CN108610453B - 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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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 72
- 239000011737 fluorine Substances 0.000 title claims abstract description 72
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000007720 emulsion polymerization reaction Methods 0.000 title description 5
- 239000000178 monomer Substances 0.000 claims abstract description 51
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 26
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013522 chelant Substances 0.000 claims abstract description 9
- 238000010556 emulsion polymerization method Methods 0.000 claims abstract description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 23
- 239000012875 nonionic emulsifier Substances 0.000 claims description 14
- -1 polyoxyethylene Polymers 0.000 claims description 14
- 239000012874 anionic emulsifier Substances 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 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
- 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 5
- 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
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 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
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical group [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 5
- ZAWGLAXBGYSUHN-UHFFFAOYSA-M sodium;2-[bis(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CC([O-])=O ZAWGLAXBGYSUHN-UHFFFAOYSA-M 0.000 claims description 5
- 239000012991 xanthate Substances 0.000 claims description 5
- 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 4
- ZIALXKMBHWELGF-UHFFFAOYSA-N [Na].[Cu] Chemical compound [Na].[Cu] ZIALXKMBHWELGF-UHFFFAOYSA-N 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
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 239000006174 pH buffer Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 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
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 claims description 2
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-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
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 4
- 230000006835 compression Effects 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 description 21
- 239000005060 rubber Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 238000004945 emulsification Methods 0.000 description 7
- 229920001973 fluoroelastomer Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006583 body weight regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229930004008 p-menthane Natural products 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
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- 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
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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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 invention relates to the field of preparation of nitrile rubber, in particular to a method for preparing fluorine-containing nitrile rubber by using a fluorine-containing monomer through a low-temperature emulsion polymerization method.
Background
Nitrile-butadiene rubber (NBR) has the advantages of excellent oil resistance, good tensile property, heat resistance, air tightness, compression deformability and the like, but is mostly used for common oil-resistant products, and is rarely applied in the field with strict environmental requirements, mainly caused by the limitation of the application temperature range and weather resistance.
The fluorine-containing high molecular polymer has excellent weather resistance, high temperature resistance, stain resistance, electrical insulation, durability and chemical resistance due to the fluorine-containing bond. Fluorine is the element with the largest electronegativity, the covalent radius of fluorine atoms is very small, the bond energy of an F-C bond is stronger than that of a C-H bond, the shielding effect of an electron cloud of the fluorine atoms on the C-C bond is stronger than that of a hydrogen atom, the polarization rate of the fluorine atoms is low, the distribution is symmetrical, and the structural characteristics enable the fluorine high molecular polymer to have unique performance. However, the fluorine-containing high molecular polymer is expensive, and the application range thereof is limited.
The fluorine-containing high molecular polymer modified NBR generally adopts a blending method, and the modification effect is general. The patent CN200610119299.8 discloses a mechanical blending and vulcanizing method of NBR and fluororubber, the fluororubber adopts vinylidene fluoride-hexafluoropropylene copolymer type or vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene trimerization type fluororubber, and the positive vulcanization time (T) of NBR and fluororubber is required to be controlled during vulcanization and bonding90) The difference is in the range of 0.3 to 12 min.
When the blending method is used for modification, the use amount of the modified polymer is large, the molecular-level uniform dispersion is difficult to realize, the use amount of the modified polymer used in polymerization modification is large or small, the molecular-level uniform dispersion is easy to realize, and the performance can be obviously improved by adding a small amount of modified monomer. Peltier et al, using fluorinated acrylate and an acrylic monomer, synthesized a stable fluorine modified acrylate emulsion using a semi-continuous seeded emulsion polymerization process, which significantly improved water resistance when the amount of fluorinated acrylate was only 2%. (Perchler Red, Shibowen, Song micro. synthetic study of organic fluorine and epoxy resin modified acrylate emulsion [ J ] China Adhesives, 2012, 21(10): 13-17).
