CN113980291B - Preparation method of eucommia ulmoides latex, eucommia ulmoides latex and eucommia ulmoides gum base composite material and preparation method - Google Patents
Preparation method of eucommia ulmoides latex, eucommia ulmoides latex and eucommia ulmoides gum base composite material and preparation method Download PDFInfo
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- CN113980291B CN113980291B CN202111359147.6A CN202111359147A CN113980291B CN 113980291 B CN113980291 B CN 113980291B CN 202111359147 A CN202111359147 A CN 202111359147A CN 113980291 B CN113980291 B CN 113980291B
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- latex
- gutta
- percha
- eucommia ulmoides
- water
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- 229920000126 latex Polymers 0.000 title claims abstract description 147
- 239000004816 latex Substances 0.000 title claims abstract description 145
- 241000208689 Eucommia ulmoides Species 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000000899 Gutta-Percha Substances 0.000 claims abstract description 83
- 240000000342 Palaquium gutta Species 0.000 claims abstract description 83
- 229920000588 gutta-percha Polymers 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 241000208688 Eucommia Species 0.000 claims abstract description 17
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 17
- 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 8
- 229920001971 elastomer Polymers 0.000 claims description 43
- 239000005060 rubber Substances 0.000 claims description 43
- 239000006229 carbon black Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 27
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 239000002174 Styrene-butadiene Substances 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- 239000011115 styrene butadiene Substances 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 10
- -1 polyoxyethylene lauryl ether Polymers 0.000 claims description 10
- 239000004094 surface-active agent Substances 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
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 8
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 8
- NMSBTWLFBGNKON-UHFFFAOYSA-N 2-(2-hexadecoxyethoxy)ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCO NMSBTWLFBGNKON-UHFFFAOYSA-N 0.000 claims description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 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
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 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
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 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
- 238000004073 vulcanization Methods 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000008394 flocculating agent Substances 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
- 239000002994 raw material Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 23
- 239000002245 particle Substances 0.000 abstract description 15
- 239000003292 glue Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- 244000043261 Hevea brasiliensis Species 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000203 mixture 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
- 230000003712 anti-aging effect Effects 0.000 description 12
- 235000021355 Stearic acid Nutrition 0.000 description 11
- 239000007788 liquid 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 238000009472 formulation Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 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 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000006228 supernatant Substances 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- QRIPJHVJKXPQBX-UHFFFAOYSA-N 1-dodecylsulfanyldodecane;sodium Chemical compound [Na].CCCCCCCCCCCCSCCCCCCCCCCCC QRIPJHVJKXPQBX-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000003208 petroleum Substances 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
- 238000001000 micrograph Methods 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
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 230000006978 adaptation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 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
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000008096 xylene 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- 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
-
- 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
- C08K9/00—Use of pretreated ingredients
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention provides a preparation method of eucommia ulmoides latex, eucommia ulmoides gum base composite material and a preparation method. The method comprises the following steps: dissolving gutta-percha in an organic solvent to obtain gutta-percha solution, and adding an oil-soluble nonionic emulsifier to obtain an oil phase; mixing an anionic emulsifier, a water-soluble nonionic emulsifier and deionized water to obtain a water phase; mixing the oil phase and the water phase, emulsifying, removing the organic solvent, and concentrating to obtain the eucommia latex. The invention prepares eucommia latex with smaller particle size, higher solid content and more stability by using the oil-soluble nonionic emulsifier in the oil phase and matching with the anionic emulsifier and the water-soluble nonionic emulsifier in the water phase, adopts wet mixing to carry out the next processing, improves the compatibility of the blending glue, and improves the dispersion of the filler, thereby improving the comprehensive mechanical property of the composite material.
Description
Technical Field
The invention relates to the technical field of rubber composite materials, in particular to a preparation method of eucommia ulmoides latex, eucommia ulmoides gum base composite materials and a preparation method.
Background
The energy crisis, environmental pollution and climate change in the current society have affected the aspects of our lives, and green sustainable development is urgent. Thus, petroleum-based synthetic polymers will eventually be replaced by renewable natural polymers. Meanwhile, china is one of countries with the largest consumption of rubber, and faces the problem of low self-supporting rate of natural rubber. As a natural growing rubber, the gutta-percha can partially replace the natural rubber, and the development of the gutta-percha is an effective way for relieving the problem of the deficiency of the natural rubber in China, and is also an important component for implementing the national strategy of the rubber.
