CN108610453A - Method for preparing fluorine-containing nitrile rubber by low-temperature emulsion polymerization - Google Patents
Method for preparing fluorine-containing nitrile rubber by low-temperature emulsion polymerization Download PDFInfo
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- CN108610453A CN108610453A CN201611144237.2A CN201611144237A CN108610453A CN 108610453 A CN108610453 A CN 108610453A CN 201611144237 A CN201611144237 A CN 201611144237A CN 108610453 A CN108610453 A CN 108610453A
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- Prior art keywords
- fluorine
- nitrile rubber
- molecular weight
- added
- emulsifier
- Prior art date
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- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 59
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 57
- 239000011737 fluorine Substances 0.000 title claims abstract description 54
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 50
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 30
- -1 Hexafluorobutyl Chemical group 0.000 claims description 18
- 239000012875 nonionic emulsifier Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 10
- 238000004945 emulsification Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 8
- 235000015424 sodium Nutrition 0.000 claims description 8
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 229940124274 edetate disodium Drugs 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 claims description 5
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 claims description 4
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 210000000481 breast Anatomy 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical group [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical group OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 2
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract 1
- 238000010556 emulsion polymerization method Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000005060 rubber Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- JTUOMQJVPHRJHA-UHFFFAOYSA-N [C].C(CCCCCCCCCCC)S Chemical compound [C].C(CCCCCCCCCCC)S JTUOMQJVPHRJHA-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 210000002381 plasma Anatomy 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZIALXKMBHWELGF-UHFFFAOYSA-N [Na].[Cu] Chemical compound [Na].[Cu] ZIALXKMBHWELGF-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229940017705 formaldehyde sulfoxylate Drugs 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HSNHLHNSJCYPNU-UHFFFAOYSA-N o-propan-2-yl propan-2-ylsulfanylmethanethioate Chemical compound CC(C)OC(=S)SC(C)C HSNHLHNSJCYPNU-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/02—Rubber derivatives containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a method for preparing fluorine-containing nitrile rubber by a low-temperature emulsion polymerization method and a product obtained by the method. The chelate type titanate coupling agent is adopted in the polymerization process, so that the ternary polymerization efficiency of the fluorine-containing monomer, acrylonitrile and butadiene can be obviously improved. The molecular weight regulator needs to be added for multiple times, and 0.2-1 part of the molecular weight regulator is preferably added for the first time; when the conversion rate reaches 40-65%, 0.05-0.2 part of molecular weight regulator is supplemented. The fluorine-containing nitrile rubber prepared by the method provided by the invention obviously improves the comprehensive performance of nitrile rubber, and the prepared fluorine-containing nitrile rubber has good oil resistance and high tensile strength, is improved by more than 20% compared with the oil resistance of the fluorine-containing nitrile rubber prepared by a common method, has the tensile strength of more than 30MPa, has outstanding high and low temperature resistance, excellent aging resistance, and has the characteristics of good elasticity, high tensile strength, low compression permanent deformation, good wear resistance, good weather resistance, good stain resistance and narrow molecular weight distribution.
Description
Technical field
The present invention relates to the preparation field of nitrile rubber, relate in particular to a kind of using low temperature lotion using fluorochemical monomer
The method that polymerization prepares fluorine-containing nitrile rubber.
Background technology
Nitrile rubber (NBR) has excellent oil resistivity, good strength and extension property, heat resistance, air-tightness, compressive deformation
The advantages that, but it is mostly used for common oil-resistant article, then application is very few to the field of environmental requirement harshness, mainly applies temperature model
It encloses and weatherability is limited caused.
Fluoro containing polymers polymer is due to containing fluorine bond and with excellent weatherability, heat-resisting quantity, resistance to soiling, electrical isolation
Property, durability and chemical resistance performance.Fluorine is the maximum element of electronegativity, and the covalent radius of fluorine atom is very small, the key of F-C keys
It can be eager to excel than c h bond, the electron cloud of fluorine atom is strong compared with hydrogen atom to the shielding action of C-C keys, and fluorine atom polarizability is low, is distributed ratio
Relatively symmetrical, these design features make fluorine high molecular polymer have unique performance.But fluoro containing polymers polymer is expensive,
It limits its scope of application.