In addition, there are reports of methods for modifying the surface of NBR with fluorine gas or fluorinated gas, including a direct fluorination method in which NBR is placed in fluorine gas under a certain temperature and pressure for a certain period of time,the latter is the reaction of NBR in a special reactor with a fluorinated gas (e.g. CF) in the reactor4、CHF3) The generated plasma gas is reacted [ E.Durand, C.Labrure, A.Tressaud, et al.surface Fluorination of Carboxylated nitrile Butadiene Rubber: [ J.XPS studio ]].Plasmas and Polymers,2002,7(4):311-325]。
In the above method, the combination of the fluoropolymer and the NBR is a two-phase structure, and does not reach a molecular-level dispersion structure.
JP Hei 1-242643A provides a rubber composition having improved cold resistance, which is obtained by preparing a terpolymer rubber of acrylonitrile, butadiene and trifluoroethyl acrylate by conventional emulsion polymerization and then hydrogenating it to form a highly saturated hydrogenated rubber, to achieve the effect of improving the cold resistance of the rubber, and a method for preparing the terpolymer rubber is not specifically indicated.
Disclosure of Invention
The invention aims to provide a method for preparing fluorine-containing nitrile rubber by using a fluorine-containing monomer through a low-temperature emulsion polymerization method, and the prepared fluorine-containing nitrile rubber can greatly improve the oil resistance, tensile strength and other properties of the fluorine-containing nitrile rubber.
A method for preparing fluorine-containing nitrile rubber by using fluorine-containing monomers through a low-temperature emulsion polymerization method comprises the following steps: based on 100 parts by mass of the total amount of butadiene and acrylonitrile, firstly adding 0.1-15 parts of fluorine-containing monomer and chelate titanate coupling agent accounting for 0.1-5% of the mass fraction of the fluorine-containing monomer into 20-50 parts of acrylonitrile monomer, fully stirring, adding the obtained mixed monomer into a reaction kettle, then, sequentially adding 80-50 parts of butadiene monomer, 150-300 parts of water, 0.6-12 parts of emulsifier, 0.05-1.5 parts 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 and 0.005-0.4 part of chelating agent into a reaction kettle, pre-emulsifying for 30-60 min, adding 0.005-0.8 part of organic hydrogen peroxide oxidant, carrying out copolymerization reaction at the polymerization reaction temperature of 1-15 ℃, supplementing 0.01-0.5 part of molecular weight regulator when the conversion rate reaches 40-65%, and adding 0.1-1 part of terminator to terminate polymerization when the conversion rate reaches 75-85%; the emulsifier is anionic emulsifier, nonionic emulsifier or composite emulsifier composed of anionic emulsifier and nonionic emulsifier.
The fluorinated monomer of the present invention is a monomer that contains fluorine and can be polymerized with other monomers, and a fluorinated acrylate monomer is recommended, and the type of the fluorinated fatty acid ester monomer is not particularly limited as long as the fluorinated fatty acid ester monomer has the following characteristics: (1) unsaturated carbon-carbon double bonds (-C ═ C-) are present in the molecular chain; (2) the copolymer is not easy to homopolymerize, tends to be copolymerized with butadiene and acrylonitrile monomers, has moderate reaction activity and can be one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoro heptyl methacrylate and hexafluorobutyl acrylate. The amount of the fluorine-containing acrylate monomer is 0.1-15 parts, preferably 0.5-10 parts.
The chelate type titanate coupling agent of the present invention is not particularly limited, and may be a chelate type 200 titanate coupling agent. The chelate type titanate coupling agent is adopted in the polymerization process to promote the ternary polymerization of the fluorine-containing monomer, the acrylonitrile and the butadiene. The fluorine-containing monomer and the chelate type titanate coupling agent are dissolved in the acrylonitrile monomer, so that the fluorine-containing monomer and the chelate type titanate coupling agent can be effectively dispersed in a polymerization system, and the ternary polymerization efficiency of the fluorine-containing monomer, the acrylonitrile and the butadiene is obviously improved. The chelating titanate coupling agent accounts for 0.1-5% of the mass fraction of the fluorine-containing monomer, preferably 0.3-3%.
