CN117986468A - Poly-stabilized nitrile-butadiene silicon rubber and preparation method and application thereof - Google Patents
Poly-stabilized nitrile-butadiene silicon rubber and preparation method and application thereof Download PDFInfo
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- CN117986468A CN117986468A CN202211372375.1A CN202211372375A CN117986468A CN 117986468 A CN117986468 A CN 117986468A CN 202211372375 A CN202211372375 A CN 202211372375A CN 117986468 A CN117986468 A CN 117986468A
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- butadiene
- acrylonitrile
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 193
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 79
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 239000002994 raw material Substances 0.000 claims abstract description 53
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 27
- 150000001993 dienes Chemical class 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 229920001971 elastomer Polymers 0.000 claims description 27
- 239000005060 rubber Substances 0.000 claims description 27
- 150000002825 nitriles Chemical class 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000004945 silicone rubber Substances 0.000 claims description 15
- 208000005156 Dehydration Diseases 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 13
- 239000012190 activator Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 56
- 239000000344 soap Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical group CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 25
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 21
- 229910052700 potassium Inorganic materials 0.000 description 21
- 239000011591 potassium Substances 0.000 description 21
- 229940096992 potassium oleate Drugs 0.000 description 21
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 16
- 239000000194 fatty acid Substances 0.000 description 16
- 229930195729 fatty acid Natural products 0.000 description 16
- 150000004665 fatty acids Chemical class 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- 239000011780 sodium chloride Substances 0.000 description 16
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 16
- 208000012839 conversion disease Diseases 0.000 description 15
- 238000007872 degassing Methods 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 15
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000006073 displacement reaction Methods 0.000 description 13
- GFSJJVJWCAMZEV-UHFFFAOYSA-N n-(4-anilinophenyl)-2-methylprop-2-enamide Chemical compound C1=CC(NC(=O)C(=C)C)=CC=C1NC1=CC=CC=C1 GFSJJVJWCAMZEV-UHFFFAOYSA-N 0.000 description 13
- 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 12
- HKLPOBRVSAUJSG-UHFFFAOYSA-N n-(4-anilinophenyl)prop-2-enamide Chemical compound C1=CC(NC(=O)C=C)=CC=C1NC1=CC=CC=C1 HKLPOBRVSAUJSG-UHFFFAOYSA-N 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 11
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 10
- 239000001103 potassium chloride Substances 0.000 description 10
- 235000011164 potassium chloride Nutrition 0.000 description 10
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 8
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 238000001035 drying Methods 0.000 description 5
- 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 description 5
- KPNYFXUDBVQRNK-UHFFFAOYSA-N 1-(4-anilinophenyl)pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1NC1=CC=CC=C1 KPNYFXUDBVQRNK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- TWKZFJUFPMMUJQ-UHFFFAOYSA-N n-(4-anilinophenyl)-2-hydroxy-2-methylpropanamide Chemical compound C1=CC(NC(=O)C(C)(O)C)=CC=C1NC1=CC=CC=C1 TWKZFJUFPMMUJQ-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229940114930 potassium stearate Drugs 0.000 description 3
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- -1 3, 5-di-tert-butyloxybenzene methyl benzoate Chemical compound 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000008149 soap solution Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- LCKPEFUXKRSTMA-UHFFFAOYSA-N 6-propan-2-yl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical group C1=CC=CC2(C(C)C)C1O2 LCKPEFUXKRSTMA-UHFFFAOYSA-N 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 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 1
- 239000005843 Thiram Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a poly-stable nitrile-butadiene silicon rubber and a preparation method and application thereof. The preparation method comprises the following steps: 1) Adding an initiator into the first raw material system to perform a first emulsion polymerization reaction, and adding a second raw material system to perform a second emulsion polymerization reaction when the polymerization conversion rate is 15-25%; 2) When the polymerization conversion rate is 40-50%, adding a third raw material system to perform a third emulsion polymerization reaction; 3) Terminating the reaction when the polymerization conversion rate is 85-89%, so as to obtain the poly-stable nitrile-butadiene silicon rubber; wherein the first raw material system comprises a reactive anti-aging agent monomer, conjugated diene, a first part of emulsifier and a first part of molecular weight regulator; the second raw material system comprises part of acrylonitrile, silicon-based monomers, a second part of emulsifying agent and a second part of molecular weight regulator; the third feed system comprises the remainder of acrylonitrile, the remainder of emulsifier and the remainder of molecular weight regulator. The poly-stabilized nitrile-butadiene silicon rubber obtained by the preparation method has excellent cold resistance.
Description
Technical Field
The invention relates to a thermoplastic elastomer, in particular to a poly-stabilized nitrile-butadiene silicon rubber, a preparation method and application thereof, and belongs to the field of rubber materials.
Background
Nitrile rubbers are widely used in oil resistant rubber products due to their excellent oil resistance, low compression set, good processability. However, long-term use in extremely cold regions also results in higher demands being placed on nitrile rubbers in terms of cold resistance.
Nitrile rubbers are emulsion copolymers obtained by free radical initiation of conjugated dienes and acrylonitrile, and therefore have a large number of unsaturated bonds therein, which leads to the phenomenon of brittle fracture in long-term low-temperature application environments.
At present, the cold resistance of rubber parts is improved by changing the molecular structure of nitrile rubber or adding other auxiliary agents, but the improvement degree of the cold resistance can not meet the requirement. Therefore, how to obtain a rubber excellent in cold resistance is a subject of long-term study in the art.
Disclosure of Invention
The invention provides a preparation method of poly-stable nitrile-butadiene silicon rubber, which is characterized in that the poly-stable nitrile-butadiene silicon rubber with excellent cold resistance is finally obtained by controlling the feeding sequence and the feeding nodes.
The invention provides a poly-stable nitrile-butadiene silicon rubber which has excellent cold resistance.
The invention also provides a rubber product, and the raw materials of the rubber product comprise poly-stabilized nitrile-butadiene silicon rubber, so that the rubber product has excellent service performance and long service cycle.
The invention provides a preparation method of poly-stable nitrile-butadiene silicon rubber, which comprises the following steps:
1) Adding an initiator into the first raw material system to perform a first emulsion polymerization reaction, and adding a second raw material system to perform a second emulsion polymerization reaction when the polymerization conversion rate is 15-25%;
2) When the polymerization conversion rate is 40-50%, adding a third raw material system to perform a third emulsion polymerization reaction;
3) Terminating the reaction when the polymerization conversion rate is 85-89%, so as to obtain the poly-stable nitrile-butadiene silicon rubber;
wherein the first raw material system at least comprises a reactive antioxidant monomer, conjugated diene, a first part of emulsifier and a first part of molecular weight regulator;
the second raw material system at least comprises part of acrylonitrile, silicon-based monomers, a second part of emulsifying agent and a second part of molecular weight regulator;
The third feed system comprises at least a residual acrylonitrile, a residual emulsifier and a residual molecular weight regulator.
The production method as described above, wherein the mass of the part of acrylonitrile is not less than 60% of the total mass of acrylonitrile.
