effects 0.000 description 11
- 239000003995 emulsifying agent Substances 0.000 description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 11
- 239000008117 stearic acid Substances 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- NMSBTWLFBGNKON-UHFFFAOYSA-N 2-(2-hexadecoxyethoxy)ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCO NMSBTWLFBGNKON-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
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- 238000000227 grinding Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000221020 Hevea Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical group N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/04—Purifying; Deproteinising
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/075—Concentrating
- C08C1/10—Concentrating by centrifugation
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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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
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
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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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
- C08J2309/08—Latex
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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
- C08J2407/00—Characterised by the use of natural rubber
- C08J2407/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention provides a preparation method of eucommia ulmoides latex, the eucommia ulmoides latex, a eucommia ulmoides gum base composite material and a preparation method. The method comprises the following steps: dissolving the crude eucommia ulmoides gum in an organic solvent to obtain a eucommia ulmoides gum solution, and adding an oil-soluble nonionic emulsifier to mix to obtain an oil phase; mixing an anionic emulsifier, a water-soluble nonionic emulsifier and deionized water to obtain a water phase; mixing oil and water phases, emulsifying, removing the organic solvent, and concentrating to obtain the eucommia ulmoides latex. According to the invention, the eucommia latex with smaller particle size, higher solid content and more stability is prepared by using the oil-soluble nonionic emulsifier in the oil phase and matching the oil-soluble nonionic emulsifier with the anionic emulsifier and the water-soluble nonionic emulsifier in the water phase, and the eucommia latex is further processed by adopting wet mixing, so that the compatibility of the co-mixed rubber is improved, the dispersion of the filler is improved, and the comprehensive mechanical property of the composite material is improved.
Description
Technical Field
The invention relates to the technical field of rubber composite materials, and further relates to a preparation method of eucommia ulmoides latex, the eucommia ulmoides latex, a eucommia ulmoides gum base composite material and a preparation method.
Background
In the modern society, energy crisis, environmental pollution and climate change influence the aspects of our life, and a green sustainable development mode is urgently needed. Thus, petroleum-based synthetic polymers will eventually be replaced by renewable natural polymers. Meanwhile, China is one of the countries with the largest rubber consumption and faces the problem of low self-sufficient rate of natural rubber. As a natural growing rubber, the gutta-percha can partially replace natural rubber, the development of the gutta-percha is an effective way for relieving the problem of the shortage of the natural rubber in China, and is an important component for implementing the strong national strategy of the rubber.
The gutta-percha is derived from eucommia ulmoides and is a novel natural growing rubber. The main structure of the gutta-percha is trans-polyisoprene which is an isomer with natural rubber produced by hevea trees. However, the trans-form structure is more regular, the molecular chain is microscopically ordered, the stacking and crystallization are easy, the characteristics are completely different from those of natural rubber, and the untreated gutta percha has the properties of a crystallized hard plastic at normal temperature. Meanwhile, researches show that the eucommia ulmoides rubber with different vulcanization crosslinking degrees can present different material characteristics, and the crosslinking degree can present the properties of thermoplastic materials, thermoelastic materials and rubber materials from low to high and is represented as unique rubber-plastic duality. Due to the unique performance, the eucommia ulmoides gum can be used for preparing more novel materials with excellent and different performances, and has great application prospects in the aspects of plastic modification and rubber blending. At present, studies on eucommia ulmoides latex are few, and a preparation method of the eucommia ulmoides latex is disclosed in patent CN112175203A, but the operation is complex, the particle size and the solid content of the latex are poor, and the stability is to be improved.
Because the gutta-percha is easy to crystallize and shows the property of hard plastics at normal temperature, the gutta-percha is not easy to be mixed with other rubbers, and the filler is not easy to disperse, so that the comprehensive mechanical properties of the blended rubber, such as tensile strength, elongation at break, permanent tensile deformation and the like, are not good; the compatibility of blended rubber and the dispersion of high filler can be improved by adopting wet mixing, but the operation is more complicated when the eucommia latex is prepared in the prior art, the prepared eucommia latex emulsion has larger particle size and lower solid content and is not stable enough, so the eucommia latex emulsion process needs to be optimized, the eucommia latex with smaller particle size, higher solid content and more stability is prepared, and meanwhile, the eucommia latex is combined with other latex to prepare the eucommia gum base composite material with better comprehensive mechanical property.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of eucommia ulmoides latex, the eucommia ulmoides latex, a eucommia ulmoides gum base composite material and a preparation method.
The invention aims to prepare a rubber composite material based on an eucommia ulmoides gum base by preparing natural eucommia ulmoides latex and adopting a wet mixing mode, solve the problems of energy consumption and pollution in the traditional dry mixing of the eucommia ulmoides gum, improve the blending performance of the eucommia ulmoides gum and other rubbers and improve the comprehensive mechanical property of the eucommia ulmoides rubber composite material.
The invention optimizes the emulsification process of the eucommia ulmoides latex, prepares the eucommia ulmoides latex with smaller particle size, higher solid content and more stability by using the oil-soluble nonionic emulsifier-polyoxyethylene ether emulsifier in the oil phase and matching with the anionic emulsifier and the water-soluble nonionic emulsifier in the water phase, and adopts wet mixing for further processing, thereby improving the compatibility of the co-mixed rubber and improving the dispersion of the filler, and further improving the comprehensive mechanical property of the composite material.