The emulsifier can be an anionic emulsifier, a nonionic emulsifier or a composite emulsifier system formed by combining the anionic emulsifier and the nonionic emulsifier. The recommended use mode of the invention is to use a composite emulsifier system, and the composite emulsifier system can improve the emulsion polymerization stability, is more suitable for the ternary polymerization reaction of butadiene, acrylonitrile and fluorine-containing monomers, is beneficial to preparing the fluorine-containing nitrile rubber and can improve the performance of the polymer.
The anionic emulsifier of the present invention is not particularly limited, and may be one or more of sodium dodecylbenzenesulfonate, synthetic fatty acid potassium, and disproportionated rosin potassium.
The nonionic emulsifier of the present invention is preferably a polyoxyethylene type nonionic emulsifier. Can be one or more of fatty alcohol polyoxyethylene ether (such as O-20 type peregal), alkylphenol polyoxyethylene ether (such as OP-10), and fatty acid polyoxyethylene (such as A-105).
When a complex emulsifier system is used, the anionic emulsifier is preferably used in an amount of 0.5 to 8.0 parts, more preferably 1.2 to 5 parts, and the nonionic emulsifier is preferably used in an amount of 0.1 to 4.0 parts, more preferably 0.5 to 2.5 parts.
In the invention, in order to copolymerize the fluorine-containing acrylate monomer with acrylonitrile and butadiene so as to introduce fluorine, a proper amount of molecular weight regulator must be added in the polymerization process. If the molecular weight regulator is not supplemented, excessive gel may be generated due to insufficient molecular weight regulation at the later stage, and the polymer properties may be affected.
The molecular weight modifier of the present invention is not particularly limited, and may be one or more of tertiary dodecyl mercaptan, n-dodecyl mercaptan, and dithiodiisopropyl xanthogen. The molecular weight regulator needs to be added for multiple times, and 0.05-1.5 parts of the molecular weight regulator is added for the first time, preferably 0.2-1 part; when the conversion rate reaches 40-65%, 0.01-0.5 part of molecular weight regulator is supplemented, preferably 0.05-0.2 part.
The pH buffer according to the present invention is not particularly limited, and may be one of sodium carbonate and sodium acetate.
The initiation system used in the present invention is an oxidation-reduction system, and the reducing agent is not particularly limited, and may be one of ferrous sulfate, cuprous sulfate, ferric sodium EDTA, and copper sodium EDTA.
The second reducing agent of the present invention is not particularly limited, and may be one of sodium formaldehyde sulfoxylate and glucose.
The chelating agent of the present invention is not particularly limited, and may be one of disodium EDTA and sodium aminotriacetate.
The pre-emulsification time is controlled to be 30-60 min.
The organic hydroperoxide oxidizing agent of the present invention is not particularly limited, and may be cumene hydroperoxide, diisopropylbenzene hydroperoxide, or p-menthane hydroperoxide.
The polymerization temperature is 1-15 ℃, and preferably 4.5-8 ℃.
The terminator of the present invention is not particularly limited, and may be one or more of diethylhydroxylamine and hydroquinone.
The method of the invention adopts a low-temperature emulsion polymerization method, in particular to a method for copolymerizing a fluorine-containing acrylate monomer with acrylonitrile and butadiene by utilizing a chelating titanate coupling agent to prepare the fluorine-containing nitrile rubber, thereby enhancing the reaction activity of the fluorine-containing acrylate monomer with the acrylonitrile and the butadiene, improving the performance of the fluorine-containing nitrile rubber, and solving the problem that the conventional nitrile rubber is not suitable for harsh conditions such as poor high and low temperature resistance, thereby widening the application field of the nitrile rubber and being capable of being used as a high-end nitrile rubber product for production. The fluorine-containing nitrile rubber prepared by the method provided by the invention obviously improves the comprehensive performance of 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 glass transition temperature reduced by more than 10 ℃), and also has the characteristics of good elasticity, high stretching strength, low compression permanent deformation, good wear resistance, good weather resistance, good stain resistance and narrow molecular weight distribution.