The preparation method as described above, wherein the mass of the first portion of the emulsifier is not less than 70% of the total mass of the emulsifier.
The preparation method is characterized in that the reaction temperature is 5-30 ℃.
The preparation method comprises the steps of 10-45% of acrylonitrile, 50-85% of conjugated diene, 0.5-2% of reactive anti-aging agent monomer and 1.0-12% of silicon-based monomer according to mass percentage.
The preparation method comprises the steps of reacting monomers, emulsifying agents, initiators and molecular weight regulators according to the mass ratio of 100: (2.5-5.5): (0.05-0.5): (0.2-3).
The preparation method comprises the steps of sequentially performing condensation treatment, filtration treatment and dehydration treatment on a reaction system after terminating the reaction, so as to obtain the poly-stable nitrile-butadiene silicone rubber.
The preparation method as described above, wherein the first raw material system further comprises an electrolyte, an activator, a dispersing agent and an oxygen scavenger.
The invention also provides a poly-stable nitrile-butadiene silicon rubber which is prepared by the preparation method according to any one of the above.
The invention also provides a rubber product, and the raw materials of the rubber product comprise the poly-stabilized nitrile-butadiene silicone rubber.
According to the preparation method of the poly-stable nitrile-butadiene silicon rubber, the reactive anti-aging agent monomer is used as a monomer to participate in polymerization, the anti-aging effect of the reactive anti-aging agent monomer is exerted to the maximum extent by adjusting the feeding sequence and the feeding nodes of other monomers, and finally the obtained poly-stable nitrile-butadiene silicon rubber has excellent cold resistance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The first aspect of the invention provides a preparation method of a poly-stabilized nitrile-butadiene silicon rubber, which comprises the following steps:
1) Adding an initiator into the first raw material system to perform a first emulsion polymerization reaction, and adding a second raw material system to perform a second emulsion polymerization reaction when the polymerization conversion rate is 15-25%;
2) When the polymerization conversion rate is 40-50%, adding a third raw material system to perform a third emulsion polymerization reaction;
3) Terminating the reaction when the polymerization conversion rate is 85-89%, so as to obtain the poly-stable nitrile-butadiene silicon rubber;
wherein the first raw material system at least comprises a reactive antioxidant monomer, conjugated diene, a first part of emulsifier and a first part of molecular weight regulator;
the second raw material system at least comprises part of acrylonitrile, silicon-based monomers, a second part of emulsifying agent and a second part of molecular weight regulator;
The third feed system comprises at least a residual acrylonitrile, a residual emulsifier and a residual molecular weight regulator.
The invention prepares the poly-stable nitrile-butadiene silicon rubber through emulsion polymerization reaction, which can be batch polymerization or continuous polymerization. The process for preparing the poly-stable nitrile-butadiene silicon rubber is completed in three steps according to the raw material feeding sequence.
In step 1), the emulsion polymerization (including the first, second and third emulsion polymerization) is initiated by adding an initiator to the first feed system. It will be appreciated that by adding an initiator to the first feed system, the presence of the initiator is able to initiate not only the first emulsion polymerization reaction, but also the second and third emulsion polymerization reactions after the addition of the second and third feed systems, respectively.
The first raw material system at least comprises a reactive antioxidant monomer, conjugated diene, a first part of emulsifier and a first part of molecular weight regulator. In the specific preparation process, for example, at least a reactive antioxidant monomer, a first part of emulsifier and a first part of molecular weight regulator are added into a polymerization reaction kettle, then the reaction kettle is subjected to nitrogen pressurization-vacuum displacement, conjugated diene is introduced into the reaction kettle, and the first raw material system is obtained by stirring.
In the present invention, the first emulsion polymerization is essentially polymerization of the reactive antioxidant monomer and the conjugated diene, and when the polymerization conversion reaches 15 to 25% as the first emulsion polymerization proceeds, the reaction system includes the reactive antioxidant monomer-conjugated diene polymer formed in addition to the reactive antioxidant monomer and the conjugated diene which are not completely reacted. At this time, a second raw material system is added to the reaction system to carry out a second emulsion polymerization. It will be appreciated that the second emulsion polymerization is essentially a polymerization reaction between acrylonitrile, a silicon-based monomer, a reactive anti-aging agent monomer-conjugated diene polymer, a reactive anti-aging agent monomer, and a conjugated diene. It should be noted that the acrylonitrile added in step 2) is only a fraction of the total amount of acrylonitrile.
In the step 2), when the polymerization conversion rate is 40-50%, adding a third raw material system comprising residual acrylonitrile, residual emulsifying agent and residual molecular weight regulator into the reaction system in the reaction kettle to carry out a third emulsion polymerization reaction. When the polymerization conversion was 85-89%, the third emulsion polymerization was terminated. Wherein the sum of the mass of part of the acrylonitrile in step 2) and the mass of the remaining acrylonitrile in the third feed system is the total mass of the acrylonitrile used in the present invention.
The polymerization conversion is generally monitored during the reaction by sampling the reaction solution and calculating the mass of monomer remaining in the current system.
The reference of the polymerization conversion rate referred to in the present invention is the total amount of the monomers charged in the present reaction system. For example, the benchmark of polymerization conversion in step 1) refers to the total mass of reactive antioxidant monomer and conjugated diene in the first feedstock system, M 1, and a polymerization conversion of 15-25% refers to M 1P/M1, where M 1P is the total mass of reactive antioxidant monomer and conjugated diene currently participating in the polymerization reaction; the basis for the polymerization conversion in step 2) is the sum of the total mass M 1 of the reactive antioxidant monomer and conjugated diene in the first feed system and the total mass M 2 of the portion of acrylonitrile and silicon-based monomer in the second feed system, and the polymerization conversion of 40-50% is M 2P/M1+M2, where M 2P is the total mass of all monomers currently participating in the polymerization (including M 1P).
As can be seen from the above steps, the polymerization reaction of the present invention includes four monomers of a reactive antioxidant, a conjugated diene, acrylonitrile and a silicon-based compound. Compared with the method that the anti-aging agent is used as an auxiliary agent to be simply and physically mixed with the polymer, the method has the advantages that the anti-aging property of the polymer can be optimized to a certain extent by introducing the reactive anti-aging agent into the main chain and the branched chain of the polymer as a monomer, and the loss of the reactive anti-aging agent in the subsequent processing process of producing the rubber product by using the polymer is avoided. Meanwhile, the polarity of the polymer can be enhanced by adding the silicon-based monomer, so that the compatibility of the poly-stabilized nitrile-butadiene silicon rubber and other high polymer materials is improved when the poly-stabilized nitrile-butadiene silicon rubber and other high polymer materials are mixed in the later period, and the brittle fracture-resistant cold-resistant rubber material which can be applied to extreme harsh environmental conditions for a long time is finally obtained; on the other hand, the intercalation of silicon atoms is conducive to the formation of organosilicon compounds, and the final poly-stable nitrile-butadiene silicon rubber has the properties of inorganic materials and organic materials due to the unique structure of organosilicon.