One of the purposes of the invention is to provide a preparation method of eucommia ulmoides latex, which comprises the following steps:
(1) dissolving the crude eucommia ulmoides gum in an organic solvent to obtain a eucommia ulmoides gum solution, and adding an oil-soluble nonionic emulsifier to mix to obtain an oil phase;
(2) mixing an anionic emulsifier, a water-soluble nonionic emulsifier and deionized water to obtain a water phase;
(3) mixing oil and water phases, emulsifying, removing the organic solvent, and concentrating to obtain the eucommia ulmoides latex.
In a preferred embodiment of the present invention,
the organic solvent is at least one of cyclohexane, dichloromethane, petroleum ether, n-hexane and xylene; and/or the presence of a gas in the gas,
the oil-soluble nonionic emulsifier is a polyoxyethylene ether nonionic emulsifier; preferably at least one of polyoxyethylene lauryl ether (AEO-3), polyoxyethylene cetyl ether (AEO-4), polyoxyethylene lauryl ether (AEO-5) and polyoxyethylene cetyl ether (Brij-52); and/or the presence of a gas in the gas,
the anionic emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl sulfide, Sodium Dodecyl Benzene Sulfonate (SDBS), sodium oleate and potassium oleate; and/or the presence of a gas in the gas,
the water-soluble nonionic emulsifier is at least one of polyoxyethylene lauryl ether, polyoxyethylene sorbitan monolaurate (Tween-20), polyoxyethylene sorbitan monopalmitate (Tween-40), polyoxyethylene sorbitan monooleate (Tween-80) and polyvinyl alcohol (PVA).
In a preferred embodiment of the present invention,
the mass of the eucommia crude gum accounts for 3-10% of that of the eucommia gum solution; preferably 5 to 7 percent;
the mass of the oil-soluble nonionic emulsifier accounts for 1-5% of the total mass of the oil phase; preferably 1.5 to 3 percent;
the mass of the anionic emulsifier accounts for 0.2 to 5 percent of the total mass of the water phase; preferably 0.5 to 1 percent;
the mass of the water-soluble nonionic emulsifier accounts for 0.2-5% of the total mass of the water phase; preferably 0.5 to 1 percent;
the volume ratio of the oil phase to the water phase is 1 (1.5-3); preferably 1: (1.5-1.8).
In a preferred embodiment of the present invention,
step (1) of carrying out a treatment,
the stirring speed of the crude eucommia ulmoides gum when being dissolved in the organic solvent is 300 r/min-700 r/min;
the temperature is 40-80 ℃;
the stirring time is 12-24 h.
A step (3) of,
the stirring speed during emulsification is 5000r/min to 12000r/min, and the emulsification time is 8min to 18 min;
removing the organic solvent by adopting a reduced pressure distillation method, wherein the temperature is 30-80 ℃, and the pressure is 0.01-0.1 Mpa;
the concentration adopts a centrifugal method, the rotating speed is 5000r/min to 12000r/min, and the time is 8min to 30 min.
The invention also aims to provide the eucommia ulmoides latex.
The eucommia ulmoides latex is prepared by the preparation method.
The invention also aims to provide a eucommia ulmoides gum base composite material prepared from the raw materials comprising the eucommia ulmoides latex.
The eucommia ulmoides gum base composite material also comprises natural latex or styrene-butadiene latex, a surfactant, pretreated filler and other rubber auxiliaries;
based on the total amount of rubber in the eucommia ulmoides latex and the natural latex or the styrene-butadiene latex as 100 parts by weight,
wherein the eucommia ulmoides rubber in the eucommia ulmoides rubber latex accounts for 5-50% of the total amount of the rubber; preferably 10% to 30%.
The eucommia ulmoides latex is used after the solid content is adjusted to be 10% -30% by deionized water, and the total rubber amount of the eucommia ulmoides latex and the natural latex or the styrene-butadiene latex comprises the eucommia ulmoides rubber in the eucommia ulmoides latex, and the natural rubber or the styrene-butadiene rubber in the natural latex or the styrene-butadiene latex.
In a preferred embodiment of the present invention,
the surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl sulfide, sodium dodecyl benzene sulfonate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monolaurate and polyoxyethylene monolaurate;
the pretreated filler is filler water dispersion liquid pre-dispersed into a certain concentration by a ball mill or a colloid mill;
the filler is a filler commonly used for rubber, and preferably at least one of carbon black and white carbon black;
the filler can be pre-dispersed into aqueous dispersion with a certain concentration by a ball mill or a colloid mill;
the other rubber auxiliaries are the auxiliaries commonly used for rubber, such as a vulcanizing agent, zinc oxide, stearic acid, an anti-aging agent, an accelerator and the like.