Drawings
FIG. 1: the infrared spectrum of the fluorine-containing nitrile rubber prepared by using the chelate type titanate coupling agent is applied.
FIG. 2: an infrared spectrum of the fluorine-containing nitrile rubber prepared without using a chelating titanate coupling agent.
FIG. 3: an infrared spectrum of common nitrile rubber prepared without using a fluorine-containing acrylate monomer.
Detailed Description
The invention is further illustrated by the following examples, but is not limited thereto, the reactor being an emulsion reactor having a capacity of 15L with a stirrer. Unless otherwise specified, "parts" and "%" referred to below mean mass fractions or mass percentages.
1. Analytical method
Mooney viscosity: the Mooney viscosity of the rubber was determined in accordance with GB/T1232.1-2000.
Swelling degree: the swelling degree of the rubber was determined according to SH/T1159-2010.
Tensile strength: the tensile stress strain properties of the rubber were determined according to GB/T528-2009.
Aging performance: the aging properties of the rubber were determined in accordance with GB/T3512-2001.
2. Raw material
Fluorine-containing acrylate monomer: 4 of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate and hexafluorobutyl acrylate, respectively, Heilongjiang Harbin Seisakul silicofluoride chemical Co.
Emulsifier A: o-20 type Pingpinga, Haian petrochemical plant of Jiangsu province.
And (3) an emulsifier B: OP-10, Shandong-West Asia chemical industries, Ltd.
And (3) an emulsifier C: a-105 type polyoxyethylene fatty acid ester emulsifier, a petroleum chemical plant of Haian in Jiangsu province.
Fluororubber: FKM 2603, chenguang chemical research institute.
Chelating titanate coupling agent: tm-200s, Yuezhiyang chemical plant.
Common titanate coupling agents: UP-201, Nanjing Qiyu chemical science and technology, Inc.
Other materials are commercially available.
Example 1
In a reaction kettle, 25 parts of acrylonitrile, 2.1 parts of hexafluorobutyl acrylate, 2.9 parts of hexafluorobutyl methacrylate mixed monomer, 0.1 part of tm-200s, 75 parts of butadiene, 150 parts of water, 2.7 parts of sodium dodecyl benzene sulfonate, 2.4 parts of emulsifier A, 0.55 part of tert-dodecyl mercaptan, 0.2 part of sodium carbonate, 0.01 part of ferrous sulfate, 0.1 part of sodium formaldehyde sulfoxylate and 0.05 part of EDTA disodium salt are added, pre-emulsification is carried out for 40min, 0.2 part of cumene hydroperoxide is added, copolymerization is carried out at the polymerization temperature controlled at 5 ℃, 0.08 part of tert-dodecyl mercaptan is added when the conversion rate reaches 50%, and 0.4 part of diethylhydroxylamine is added when the conversion rate reaches 80% to terminate polymerization. The properties of the resulting fluoronitrile rubber are shown in Table 1.
Comparative example 1
The procedure is as in example 1, but not adding tm-200 s. The properties of the resulting fluoronitrile rubber are shown in Table 1.
Comparative example 2
The procedure is as in example 1, except that 2.1 parts hexafluorobutyl acrylate, 2.9 parts hexafluorobutyl methacrylate mixed monomer and 0.1 part tm-200s are changed to 1.25 parts acrylonitrile and 3.75 parts butadiene. The properties of the resulting nitrile rubber are shown in Table 1.