And fluoro containing polymers polymer modification NBR generally uses blending method, modified effect general.Patent
A kind of mechanical blending vulcanization process of NBR and fluorubber is disclosed in CN200610119299.8, fluorubber uses vinylidene-
Hexafluoropropene copoly type or vinylidene fluoride, tetrafluoroethene and hexafluoropropene trimerization type fluorubber, when sulfuration adhesion, need to control NBR
With the sulfurizing time (T of fluorubber90) difference within the scope of 0.3~12min.
When blending method is modified, polymer-modified dosage is big, and molecular level difficult to realize is evenly dispersed, and used when polymeric modification
Polymer-modified dosage it is more or it is few all easily realize that molecular level is evenly dispersed, the often addition of minimal amount of modified monomer can make
Performance acquirement is notable to be promoted.Pei's generation it is red et al. using fluorinated acrylic ester with acrylic ester monomer using semi-continuous seed breast
Liquid polymerization has synthesized the fluorin modified crylic acid ester lotion stablized, and fluorinated acrylic ester dosage is just remarkably improved when being only 2%
Improve water resistance.(study on the synthesis [J] of Pei Shihong, stone blog article, Song Wei Organic fluorides and epoxy resin modification acrylic acid ester emulsion
Chinese adhesive, 2012,21 (10):13-17).
Method, which has direct fluorination, to be reported to the method that the surfaces NBR are modified using fluorine gas or fluorinated gas in addition, having
It is fluorinated with plasma enhancing, the former is that NBR is placed in a period of time, Hou Zheshi in fluorine gas under certain temperature and pressure condition
By fluorinated gas (such as CF in NBR and this reactor in special reaction device4、CHF3) generate plasma gas reacted
[E.Durand, C.Labrugere, A.Tressaud, et al.Surface Fluorination of Carboxylated
Nitrile Butadiene Rubber:An XPS Study[J].Plasmas and Polymers,2002,7(4):311-
325]。
In the above method, the combination of fluoro containing polymers polymer and NBR belong to two phase structure, do not reach point of molecular level
Dissipating bind structure.
The flat 1-242643A of JP provide a kind of rubber composition improving cold resistance, are prepared by conventional emulsion polymerization
Acrylonitrile, butadiene and acrylic acid trifluoro ethyl ester terpolymer rubber then make it that hydrogen be added to form high saturation hydrorubber,
To achieve the effect that improve rubber cold resistance, the preparation method of its terpolymer rubber is not specifically noted.
Invention content
Fluorine-containing butyronitrile rubber being prepared using emulsion polymerization at low temperature using fluorochemical monomer the purpose of the present invention is to provide a kind of
The method of glue, obtained fluorine-containing nitrile rubber can greatly improve the performances such as fluorine-containing nitrile rubber oil resistivity, tensile strength.
A method of fluorine-containing nitrile rubber being prepared using emulsion polymerization at low temperature using fluorochemical monomer：With butadiene and third
Two kinds of monomer total amounts of alkene nitrile are 100 mass parts meters, are first 0.1 with fluorochemical monomer mass fraction is accounted for by 0.1~15 part of fluorochemical monomer
~5% chelating titanate coupling agent is added in 20~50 parts of acrylonitrile monemers, the mixing list that will be obtained after being sufficiently stirred
Body is added in reaction kettle, then sequentially adds 80~50 parts of divinylic monomers, 150~300 parts of water, 0.6~12 in a kettle
Part emulsifier, 0.05~1.5 part of molecular weight regulator, 0.1~1.0 part of pH buffer, 0.0005~0.2 part of reducing agent, 0.005
~0.4 part of second reducing agent, 0.005~0.4 part of chelating agent, 30~60min of pre-emulsification add 0.005~0.8 part of organic mistake
Hydrogen species oxidant is aoxidized, it is made to carry out copolyreaction under 1~15 DEG C of polymeric reaction temperature, when conversion ratio reaches 40~65% again
0.01~0.5 part of molecular weight regulator is added, 0.1~1 part of terminator is added when conversion ratio reaches 75~85% and terminates polymerization；
Emulsifier is the composite emulsifying of anion emulsifier, nonionic emulsifier or anion emulsifier and nonionic emulsifier composition
Agent.