The invention also provides a preparation method of the eucommia ulmoides gum base composite material, which comprises the following steps:
uniformly mixing the eucommia ulmoides latex, the natural latex or the butadiene styrene latex and the surfactant to obtain blended latex, adding the pretreated filler into the blended latex, uniformly stirring, flocculating, washing and drying to obtain masterbatch, plasticating the masterbatch in an open mill, adding other rubber auxiliaries, uniformly mixing, discharging sheets, and vulcanizing to obtain the eucommia ulmoides gum base composite material.
In a preferred embodiment of the present invention,
the stirring speed is 300r/min to 800r/min, and the stirring time is 10min to 30 min;
the flocculation is carried out by adopting a method of spray drying or adding a flocculating agent;
the flocculating agent is one of acetic acid, formic acid, absolute ethyl alcohol and anhydrous calcium chloride;
the vulcanization temperature is 143-150 ℃;
the vulcanizing time is 10 min-40 min.
The invention can adopt the following technical scheme:
preparing eucommia latex:
the gutta-percha is taken according to the specified dosage and added into the organic solvent, and is dissolved for 12 to 24 hours at the temperature of between 40 and 80 ℃ to prepare the glue solution with a certain concentration. And adding the oil-soluble nonionic emulsifier with the specified dosage into the prepared glue solution, and uniformly stirring to obtain an oil phase.
Adding the anionic emulsifier and the water-soluble nonionic emulsifier with the specified dosage into deionized water, and uniformly stirring to obtain a water phase. And adding the oil phase and the water phase into a high-speed stirrer according to the proportion, and stirring at a high speed under the control of specified time and rotating speed to obtain the eucommia ulmoides coarse latex.
Evaporating the obtained eucommia crude latex at a certain temperature and pressure, removing the organic solvent to obtain eucommia dilute latex, centrifuging the obtained eucommia dilute latex at a certain rotating speed for a period of time, and removing a large amount of water to obtain the eucommia latex.
Preparing an eucommia-based composite material:
the eucommia ulmoides latex preferably has a solid content of 10-30%, is added into another latex such as natural rubber, styrene-butadiene latex and the like according to a certain proportion, meanwhile, a surfactant with a specified dosage is added as a stabilizer, and is stirred for a specified time at a specified rotating speed to obtain a combined latex.
Adding the carbon black or the white carbon black subjected to pre-dispersion into the blend latex, stirring at a certain rotating speed, flocculating by adopting a certain method after uniform dispersion, cleaning for 5-8 times in clear water, and drying in an oven at 60 ℃ for 20 hours.
Plasticating the dried masterbatch on an open mill, adjusting the roller spacing to be small, beating three triangular bags and three coiled wrapping rollers, adding other rubber auxiliaries, and then vulcanizing and molding.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the process of preparing the eucommia ulmoides latex, an emulsification system is optimized, the oil-soluble polyoxyethylene ether nonionic emulsifier is introduced for the first time, and the emulsifiers are added into both oil phases and water phases, so that the emulsification effect is improved, and the prepared eucommia ulmoides latex has smaller particle size and higher solid content;
(2) in the process of preparing the eucommia ulmoides latex, the emulsification process is simplified, the pH value of an emulsification system does not need to be adjusted, and the prepared eucommia ulmoides latex is small in particle size and better in particle size uniformity. (ii) a
(3) According to the invention, the filler and the latex are mixed by an emulsion co-coagulation method, so that the energy consumption in the mixing process is reduced, the dust pollution in the filler mixing process is reduced, and the green development concept is met;
(4) the invention mixes the eucommia latex with other latexes and fillers for the first time, so that the rubber network and the filler network are dispersed more uniformly, and the comprehensive mechanical properties of the composite material, such as tensile strength, elongation at break, permanent tensile deformation and the like, are improved.
Drawings
FIG. 1 is a scanning electron micrograph of an eucommia ulmoides latex prepared in example 1;
FIG. 2 is a scanning electron micrograph of the eucommia ulmoides latex prepared in example 2;
FIG. 3 is a scanning electron micrograph of an eucommia latex prepared in example 3;
FIG. 4 is a scanning electron micrograph of an eucommia latex prepared in example 4;
FIG. 5 is a scanning electron micrograph of the eucommia ulmoides latex prepared in example 5.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
The raw materials used in the examples are all conventional commercially available raw materials.
And (4) testing standard:
latex particle size testing: GB/T19627-;
latex Zeta potential test: GB/T32668-2016;
solid content of latex: GB/T8299-2008;
tensile strength, elongation at break, 100% stress at elongation at: GB T528-2009;
rubber hardness: GB/T531.1-2008.
The parts of the following examples and comparative examples are parts by weight.
Examples 1 to 4
Preparation of eucommia ulmoides latex:
adding crude gutta-percha and cyclohexane into a three-neck flask, and stirring for 24 hours at 70 ℃ at 500r/min to obtain 3-10% gutta-percha solutions with different mass concentrations. And respectively adding oil-soluble emulsifier polyoxyethylene ether Brij-52 accounting for 1-5% of the total mass of the oil phase into the gutta percha solution, and fully dissolving to obtain the oil phase.
Adding anionic emulsifier Sodium Dodecyl Benzene Sulfonate (SDBS) accounting for 0.2-5% of the total mass of the water phase and nonionic emulsifier polyoxyethylene sorbitan monolaurate (Tween 20) accounting for 0.5-5% of the total mass of the water phase into water, and fully dissolving to obtain the water phase.