And the invention also carries out classified batch addition on the monomer by controlling the proper adding node. Specifically, the reactive anti-aging agent and the conjugated diene are polymerized, and a second raw material system comprising part of acrylonitrile and silicon-based monomers is added when the polymerization conversion rate is 15-25%. On one hand, the acrylonitrile and the silicon-based monomer are added after the reactive anti-aging agent, so that the proportion of the reactive anti-aging agent in the main chain of the polymer can be effectively increased by reducing or inhibiting the rejection and the competitive polymerization influence of the acrylonitrile and the silicon-based monomer on the embedding of the reactive anti-aging agent into the main chain of the conjugated diene, the anti-aging effect of the reactive anti-aging agent is exerted to a greater extent, the cold resistance of the polymer is obviously improved, and the improvement degree on other mechanical properties of the polymer is also more prominent; on the other hand, when the polymerization conversion rate reaches 15-25%, part of acrylonitrile and silicon-based monomers are added to ensure the branching degree and more effective block distribution of the polymer, so that the requirement of a more severe application environment on the high cold resistance of the polymer can be met. In addition, when the polymerization conversion rate reaches 40-50%, the distribution of polar groups on the molecular chain of the polymer can be adjusted by adding the residual acrylonitrile, so that the performance, particularly the cold resistance, of the polymer is further improved.
The invention adds the reactive anti-aging agent into the reaction system in advance than the acrylonitrile and the silicon-based monomer, specifically, adds partial acrylonitrile and the silicon-based monomer when the polymerization conversion rate of the reactive anti-aging agent and the conjugated diene reaches 15-25%, and adds the rest propylene when the polymerization conversion rate reaches 40-50%. The addition sequence and the selection of the addition nodes are beneficial to the maximum exertion of the anti-aging effect of the reactive anti-aging agent on the polymer, the promotion of the branching degree of the polymer and the effective exertion of the functions of various functional groups, and finally the poly-stable nitrile-butadiene silicon rubber with excellent cold resistance and physical and mechanical strength is obtained.
In addition, in the process of preparing the poly-stable nitrile silicone rubber, the emulsifier and the molecular weight regulator are also added in batches. Wherein the emulsifier is divided into three parts (a first part of emulsifier, a second part of emulsifier and the rest of emulsifier), and the total amount of the emulsifier is added through a first raw material system, a second raw material system and a third raw material system; the molecular weight regulator is divided into three parts (a first part of molecular weight regulator, a second part of molecular weight regulator and the residual molecular weight regulator), and the addition of the total molecular weight regulator is completed through the first raw material system, the second raw material system and the third raw material system. Specifically, the operation of adding the emulsifier in batches is favorable for improving the solubility and the emulsification of the monomer, ensures that unreacted monomer and a molecular weight regulator diffuse into the generated micelle, and ensures that the emulsion polymerization reaction is smoothly carried out; the operation of adding the molecular weight regulator in batches is mainly used for regulating the reaction speed and regulating the molecular structure of the polymer.
The specific compound used as the emulsifier or molecular weight regulator in each part may be independently selected, and any two parts may be the same or different. For example, the first portion of emulsifier, the second portion of emulsifier, and the remaining portion of emulsifier may be the same compound, or the first portion of emulsifier and the remaining portion of emulsifier may be the same compound, and the second portion of emulsifier may be another compound different from the first portion of emulsifier.
The present invention is not limited to the termination method of the reaction, and for example, the termination method of the present invention may be used in which a termination agent is added so that the polymerization conversion rate is 85 to 89%. After termination of the reaction, the reaction system may be subjected to a series of post-treatments to obtain a solid phase of the poly-stabilized nitrile-butadiene silicone rubber. In one embodiment, the post-treatment includes a coagulation treatment, a filtration treatment, and a dehydration treatment in that order. Wherein, the coagulation treatment is, for example, adding a mixed solution of sodium chloride aqueous solution and dilute sulfuric acid into a reaction system to precipitate a polymer, then filtering the precipitated polymer, and drying a solid phase obtained by filtering at 90-96 ℃ until the moisture content is below 0.5%, thereby preparing the poly-stabilized nitrile-butadiene silicon rubber.
In a specific preparation process, in order to further promote the smooth progress of the emulsion polymerization reaction, the first raw material system further comprises an electrolyte, an activator, a dispersing agent and an deoxidizer. Illustratively, adding a first part of emulsifier, an activator and a dispersing agent into a reaction kettle containing water, stirring and dissolving, adding a reactive anti-aging agent monomer, a first part of molecular weight regulator and electrolyte, performing nitrogen aeration-vacuum displacement treatment, adding an deoxidizer and conjugated diene, and stirring to obtain a first raw material system.
The present invention is not limited to the specific choice of each raw material, for example, the reactive antioxidant monomer is selected from one or more of N- (4-anilinophenyl) acrylamide (NAPA), N- (3, 5-di-tert-butyloxybenzene methyl benzoate) maleimide, N- (4-anilinophenyl) Maleimide (MC), N- (4-anilinophenyl) -2-hydroxyisobutyramide, N- (4-anilinophenyl) methacrylamide (NAPM); the conjugated diene is selected from butadiene and/or isoprene, preferably butadiene; the emulsifier is one or more selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium oleate, synthetic fatty acid potassium soap, disproportionated rosin potassium soap, and beta-sodium naphthalene sulfonate formaldehyde condensate; the molecular weight regulator is selected from tertiary dodecyl mercaptan and/or n-dodecyl mercaptan; the dispersing agent is selected from beta-sodium naphthalene sulfonate formaldehyde condensate; the silicon-based monomer is various organic silicon intermediates prepared by hydrolysis (or alcoholysis) and cleavage of organic silicon monomers, is a direct raw material of synthetic silicon rubber, silicon oil and silicon resin, and is exemplified by one or more of linear or cyclic siloxane oligomers selected from hexamethyldisiloxane (MM), hexamethylcyclotrisiloxane (D3), octamethyl cyclotetrasiloxane (D4) and dimethyl cyclosiloxane mixture (DMC); the initiator is selected from cumene oxide, dicumyl peroxide, ammonium persulfate, tert-butyl hydroperoxide, hydrogen peroxide and hydrogen peroxide pairOne or more of alkanes; the electrolyte is selected from one or more of potassium chloride, potassium phosphate and sodium pyrophosphate; the activator is one or more selected from EDTA-4NA, EDTA-FENA, and radix asparagi officinalis; the deoxidizer is selected from sodium dithionite; the terminator is selected from one or more of sodium thiram, hydroxylamine sulfate, diethyl hydroxylamine and sodium nitrite, preferably hydroxylamine sulfate and diethyl hydroxylamine.
In one embodiment, the mass of acrylonitrile in the second feed system (i.e., the mass of a portion of acrylonitrile) is no less than 60% of the total mass of acrylonitrile (the sum of the mass of a portion of acrylonitrile in the second feed system and the mass of the remaining acrylonitrile in the third feed system). Further, the mass of acrylonitrile in the second raw material system is 66-75% of the total mass of acrylonitrile.