Fluorochemical monomer of the present invention refers to fluorine-containing and use can be recommended to contain with the monomer of other monomer polymerizations
The type of perfluoroalkyl acrylate esters monomer, fluorine-containing fatty acid ester monomer is not particularly limited, as long as having following characteristics：
(1) there is unsaturated carbon-carbon double bond (- C=C-) in strand；(2) it is not susceptible to homopolymerization, and is tended to and butadiene, acrylonitrile
Monomer is copolymerized, and reactivity is moderate, can be trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, methyl
It is one or more in dodecafluorhe-ptylacrylate, hexafluorobutyl acrylate.The dosage of acrylate containing fluorine monomer be 0.1~
15 parts, preferably 0.5~10 part.
Chelating titanate coupling agent of the present invention does not limit especially, can be 200 type titanate esters of chelating
Coupling agent.In the course of the polymerization process use chelating titanate coupling agent can promote fluorochemical monomer, acrylonitrile and butadiene three
Member copolymerization.Fluorochemical monomer and chelating titanate coupling agent, which are dissolved in, can make fluorochemical monomer and chelating type titanium in acrylonitrile monemer
Acid esters coupling agent is effectively dispersed in polymerization system, significantly improves the ternary polymerization effect of fluorochemical monomer and acrylonitrile and butadiene
Rate.Chelating titanate coupling agent dosage is 0.1~5% to account for fluorochemical monomer mass fraction, preferably 0.3~3%.
Emulsifier of the present invention can also be cloudy either anion emulsifier can also be nonionic emulsifier
The complex emulsifier that ionic emulsifying agent is combined into nonionic emulsifier.The occupation mode that the present invention recommends is using compound
Emulsifier system, complex emulsifier can improve stability of emulsion polymerization, be more suitable for butadiene, acrylonitrile, fluorochemical monomer
Binary polymerization reaction, be conducive to prepare fluorine-containing nitrile rubber and the performance of polymer can be improved.
Anion emulsifier of the present invention does not limit especially, can be neopelex, synthesis
It is one or more in aliphatic acid potassium, disproportionated rosin acid potassium.
Nonionic emulsifier of the present invention is preferably with polyoxyethylene-type nonionic emulsifier.It can be poly alkyl alcohol
In ethylene oxide ether (such as O-20 types peregal), alkyl phenol polyoxyethylene ether (such as OP-10), aliphatic acid polyethenoxy (such as A-105)
It is one or more.
When using complex emulsifier, the dosage of anion emulsifier is preferably 0.5~8.0 part, more preferably 1.2~
5 parts, the dosage of nonionic emulsifier is preferably 0.1~4.0 part, more preferably 0.5~2.5 part.
In the present invention, to make acrylate containing fluorine monomer and acrylonitrile, butadiene be copolymerized, to introduce fluorine member
Element must add appropriate molecular weight regulator in the course of the polymerization process.It, can be due to the later stage point if not adding molecular weight regulator
Son amount adjusts insufficient, it is possible to create excessive gel affects polymer performance.
Molecular weight regulator of the present invention does not limit especially, can be tert-dodecyl mercaptan, positive 12 carbon
It is one or more in mercaptan, isopropyl xanthogen disulfide.Molecular weight regulator needs repeatedly to be added, first to be added
0.05~1.5 part of molecular weight regulator, preferably 0.2~1 part；0.01~0.5 part point is added when conversion ratio reaches 40~65% again
Son amount conditioning agent, preferably 0.05~0.2 part.
PH buffer of the present invention does not limit especially, can be one kind in sodium carbonate, sodium acetate.