The volume ratio of oil to water is 1: (1.5-3), sequentially adding the water phase and the oil phase into a high-speed stirrer, and stirring at a rotating speed of 8000r/min for 10min to obtain eucommia crude latex; evaporating the obtained crude Eucommiae cortex latex at 40 deg.C and vacuum degree of-0.9 Mpa for 1 hr to remove organic solvent to obtain diluted Eucommiae cortex latex; centrifuging and concentrating the prepared eucommia ulmoides dilute latex at the rotating speed of 10000r/min for 10min, and removing the centrifuged lower clear liquid to obtain the eucommia ulmoides latex.
Specific conditions of examples 1 to 4 are shown in Table 1.
Examples 5 to 7
Preparation of eucommia ulmoides latex:
crude gutta-percha and cyclohexane were added to a three-necked flask, and stirred at 70 ℃ at 500r/min for 24 hours to obtain a 7% gutta-percha solution having a mass concentration. Respectively adding polyoxyethylene ether AEO-3 (or AEO-5 or Brij-52) as oil-soluble emulsifier in an amount of 2.5% of the total mass of the oil phase into the gutta percha solution, and dissolving completely to obtain the oil phase.
Adding sodium dodecyl sulfate (or sodium dodecyl sulfide or sodium oleate) which is an anionic emulsifier accounting for 2% of the total mass of the water phase and polyoxyethylene lauryl ether (or polyoxyethylene sorbitan monopalmitate (Tween-40) or polyoxyethylene sorbitan monooleate (Tween-80)) which is a nonionic emulsifier accounting for 2% of the total mass of the water phase into water, and fully dissolving to obtain the water phase.
The volume ratio of oil to water is 1: 3, sequentially adding the water phase and the oil phase into a high-speed stirrer, and stirring at the rotating speed of 10000r/min for 10min to obtain eucommia crude latex; evaporating the prepared eucommia crude latex at 45 ℃ and under the vacuum degree of-0.85 Mpa for 1.5h to remove the organic solvent to obtain eucommia dilute latex; centrifuging and concentrating the prepared eucommia ulmoides dilute latex at the rotating speed of 9000r/min for 15min, and removing the centrifuged lower clear liquid to obtain the eucommia ulmoides latex.
Specific conditions of examples 5 to 7 are shown in Table 1.
Example 8
Preparation of eucommia ulmoides latex:
adding the crude gutta-percha into dichloromethane, and stirring at the temperature of 40 ℃ at the speed of 500r/min for 24 hours to obtain a gutta-percha solution with the mass concentration of 5%. And adding oil-soluble emulsifier polyoxyethylene ether Brij-52 accounting for 2% of the total mass of the oil phase into the gutta percha solution, and fully dissolving to obtain the oil phase.
Adding Sodium Dodecyl Benzene Sulfonate (SDBS) and polyvinyl alcohol 1788(PVA-1788), which are anionic emulsifiers accounting for 2% of the total mass of the water phase, into water respectively, and fully dissolving to obtain the water phase.
Sequentially adding the water phase and the oil phase into a high-speed stirrer at a volume ratio of 1:2, and stirring at a rotating speed of 9000r/min for 10min to obtain eucommia ulmoides coarse latex; evaporating the prepared eucommia crude latex at 40 ℃ for 5h to remove the organic solvent to obtain eucommia dilute latex; centrifuging and concentrating the prepared eucommia ulmoides dilute latex at the rotating speed of 10000r/min for 15min, and removing the centrifuged lower clear liquid to obtain the eucommia ulmoides latex.
Specific conditions for example 8 are shown in table 1.
Example 9
Preparation of eucommia ulmoides latex:
adding the crude gutta-percha into petroleum ether, and stirring at 70 ℃ at a speed of 500r/min for 24h to obtain a gutta-percha solution with a mass concentration of 5%. And adding oil-soluble emulsifier polyoxyethylene ether Brij-52 accounting for 2% of the total mass of the oil phase into the gutta percha solution, and fully dissolving to obtain the oil phase.
Adding Sodium Dodecyl Benzene Sulfonate (SDBS) which is 2 percent of the total mass of the water phase as an anionic emulsifier and polyoxyethylene sorbitan monooleate (Tween-80) into water respectively, and fully dissolving to obtain the water phase.
And (3) adding the water phase and the oil phase into a high-speed stirrer in sequence at the volume ratio of 1:2, and stirring at the rotating speed of 9000r/min for 15min to obtain the eucommia ulmoides coarse latex. Evaporating the prepared eucommia ulmoides crude latex at 45 ℃ and under the vacuum degree of-0.85 Mpa for 2h to remove the organic solvent to obtain the eucommia ulmoides dilute latex. Centrifuging and concentrating the prepared eucommia ulmoides dilute latex at the rotating speed of 10000r/min for 15min, and removing the centrifuged lower clear liquid to obtain the eucommia ulmoides latex.
Specific conditions for example 9 are shown in table 1.