Gutta-percha is derived from Du Zhongshu and is a novel natural growth rubber. Gutta percha has a main structure of trans-polyisoprene and is an isomer with natural rubber produced by Hevea. However, the trans-form structure is more regular, the molecular chains are microscopically ordered, the crystals are easy to accumulate and crystallize, the characteristics of the gutta-percha are completely different from those of natural rubber, and the untreated gutta-percha shows the property of being a crystalline hard plastic at normal temperature. Meanwhile, the gutta percha with different vulcanization crosslinking degrees is found to have different material characteristics through researches, and the crosslinking degrees can be changed from low to high to show the properties of thermoplastic materials, thermoelastic materials and rubber materials, and the gutta percha has unique rubber-plastic dual properties. Because of the unique performance, the eucommia ulmoides gum can be used for preparing more novel materials with excellent and different performances, and has a great application prospect in the aspects of plastic modification and rubber blending. At present, less researches are carried out on eucommia ulmoides latex, and patent CN112175203A discloses a preparation method of eucommia ulmoides latex, but the operation is complex, the latex particle size and the solid content are also poor, and the stability is also required to be improved.
Because gutta percha is easy to crystallize and is in the nature of hard plastic at normal temperature, gutta percha is not easy to mix with other rubber and filler is not easy to disperse, so that the comprehensive mechanical properties of the blend rubber such as tensile strength, elongation at break, tensile permanent deformation and the like are not good; the compatibility of the blending rubber and the dispersion of high fillers can be improved by adopting wet mixing, but in the prior art, when the eucommia ulmoides latex is prepared, the operation is complex, the prepared eucommia ulmoides latex has larger particle size and lower solid content, and is not stable enough, so that the eucommia ulmoides latex process needs to be optimized, the eucommia ulmoides latex with smaller particle size and higher solid content is prepared, and meanwhile, the eucommia ulmoides latex is combined with other latexes to prepare the eucommia ulmoides rubber-based 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, eucommia ulmoides gum base composite material and a preparation method.
The invention aims to solve the problems of energy consumption and pollution in the traditional dry mixing of gutta-percha by preparing natural gutta-percha latex and preparing a gutta-percha base-based rubber composite material by adopting a wet mixing mode, improve the blending performance of gutta-percha and other rubbers and improve the comprehensive mechanical property of the gutta-percha composite material.
The invention optimizes the gutta-percha emulsifying process, prepares the gutta-percha latex with smaller particle diameter, higher solid content and more stability by using the oil-soluble nonionic emulsifier-polyoxyethylene ether emulsifier in an oil phase and matching with the anionic emulsifier and the water-soluble nonionic emulsifier in a water phase, adopts wet mixing to carry out the next processing, improves the compatibility of the blending glue, improves the dispersion of the filler, and further improves the comprehensive mechanical property of the composite material.
The invention aims at providing a preparation method of eucommia ulmoides latex, which comprises the following steps:
(1) Dissolving gutta-percha in an organic solvent to obtain gutta-percha solution, and adding an oil-soluble nonionic emulsifier 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 the oil phase and the water phase, emulsifying, removing the organic solvent, and concentrating to obtain the eucommia 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 number of the groups of groups,
the oil-soluble nonionic emulsifier is 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 number of the groups of groups,
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 number of the groups of groups,
the water-soluble nonionic emulsifier is at least one of laurinol polyoxyethylene 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 gutta-percha is 3-10% of that of the gutta-percha solution; preferably 5% -7%;
the mass of the oil-soluble nonionic emulsifier accounts for 1% -5% of the total mass of the oil phase; preferably 1.5% -3%;
the mass of the anionic emulsifier accounts for 0.2-5% of the total mass of the water phase; preferably 0.5% -1%;
the mass of the water-soluble nonionic emulsifier accounts for 0.2-5% of the total mass of the water phase; preferably 0.5% -1%;
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),
the stirring speed of the eucommia ulmoides coarse gum when the eucommia ulmoides coarse gum is dissolved in an organic solvent is 300-700 r/min;
the temperature is 40-80 ℃;
the stirring time is 12-24 hours.
Step (3),
the stirring speed during emulsification is 5000 r/min-12000 r/min, and the emulsification time is 8 min-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;
concentrating by adopting a centrifugal method, wherein the rotating speed is 5000-12000 r/min, and the time is 8-30 min.
The second object of the present invention is to provide a eucommia ulmoides latex.
The eucommia ulmoides latex is prepared by the preparation method.
