CN117986499A - Carboxyl poly-stable styrene-butadiene rubber and preparation method and application thereof - Google Patents
Carboxyl poly-stable styrene-butadiene rubber and preparation method and application thereof Download PDFInfo
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- CN117986499A CN117986499A CN202211372672.6A CN202211372672A CN117986499A CN 117986499 A CN117986499 A CN 117986499A CN 202211372672 A CN202211372672 A CN 202211372672A CN 117986499 A CN117986499 A CN 117986499A
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- Prior art keywords
- styrene
- reaction
- butadiene rubber
- added
- emulsifier
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 76
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 205
- 238000006243 chemical reaction Methods 0.000 claims abstract description 196
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 81
- 239000000178 monomer Substances 0.000 claims abstract description 75
- 239000002994 raw material Substances 0.000 claims abstract description 49
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 42
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 30
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 29
- 150000001993 dienes Chemical class 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 230000003712 anti-aging effect Effects 0.000 claims description 27
- 229920001971 elastomer Polymers 0.000 claims description 26
- 239000005060 rubber Substances 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 17
- 239000012190 activator Substances 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 208000005156 Dehydration Diseases 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000000344 soap Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 34
- 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 238000003756 stirring Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000203 mixture Substances 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 22
- 229910052700 potassium Inorganic materials 0.000 description 22
- 239000011591 potassium Substances 0.000 description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 20
- 229940096992 potassium oleate Drugs 0.000 description 20
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 17
- 235000014113 dietary fatty acids Nutrition 0.000 description 17
- 239000000194 fatty acid Substances 0.000 description 17
- 229930195729 fatty acid Natural products 0.000 description 17
- 150000004665 fatty acids Chemical class 0.000 description 17
- 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
- 238000007872 degassing Methods 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 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
- 238000006073 displacement reaction Methods 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 239000001103 potassium chloride Substances 0.000 description 10
- 235000011164 potassium chloride Nutrition 0.000 description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000000693 micelle Substances 0.000 description 6
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 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 5
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 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
- 239000001530 fumaric acid Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229940048086 sodium pyrophosphate Drugs 0.000 description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- IWQLXFICQJMUGN-UHFFFAOYSA-N C=O.[Na].C1=C(C=CC2=CC=CC=C12)S(=O)(=O)O Chemical compound C=O.[Na].C1=C(C=CC2=CC=CC=C12)S(=O)(=O)O IWQLXFICQJMUGN-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
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 4
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 4
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 229940091181 aconitic acid Drugs 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-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
- 239000012467 final product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 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
- 150000003254 radicals Chemical class 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 3
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 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
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 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
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 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
- 238000012360 testing method Methods 0.000 description 2
- 229960002703 undecylenic acid Drugs 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- -1 3, 5-di-tert-butyloxybenzene methyl benzoate Chemical compound 0.000 description 1
- 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
- 241001391944 Commicarpus scandens 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
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000005843 Thiram Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 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
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 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
- 230000007774 longterm Effects 0.000 description 1
- 239000005267 main chain polymer Substances 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
- 239000000463 material Substances 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
- 230000036961 partial effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005070 sampling Methods 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
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a carboxyl poly-stable styrene-butadiene rubber and a preparation method and application thereof, wherein 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 10-20%; 2) When the polymerization conversion rate is 45-50%, adding a third raw material system to perform a third emulsion polymerization reaction; 3) Terminating the reaction when the polymerization conversion rate is 75-80%, so as to obtain carboxyl poly-stable styrene-butadiene rubber; wherein the first feed system comprises at least a reactive antioxidant monomer, a conjugated diene, a first portion of styrene, a first portion of emulsifier, and a first portion of molecular weight regulator; the second raw material system comprises residual styrene, carboxylic acid monomers, a second part of emulsifying agent and a second part of molecular weight regulator; the third feed system comprises the remaining emulsifier and the remaining molecular weight regulator. The carboxyl poly-stable styrene-butadiene rubber prepared by the preparation method has good wear resistance and high hardness.
Description
Technical Field
The invention relates to a thermoplastic elastomer, in particular to carboxyl poly-stable styrene-butadiene rubber and a preparation method and application thereof, and belongs to the field of rubber materials.