Initiation system used in the present invention is oxidation-reduction system, and the reducing agent does not limit especially, can
To be one kind in ferrous sulfate, cuprous sulfate, NaFeEDTA sodium salt, EDTA copper sodiums.
Second reducing agent of the present invention does not limit especially, can be in rongalite, glucose
One kind.
Chelating agent of the present invention does not limit especially, can be in EDETATE DISODIUM, aminotriacetic acid sodium
It is a kind of.
Pre-emulsification time control of the present invention is in 30~60min.
Organic hydroperoxide class oxidant of the present invention does not limit especially, can be hydrogen peroxide isopropyl
Benzene, di-isopropylbenzene hydroperoxide, hydrogen peroxide are to one kind in Meng's alkane.
Polymeric reaction temperature of the present invention is preferably controlled in 4.5~8 DEG C at 1~15 DEG C.
Terminator of the present invention does not limit especially, can be one kind in diethyl hydroxylamine, hydroquinone
Or it is a variety of.
The method of the present invention makes fluorine-containing using emulsion polymerization at low temperature in particular with chelating titanate coupling agent
Esters monomer and acrylonitrile, butadiene copolymer method prepares fluorine-containing nitrile rubber, enhance acrylate containing fluorine monomer and
The reactivity of acrylonitrile, butadiene improves the performance of fluorine-containing nitrile rubber, solves the not applicable harshness of previous nitrile rubber
The poor problem of condition such as high and low temperature resistance can be used as high-end butyronitrile rubber so as to widen the application field of nitrile rubber
Glue product is produced.The fluorine-containing nitrile rubber that the method for the present invention is prepared significantly improves the comprehensive performance of nitrile rubber, made
Standby fluorine-containing nitrile rubber oil resistivity is good, tensile strength is high, is improved than fluorine-containing nitrile rubber oil resistivity prepared by commonsense method
20% or more, tensile strength is in 30MPa or more, while (ageing-resistant performance is excellent, glass transition temperature for high and low temperature resistance protrusion
Degree reduces by 10 DEG C or more), also with elasticity is good, stretching strength is high, compression set is low, wearability is good, good weatherability, resistant
The characteristics of property is good, narrow molecular weight distribution.
Description of the drawings
Fig. 1：Using the infared spectrum for the fluorine-containing nitrile rubber that the present invention is prepared using chelating titanate coupling agent.
Fig. 2：The infared spectrum of fluorine-containing nitrile rubber prepared by unused chelating titanate coupling agent.
Fig. 3：The infared spectrum of common nitrile rubber prepared by unused acrylate containing fluorine monomer.
Specific implementation mode
The present invention is further elaborated by following embodiment, but the present invention is not limited only to embodiment, reactor is band
There is the poly- reaction kettle of breast that the capacity of blender is 15L.Unless otherwise specified, below-mentioned " part ", " % " refer both to quality point
Number or mass percent.
1, analysis method
Mooney viscosity：The Mooney viscosity of rubber is measured by GB/T 1232.1-2000.
Swellbility：The swellbility of rubber is measured by SH/T 1159-2010.
Tensile strength：The tensile stress-strain performance of rubber is measured by GB/T 528-2009.
Ageing properties：The ageing properties of rubber are measured by GB/T 3512-2001.
2, raw material
Acrylate containing fluorine monomer：4 kinds, respectively trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, first
Base dodecafluorhe-ptylacrylate, hexafluorobutyl acrylate, Harbin City, Heilongjiang Province Xue Jiafu chemistry of silicones Co., Ltd.
Emulsifier A：O-20 type peregals, Jiangsu Hai'an Petrochemical Plant.
Emulsifier B：OP-10, Shandong West Asia chemical industry Co., Ltd.
Emulsifier C：A-105 type polyoxyethylene carboxylate emulsifiers, Jiangsu Hai'an Petrochemical Plant.
Fluorubber：FKM 2603, morning twilight chemical research institute.
Chelating titanate coupling agent：Tm-200s, Yizheng City chemical plant Tian Yang.
Common titanate coupling agent：UP-201, Nanjing flag space chemistry Science and Technology Ltd..