As described above, in the preparation process, the emulsifier is added into the reaction system in three steps, wherein the first portion of the emulsifier is added into the reaction system through the first raw material system, the second portion of the emulsifier is added into the reaction system through the second raw material system, and the remaining emulsifier is added into the reaction system through the third raw material system. In a specific embodiment, the mass of the first portion of emulsifier is not less than 70% of the total mass of the emulsifier, and further, the mass of the first portion of emulsifier is 70-85% of the total mass of the emulsifier. That is, not less than 70% of the total mass of the emulsifiers is used as the first portion of the emulsifiers, and not more than 30% of the remaining emulsifiers are used as the second portion of the emulsifiers and the remaining emulsifiers, respectively. The present invention is not limited to the mass ratio of the second portion of emulsifier to the remaining emulsifier. The inventors have found that when the mass of the first portion of emulsifier is not less than 70% of the total mass of the emulsifier, it is advantageous to initially form more micelles at the reaction site and thus become the main reactive center.
The invention does not limit the adding proportion of each part of molecular weight regulator.
The reaction temperature of the emulsion polymerization reaction is 5-30 ℃, and the specific reaction temperature can be determined according to actual requirements. The higher the temperature is, the faster the activity and reaction rate of the reaction monomer are, and the occurrence probability of branched chain reactions such as grafting, blocking and the like can be increased, so that more body-type molecular structures are formed, and the purposes of changing and improving the performance of the polymer are achieved.
The present invention is not limited to the amount of each monomer added, and the specific amount added may be determined according to the target molecular weight of the poly-stabilized nitrile silicone rubber and the target ratio to each block.
In a specific embodiment, when the reaction monomer comprises 10-45% of acrylonitrile, 50-85% of conjugated diene, 0.5-2% of reactive anti-aging agent monomer and 1.0-12% of silicon-based monomer according to mass percent, the preparation of the poly-stable nitrile-butadiene silicon rubber with more excellent cold resistance is facilitated. Further, the reaction monomer comprises 20-40% of acrylonitrile, 58-71% of conjugated diene, 1.0-1.85% of reactive anti-aging agent monomer and 1.0-10% of silicon-based monomer according to mass percent.
In addition, when the mass ratio of the reaction monomer, the emulsifier, the initiator and the molecular weight regulator is 100: (2.5-5.5): (0.05-0.5): (0.2-3), the emulsion polymerization reaction can be smoothly carried out at the lowest cost.
In a second aspect, the present invention provides a poly-stable nitrile silicone rubber obtained according to the preparation method of the first aspect. Generally, the poly-stabilized nitrile-butadiene silicon rubber is in a milky white or beige flake or particle shape, the volatile content is less than or equal to 1.0%, and the total ash content is less than or equal to 1.2%.
Due to the particularity of the preparation method, the cold resistance of the poly-stabilized nitrile-butadiene silicon rubber obtained by the method is remarkable, the branching degree is high, the physical and mechanical strength such as excellent elongation at break, tensile strength and 300% stretching stress is shown, the poly-stabilized nitrile-butadiene silicon rubber can be used for a long time in a severe application environment with high deformation and low temperature, the damage rate or the maintenance rate is extremely low, and the application range of rubber products is widened.
Specifically, the glass transition temperature (Tg) of the poly-stabilized nitrile silicone rubber is-80 to-65 ℃, and the raw rubber has Mooney viscosity40-70 Percent, 18-44 percent of combined acrylonitrile, less than 3.0 percent of gel content, 50-70 percent of Shore A hardness, 45-56 KN/m of tearing strength, 280-550 percent of elongation at break, 25-38MPa of tensile strength and 11-14MPa of 300 percent of stretching stress.
The third aspect of the invention also provides a rubber product, the raw material of which is the poly-stabilized nitrile-butadiene silicon rubber of the second aspect. Illustratively, the rubber article of the present invention is obtained by subjecting raw materials including a poly-stabilized nitrile-butadiene silicone rubber to operations such as mastication, kneading, molding, vulcanization, etc.
The present invention is not limited to the specific form of the rubber product, and may be, for example, a seal, a hose, an O-ring, a rubber roller, a rubber shoe, or the like.
The invention is not limited to the application field of the rubber product, and can be any field with the application requirement of the rubber product, such as the petrochemical field, the aerospace field, the automobile field, the ship field and the like.
The raw material of the rubber product is the poly-stabilized nitrile-butadiene silicon rubber, so that the rubber product has excellent weather resistance, particularly has outstanding cold resistance, and can be suitable for application environments with high cold and high deformation.
The preparation method of the poly-stabilized nitrile-butadiene silicone rubber of the invention is described in detail below by way of specific examples.
The individual raw materials in the examples are as follows
Emulsifying agent: synthesizing fatty acid potassium soap; potassium oleate soap; disproportionated rosin potassium soap; sodium dodecyl sulfate; sodium dodecyl benzene sulfonate; emulsifier AD (composite aqueous solution of disproportionated rosin potassium soap, synthetic fatty acid potassium soap and beta-sodium naphthalene sulfonate formaldehyde condensate); emulsifier AK (composite aqueous solution of disproportionated rosin potassium soap, sodium dodecyl sulfate and beta-sodium naphthalene sulfonate formaldehyde condensate); emulsifier AH (composite aqueous solution of disproportionated rosin potassium soap, sodium dodecyl benzene sulfonate and beta-sodium naphthalene sulfonate formaldehyde condensate)
Diffusion agent: beta-sodium naphthalene sulfonate formaldehyde condensate
And (3) an activation phase: mixed aqueous solution of EDTA-4NA, EDTA-FENA and asparagus block (mass ratio of 4:3:2)
Termination agent: sodium nitrite aqueous solution
Example 1
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3500 ml of water, 1400 g of emulsifier AK and 10.5 g of active phase are added into a 10-liter reaction kettle, the mixture is dispersed and dissolved under stirring, 36.8 g of N- (4-anilinophenyl) acrylamide (NAPA) and 4.8 g of tertiary dodecyl mercaptan are added, 15.8 g of potassium chloride are added, 0.5792 g of sodium dithionite is added after nitrogen aeration-vacuum displacement, 1536.84 g of butadiene is then added, and after stirring for 30 minutes, 1.4569 g of dicumyl peroxide is added through a charging gun barrel, and the temperature is controlled to be 12+/-1 ℃ for reaction;
When the conversion rate reaches 15-20%, adding a mixture of 185 g of synthetic fatty acid potassium soap, 368.46 g of acrylonitrile, 113 g of hexamethyldisiloxane (MM) and 12.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 40-50%, 195 g of potassium oleate soap, 200 g of acrylonitrile and 8.95 g of n-dodecyl mercaptan are added for continuous reaction, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added for stopping the reaction, flash evaporation and degassing are carried out, 1200 g of sodium chloride aqueous solution and 100 g of dilute sulfuric acid solution are added for condensation, and after filtration and dehydration, the mixture is dried at 95 ℃ until the water content is below 0.5%, so that the poly-stable nitrile butadiene silicon rubber of the embodiment is obtained.