The invention also provides an gutta-percha-based composite material prepared from the raw materials comprising the gutta-percha latex.
The gutta-percha-based composite material also comprises natural latex or styrene-butadiene latex, a surfactant, pretreated filler and other rubber auxiliary agents;
based on 100 weight portions of the total rubber in the eucommia latex and the natural latex or the styrene-butadiene latex,
wherein, the gutta-percha in the gutta-percha latex accounts for 5 to 50 percent of the total rubber; preferably 10% to 30%.
The eucommia ulmoides latex is used after the solid content is regulated to 10-30% by deionized water, and the total rubber content of the eucommia ulmoides latex and the natural latex or the butadiene styrene latex comprises eucommia ulmoides rubber in the eucommia ulmoides latex, natural rubber in the natural latex or the butadiene styrene latex or butadiene styrene rubber.
In a preferred embodiment of the present invention,
the surfactant is at least one of sodium dodecyl sulfonate, sodium dodecyl sulfide, sodium dodecyl benzene sulfonate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monolaurate and polyoxyethylene monolaurate;
the pretreated filler is water dispersion of filler which is pre-dispersed into a certain concentration by a ball mill or a colloid mill;
the filler is a filler commonly used for rubber, 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 using a ball mill and a colloid mill;
the other rubber auxiliary agents are auxiliary agents commonly used for rubber, such as vulcanizing agents, zinc oxide, stearic acid, anti-aging agents, accelerators and the like.
The fourth object of the invention is to provide a preparation method of gutta-percha-based composite material, comprising the following steps:
mixing the eucommia ulmoides latex, the natural latex or the styrene-butadiene latex and the surfactant uniformly to obtain a mixed latex, adding the pretreated filler into the mixed latex, stirring uniformly, flocculating, washing and drying to obtain a masterbatch, plasticating the masterbatch in an open mill, adding other rubber additives, mixing uniformly, discharging slices, and vulcanizing to obtain the eucommia ulmoides rubber-based composite material.
In a preferred embodiment of the present invention,
the stirring speed is 300 r/min-800 r/min, and the stirring time is 10 min-30 min;
the flocculation adopts a spray drying method or a method of adding a flocculating agent;
the flocculant 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 adopts the following technical scheme:
preparing eucommia ulmoides latex:
the gutta-percha is measured and added into an organic solvent according to the regulation, and is dissolved for 12 to 24 hours at the temperature of between 40 and 80 ℃ to prepare the glue solution with certain concentration. Adding a specified amount of oil-soluble nonionic emulsifier into the prepared glue solution, and uniformly stirring to obtain an oil phase.
Adding the anionic emulsifier and the water-soluble nonionic emulsifier with specified dosage into deionized water, and uniformly stirring to obtain a water phase. Adding the oil phase and the water phase into a high-speed stirrer according to the proportion, and stirring at high speed under the control of the specified time and the rotating speed to obtain the eucommia ulmoides coarse latex.
Evaporating the obtained eucommia ulmoides coarse latex at a certain temperature and under a certain pressure, removing the organic solvent to obtain eucommia ulmoides thin latex, centrifuging the obtained eucommia ulmoides thin latex at a certain rotating speed for a period of time, and removing a large amount of water to obtain eucommia ulmoides latex.
Preparing Du Zhongji composite material:
the eucommia latex is preferably 10-30% solid content, which is added into another latex such as natural rubber, styrene-butadiene latex, etc. according to a certain proportion, and meanwhile, a prescribed amount of surfactant is added as a stabilizer, and the mixture is stirred for a prescribed time at a prescribed rotation speed, thus obtaining the combined latex.
Adding pre-dispersed carbon black or white carbon black into the combined latex, stirring at a certain rotating speed, uniformly dispersing, flocculating by adopting a certain method, cleaning in clear water for 5-8 times, and drying in a 60 ℃ oven for 20 hours.
Plasticating the dried masterbatch on an open mill, adjusting the roll spacing, rolling three triangular bags and three post-rolling bag rollers, adding other rubber additives, and vulcanizing and forming.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the process of preparing the eucommia ulmoides latex, an emulsifying system is optimized, the oil-soluble polyoxyethylene ether nonionic emulsifier is introduced for the first time, and the emulsifier is added into both oil-water phases, so that the emulsifying effect is improved, the particle size of the prepared eucommia ulmoides latex is smaller, and the solid content is higher;
(2) In the process of preparing the eucommia ulmoides latex, the emulsification process is simplified, the pH value of an emulsification system is not required to be regulated, and the prepared eucommia ulmoides latex has small particle size and better uniformity of particle size. The method comprises the steps of carrying out a first treatment on the surface of the
(3) According to the invention, the filler is mixed with the latex by an emulsion co-coagulation method, so that the energy consumption in the mixing process is reduced, the dust pollution during the mixing of the filler is reduced, and the method accords with the concept of green development;
(4) The invention mixes the eucommia latex with other latex and filler 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, tensile permanent deformation and the like are improved.