Other materials are commercially available.
Embodiment 1
In a kettle, 25 parts of acrylonitrile, 2.1 parts of hexafluorobutyl acrylates, 2.9 parts of methacrylic acid hexafluoro fourths are first added
Ester mix monomer and 0.1 part of tm-200s, 75 parts of butadiene, 150 parts of water, 2.7 parts of neopelexes, 2.4 parts of emulsifications
Agent A, 0.55 part of tert-dodecyl mercaptan, 0.2 part of sodium carbonate, 0.01 part of ferrous sulfate, 0.1 part of rongalite, 0.05 part
EDETATE DISODIUM, pre-emulsification 40min add 0.2 part of cumyl hydroperoxide, and temperature control carries out under 5 DEG C of polymeric reaction temperatures
Copolyreaction adds 0.08 part of tert-dodecyl mercaptan when conversion ratio reaches 50%, 0.4 is added when conversion ratio reaches 80%
Part diethyl hydroxylamine terminates polymerization.Obtained fluorine-containing nitrile rubber performance is as shown in table 1.
Comparative example 1
Process is not added with tm-200s with embodiment 1.Obtained fluorine-containing nitrile rubber performance is as shown in table 1.
Comparative example 2
Process mixes 2.1 parts of hexafluorobutyl acrylates, 2.9 parts of Hexafluorobutyl mathacrylates single with embodiment 1
Body and 0.1 part of tm-200s are changed to 1.25 parts of acrylonitrile and 3.75 parts of butadiene.Obtained nitrile rubber performance is as shown in table 1.
Fig. 1, Fig. 2 and Fig. 3 are the infared spectrum of the rubber prepared by embodiment 1, comparative example 1 and comparative example 2 respectively.Fig. 1
In 1187.58cm-1And 1746.20cm-1All it is the characteristic peak of C-F keys, and does not have such characteristic peak in Fig. 2 and Fig. 3.Comparison
Although also adding fluorochemical monomer in polymerization process in example 1, without adding chelating titanate coupling agent tm-200s, thus
It may lead to the ingredient for not having or having minute quantity fluorine in polymerizate.Comparative example 3 is without being added fluorochemical monomer, therefore polymerizate
Necessarily without the ingredient of fluorine.Since the dosage relative monomer dosage of chelating titanate coupling agent is few, so in infared spectrum
In do not observe the ingredient of chelating titanate coupling agent.
Comparative example 3
Process is with embodiment 1, but the phase is added at one time 0.58 part of 12 carbon sulphur of uncle before the reaction by molecular weight regulator
Alcohol.Obtained fluorine-containing nitrile rubber performance is as shown in table 1.
Comparative example 4
Using nitrile rubber made from 4.5 parts of 2603 blending and modifying comparative examples 2 of fluorubber FKM.
Comparative example 5
Tm-200s is changed to UP-201 by process with embodiment 1.Obtained nitrile rubber performance is as shown in table 1.
Embodiment 2
In a kettle, 20 parts of acrylonitrile and 10 parts of dodecafluoroheptyl methacrylate mix monomers and 0.45 are first added
Part tm-200s, 80 parts of butadiene, 250 parts of water, 1.8 parts of neopelexes, 5.5 parts of synthetic fatty acid potassium, 2.5 parts of breasts
Agent B, 1 part of emulsifier C, 1.2 parts of dodecyl mercaptan carbons, 0.5 part of sodium carbonate, 0.09 part of NaFeEDTA sodium salt, 0.36 part of glucose,
0.2 part of aminotriacetic acid sodium, pre-emulsification 50min add 0.4 part of di-isopropylbenzene hydroperoxide, and temperature control is in 8 DEG C of polymerisation temperature
Degree is lower to carry out copolyreaction, 0.08 part of dodecyl mercaptan carbon is added when conversion ratio reaches 42%, when conversion ratio reaches 75%
When 0.3 part of hydroquinone is added and 0.3 part of diethyl hydroxylamine terminates polymerization.Obtained fluorine-containing nitrile rubber performance is as shown in table 1.