FIG. 1, FIG. 2 and FIG. 3 are infrared spectra of rubbers prepared in example 1, comparative example 1 and comparative example 2, respectively. 1187.58cm in FIG. 1-1And 1746.20cm-1Are characteristic peaks of the C-F bond, whereas fig. 2 and 3 do not have such characteristic peaks. In comparative example 1, no chelating titanate coupling agent tm-200s was added although a fluorine-containing monomer was also added during the polymerization, thereby possibly resulting in a component having no or a very small amount of fluorine in the polymerization product. Comparative example 3 no fluorine-containing monomer was added, and thus the polymerization product had no fluorine component necessarily. Because the amount of the chelating titanate coupling agent is very small relative to the amount of the monomer, the components of the chelating titanate coupling agent are not observed in an infrared spectrum.
Comparative example 3
The procedure is as in example 1, but 0.58 part of tert-dodecyl mercaptan is added in one portion to the molecular weight regulator at the early stage of the reaction. The properties of the resulting fluoronitrile rubber are shown in Table 1.
Comparative example 4
The nitrile rubber from comparative example 2 was modified by blending with 4.5 parts of the fluoro rubber FKM 2603.
Comparative example 5
The procedure is the same as in example 1, but tm-200s is changed to UP-201. The properties of the resulting nitrile rubber are shown in Table 1.
Example 2
In a reaction kettle, 20 parts of acrylonitrile and 10 parts of dodecafluoroheptyl methacrylate mixed monomer, 0.45 part of tm-200s, 80 parts of butadiene, 250 parts of water, 1.8 parts of sodium dodecyl benzene sulfonate, 5.5 parts of synthetic fatty acid potassium, 2.5 parts of emulsifier B, 1 part of emulsifier C, 1.2 parts of n-dodecanethiol, 0.5 part of sodium carbonate, 0.09 part of ferric EDTA sodium salt, 0.36 part of glucose and 0.2 part of sodium aminotriacetate are added, pre-emulsification is carried out for 50min, 0.4 part of dicumyl peroxide is added, copolymerization is carried out at the polymerization temperature controlled at 8 ℃, 0.08 part of n-dodecanethiol is added when the conversion rate reaches 42%, and 0.3 part of hydroquinone and 0.3 part of diethylhydroxylamine are added when the conversion rate reaches 75% to terminate polymerization. The properties of the resulting fluoronitrile rubber are shown in Table 1.
Comparative example 6
The procedure is as in example 2, but not adding tm-200 s. The properties of the resulting nitrile rubber are shown in Table 1.
Example 3
In a reaction kettle, 45 parts of acrylonitrile and 1 part of hexafluorobutyl acrylate mixed monomer, 0.0011 part of tm-200s, 55 parts of butadiene, 300 parts of water, 1 part of synthetic potassium fatty acid, 4 parts of disproportionated potassium rosinate, 0.5 part of emulsifier C, 0.2 part of tert-dodecyl mercaptan, 0.1 part of dithiodiisopropyl xanthate, 0.1 part of sodium acetate, 0.001 part of cuprous sulfate, 0.006 part of sodium formaldehyde sulfoxylate, 0.01 part of EDTA disodium salt are added for pre-emulsification for 30min, 0.007 part of hydrogen peroxide is added to p-menthane, copolymerization is carried out at a polymerization temperature controlled at 14 ℃, 0.035 part of n-dodecyl mercaptan and 0.015 part of dithiodiisopropyl xanthate are added when the conversion rate reaches 45%, and 0.04 part of diethyl hydroxylamine and 0.07 part of hydroquinone are added to terminate polymerization when the conversion rate reaches 84%. The properties of the resulting fluoronitrile rubber are shown in Table 1.
Example 4
In a reaction kettle, 33 parts of acrylonitrile and 14 parts of trifluoroethyl methacrylate mixed monomer, 0.056 part of 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 n-dodecyl mercaptan, 0.95 part of sodium acetate, 0.16 part of EDTA copper sodium salt, 0.2 part of glucose and 0.5 part of sodium aminotriacetate are added for pre-emulsification for 60min, 0.72 part of diisopropylbenzene hydroperoxide is added, copolymerization is carried out at the polymerization reaction temperature of 1 ℃, 0.015 part of n-dodecyl mercaptan is added when the conversion rate reaches 63%, and 0.95 part of diethylhydroxylamine is added to terminate polymerization when the conversion rate reaches 79%. The properties of the resulting fluoronitrile rubber are shown in Table 1.