Drawings
FIG. 1 is a scanning electron microscope picture of eucommia ulmoides latex prepared in example 1;
FIG. 2 is a scanning electron microscope picture of eucommia ulmoides latex prepared in example 2;
FIG. 3 is a scanning electron microscope picture of eucommia ulmoides latex prepared in example 3;
FIG. 4 is a scanning electron microscope image of eucommia ulmoides latex prepared in example 4;
FIG. 5 is a scanning electron microscope image of eucommia ulmoides latex prepared in example 5.
Detailed Description
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall within the scope of the present invention.
The starting materials used in the examples were all conventional commercially available.
Test standard:
latex particle size testing: GB/T19627-2005;
latex Zeta potential test: GB/T32668-2016;
latex solids content: GB/T8299-2008;
tensile strength, elongation at break, 100% tensile stress, 300% tensile stress, permanent set: 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 gutta-percha and cyclohexane into a three-neck flask, and stirring at the temperature of 70 ℃ for 24 hours at the speed of 500r/min to obtain gutta-percha solutions with different mass concentrations of 3% -10%. And respectively adding an 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 an anionic emulsifier Sodium Dodecyl Benzene Sulfonate (SDBS) accounting for 0.2-5% of the total mass of the water phase and a nonionic emulsifier polyoxyethylene sorbitan monolaurate (Tween 20) accounting for 0.5-5% of the total mass of the water phase into the water, and fully dissolving to obtain the water phase.
The volume ratio of oil to water is 1: (1.5-3), adding the water phase and the oil phase into a high-speed stirrer in sequence, and stirring for 10min at a rotating speed of 8000r/min to obtain eucommia ulmoides coarse latex; evaporating the prepared eucommia ulmoides coarse latex at 40deg.C under vacuum degree of-0.9 Mpa for 1 hr to remove organic solvent to obtain eucommia ulmoides thin latex; centrifuging and concentrating the prepared eucommia ulmoides dilute latex at a rotating speed of 10000r/min for 10min, and removing the centrifuged supernatant to obtain eucommia ulmoides latex.
The specific conditions of examples 1 to 4 are shown in Table 1.
Examples 5 to 7
Preparation of eucommia ulmoides latex:
adding gutta-percha and cyclohexane into a three-neck flask, and stirring at a temperature of 70 ℃ for 24 hours at 500r/min to obtain a gutta-percha solution with a mass concentration of 7%. And (3) respectively adding an oil-soluble emulsifier polyoxyethylene ether AEO-3 (or AEO-5 or Brij-52) accounting for 2.5% 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 sulfonate (or sodium dodecyl sulfide or sodium oleate) accounting for 2% of the total mass of the water phase and nonionic emulsifier polyoxyethylene lauryl ether (or polyoxyethylene sorbitan monopalmitate (tween-40) or polyoxyethylene sorbitan monooleate (tween-80)) accounting for 2% of the total mass of the water phase into water respectively, and fully dissolving to obtain the water phase.
The volume ratio of oil to water is 1:3, adding the water phase and the oil phase into a high-speed stirrer sequentially, and stirring at 10000r/min for 10min to obtain coarse eucommia ulmoides latex; evaporating the prepared eucommia ulmoides coarse latex at 45deg.C under vacuum degree of-0.85 Mpa for 1.5 hr to remove organic solvent to obtain eucommia ulmoides thin latex; and (3) centrifuging and concentrating the prepared eucommia ulmoides dilute latex for 15min at the rotating speed of 9000r/min, and removing the centrifuged supernatant to obtain the eucommia ulmoides latex.
The specific conditions of examples 5 to 7 are shown in Table 1.
Example 8
Preparation of eucommia ulmoides latex:
adding gutta-percha into dichloromethane, and stirring at 40deg.C and 500r/min for 24 hr to obtain gutta-percha solution with mass concentration of 5%. Adding an 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 anionic emulsifier Sodium Dodecyl Benzene Sulfonate (SDBS) and polyvinyl alcohol 1788 (PVA-1788) accounting for 2% of the total mass of the water phase into water respectively, and fully dissolving to obtain the water phase.