Example 2
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3500 ml of water, 1580 g of emulsifying agent AD and 12.5 g of active phase are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 37.89 g of N- (benzoic acid-3, 5-di-tert-butyl hydroxy methyl ester) maleimide, 5.8 g of tert-dodecyl mercaptan, 12 g of potassium phosphate, and 0.1992 g of sodium hydrosulfite after nitrogen inflation-vacuum replacement are added, 1473.68 g of isoprene is then added, and after stirring for 30 minutes, 3.8526 g of dicumyl peroxide is added through a charging gun barrel, and the temperature is controlled to be 12+/-1 ℃ for reaction;
when the conversion rate reaches 15-20%, adding a mixture of 155 g of potassium oleate soap, 431.57 g of acrylonitrile, 151.8 g of hexamethylcyclotrisiloxane (D3) and 12.8 g of tertiary dodecyl mercaptan, and then continuing the reaction;
2) 45 g of potassium oleate soap, 200.46 g of acrylonitrile and 3.95 g of n-dodecyl mercaptan are added when the conversion rate reaches 40-50%, the reaction is continued, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added to stop the reaction, flash evaporation and degassing are carried out, 1250 g of sodium chloride aqueous solution and 80 g of dilute sulfuric acid solution are added to be condensed, and after filtration and dehydration, the mixture is dried at 95 ℃ until the moisture content is below 0.5%, so that the poly-stable nitrile butadiene silicon rubber of the embodiment is obtained.
Example 3
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3500 ml of water, 1650 g of emulsifying agent AH and 10.8 g of active phase are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 36.70 g of N- (4-phenylaminophenyl) Maleimide (MC), 8.5 g of tertiary dodecyl mercaptan, 4.8g of sodium pyrophosphate, 0.5792 g of sodium dithionite are added after nitrogen aeration-vacuum displacement, 1684.21 g of butadiene is then added, 4.4429 g of dicumyl peroxide is added through a charging gun barrel after stirring for 30 minutes, and the temperature is controlled to be 12+/-1 ℃ for reaction;
when the conversion rate reaches 17-22%, adding a mixture of 95 g of synthetic fatty acid potassium soap, 294.9 g of acrylonitrile, 210 g of octamethyl cyclotetrasiloxane (D4) and 10.5 g of tertiary dodecyl mercaptan to continue the reaction;
2) When the conversion rate reaches 40-50%, adding 100 g of emulsifying agent AD, 126.3 g of acrylonitrile and 6.95 g of tertiary dodecyl mercaptan, continuing to react, maintaining the reaction temperature until the reaction conversion rate reaches 85-89%, adding a terminator to stop the reaction, flash evaporating, degassing, adding 1200 g of sodium chloride aqueous solution and 150 g of dilute sulfuric acid solution, condensing, filtering, dehydrating, and drying at 95 ℃ until the moisture content is below 0.5%, thereby obtaining the poly-stable nitrile butadiene silicon rubber of the embodiment.
Example 4
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3200 ml of water and 1650 g of synthetic fatty acid potassium soap solution and 9.8 g of activated phase are added into a 10-liter reaction kettle, 66.9 g of beta-naphthalene sodium sulfonate formaldehyde condensate solution are dispersed and dissolved under stirring, 31.8 g of N- (4-anilinophenyl) -2-hydroxyisobutyramide, 5.7 g of tertiary dodecyl mercaptan, 12 g of potassium chloride and 0.5792 g of sodium hydrosulfite are added after nitrogen aeration-vacuum displacement, 1368.45 g of butadiene are added, 5.92 g of dicumyl peroxide is added through a charging gun barrel after stirring for 30 minutes, and the temperature is controlled to 18+/-1 ℃ for reaction;
adding an emulsifier AD 95 g, acrylonitrile 515.84 g, a dimethyl cyclosiloxane mixture (DMC) 165.16 g and a mixture of tertiary dodecyl mercaptan 12 g when the conversion rate reaches 20-25%, and continuing the reaction;
2) When the conversion rate reaches 40-50%, 120 g of potassium oleate soap, 221 g of acrylonitrile and 8.95 g of n-dodecyl mercaptan are added for continuous reaction, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added for stopping the reaction, flash evaporation and degassing are carried out, 1000 g of sodium chloride aqueous solution and 200 g of dilute sulfuric acid solution are added for condensation, filtration and dehydration are carried out, and then the mixture is dried at 95 ℃ until the moisture content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the embodiment.
Example 5
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3500 ml of water, 1200 g of emulsifier potassium oleate solution, 238 g of potassium stearate solution and 22.5 g of active phase are added into a 10-liter reaction kettle, 90.6 g of beta-sodium naphthalene sulfonate formaldehyde condensate solution is dispersed and dissolved under stirring, 37.5 g of N- (4-anilinophenyl) methacrylamide (NAPM), 5.8 g of tertiary dodecyl mercaptan, 16 g of potassium chloride are added, after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, then 1263.2 g of butadiene is added, after stirring for 30 minutes, 7.4569 g of dicumyl peroxide is added through a charging gun barrel, and the temperature is controlled to 8+/-1 ℃ for reaction;
when the conversion rate reaches 15-20%, adding a mixture of 85 g of synthetic fatty acid potassium soap, 589.1 g of acrylonitrile, 50.9 g of hexamethyldisiloxane (MM), 22 g of hexamethylcyclotrisiloxane (D3) and 10.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 40-50%, 98 g of potassium oleate soap, 252.6 g of acrylonitrile and 4.95 g of n-dodecyl mercaptan are added for continuous reaction, a terminator is added for stopping the reaction after the reaction temperature is kept until the reaction conversion rate reaches 85-89%, flash evaporation and degassing are carried out, 1200 g of sodium chloride aqueous solution and 100g of dilute sulfuric acid solution are added for condensation, and after filtration and dehydration, the mixture is dried at 95 ℃ until the moisture content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the embodiment.
Example 6
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3500 ml of water, 1550 g of emulsifying agent AH and 10.5 g of active phase are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 11.5 g of N- (4-anilinophenyl) acrylamide (NAPA), 25.3 g of N- (4-anilinophenyl) methacrylamide (NAPM), 4.8 g of tertiary dodecyl mercaptan, 15 g of potassium chloride, and after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1536.84 g of butadiene is then added, and after stirring for 30 minutes, hydrogen peroxide is added into the kettle through a charging gun barrel 1.8558 G of alkane is reacted at the temperature of 12+/-1 ℃;
When the conversion rate reaches 18-25%, adding a mixture of 85 g of synthetic fatty acid potassium soap, 397.93 g of acrylonitrile, 52 g of hexamethylcyclotrisiloxane (D3), 53.8 g of octamethyl cyclotetrasiloxane (D4) and 12.8 g of tertiary dodecyl mercaptan to continue the reaction;
2) When the conversion rate reaches 40-50%, adding 100 g of potassium oleate soap, 171 g of acrylonitrile and 8.95 g of n-dodecyl mercaptan, continuing to react, maintaining the reaction temperature until the reaction conversion rate reaches 85-89%, adding a terminator to stop the reaction, flash evaporating for degassing, adding 1200 g of sodium chloride aqueous solution and 100 g of dilute sulfuric acid solution, condensing, filtering, dehydrating, and drying at 95 ℃ until the water content is below 0.5%, thereby obtaining the poly-stable nitrile butadiene silicon rubber of the embodiment.