Example 10
Preparation of eucommia ulmoides latex:
adding the crude gutta-percha into n-hexane, and stirring at 70 ℃ at 500r/min for 24h to obtain a gutta-percha solution with the mass concentration of 5%. And adding oil-soluble emulsifier polyoxyethylene ether Brij-52 accounting for 2% of the total mass of the oil phase into the gutta percha solution, and fully dissolving to obtain the oil phase.
Adding 2% of anionic emulsifier Sodium Dodecyl Benzene Sulfonate (SDBS) and polyoxyethylene sorbitan monopalmitate (Tween-40) which account for the total mass of the water phase into water respectively, and fully dissolving to obtain the water phase.
Sequentially adding the water phase and the oil phase into a high-speed stirrer at a volume ratio of 1:2, and stirring at a rotating speed of 9000r/min for 15min to obtain eucommia ulmoides coarse latex; evaporating the prepared eucommia crude latex at 45 ℃ and under the vacuum degree of-0.85 Mpa for 2h to remove the organic solvent to obtain eucommia dilute latex; centrifuging and concentrating the prepared eucommia ulmoides dilute latex at the rotating speed of 10000r/min for 15min, and removing the centrifuged lower clear liquid to obtain the eucommia ulmoides latex.
Specific conditions for example 10 are shown in table 1.
Comparative example 1
The preparation method in patent CN112175203a, example 1, was adopted:
(1) freezing 400 parts of eucommia seed shells at the temperature of minus 5 ℃ for 40 minutes, then crushing the eucommia seed shells in a high-speed crusher, and sieving the eucommia seed shell powder to control the particle size of the eucommia seed shell powder to be less than 0.5 mm; dissolving eucommia seed shell powder by using 1000 parts of cyclohexane at 70 ℃ and at the stirring speed of 500r/min, extracting for 5 hours, centrifuging the extract liquid for 5 minutes by using a high-speed centrifuge at the speed of 3500r/min, and filtering the eucommia ulmoides gum extract liquid by using 40-mesh nylon cloth to obtain eucommia ulmoides gum liquid with the solid content of 10%;
(2) taking 1000 parts of the eucommia ulmoides gum solution with the solid content of 10% prepared in the step (1), adding the eucommia ulmoides gum solution into a glass reaction kettle, adding 3.5 parts of oleic acid, 1.0 part of span 80 and 1.5 parts of an anti-aging agent SP, and stirring for 5 hours at the rotation speed of 500r/min and the temperature of 70 ℃ to obtain a eucommia ulmoides gum crude emulsion;
(3) adding 5 parts of water-based emulsifier triethanolamine, 5 parts of pH regulator potassium hydroxide, 0.5 part of mechanical stabilizer potassium laurate, 0.05 part of defoamer WBA, 0.1 part of webbed agent n-butanol and 1100 soft water into a reaction kettle, heating to 70 ℃, adding the eucommia ulmoides gum crude emulsion prepared in the step (2), distilling at the stirring speed of 500r/min and the vacuum degree of not more than-0.05 MPa, and emulsifying for 15 minutes at the shearing speed of 8500r/min when the mixed solution is converted into a water phase from an oil phase after distilling for 6 hours, so that the mixed solution becomes a water-based emulsion;
(4) standing the emulsified liquid for 24 hours, and filtering to obtain the gutta-percha latex with the solid content of 15%.
Example 11
Preparing a eucommia ulmoides gum base composite material:
the eucommia ulmoides latex and the natural latex prepared in the example 1 are added with deionized water to adjust the solid content to 10%, the eucommia ulmoides latex is added into the natural latex according to the formula, sodium dodecyl benzene sulfonate is added, and the mixture is stirred for 20min at the rotating speed of 500r/min to obtain stable combined latex.
Adding carbon black N330 and deionized water into a ball mill together, and grinding for 4h to obtain carbon black water dispersion liquid. Adding the carbon black dispersion liquid into the combined latex according to the formula, and stirring at the rotating speed of 500r/min for 30min to obtain uniform carbon black combined latex dispersion liquid. Pouring the prepared carbon black dispersion into absolute ethyl alcohol for flocculation, washing in clear water, and drying at 60 ℃ for 24 hours to obtain the master batch.
Plasticating the prepared master batch in an open mill at 80 ℃ for 1min, sequentially adding zinc oxide, stearic acid, anti-aging agent 4010NA, accelerator DZ and sulfur according to a formula, uniformly mixing, then taking out a sheet, and finally vulcanizing at 143 ℃ and 15Mpa for 20min to obtain the composite material.
The specific test conditions for example 11 are shown in Table 2.
Comparative example 2
Plasticating eucommia ulmoides gum in an open mill at 90 ℃ for 2min, then adding natural rubber for plasticating for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, carbon black N330, a promoter DZ and sulfur according to a formula, uniformly mixing, then taking out a sheet, and finally vulcanizing at 143 ℃ and 15Mpa for 20min to obtain the composite material.
The specific test conditions of comparative example 2 are shown in table 2.
Example 12
Preparing a eucommia ulmoides gum base composite material:
the eucommia ulmoides latex and the natural latex prepared in the example 2 are added with deionized water to adjust the solid content to 15%, the eucommia ulmoides latex is added into the natural latex according to the formula, polyoxyethylene lauryl ether is added, and the mixture is stirred for 20min at the rotating speed of 500r/min to obtain stable combined latex.