Comparative example 6
Process is not added with tm-200s with embodiment 2.Obtained nitrile rubber performance is as shown in table 1.
Embodiment 3
In a kettle, 45 parts of acrylonitrile and 1 part of hexafluorobutyl acrylate mix monomer and 0.0011 part of tm- is first added
200s, 55 parts of butadiene, 300 parts of water, 1 part of synthetic fatty acid potassium, 4 parts of disproportionated rosin acid potassium, 0.5 part of emulsifier C, 0.2 part of uncle
DDM dodecyl mercaptan, 0.1 part of isopropyl xanthogen disulfide, 0.1 part of sodium acetate, 0.001 part of cuprous sulfate, 0.006 part of first
Aldehyde sodium bisulphite, 0.01 part of EDETATE DISODIUM, pre-emulsification 30min add 0.007 part of hydrogen peroxide to Meng's alkane, and temperature control exists
Carry out copolyreaction under 14 DEG C of polymeric reaction temperatures, added when conversion ratio reaches 45% 0.035 part of dodecyl mercaptan carbon and
0.04 part of diethyl hydroxylamine and 0.07 part are added when conversion ratio reaches 84% for 0.015 part of isopropyl xanthogen disulfide
Hydroquinone terminates polymerization.Obtained fluorine-containing nitrile rubber performance is as shown in table 1.
Embodiment 4
In a kettle, 33 parts of acrylonitrile and 14 parts of trifluoroethyl methacrylate mix monomers and 0.056 are first added
Part tm-200s, 67 parts of butadiene, 200 parts of water, 1.2 parts of synthetic fatty acid potassium, 0.15 part of emulsifier A, 0.08 part of positive 12 carbon sulphur
Alcohol, 0.95 part of sodium acetate, 0.16 part of EDTA copper sodium, 0.2 part of glucose, 0.5 part of aminotriacetic acid sodium, pre-emulsification 60min, then
0.72 part of di-isopropylbenzene hydroperoxide is added, temperature control carries out copolyreaction under 1 DEG C of polymeric reaction temperature, reaches in conversion ratio
0.015 part of dodecyl mercaptan carbon is added when 63%, and 0.95 part of diethyl hydroxylamine is added when conversion ratio reaches 79% and terminates and gathers
It closes.Obtained fluorine-containing nitrile rubber performance is as shown in table 1.
Embodiment 5
In a kettle, 45 parts of acrylonitrile and 1 part of hexafluorobutyl acrylate mix monomer and 0.03 part of tm- is first added
200s, 55 parts of butadiene, 300 parts of water, 1.5 parts of synthetic fatty acid potassium, 4 parts of disproportionated rosin acid potassium, 0.2 part of tert-dodecyl mercaptan,
0.1 part of isopropyl xanthogen disulfide, 0.1 part of sodium acetate, 0.001 part of cuprous sulfate, 0.006 part of formaldehyde sulfoxylate hydrogen
Sodium, 0.01 part of EDETATE DISODIUM, pre-emulsification 30min add 0.007 part of hydrogen peroxide to Meng's alkane, and temperature control polymerize instead at 14 DEG C
Copolyreaction is carried out at a temperature of answering, and 0.035 part of dodecyl mercaptan carbon and 0.015 part of two sulphur are added when conversion ratio reaches 45%
For diisopropyl xanthate, 0.04 part of diethyl hydroxylamine is added when conversion ratio reaches 84% and 0.07 part of hydroquinone terminates
Polymerization.Obtained fluorine-containing nitrile rubber performance is as shown in table 1.
Embodiment 6
In a kettle, 33 parts of acrylonitrile and 14 parts of trifluoroethyl methacrylate mix monomers and 0.35 part is first added
Tm-200s, 67 parts of butadiene, 200 parts of water, 1.35 parts of emulsifier A, 0.08 part of dodecyl mercaptan carbon, 0.95 part of sodium acetate, 0.16
Part EDTA copper sodiums, 0.2 part of glucose, 0.5 part of aminotriacetic acid sodium, pre-emulsification 60min add 0.72 part of hydrogen peroxide two
Isopropylbenzene, temperature control carry out copolyreaction under 1 DEG C of polymeric reaction temperature, and 0.015 part is being added when conversion ratio reaches 63% just
0.95 part of diethyl hydroxylamine termination polymerization is added when conversion ratio reaches 79% for DDM dodecyl mercaptan.Obtained fluorine-containing nitrile rubber
Performance is as shown in table 1.