Example 7
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3500 ml of water, 1580 g of emulsifying agent AD and 12.8 g of activating phase are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 21.89 g of N- (benzoic acid-3, 5-di-tert-butyl hydroxy methyl ester) maleimide, 15.9 g of N- (4-anilinophenyl) acrylamide (NAPA), 5.8 g of tert-dodecyl mercaptan, 10 g of potassium phosphate, 0.1992 g of sodium dithionite is added after nitrogen gas inflation-vacuum replacement, 1473.68 g of isoprene is added, and after stirring for 30 minutes, 4.1526 g of tert-butyl hydroperoxide is added through a charging gun barrel, and the temperature is controlled to be 12+/-1 ℃ for reaction;
When the conversion rate reaches 15-20%, adding a mixture of 155 g of potassium oleate soap, 442.1 g of acrylonitrile, 91 g of hexamethyldisiloxane (MM), 66.2 g of octamethyl cyclotetrasiloxane (D4) and 12.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) 45 g of potassium oleate soap, 189.5 g of acrylonitrile and 3.95 g of n-dodecyl mercaptan are added when the conversion rate reaches 40-50%, the reaction is continued, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added to stop the reaction, flash evaporation and degassing are carried out, 1250 g of sodium chloride aqueous solution and 80 g of dilute sulfuric acid solution are added to form a mixed solution, the mixed solution is coagulated, filtered and dehydrated, and then the mixed solution is dried at 95 ℃ until the moisture content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the embodiment.
Example 8
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3500 ml of water, 1657 g of emulsifying agent AD and 10.8 g of active phase are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 35.98 g of N- (4-phenylaminophenyl) Maleimide (MC), 5.5 g of tertiary dodecyl mercaptan, 3.2 g of ferrous sulfate, 2.8 g of sodium pyrophosphate, and 0.5792 g of sodium dithionite are added after nitrogen aeration-vacuum displacement, 1684.21 g of butadiene is then added, 3.1429 g of dicumyl peroxide and 1.2896 g of hydrogen peroxide are added through a charging gun barrel after stirring for 30 minutes, and the temperature is controlled to be 12+/-1 ℃ for reaction;
when the conversion rate reaches 16-22%, adding a mixture of 85 g of synthetic fatty acid potassium soap, 294.8 g of acrylonitrile, 100 g of hexamethyldisiloxane (MM), 105 g of hexamethylcyclotrisiloxane (D3) and 10.5 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 40-50%, 102 g of emulsifier AK, 126.3 g of acrylonitrile and 9.95 g of tertiary dodecyl mercaptan are added, the reaction is continued, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added to stop the reaction, flash evaporation and degassing are carried out, 1200 g of sodium chloride aqueous solution and 150 g of dilute sulfuric acid solution are added to be condensed, and after filtration and dehydration, the mixture is dried at 95 ℃ until the moisture content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the embodiment.
Example 9
The preparation method of the poly-stable nitrile-butadiene silicon rubber comprises the following steps:
1) 3500 ml of water, 1260 g of emulsifier potassium oleate solution, 238 g of potassium stearate solution and 22.6 g of active phase are added into a 10-liter reaction kettle, 75.6 g of beta-sodium naphthalene sulfonate formaldehyde condensate solution is dispersed and dissolved under stirring, 39.5 g of N- (4-anilinophenyl) methacrylamide (NAPM), 5.8 g of tertiary dodecyl mercaptan, 12 g of potassium chloride solution are added, after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1263.2 g of butadiene is added, after stirring for 30 minutes, 12.95 g of ammonium persulfate is added through a charging gun barrel, and the temperature is controlled to 20+/-1 ℃ for reaction;
When the conversion rate reaches 16-19%, adding 85 g of synthetic fatty acid potassium soap, 589.5 g of acrylonitrile, 31.8 g of hexamethylcyclotrisiloxane (D3), 41.5 g of dimethyl cyclosiloxane mixture (DMC) and 10.8 g of tertiary dodecyl mercaptan to continue the reaction;
2) When the conversion rate reaches 40-50%, 95 g of potassium oleate soap, 252.6 g of acrylonitrile and 4.95 g of n-dodecyl mercaptan are added for continuous reaction, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added for stopping the reaction, flash evaporation and degassing are carried out, 1200 g of sodium chloride aqueous solution and 100g of dilute sulfuric acid solution are added for condensation, and after filtration and dehydration, the mixture is dried at 95 ℃ until the moisture content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the embodiment.
Comparative example 1
Substantially the same as in example 1 was conducted except that acrylonitrile in the second raw material system was added with the first raw material system. The preparation method comprises the following steps:
1) 3500 ml of water, 1400 g of emulsifier AK and 10.5 g of active phase are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 36.8 g of N- (4-anilinophenyl) acrylamide (NAPA), 4.8 g of tertiary dodecyl mercaptan, 368.46 g of acrylonitrile, 15.8 g of potassium chloride and after nitrogen inflation-vacuum replacement, 0.5792 g of sodium hydrosulfite are added, 1536.84 g of butadiene is then added, stirring is carried out for 30 minutes, 1.4569 g of dicumyl peroxide is added through a charging barrel, and the temperature is controlled to be 12+/-1 ℃ for reaction;
When the conversion rate reaches 15-20%, adding 185 g of synthetic fatty acid potassium soap, 113 g of hexamethyldisiloxane (MM) and 12.8 g of tertiary dodecyl mercaptan into the mixture, and then continuing the reaction;
2) When the conversion rate reaches 40-50%, 195 g of potassium oleate soap, 200 g of acrylonitrile and 8.95 g of n-dodecyl mercaptan are added for continuous reaction, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added for stopping the reaction, flash evaporation and degassing are carried out, 1200 g of sodium chloride aqueous solution and 100 g of dilute sulfuric acid solution are added for condensation, filtration and dehydration are carried out, and then the mixture is dried at 95 ℃ until the moisture content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the comparative example.
Comparative example 2
Substantially the same procedure as in example 2 was followed except that all of the monomer was added with the first feed system. The preparation method comprises the following steps:
1) 3500 ml of water, 1580 g of emulsifying agent AD and 12.5 g of activating phase are added into a 10-liter reaction kettle, the mixture is dispersed and dissolved under stirring, 37.89 g of N- (benzoic acid-3, 5-di-tert-butyl hydroxy-phenyl methyl ester) maleimide, 632.03 g of acrylonitrile, 151.8 g of hexamethyl-cyclotrisiloxane (D3), 5.8 g of tert-dodecyl mercaptan, 12 g of potassium phosphate, 0.1992 g of sodium dithionite are added after nitrogen gas charging-vacuum replacement, 1473.68 g of isoprene is added, 3.8526 g of dicumyl peroxide is added through a charging gun barrel after stirring for 30 minutes, and the temperature is controlled to be 12+/-1 ℃ for reaction;
when the conversion rate reaches 15-20%, adding 155 g of potassium oleate soap and 12.8 g of tertiary dodecyl mercaptan mixture, and then continuing to react;
2) 45 g of potassium oleate soap and 3.95 g of n-dodecyl mercaptan are added when the conversion rate reaches 40-50%, the reaction is continued, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added to stop the reaction, flash evaporation and degassing are carried out, 1250 g of sodium chloride aqueous solution and 80g of dilute sulfuric acid solution are added to be condensed, filtration and dehydration are carried out, and then the mixture is dried at 95 ℃ until the water content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the comparative example.