Adding carbon black N330 and deionized water into a ball mill together, and grinding for 4h to obtain carbon black water dispersion liquid with solid content of 10%. Adding the carbon black dispersion liquid into the combined latex according to the formula, and stirring at the rotating speed of 500r/min for 30min to obtain uniform carbon black combined latex dispersion liquid. Pouring the prepared carbon black dispersion into absolute ethyl alcohol for flocculation, washing in clear water, and drying at 60 ℃ for 24 hours to obtain the master batch.
Plasticating the prepared master batch in an open mill at 80 ℃ for 1min, sequentially adding zinc oxide, stearic acid, anti-aging agent 4010NA, accelerator DZ and sulfur according to a formula, uniformly mixing, then taking out a sheet, and finally vulcanizing at 143 ℃ and 15Mpa for 20min to obtain the composite material.
The specific test conditions for example 12 are shown in Table 2.
Comparative example 3
Plasticating eucommia ulmoides gum in an open mill at 90 ℃ for 2min, then adding natural rubber for plasticating for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, carbon black N330, a promoter DZ and sulfur according to a formula, uniformly mixing, then taking out a sheet, and finally vulcanizing at 143 ℃ and 15Mpa for 20min to obtain the composite material.
The specific test conditions of comparative example 3 are shown in table 2.
Examples 13 to 15
Preparing a eucommia ulmoides gum base composite material:
the eucommia ulmoides latex and the natural latex prepared in the example 3 are added with deionized water to adjust the solid content to 30%, the eucommia ulmoides latex is added into the natural latex according to the formula, and tween 20 is added, and the mixture is stirred for 30min at the rotating speed of 600r/min to obtain stable combined latex.
Adding white carbon black VN3, a silane coupling agent Si-747 with the mass of 10% of white carbon black and deionized water into a colloid mill together, grinding for 30min to obtain a white carbon black water dispersion liquid with the solid content of 10%, and pretreating the white carbon black water dispersion liquid for 3h at 80 ℃. And adding the white carbon black dispersion liquid into the mixed latex according to the formula, and stirring at the rotating speed of 500r/min for 30min to obtain the uniform white carbon black mixed latex dispersion liquid. And (3) dropwise adding 10% formic acid solution into the prepared dispersion liquid for flocculation, standing for 12 hours, dehydrating, washing, and drying at 60 ℃ for 24 hours to obtain the master batch.
Plasticating the prepared master batch in an open mill for 2min, sequentially adding zinc oxide, stearic acid and an anti-aging agent 4010NA, uniformly mixing, placing in an internal mixer at 150 ℃ for heat preservation and modification for 5min, taking out, cooling, sequentially adding an accelerator D, an accelerator NS and sulfur in the open mill according to a formula, uniformly mixing, taking out, and finally vulcanizing at 143 ℃ and 15Mpa for 15min to obtain the composite material.
The specific test conditions for examples 13-15 are shown in Table 3.
Comparative examples 4 to 6
Plasticating the eucommia ulmoides gum in a 90 ℃ open mill for 2min, then adding natural rubber for plasticating for 1min, sequentially adding zinc oxide, stearic acid and an anti-aging agent 4010NA according to a formula, then adding white carbon black and a silane coupling agent, uniformly mixing, placing in a 150 ℃ internal mixer for heat preservation and modification for 5min, taking out, cooling, sequentially adding an accelerator D, an accelerator NS and sulfur in the open mill, uniformly mixing, then taking out, and finally vulcanizing for 15min at 143 ℃ and 15Mpa to obtain the composite material.
The specific test conditions of comparative examples 4 to 6 are shown in Table 3.
Example 16
Preparing a eucommia ulmoides gum base composite material:
the eucommia ulmoides latex and the natural latex prepared in the example 4 are added with deionized water to adjust the solid content to 15%, the eucommia ulmoides latex is added into the natural latex according to the formula, polyoxyethylene monolaurate is added, and the mixture is stirred for 30min at the rotating speed of 600r/min to obtain stable combined latex.
Adding white carbon black VN3, a silane coupling agent Si-747 with the mass of 10% of white carbon black and deionized water into a colloid mill together, grinding for 30min to obtain a white carbon black water dispersion liquid with the solid content of 10%, and pretreating the white carbon black water dispersion liquid for 3h at 80 ℃. And adding the white carbon black dispersion liquid into the mixed latex according to the formula, and stirring at the rotating speed of 500r/min for 30min to obtain the uniform white carbon black mixed latex dispersion liquid. And (3) dropwise adding 10% formic acid solution into the prepared dispersion liquid for flocculation, standing for 12 hours, dehydrating, washing, and drying at 60 ℃ for 24 hours to obtain the master batch.
Plasticating the prepared master batch in an open mill for 2min, sequentially adding zinc oxide, stearic acid and an anti-aging agent 4010NA, uniformly mixing, placing in an internal mixer at 150 ℃ for heat preservation and modification for 5min, taking out, cooling, sequentially adding an accelerator CZ, an accelerator D and sulfur in the open mill according to a formula, uniformly mixing, taking out, and finally vulcanizing at 143 ℃ and 15Mpa for 15min to obtain the composite material.