Example 5
In a reaction kettle, 45 parts of acrylonitrile and 1 part of hexafluorobutyl acrylate mixed monomer, 0.03 part of tm-200s, 55 parts of butadiene, 300 parts of water, 1.5 parts of synthetic potassium fatty acid, 4 parts of disproportionated potassium rosinate, 0.2 part of tert-dodecyl mercaptan, 0.1 part of dithiodiisopropyl xanthate, 0.1 part of sodium acetate, 0.001 part of cuprous sulfate, 0.006 part of sodium formaldehyde sulfoxylate, 0.01 part of EDTA disodium salt are added for pre-emulsification for 30min, 0.007 part of hydrogen peroxide is added for menthane, copolymerization is carried out at a polymerization temperature controlled at 14 ℃, 0.035 part of n-dodecyl mercaptan and 0.015 part of dithiodiisopropyl xanthate are added when the conversion rate reaches 45%, and 0.04 part of diethyl hydroxylamine and 0.07 part of hydroquinone are added when the conversion rate reaches 84% to terminate polymerization. The properties of the resulting fluoronitrile rubber are shown in Table 1.
Example 6
In a reaction kettle, 33 parts of acrylonitrile and 14 parts of trifluoroethyl methacrylate mixed monomer, 0.35 part of tm-200s, 67 parts of butadiene, 200 parts of water, 1.35 parts of emulsifier A, 0.08 part of n-dodecyl mercaptan, 0.95 part of sodium acetate, 0.16 part of EDTA copper sodium salt, 0.2 part of glucose and 0.5 part of sodium aminotriacetate are added for pre-emulsification for 60min, 0.72 part of dicumyl peroxide is added, the temperature is controlled at 1 ℃ for polymerization reaction, 0.015 part of n-dodecyl mercaptan is added when the conversion rate reaches 63%, and 0.95 part of diethylhydroxylamine is added when the conversion rate reaches 79% to terminate the polymerization. The properties of the resulting fluoronitrile rubber are shown in Table 1.
TABLE 1 nitrile rubber Properties
Through the analysis of the examples and the comparative examples, the fluorine-containing nitrile rubber prepared by adding the chelating type titanate coupling agent by the method of the invention has the advantages that compared with the fluorine-containing nitrile rubber prepared without adding the chelating type titanate coupling agent, the swelling degree is reduced by more than 7 percent, the glass transition temperature is reduced by more than 10 ℃, and the tensile strength is more than 30 MPa; after an aging test, the oil resistance and the mechanical property of the rubber are slightly changed and have the same performance, and the oil resistance and the mechanical property of the rubber are obviously reduced and can not be used normally. The performances of the fluorine-containing nitrile rubber prepared without the chelating type titanate coupling agent are close to those of the nitrile rubber without the fluorine-containing monomer, which shows that the fluorine-containing monomer can not be effectively copolymerized with acrylonitrile and butadiene after the chelating type titanate coupling agent is not added. The performance of the fluorine-containing nitrile rubber prepared by adding the common titanate coupling agent is similar to that of the nitrile rubber without adding the fluorine-containing monomer, and the reason is that the common titanate coupling agent is hydrolyzed so as to lose efficacy. For the fluorine-containing nitrile rubber prepared by introducing the fluorine-containing acrylate monomer, the performance of the fluorine-containing nitrile rubber prepared by adding the molecular weight regulator for multiple times is obviously superior to that of the fluorine-containing nitrile rubber prepared by adding the molecular weight regulator for one time. Compared with the original common nitrile rubber, the rubber performance obtained by blending a small amount of fluororubber and the common nitrile rubber has unobvious performance change, namely the purpose of improving the performance cannot be achieved.