Background
Styrene-butadiene rubber has been widely used in the fields of tire manufacturing and the like because of its excellent heat aging resistance, low compression set, good processability, and the like. However, there are often sharp objects on the ground, and suitable tires need not only be wear resistant, but also have a high hardness and are not easily pierced. Therefore, the high requirements on the wear resistance and hardness of the styrene-butadiene rubber are put forward.
Styrene-butadiene rubber is an emulsion copolymer obtained by radical initiation of conjugated diene and styrene, and thus a large amount of double bond structure exists therein. Because the double bond structure is easy to break to form free radical, degradation reaction occurs, so that the molecular chain is short, the body type molecular structure is unevenly distributed, and the wear resistance and hardness of the styrene-butadiene rubber are reduced.
At present, the wear resistance and hardness of styrene-butadiene rubber are improved by changing the molecular structure of the styrene-butadiene rubber. For example, carboxyl monomers, silicone-based monomers are incorporated therein, but the degree of improvement in wear resistance and hardness is far from being satisfactory. Therefore, how to obtain a rubber having good abrasion resistance and high hardness is a subject of long-term study in the art.
Disclosure of Invention
The invention provides a preparation method of carboxyl poly-stable styrene-butadiene rubber, which is used for controlling a charging sequence and a charging node to finally obtain Ding Bengui rubber with good wear resistance and high hardness.
The invention provides a carboxyl-group-containing poly-stable styrene-butadiene rubber which is excellent in wear resistance and hardness.
The invention also provides a rubber product, and the raw materials of the rubber product comprise carboxyl poly-stable styrene-butadiene rubber, so that the rubber product has excellent service performance and long service period.
The invention provides a preparation method of carboxyl poly-stable styrene-butadiene 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 10-20%;
2) When the polymerization conversion rate is 45-50%, adding a third raw material system to perform a third emulsion polymerization reaction;
3) Terminating the reaction when the polymerization conversion rate is 75-80%, so as to obtain the carboxyl poly-stable styrene-butadiene rubber;
Wherein the first raw material system at least comprises a reactive antioxidant monomer, conjugated diene, a first part of styrene, a first part of emulsifier and a first part of molecular weight regulator;
The second raw material system at least comprises residual styrene, carboxylic acid monomers, a second part of emulsifying agent and a second part of molecular weight regulator;
the third feed system comprises at least a residual emulsifier and a residual molecular weight regulator.
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; and/or the number of the groups of groups,
The mass of the first portion of styrene is not less than 60% of the total mass of styrene.
The preparation method is characterized in that the reaction temperature is 5-30 ℃.
The preparation method comprises the steps of 10-49% of styrene, 50-85% of conjugated diene, 0.5-2% of reactive anti-aging agent monomer and 0.1-20% of carboxylic acid monomer according to mass percentage.
The preparation method comprises the steps of 14-46% of styrene, 50-82% of conjugated diene, 1.0-1.85% of reactive anti-aging agent monomer and 3.0-20% of carboxylic acid 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, and obtaining the carboxyl poly-stable styrene-butadiene 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 the carboxyl poly-stable styrene-butadiene 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 carboxyl poly-stable styrene-butadiene rubber.
According to the preparation method of the carboxyl poly-stable styrene-butadiene rubber, the reactive anti-aging agent monomer is used as a monomer to participate in polymerization of the carboxyl poly-stable styrene-butadiene rubber, the anti-aging effect of the reactive anti-aging agent monomer is exerted to the greatest extent by adjusting the feeding sequence and the feeding nodes of other monomers, meanwhile, the effect that carboxyl groups are uniformly distributed on the surface of a molecular chain is exerted to the greatest extent, the formed structure is high in uniformity, and finally, the obtained carboxyl poly-stable styrene-butadiene rubber is good in wear resistance and high in hardness.
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 invention provides a preparation method of carboxyl poly-stable styrene-butadiene 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 10-20%;
2) When the polymerization conversion rate is 45-50%, adding a third raw material system to perform a third emulsion polymerization reaction;
3) Terminating the reaction when the polymerization conversion rate is 75-80%, so as to obtain the carboxyl poly-stable styrene-butadiene rubber;
Wherein the first raw material system at least comprises a reactive antioxidant monomer, conjugated diene, a first part of styrene, a first part of emulsifier and a first part of molecular weight regulator;
The second raw material system at least comprises residual styrene, carboxylic acid monomers, a second part of emulsifying agent and a second part of molecular weight regulator;
the third feed system comprises at least a residual emulsifier and a residual molecular weight regulator.