The specific test conditions for example 16 are shown in Table 4.
Comparative example 7
Plasticating the eucommia ulmoides gum in a 90 ℃ open mill for 2min, then adding natural rubber for plasticating for 1min, sequentially adding zinc oxide, stearic acid and an anti-aging agent 4010NA according to a formula, then adding white carbon black and a silane coupling agent, uniformly mixing, placing in a 150 ℃ internal mixer for heat preservation and modification for 5min, taking out, cooling, sequentially adding an accelerator CZ, an accelerator D and sulfur in the open mill, uniformly mixing, then taking out, and finally vulcanizing at 143 ℃ and 15Mpa for 15min to obtain the composite material.
The specific test conditions of comparative example 7 are shown in Table 4.
Example 17
Preparing a eucommia ulmoides gum base styrene-butadiene rubber composite material:
the eucommia ulmoides latex and the styrene-butadiene latex prepared in the example 5 are added with deionized water to adjust the solid content to 10%, the eucommia ulmoides latex is added into the styrene-butadiene latex according to the formula, sodium dodecyl benzene sulfonate is added, and the mixture is stirred for 20min at the rotating speed of 500r/min to obtain stable combined latex.
Adding carbon black N330 and deionized water into a ball mill together, and grinding for 4h to obtain carbon black water dispersion liquid with solid content of 10%. Adding the carbon black dispersion liquid into the combined latex according to the formula, and stirring at the rotating speed of 500r/min for 30min to obtain uniform carbon black combined latex dispersion liquid. Pouring the prepared carbon black dispersion into absolute ethyl alcohol for flocculation, washing in clear water, and drying at 60 ℃ for 24 hours to obtain the master batch.
Plasticating the prepared master batch in an open mill at 80 ℃ for 1min, sequentially adding zinc oxide, stearic acid, antioxidant 4010NA, accelerator DZ, accelerator TMTD and sulfur according to a formula, uniformly mixing, then taking out a sheet, and finally vulcanizing at 143 ℃ and 15Mpa for 15min to obtain the composite material.
The specific test conditions for example 17 are shown in Table 4.
Comparative example 8
Preparing a eucommia ulmoides gum base composite material:
plasticating the eucommia ulmoides gum in an open mill at 90 ℃ for 2min, then adding the styrene butadiene rubber for plasticating for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, carbon black N330, a promoter DZ, a promoter TMTD and sulfur according to a formula, uniformly mixing, then taking out a sheet, and finally vulcanizing at 143 ℃ and 15Mpa for 15min to obtain the composite material.
The specific test conditions of comparative example 8 are shown in Table 4.
TABLE 1 particle diameter and solid content of eucommia ulmoides latices obtained in examples 1 to 10 and comparative example 1
Compared with a comparative example 1, the average particle size of the examples 1-10 is smaller, the Zeta potential is lower, the solid content is higher, and the effects of the examples 2-4 are more obvious, which proves that the emulsifying method disclosed by the invention is better in effect, the polyoxyethylene ether oil-soluble nonionic emulsifier is firstly used in the oil phase and interacts with the anionic emulsifier and the water-soluble nonionic emulsifier in the water phase, so that the emulsifying process is simpler and more convenient, the emulsifying effect is better, the particle size of the prepared latex is smaller, and the stability is higher. Fig. 1 to 5 show that the eucommia ulmoides latex prepared by the present invention has a smaller particle size, and shows that the three-phase emulsifier used in the present invention has a good emulsification effect under the combined action.
TABLE 2 formulation of eucommia ulmoides gum base composite material of examples 11-12 and comparative examples 2-3
TABLE 3 formulation of eucommia ulmoides gum base composite material of examples 13-15 and comparative examples 4-6
TABLE 4 formulation of eucommia ulmoides gum based composite material of examples 16-17 and comparative examples 7-8
TABLE 5 mechanical properties of composites prepared in examples 11 to 17 and comparative examples 2 to 8
The prepared eucommia ulmoides latices were applied to rubber composites, and example 11 and comparative example 2, example 12 and comparative example 3, example 13 and comparative example 4, example 14 and comparative example 5, example 15 and comparative example 6, example 16 and comparative example 7, and example 17 and comparative example 8 were compared, respectively.
As can be seen from table 5, compared with the comparative examples, the mechanical properties of the eucommia ulmoides gum base composite material prepared in the examples are better, which is reflected by higher elongation at break and higher tensile strength, because the eucommia ulmoides latex prepared by the invention has small particle size, is mixed with natural latex in a liquid phase, the eucommia ulmoides gum is more dispersed in natural rubber, the rubber network is more uniformly dispersed, meanwhile, the filler is mixed with rubber in the liquid phase, the filler network is more uniformly dispersed in the rubber, the reinforcing capacity of the filler is improved through the interaction of the rubber network and the filler network, and the mechanical properties of the composite material are improved.