1 nitrile rubber performance of table
It is found by the analysis of embodiment and comparative example, chelating titanate coupling agent, which is added, using the method for the present invention prepares
Fluorine-containing nitrile rubber with not plus chelating titanate coupling agent prepare fluorine-containing nitrile rubber compared with, swellbility reduce by 7% with
On, glass transition temperature is reduced at 10 DEG C or more, and tensile strength is all in 30MPa or more；After degradation, the former oil resistivity and mechanics
Performance change is smaller, and performance is fine, and the latter's oil resistivity and mechanical property significantly reduce, hardly can normal use.Not plus chela
Fluorine-containing nitrile rubber prepared by mould assembly titanate coupling agent is close with the nitrile rubber performance for being not added with fluorochemical monomer, this explanation is not added with
After entering chelating titanate coupling agent, fluorochemical monomer cannot be effectively copolymerized with acrylonitrile and butadiene.Common metatitanic acid is added
Fluorine-containing nitrile rubber prepared by ester coupling agent is also approached with the nitrile rubber performance for being not added with fluorochemical monomer, and reason may be common titanium
Acid esters coupling agent is hydrolyzed, to fail.The fluorine-containing nitrile rubber prepared for introducing acrylate containing fluorine monomer is more
The secondary performance that fluorine-containing nitrile rubber prepared by molecular weight regulator is added is substantially better than prepared by primary addition molecular weight regulator
Fluorine-containing nitrile rubber.The rubber performance that a small amount of fluorubber and common nitrile rubber are blended and former common nitrile rubber phase
Than, performance change unobvious, namely be not achieved and put forward high performance purpose.
Claims (13)
1. a kind of using the method that emulsion polymerization at low temperature prepares fluorine-containing nitrile rubber using fluorochemical monomer：With butadiene and propylene
Two kinds of monomer total amounts of nitrile be 100 mass parts meters, first by 0.1~15 part of fluorochemical monomer and account for fluorochemical monomer mass fraction be 0.1~
5% chelating titanate coupling agent is added in 20~50 parts of acrylonitrile monemers, the mix monomer that will be obtained after being sufficiently stirred
Be added reaction kettle in, then sequentially add in a kettle 80~50 parts of divinylic monomers, 150~300 parts of water, 0.6~12 part
Emulsifier, 0.05~1.5 part of molecular weight regulator, 0.1~1.0 part of pH buffer, 0.0005~0.2 part of reducing agent, 0.005~
0.4 part of second reducing agent, 0.005~0.4 part of chelating agent, 30~60min of pre-emulsification add 0.005~0.8 part of organic peroxy
Change hydrogen species oxidant, so that it is carried out copolyreaction under 1~15 DEG C of polymeric reaction temperature, conversion ratio is mended again when reaching 40~65%
Add 0.01~0.5 part of molecular weight regulator, 0.1~1 part of terminator is added when conversion ratio reaches 75~85% and terminates polymerization；Breast
Agent is the compound emulsifying agent of anion emulsifier, nonionic emulsifier or anion emulsifier and nonionic emulsifier composition.
2. according to the method described in claim 1, it is characterized in that：Fluorochemical monomer uses acrylate containing fluorine monomer, best
It is in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, hexafluorobutyl acrylate
It is one or more.
3. method according to claim 1 or 2, it is characterised in that：Fluorochemical monomer dosage is 0.5~10 part.
4. according to the method described in claim 1, it is characterized in that：Chelating titanate coupling agent is 200 type titanate esters of chelating
Coupling agent.
5. according to the method described in claim 1, it is characterized in that：Chelating titanate coupling agent dosage is fluorochemical monomer quality
The 0.3~3% of score.