The oil-water volume ratio is 1:2, the water phase and the oil phase are added into a high-speed stirrer in sequence, and stirred for 10min at the rotating speed of 9000r/min to obtain eucommia coarse latex; evaporating the prepared eucommia ulmoides coarse latex at 40 ℃ for 5 hours to remove the organic solvent to obtain eucommia ulmoides thin latex; centrifuging and concentrating the prepared eucommia ulmoides dilute latex at a rotating speed of 10000r/min for 15min, and removing the centrifuged supernatant to obtain eucommia ulmoides latex.
The specific conditions for example 8 are shown in Table 1.
Example 9
Preparation of eucommia ulmoides latex:
adding gutta-percha into petroleum ether, and stirring at 70deg.C and 500r/min for 24 hr to obtain gutta-percha solution with mass concentration of 5%. Adding an 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 anionic emulsifier Sodium Dodecyl Benzene Sulfonate (SDBS) and polyoxyethylene sorbitan monooleate (Tween-80) accounting for 2% of the total mass of the water phase into water respectively, and dissolving completely to obtain the water phase.
The oil-water volume ratio is 1:2, the water phase and the oil phase are added into a high-speed stirrer in sequence, and stirred for 15min at the rotating speed of 9000r/min to obtain the eucommia ulmoides coarse latex. Evaporating the prepared coarse latex of eucommia ulmoides at 45deg.C under vacuum degree of-0.85 Mpa for 2 hr to remove organic solvent to obtain diluted latex of eucommia ulmoides. Centrifuging and concentrating the prepared eucommia ulmoides dilute latex at a rotating speed of 10000r/min for 15min, and removing the centrifuged supernatant to obtain eucommia ulmoides latex.
The specific conditions for example 9 are shown in Table 1.
Example 10
Preparation of eucommia ulmoides latex:
adding gutta-percha into n-hexane, and stirring at 70deg.C and 500r/min for 24 hr to obtain gutta-percha solution with mass concentration of 5%. Adding an 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 anionic emulsifier Sodium Dodecyl Benzene Sulfonate (SDBS) and polyoxyethylene sorbitan monopalmitate (Tween-40) accounting for 2% of the total mass of the water phase into water respectively, and fully dissolving to obtain the water phase.
The oil-water volume ratio is 1:2, the water phase and the oil phase are added into a high-speed stirrer in sequence, and stirred for 15min at the rotating speed of 9000r/min to obtain eucommia coarse latex; evaporating the prepared eucommia ulmoides coarse latex at 45deg.C under vacuum degree of-0.85 Mpa for 2 hr to remove organic solvent to obtain eucommia ulmoides thin latex; centrifuging and concentrating the prepared eucommia ulmoides dilute latex at a rotating speed of 10000r/min for 15min, and removing the centrifuged supernatant to obtain eucommia ulmoides latex.
The specific conditions for example 10 are shown in Table 1.
Comparative example 1
The preparation method of example 1 of patent CN112175203A was used:
(1) Freezing 400 parts of eucommia ulmoides seed shells at the temperature of minus 5 ℃ for 40 minutes, then crushing the eucommia ulmoides seed shells in a high-speed crusher, and sieving eucommia ulmoides seed shell powder to control the particle size of the eucommia ulmoides seed shell powder to be below 0.5 mm; dissolving eucommia ulmoides seed shell powder with 1000 parts of cyclohexane at 70 ℃ and stirring speed of 500r/min for extraction for 5 hours, centrifuging the extract liquid with a high-speed centrifuge at 3500r/min for 5min, and filtering the eucommia ulmoides gum extract liquid with 40 meshes of nylon cloth to obtain eucommia ulmoides gum solution with solid content of 10%;
(2) 1000 parts of gutta-percha with the solid content of 10% prepared in the step (1) are taken and added into a glass reaction kettle, and then 3.5 parts of oleic acid, 1.0 part of span 80 and 1.5 parts of anti-aging agent SP are added, and stirred for 5 hours under the conditions that the rotating speed is 500r/min and the temperature is 70 ℃ to obtain gutta-percha 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 webmaster normal butanol and 1100 soft water into a reaction kettle, heating to 70 ℃, adding the gutta-percha 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 when the mixed solution is converted from an oil phase to an aqueous phase after distilling for 6 hours, emulsifying for 15 minutes at the shearing speed of 8500r/min, and converting the mixed solution into an aqueous emulsion;
(4) And standing the emulsified emulsion for 24 hours, and filtering to obtain the gutta-percha latex with the solid content of 15%.