Claims (18)
1. A method for preparing fluorine-containing nitrile rubber by using fluorine-containing monomers through a low-temperature emulsion polymerization method comprises the following steps: based on 100 parts by mass of the total amount of butadiene and acrylonitrile, firstly adding 0.1-15 parts of fluorine-containing monomer and chelate titanate coupling agent accounting for 0.1-5% of the mass fraction of the fluorine-containing monomer into 20-50 parts of acrylonitrile monomer, fully stirring, adding the obtained mixed monomer into a reaction kettle, then, sequentially adding 80-50 parts of butadiene monomer, 150-300 parts of water, 0.6-12 parts of emulsifier, 0.05-1.5 parts 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 and 0.005-0.4 part of chelating agent into a reaction kettle, pre-emulsifying for 30-60 min, adding 0.005-0.8 part of organic hydrogen peroxide oxidant, carrying out copolymerization reaction at the polymerization reaction temperature of 1-15 ℃, supplementing 0.01-0.5 part of molecular weight regulator when the conversion rate reaches 40-65%, and adding 0.1-1 part of terminator to terminate polymerization when the conversion rate reaches 75-85%; the emulsifier is anionic emulsifier, nonionic emulsifier or composite emulsifier composed of anionic emulsifier and nonionic emulsifier.
2. The method of claim 1, wherein: the fluorine-containing monomer adopts fluorine-containing acrylate monomer.
3. The method of claim 2, wherein: the fluorine-containing acrylate monomer is one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate and hexafluorobutyl acrylate.
4. The method according to claim 1 or 2, characterized in that: the amount of the fluorine-containing monomer is 0.5-10 parts.
5. The method of claim 1, wherein: the chelating titanate coupling agent is a chelating 200-type titanate coupling agent.
6. The method of claim 1, wherein: the dosage of the chelating titanate coupling agent is 0.3-3% of the mass fraction of the fluorine-containing monomer.
7. The method of claim 1, wherein: the anionic emulsifier is one or more of sodium dodecyl benzene sulfonate, synthetic fatty acid potassium and disproportionated rosin potassium.
8. The method of claim 1, wherein: the nonionic emulsifier is polyoxyethylene nonionic emulsifier.
9. The method of claim 8, wherein: the polyoxyethylene type nonionic emulsifier is one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene and fatty acid polyoxyethylene.
10. The method of claim 1, wherein: the molecular weight regulator is one or more of tertiary dodecyl mercaptan, n-dodecyl mercaptan or dithiodiisopropyl xanthate.
11. The method of claim 10, wherein: the molecular weight regulator needs to be added in multiple times.
12. The method of claim 11, wherein: 0.2-1 part of the molecular weight regulator is added for the first time, and 0.05-0.2 part of the molecular weight regulator is supplemented when the conversion rate reaches 40-65%.
13. The method of claim 1, wherein: the emulsifier is a composite emulsifier, wherein the dosage of the anionic emulsifier is 0.5-8.0 parts, and the dosage of the nonionic emulsifier is 0.1-4.0 parts.
14. The method of claim 13, wherein: the dosage of the anionic emulsifier is 1.2-5 parts, and the dosage of the nonionic emulsifier is 0.5-2.5 parts.
15. The method of claim 1, wherein: the pH buffer is sodium carbonate or sodium acetate.
16. The method of claim 1, wherein: the reducing agent is ferrous sulfate, cuprous sulfate, EDTA ferric sodium salt or EDTA copper sodium salt; the second reducing agent is sodium formaldehyde sulfoxylate or glucose; the chelating agent is EDTA disodium salt or sodium aminotriacetate.
17. The method of claim 1, wherein: the organic hydroperoxide oxidizing agent is cumene hydroperoxide, diisopropylbenzene hydroperoxide or p-menthane hydroperoxide.
18. The method according to claim 1, wherein the polymerization temperature is controlled to be 4.5 to 8 ℃; the terminating agent is one or more of diethylhydroxylamine and hydroquinone.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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