Comparative example 3
Substantially the same as in example 3 was conducted except that octamethyl cyclotetrasiloxane was added at a conversion of 40 to 50%. The preparation method comprises the following steps:
1) 3500 ml of water, 1650 g of emulsifying agent AH and 10.8 g of active phase are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 36.70 g of N- (4-phenylaminophenyl) Maleimide (MC), 8.5 g of tertiary dodecyl mercaptan, 4.8g of sodium pyrophosphate, 0.5792 g of sodium dithionite are added after nitrogen aeration-vacuum displacement, 1684.21 g of butadiene is then added, 4.4429 g of dicumyl peroxide is added through a charging gun barrel after stirring for 30 minutes, and the temperature is controlled to be 12+/-1 ℃ for reaction;
When the conversion rate reaches 17-22%, adding a mixture of 95 g of synthesized fatty acid potassium soap and 10.5 g of acrylonitrile 294.9 g of tertiary dodecyl mercaptan to continue the reaction;
2) When the conversion rate reaches 40-50%, adding 100 g of emulsifying agent AD, 126.3 g of acrylonitrile, 210 g of octamethyl cyclotetrasiloxane (D4) and 6.95 g of tertiary dodecyl mercaptan, continuing to react, maintaining the reaction temperature until the reaction conversion rate reaches 85-89%, adding a terminator to stop the reaction, flash evaporating and degassing, adding 1200 g of sodium chloride aqueous solution and 150 g of dilute sulfuric acid solution to form a mixed solution, condensing, filtering and dehydrating, and drying at 95 ℃ until the water content is below 0.5%, thus obtaining the poly-stable nitrile-butadiene silicon rubber of the comparative example.
Comparative example 4
Substantially the same as in example 4 was conducted, except that the whole acrylonitrile was added together in the third raw material system when the conversion rate reached 40 to 50%. The preparation method comprises the following steps:
1) 3200 ml of water and 1650 g of synthetic fatty acid potassium soap solution and 9.8 g of activated phase are added into a 10-liter reaction kettle, 66.9 g of beta-naphthalene sodium sulfonate formaldehyde condensate solution are dispersed and dissolved under stirring, 31.8 g of N- (4-anilinophenyl) -2-hydroxyisobutyramide, 5.7 g of tertiary dodecyl mercaptan, 12 g of potassium chloride and 0.5792 g of sodium hydrosulfite are added after nitrogen aeration-vacuum displacement, 1368.45 g of butadiene are added, 5.92 g of dicumyl peroxide is added through a charging gun barrel after stirring for 30 minutes, and the temperature is controlled to 18+/-1 ℃ for reaction;
Adding an emulsifier AD 95 g, a dimethyl cyclosiloxane mixture (DMC) 165.16 g and a mixture of tertiary dodecyl mercaptan 12 g when the conversion rate reaches 20-25%, and continuing the reaction;
2) When the conversion rate reaches 40-50%, 120 g of potassium oleate soap, 736.84 g of acrylonitrile and 8.95 g of n-dodecyl mercaptan are added for continuous reaction, the reaction temperature is kept until the reaction conversion rate reaches 85-89%, a terminator is added for stopping the reaction, flash evaporation and degassing are carried out, 1000 g of sodium chloride aqueous solution and 200 g of dilute sulfuric acid solution are added for coagulation, and after filtration and dehydration, the mixture is dried at 95 ℃ until the water content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the comparative example.
Comparative example 5
Substantially the same as in example 5 was conducted, except that the second raw material system (synthetic fatty acid potassium soap, part of acrylonitrile, butyl acrylate, t-dodecyl mercaptan) was added when the conversion rate reached 30 to 35%. The preparation method comprises the following steps:
1) 3500 ml of water, 1200 g of emulsifier potassium oleate solution, 238 g of potassium stearate solution and 22.5 g of active phase are added into a 10-liter reaction kettle, 90.6 g of beta-sodium naphthalene sulfonate formaldehyde condensate solution is dispersed and dissolved under stirring, 37.5 g of N- (4-anilinophenyl) methacrylamide (NAPM), 5.8 g of tertiary dodecyl mercaptan, 16 g of potassium chloride are added, after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, then 1263.2 g of butadiene is added, after stirring for 30 minutes, 7.4569 g of dicumyl peroxide is added through a charging gun barrel, and the temperature is controlled to 8+/-1 ℃ for reaction;
When the conversion rate reaches 30-35%, adding a mixture of 85 g of synthetic fatty acid potassium soap, 589.1 g of acrylonitrile, 50.9 g of hexamethyldisiloxane (MM), 22 g of hexamethylcyclotrisiloxane (D3) and 10.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 40-50%, 98 g of potassium oleate soap, 252.6 g of acrylonitrile and 4.95 g of n-dodecyl mercaptan are added for continuous reaction, the reaction temperature is controlled until the reaction conversion rate reaches 85-89%, a terminator is added for stopping the reaction, flash evaporation and degassing are carried out, 1200 g of sodium chloride aqueous solution and 100g of dilute sulfuric acid solution are added for condensation, and after filtration and dehydration, the mixture is dried at 95 ℃ until the moisture content is below 0.5%, thus obtaining the poly-stable nitrile butadiene silicon rubber of the comparative example.
Comparative example 6
Substantially the same as in example 6 was conducted except that the remaining emulsifier and the remaining molecular weight modifier were added together with the second raw material system. The preparation method comprises the following steps:
1) 3500 ml of water, 1550 g of emulsifying agent AH and 10.5 g of active phase are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 11.5 g of N- (4-anilinophenyl) acrylamide (NAPA), 25.3 g of N- (4-anilinophenyl) methacrylamide (NAPM), 4.8 g of tertiary dodecyl mercaptan, 15 g of potassium chloride, and after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1536.84 g of butadiene is then added, and after stirring for 30 minutes, hydrogen peroxide is added into the kettle through a charging gun barrel 1.8558 G of alkane is reacted at the temperature of 12+/-1 ℃;
When the conversion rate reaches 18-25%, adding a mixture of 85 g of synthetic fatty acid potassium soap, 100g of potassium oleate soap, 397.93 g of acrylonitrile, 52 g of hexamethylcyclotrisiloxane (D3), 53.8 g of octamethyl cyclotetrasiloxane (D4), 8.95 g of n-dodecyl mercaptan and 12.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) Adding 171 g of acrylonitrile when the conversion rate reaches 40-50%, continuing the reaction, maintaining the reaction temperature until the reaction conversion rate reaches 85-89%, adding a terminator to terminate the reaction, flash evaporating for degassing, adding a mixed solution of 1200 g of sodium chloride aqueous solution and 100 g of dilute sulfuric acid solution for condensation, filtering for dehydration, and drying at 95 ℃ until the moisture content is below 0.5%. The poly-stabilized nitrile silicone rubber of this comparative example was obtained.