Example 11
Preparation of gutta-percha-based composite:
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 and combined latex.
Adding carbon black N330 and deionized water into a ball mill together, and grinding for 4 hours to obtain carbon black aqueous dispersion. The carbon black dispersion was added to the above-mentioned co-latex according to the formulation, and stirred at 500r/min for 30min to obtain a uniform carbon black co-latex dispersion. Pouring the prepared carbon black dispersion liquid into absolute ethyl alcohol for flocculation, washing in clear water, and drying at 60 ℃ for 24 hours to obtain master batch.
And plasticating the prepared master batch in an open mill at 80 ℃ for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, an accelerator DZ and sulfur according to a formula, uniformly mixing, discharging tablets, and finally vulcanizing at 143 ℃ under 15Mpa for 20min to obtain the composite material.
The specific test conditions for example 11 are shown in Table 2.
Comparative example 2
Plasticating gutta percha in an open mill at 90 ℃ for 2min, adding natural rubber for plasticating for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, carbon black N330, an accelerator DZ and sulfur according to a formula, uniformly mixing, discharging slices, and vulcanizing at 143 ℃ under 15Mpa for 20min to obtain the composite material.
The specific test conditions of comparative example 2 are shown in table 2.
Example 12
Preparation of gutta-percha-based composite:
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 and combined latex.
Carbon black N330 and deionized water are added into a ball mill together and ground for 4 hours to obtain carbon black aqueous dispersion with the solid content of 10 percent. The carbon black dispersion was added to the above-mentioned co-latex according to the formulation, and stirred at 500r/min for 30min to obtain a uniform carbon black co-latex dispersion. Pouring the prepared carbon black dispersion liquid into absolute ethyl alcohol for flocculation, washing in clear water, and drying at 60 ℃ for 24 hours to obtain master batch.
And plasticating the prepared master batch in an open mill at 80 ℃ for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, an accelerator DZ and sulfur according to a formula, uniformly mixing, discharging tablets, and finally vulcanizing at 143 ℃ under 15Mpa for 20min to obtain the composite material.
The specific test conditions for example 12 are shown in Table 2.
Comparative example 3
Plasticating gutta percha in an open mill at 90 ℃ for 2min, adding natural rubber for plasticating for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, carbon black N330, an accelerator DZ and sulfur according to a formula, uniformly mixing, discharging slices, and vulcanizing at 143 ℃ under 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
Preparation of gutta-percha-based composite:
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, tween 20 is added, and the mixture is stirred for 30min at the rotating speed of 600r/min to obtain stable and combined latex.
Adding white carbon black VN3, a silane coupling agent Si-747 with the mass of 10% of the white carbon black and deionized water into a colloid mill together, grinding for 30min to obtain white carbon black aqueous dispersion with the solid content of 10%, and pre-treating the white carbon black aqueous dispersion for 3h at 80 ℃. Adding the white carbon black dispersion liquid into the combined latex according to the formula, and stirring for 30min at a rotating speed of 500r/min to obtain uniform white carbon black combined latex dispersion liquid. And (3) dropwise adding 10% formic acid solution into the prepared dispersion liquid to flocculate, standing for 12 hours, dehydrating, washing, and drying at 60 ℃ for 24 hours to obtain master batch.
And 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, discharging slices, and finally vulcanizing at 143 ℃ for 15min to obtain the composite material.
The specific test conditions for examples 13 to 15 are shown in Table 3.
Comparative examples 4 to 6
Plasticating gutta percha in an open mill at 90 ℃ 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 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, uniformly mixing, discharging slices, and finally vulcanizing at 143 ℃ under 15Mpa for 15min to obtain the composite material.
The specific test conditions of comparative examples 4 to 6 are shown in Table 3.
Example 16
Preparation of gutta-percha-based composite:
the eucommia ulmoides latex and the natural latex prepared in example 4 were added with deionized water to adjust the solid content to 15%, the eucommia ulmoides latex was added to the natural latex according to the formulation, and polyoxyethylene monolaurate was added thereto, and stirred at 600r/min for 30min to obtain a stable and combined latex.