According to the invention, multiple emulsifiers are used in a matching manner, so that the emulsifying effect is better, the average particle size of the prepared eucommia ulmoides latex is smaller, the Zeta potential is lower, and the stability is higher. When the prepared eucommia ulmoides latex and the natural latex are mixed in a liquid phase, the eucommia ulmoides latex is easier to disperse in natural rubber, the rubber network compatibility is better, the dispersion is more uniform, the reinforcing capacity of the filler is improved, and the mechanical property of the composite material is improved.
Claims (10)
1. A preparation method of eucommia ulmoides latex is characterized by comprising the following steps:
(1) dissolving the crude eucommia ulmoides gum in an organic solvent to obtain a eucommia ulmoides gum solution, and adding an oil-soluble nonionic emulsifier to mix to obtain an oil phase;
(2) mixing an anionic emulsifier, a water-soluble nonionic emulsifier and deionized water to obtain a water phase;
(3) mixing oil and water phases, emulsifying, removing the organic solvent, and concentrating to obtain the eucommia ulmoides latex.
2. The method for preparing eucommia ulmoides latex according to claim 1, wherein:
the organic solvent is at least one of cyclohexane, dichloromethane, petroleum ether, n-hexane and xylene; and/or the presence of a gas in the gas,
the oil-soluble nonionic emulsifier is a polyoxyethylene ether nonionic emulsifier; preferably at least one of polyoxyethylene dodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene dodecyl ether and polyoxyethylene cetyl ether; and/or the presence of a gas in the gas,
the anionic emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl sulfide, sodium dodecyl benzene sulfonate, sodium oleate and potassium oleate; and/or the presence of a gas in the gas,
the water-soluble nonionic emulsifier is at least one of polyoxyethylene lauryl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate and polyvinyl alcohol.
3. The method for preparing eucommia ulmoides latex according to claim 1, wherein:
the mass of the eucommia crude gum accounts for 3-10% of that of the eucommia gum solution; preferably 5 to 7 percent; and/or the presence of a gas in the gas,
the mass of the oil-soluble nonionic emulsifier accounts for 1-5% of the total mass of the oil phase; preferably 1.5 to 3 percent; and/or the presence of a gas in the gas,
the mass of the anionic emulsifier accounts for 0.2 to 5 percent of the total mass of the water phase; preferably 0.5 to 1 percent; and/or the presence of a gas in the gas,
the mass of the water-soluble nonionic emulsifier accounts for 0.2-5% of the total mass of the water phase; preferably 0.5 to 1 percent; and/or the presence of a gas in the gas,
the volume ratio of the oil phase to the water phase is 1 (1.5-3); preferably 1: (1.5-1.8).
4. The method for preparing eucommia ulmoides latex according to claim 1, wherein:
step (1) of carrying out a treatment,
the stirring speed of the crude eucommia ulmoides gum when being dissolved in the organic solvent is 300 r/min-700 r/min;
the temperature is 40-80 ℃;
the stirring time is 12-24 h;
a step (3) of,
the stirring speed during emulsification is 5000r/min to 12000 r/min;
the emulsifying time is 8-18 min.
5. An eucommia ulmoides latex prepared by the method according to any one of claims 1 to 4.
6. A eucommia ulmoides gum based composite material prepared from raw materials comprising the eucommia ulmoides latex of claim 5, wherein:
the eucommia ulmoides gum base composite material also comprises natural latex or styrene-butadiene latex, a surfactant, pretreated filler and other rubber auxiliaries;
based on the total amount of rubber in the eucommia ulmoides latex and the natural latex or the styrene-butadiene latex as 100 parts by weight,
eucommia ulmoides latex and natural latex or
Wherein the eucommia ulmoides rubber in the eucommia ulmoides rubber latex accounts for 5-50% of the total amount of the rubber.
7. A eucommia ulmoides gum based composite material according to claim 6, wherein:
wherein the eucommia ulmoides rubber in the eucommia ulmoides rubber latex accounts for 10-30% of the total amount of the rubber.
8. The eucommia ulmoides gum based composite material of claim 6, wherein:
the surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl sulfide, sodium dodecyl benzene sulfonate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monolaurate and polyoxyethylene monolaurate;
the pretreated filler is filler water dispersion liquid pre-dispersed by a ball mill or a colloid mill;
the filler is at least one of carbon black and white carbon black.
9. A method of preparing a eucommia ulmoides gum based composite material according to any one of claims 6 to 8, comprising:
mixing natural latex or styrene-butadiene latex, the eucommia ulmoides latex and a surfactant uniformly to obtain blended latex, adding the pretreated filler into the blended latex, stirring uniformly, flocculating, washing and drying to obtain masterbatch, plasticating the masterbatch in an open mill, adding other rubber auxiliaries, mixing uniformly, discharging sheets, and vulcanizing to obtain the eucommia ulmoides gum base composite material.
10. The method of preparing a eucommia ulmoides gum based composite material of claim 9, wherein:
the stirring speed is 300r/min to 800r/min, and the stirring time is 10min to 30 min;
the flocculation is carried out by adopting a method of spray drying or adding a flocculating agent;
the flocculating agent is one of acetic acid, formic acid, absolute ethyl alcohol and anhydrous calcium chloride;
the vulcanization temperature is 143-150 ℃;
the vulcanizing time is 10 min-40 min.
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