Test examples
The measurements of the relevant parameters were carried out on the poly-stabilized nitrile silicone rubber of all examples according to the following method, the results of which are shown in Table 1.
1. Mooney viscosity: GB/T1232.1-2000 determination of unvulcanized rubber part 1 Using a disk shear viscometer
2. Glass transition temperature (Tg): reference is made to GB/T29611-2013 Differential Scanning Calorimetry (DSC) of determination of the glass transition temperature (Tg) of raw rubber;
3. Combining acrylonitrile: method for measuring content of bound acrylonitrile in SH/T1157.2-2015 acrylonitrile-butadiene rubber (NBR)
4. Gel content: determination of SH/T1050-2014 synthetic raw rubber gel content
5. 100% Stress at definite elongation: measurement of tensile stress Strain Properties of GB/T528-2009 vulcanized rubber or thermoplastic rubber
6. Elongation at break and tensile strength: determination of high temperature tensile Strength and elongation at Break of GBT 6037-1985 vulcanized rubber
TABLE 1
In Table 1, ". Gtoreq.s." means a range of "not lower than the present value and less than the present value +9 units".
As can be seen from table 1:
1. Compared with the comparative example, the glass transition temperature is lower, so that the poly-stabilized nitrile-butadiene silicon rubber prepared by the preparation method has more excellent service performance in low-temperature areas;
2. The poly-stabilized nitrile silicone rubber in the examples clearly has more excellent performance in terms of physical and mechanical strength than the comparative examples.
3. Comparative example 1 and comparative example 1 show that, since the acrylonitrile addition in comparative example 1 is advanced, the effect of the insertion of the reactive antioxidant in the polybutadiene main chain is affected, the reactive antioxidant grafted on the polymer main chain is small, the degradation of the polymer during processing affects the related properties, and the polymerization coordination effect of the siloxane with the acrylonitrile during the reaction is also affected;
As is clear from comparative examples 2 and 2, since the reactive monomers in comparative example 2 were not added in batches, the control sequence of the polymerization reaction was changed, the polymerization reaction was in disordered free polymerization, the reactive anti-aging agent, acrylonitrile and silicon-based monomer gave a racing effect on isoprene, the distribution of the reactive anti-aging agent on the polymer main chain was affected, and the polymer was obtained by disordered copolymerization of various monomers, and the performance was significantly deteriorated;
As can be seen from comparative examples 3 and 3, the silicon-based monomer in comparative example 3 is added into the reaction system too late, the emulsion particles of the poly-stabilized nitrile rubber with larger particle size are formed by the early reaction, the silicon-based monomer loses the best opportunity of embedding the molecular main chain of the polymer, the reaction is mainly that the silicon-based monomer is grafted on the molecular surface of the poly-stabilized nitrile rubber formed in the early stage, and the functional group distribution on the molecular chain is obviously inferior to that of example 3;
As can be seen from comparative examples 4 and 4, the molecular main chain formed in the early stage is silicon-based poly-stable butadiene rubber particles and has larger particle size, and the acrylonitrile is added when the conversion rate reaches 40-50%, and the effect of grafting acrylonitrile with large particle size is not as good as that of grafting and embedding with small particle size when the acrylonitrile is added when the conversion rate reaches 20-25%, so that the change of the adding time and the reaction sequence affects the performance characterization of the final product;
As is clear from comparative examples 5 and 5, since the particle size of the main chain molecules of butadiene and NAPM embedded in the former stage of comparative example 5 is too large, the uniformity of grafting and blocking reactions of acrylonitrile, hexamethyldisiloxane (MM) and hexamethylcyclotrisiloxane (D3) on the main chain is affected, the branching degree of the formed multipolymer molecules is relatively smaller than that of the multipolymer formed by adding acrylonitrile and the like when the conversion rate reaches 15-20%, the bonding effect of the acrylonitrile and the silicon-based monomer is poor, and the performance of the final comparative example is inferior to that of the example;
As is clear from comparative examples 6 and 6, in comparative example 6, potassium oleate soap and n-dodecyl mercaptan are not added at a conversion rate of 40 to 45%, so that no solubilized micelle is formed in the latter stage of the reaction, and the re-diffusion of unreacted monomers and molecular weight regulators into the formed micelle is affected, and the molecular weight of the resultant is small and branched, so that the performance of examples cannot be achieved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the poly-stable nitrile-butadiene silicon rubber is characterized by comprising the following steps of:
1) Adding an initiator into the first raw material system to perform a first emulsion polymerization reaction, and adding a second raw material system to perform a second emulsion polymerization reaction when the polymerization conversion rate is 15-25%;
2) When the polymerization conversion rate is 40-50%, adding a third raw material system to perform a third emulsion polymerization reaction;
3) Terminating the reaction when the polymerization conversion rate is 85-89%, so as to obtain the poly-stable nitrile-butadiene silicon rubber;
wherein the first raw material system at least comprises a reactive antioxidant monomer, conjugated diene, a first part of emulsifier and a first part of molecular weight regulator;
the second raw material system at least comprises part of acrylonitrile, silicon-based monomers, a second part of emulsifying agent and a second part of molecular weight regulator;
The third feed system comprises at least a residual acrylonitrile, a residual emulsifier and a residual molecular weight regulator.
2. The method according to claim 1, wherein the mass of the part of acrylonitrile is not less than 60% of the total mass of acrylonitrile.
3. The method of claim 1 or 2, wherein the mass of the first portion of emulsifier is not less than 70% of the total mass of the emulsifier.
4. A process according to any one of claims 1 to 3, wherein the reaction temperature is from 5 to 30 ℃.
5. The preparation method according to any one of claims 1 to 4, wherein the reactive monomer comprises, by mass, 10 to 45% of acrylonitrile, 50 to 85% of conjugated diene, 0.5 to 2% of reactive anti-aging agent monomer, and 1.0 to 12% of silicon-based monomer.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the reactive monomer, the emulsifier, the initiator and the molecular weight regulator is 100: (2.5-5.5): (0.05-0.5): (0.2-3).
7. The preparation method according to claim 1, wherein the reaction system is subjected to coagulation treatment, filtration treatment and dehydration treatment in this order after termination of the reaction to obtain the poly-stable nitrile-butadiene silicone rubber.
8. The method of claim 1, wherein the first feedstock system further comprises an electrolyte, an activator, a diffusion agent, and an oxygen scavenger.
9. A poly-stable nitrile silicone rubber, characterized in that it is obtained according to the preparation method of any one of claims 1-8.
10. A rubber article, wherein the raw material of the rubber article comprises the poly-stabilized nitrile-butadiene silicone rubber according to claim 9.
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