Adding white carbon black VN3, a silane coupling agent Si-747 with the mass of 10% of the white carbon black and deionized water into a colloid mill together, grinding for 30min to obtain white carbon black aqueous dispersion with the solid content of 10%, and preprocessing the white carbon black aqueous dispersion for 3h at 80 ℃. Adding the white carbon black dispersion liquid into the combined latex according to the formula, and stirring for 30min at a rotating speed of 500r/min to obtain uniform white carbon black combined latex dispersion liquid. And (3) dropwise adding 10% formic acid solution into the prepared dispersion liquid to flocculate, standing for 12 hours, dehydrating, washing, and drying at 60 ℃ for 24 hours to obtain master batch.
And 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, discharging slices, and finally vulcanizing at 143 ℃ under 15Mpa for 15min to obtain the composite material.
The specific test conditions for example 16 are shown in Table 4.
Comparative example 7
Plasticating gutta percha in an open mill at 90 ℃ 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 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, uniformly mixing, discharging slices, and finally vulcanizing at 143 ℃ under 15Mpa for 15min to obtain the composite material.
The specific test conditions of comparative example 7 are shown in Table 4.
Example 17
Preparation of gutta-percha-based 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 and combined latex.
Carbon black N330 and deionized water are added into a ball mill together and ground for 4 hours to obtain carbon black aqueous dispersion with the solid content of 10 percent. The carbon black dispersion was added to the above-mentioned co-latex according to the formulation, and stirred at 500r/min for 30min to obtain a uniform carbon black co-latex dispersion. Pouring the prepared carbon black dispersion liquid into absolute ethyl alcohol for flocculation, washing in clear water, and drying at 60 ℃ for 24 hours to obtain master batch.
And plasticating the prepared master batch in an open mill at 80 ℃ for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, an accelerator DZ, an accelerator TMTD and sulfur according to a formula, uniformly mixing, discharging tablets, and finally vulcanizing at 143 ℃ for 15min under 15Mpa to obtain the composite material.
The specific test conditions for example 17 are shown in Table 4.
Comparative example 8
Preparation of gutta-percha-based composite:
plasticating gutta percha in an open mill at 90 ℃ for 2min, adding styrene-butadiene rubber for plasticating for 1min, sequentially adding zinc oxide, stearic acid, an anti-aging agent 4010NA, carbon black N330, an accelerator DZ, an accelerator TMTD and sulfur according to a formula, uniformly mixing, discharging slices, and finally vulcanizing at 143 ℃ for 15min under 15Mpa to obtain the composite material.
The specific test conditions of comparative example 8 are shown in Table 4.
TABLE 1 particle size and solid content of eucommia ulmoides latices obtained in examples 1 to 10 and comparative example 1
Compared with comparative example 1, the average particle size of examples 1 to 10 is smaller, the Zeta potential is lower, the solid content is higher, and the effects of examples 2 to 4 are more obvious, so that the emulsification method of the invention has better effects, and 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 emulsification process is simpler and more convenient, the emulsification effect is better, and the prepared latex has smaller particle size and higher stability. Figures 1-5 show that the eucommia latex prepared by the invention has smaller particle size, and shows that the three-phase emulsifier used by the invention has good emulsification effect under the combined action.
Table 2 formulations of gutta-percha-based composite materials of examples 11 to 12 and comparative examples 2 to 3
Table 3 formulations of gutta-percha-based composite materials of examples 13 to 15 and comparative examples 4 to 6
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Table 4 formulations of gutta-percha-based composite materials of examples 16 to 17 and comparative examples 7 to 8
TABLE 5 mechanical Properties of the composite materials obtained in examples 11 to 17 and comparative examples 2 to 8
The prepared eucommia latices were respectively applied to rubber composite materials, 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 respectively compared.
As can be seen from Table 5, compared with the comparative example, the gutta-percha-based composite material prepared in the example has better mechanical properties, which is reflected in higher elongation at break and higher tensile strength, because the gutta-percha latex prepared in the invention has small particle size, is mixed with natural latex in liquid phase, gutta-percha is more dispersed in natural rubber, the rubber network is more uniformly dispersed, meanwhile, the filler is mixed with rubber in liquid phase, the filler network is more uniformly dispersed in rubber, and the reinforcing capacity of the filler and the mechanical properties of the composite material are improved through the interaction of the rubber network and the filler network.