6. according to the method described in claim 1, it is characterized in that：Anion emulsifier is neopelex, synthesis
It is one or more in aliphatic acid potassium, disproportionated rosin acid potassium.
7. according to the method described in claim 1, it is characterized in that：Nonionic emulsifier uses polyoxyethylene-type non-ionic emulsifier
It is one or more in agent, preferably fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, aliphatic acid polyethenoxy.
8. according to the method described in claim 1, it is characterized in that：Molecular weight regulator is tert-dodecyl mercaptan, positive 12 carbon
It is one or more in mercaptan or isopropyl xanthogen disulfide；Molecular weight regulator needs repeatedly to be added, preferably for the first time
0.2~1 part of molecular weight regulator is added；0.05~0.2 part of molecular weight regulator is added when conversion ratio reaches 40~65% again.
9. according to the method described in claim 1, it is characterized in that：Emulsifier is compound emulsifying agent, wherein anion emulsifier
Dosage is 0.5~8.0 part, and nonionic emulsifier dosage is 0.1~4.0 part；Preferably anion emulsifier dosage is 1.2~5
Part, nonionic emulsifier dosage is 0.5~2.5 part.
10. according to the method described in claim 1, it is characterized in that：PH buffer is sodium carbonate or sodium acetate.
11. according to the method described in claim 1, it is characterized in that：Reducing agent is ferrous sulfate, cuprous sulfate, NaFeEDTA sodium
Salt or EDTA copper sodiums；Second reducing agent is rongalite or glucose；Chelating agent is EDETATE DISODIUM or amino three
Sodium acetate.
12. according to the method described in claim 1, it is characterized in that：Organic hydroperoxide class oxidant is hydrogen peroxide isopropyl
Benzene, di-isopropylbenzene hydroperoxide or hydrogen peroxide are to Meng's alkane.
13. according to the method described in claim 1, it is characterized in that polymeric reaction temperature control is at 4.5~8 DEG C；Terminator is
It is one or more in diethyl hydroxylamine, hydroquinone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159497A (en) * | 2020-09-28 | 2021-01-01 | 湖北分聚新材料有限公司 | Preparation method of fluorine-silicon modified butyronitrile latex applied to medical butyronitrile gloves |
| CN113372504A (en) * | 2021-06-09 | 2021-09-10 | 北京化工大学 | Fluorine-containing hydrogenated nitrile rubber material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956417A (en) * | 1988-03-24 | 1990-09-11 | Nippon Zeon Co., Ltd. | Nitrile group-containing highly saturated copolymer rubber and rubber composition having improved cold resistance |
| CN103665264A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | High-performance oil-resistant acrylonitrile-butadiene rubber |
| CN105837752A (en) * | 2015-01-15 | 2016-08-10 | 中国石油天然气股份有限公司 | Preparation method of cold-resistant nitrile rubber |
-
2016
- 2016-12-13 CN CN201611144237.2A patent/CN108610453B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956417A (en) * | 1988-03-24 | 1990-09-11 | Nippon Zeon Co., Ltd. | Nitrile group-containing highly saturated copolymer rubber and rubber composition having improved cold resistance |
| CN103665264A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | High-performance oil-resistant acrylonitrile-butadiene rubber |
| CN105837752A (en) * | 2015-01-15 | 2016-08-10 | 中国石油天然气股份有限公司 | Preparation method of cold-resistant nitrile rubber |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159497A (en) * | 2020-09-28 | 2021-01-01 | 湖北分聚新材料有限公司 | Preparation method of fluorine-silicon modified butyronitrile latex applied to medical butyronitrile gloves |
| CN112159497B (en) * | 2020-09-28 | 2022-12-06 | 湖北分聚新材料有限公司 | Preparation method of fluorine-silicon modified butyronitrile latex applied to medical butyronitrile gloves |
| CN113372504A (en) * | 2021-06-09 | 2021-09-10 | 北京化工大学 | Fluorine-containing hydrogenated nitrile rubber material and preparation method and application thereof |
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