The invention uses a plurality of emulsifying agents, the emulsifying effect is better, the average grain diameter of the prepared eucommia 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 the natural rubber, the compatibility of a rubber network 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 (8)
1. A method for preparing eucommia ulmoides latex, which is characterized by comprising the following steps:
(1) Dissolving gutta-percha in an organic solvent to obtain gutta-percha solution, and adding an oil-soluble nonionic emulsifier 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 organic solvent, concentrating to obtain the eucommia latex;
the oil-soluble nonionic emulsifier is at least one of AEO-3, AEO-4, AEO-5 and Brij-52;
the anionic emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium oleate and potassium oleate;
the water-soluble nonionic emulsifier is at least one of laurinol polyoxyethylene ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate and polyvinyl alcohol 1788;
the organic solvent is cyclohexane;
the mass of the gutta-percha is 3% -10% of that of the gutta-percha solution;
the mass of the oil-soluble nonionic emulsifier accounts for 1% -5% of the total mass of the oil phase;
the mass of the anionic emulsifier accounts for 0.2% -5% of the total mass of the water phase;
the mass of the water-soluble nonionic emulsifier accounts for 0.2% -5% of the total mass of the water phase;
the volume ratio of the oil phase to the water phase is 1 (1.5-3);
in the step (1), the step of (a),
the stirring speed of the eucommia ulmoides rough rubber dissolved in the organic solvent is 300-700 r/min;
the temperature is 40-80 ℃;
stirring time is 12-24 hours;
in the step (3), the step of (c),
the stirring speed during emulsification is 5000 r/min-12000 r/min;
the emulsification time is 8-18 min.
2. The method for preparing eucommia latex according to claim 1, wherein:
the mass of the gutta-percha is 5% -7% of that of the gutta-percha solution; and/or the number of the groups of groups,
the mass of the oil-soluble nonionic emulsifier accounts for 1.5% -3% of the total mass of the oil phase; and/or the number of the groups of groups,
the mass of the anionic emulsifier accounts for 0.5% -1% of the total mass of the water phase; and/or the number of the groups of groups,
the mass of the water-soluble nonionic emulsifier accounts for 0.5% -1% of the total mass of the water phase; and/or the number of the groups of groups,
the volume ratio of the oil phase to the water phase is 1: (1.5-1.8).
3. An eucommia latex prepared by the method of claim 1 or 2.
4. Gutta-percha-based composite material made from a raw material comprising the gutta-percha latex as claimed in claim 3, characterized in that:
the gutta-percha-based composite material also comprises natural latex or styrene-butadiene latex, a surfactant, pretreated filler and other rubber auxiliary agents;
based on 100 weight portions of the total rubber in the eucommia latex and the natural latex or the styrene-butadiene latex,
eucommia latex and natural latex or
100 parts by weight of total rubber in styrene-butadiene latex;
0.5-10 parts by weight of a surfactant;
10-70 parts by weight of pretreated filler;
10-25 parts by weight of other rubber additives;
wherein the gutta-percha in the gutta-percha latex accounts for 5% -50% of the total rubber.
5. The gutta percha-based composite material as in claim 4 wherein:
eucommia latex and natural latex or
100 parts by weight of total rubber in styrene-butadiene latex;
1-5 parts by weight of a surfactant;
30-70 parts by weight of pretreated filler;
11-18 parts by weight of other rubber additives;
wherein the gutta-percha in the gutta-percha latex accounts for 10% -30% of the total rubber.
6. The gutta percha-based composite material as in claim 4 wherein:
the surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyoxyethylene lauryl ether and polyoxyethylene sorbitan monolaurate;
the pretreated filler is filler water dispersion pre-dispersed by a ball mill or a colloid mill;
the filler is at least one of carbon black and white carbon black.
7. A method for preparing the gutta percha-based composite material as in any one of claims 4 to 6, characterized in that said method comprises:
mixing natural latex or styrene-butadiene latex with the eucommia ulmoides latex and the surfactant uniformly to obtain a mixed latex, adding the pretreated filler into the mixed latex, stirring uniformly, flocculating, washing and drying to obtain a masterbatch, plasticating the masterbatch in an open mill, adding other rubber additives, mixing uniformly, discharging slices, and vulcanizing to obtain the eucommia ulmoides rubber-based composite material.
8. The method for preparing gutta percha-based composite material as in claim 7, wherein:
the stirring speed is 300 r/min-800 r/min, and the stirring time is 10 min-30 min;
the flocculation adopts a spray drying method or a method of adding a flocculating agent;
the flocculant is one of acetic acid, formic acid, absolute ethyl alcohol and anhydrous calcium chloride;
the vulcanization temperature is 143-150 ℃;
the vulcanization time is 10 min-40 min.
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