The carboxyl polymerization stable styrene-butadiene rubber is prepared by emulsion polymerization reaction, and can be batch polymerization or continuous polymerization. The process for preparing the carboxyl poly-stable styrene-butadiene 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 styrene, a first part of emulsifier and a first part of molecular weight regulator. In the specific preparation process, for example, at least a reactive anti-aging agent monomer, a first part of styrene, 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 reaction kettle is stirred to obtain a first raw material system.
In the present invention, the first emulsion polymerization is essentially polymerization of the reactive antioxidant monomer, the first part of styrene and the conjugated diene, and when the polymerization conversion reaches 10 to 20% along with the progress of the first emulsion polymerization, the reaction system comprises not only the reactive antioxidant monomer, the styrene and the conjugated diene which are not completely reacted, but also the generated reactive antioxidant monomer-conjugated diene-styrene main chain polymer. At this time, a second raw material system is added to the reaction system to carry out a second emulsion polymerization. It can be appreciated that the essence of the second emulsion polymerization is the polymerization between the remaining styrene, carboxylic acid monomer, backbone polymer, reactive antioxidant monomer, and conjugated diene.
In the step 2), when the polymerization conversion rate is 45-50%, adding a third raw material system comprising the residual emulsifying agent and the residual molecular weight regulator into the reaction system in the reaction kettle to carry out a third emulsion polymerization reaction. Since the reaction monomers have already been added in step 1) and step 2), the third emulsion polymerization is essentially a continuation of the second emulsion polymerization. When the polymerization conversion is 75 to 80%, the third emulsion polymerization is terminated.
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 reference to the polymerization conversion in step 1) refers to the total mass of reactive antioxidant monomer, conjugated diene, first portion of styrene M 1 in the first feed system, and the polymerization conversion of 10-20% refers to M 1P/M1, where M 1P is the total mass of reactive antioxidant monomer, conjugated diene, first portion of styrene currently participating in the polymerization reaction; the basis for the polymerization conversion in step 2) is the sum of the total mass of reactive antioxidant monomer, conjugated diene, first portion of styrene, M 1, and the total mass of residual styrene, carboxylic acid monomer, M 2, in the first feed system, and the polymerization conversion of 45-50% 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 comprises four monomers of reactive antioxidants, conjugated dienes, styrenes, carboxylic acid monomers. 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 of the polymer as a monomer, and the loss of the reactive anti-aging agent in the subsequent processing process of producing rubber products by using the polymer is avoided. In addition, the introduction of the carboxylic acid monomer is used for carrying out molecular surface grafting polymerization reaction, so that the main chain or branched chain of the rubber molecule is grafted with more carboxylic acid structures, and a body type molecular structure with higher branching degree is formed.
And the invention also carries out classified batch addition on the monomer by controlling the proper adding node. Specifically, the reactive anti-aging agent monomer, conjugated diene and first part of styrene are polymerized, and when the polymerization conversion rate is 10-20%, a second raw material system comprising the residual styrene and carboxylic acid monomer is added. On one hand, the residual styrene and carboxylic acid monomers 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 influence of the residual styrene and carboxylic acid monomers on the rejection and the racing polymerization of the reactive anti-aging agent embedded into the main chain of the conjugated diene molecule, the anti-aging effect of the reactive anti-aging agent is exerted to a greater extent, the high temperature resistance of the polymer is remarkably improved, and the improvement degree of the mechanical property of the polymer is also more remarkable; on the other hand, when the polymerization conversion rate reaches 10-20%, the residual styrene and carboxylic acid monomers are added to ensure the branching degree and more effective block distribution of the polymer, so that the molecular level dispersion uniformity of the carboxylic acid monomers can be realized, the carboxyl groups are uniformly distributed on the surface of a molecular chain, the formed structure is high in uniformity, and the wear resistance and hardness of the polymer can be remarkably improved, thereby meeting the requirements of more severe application environments on the wear resistance and hardness of the polymer. In addition, the mode of adding the styrene in batches can also be used for adjusting the reaction rate, so that the formation of the high-molecular copolymer is facilitated.
The invention adds the reactive anti-aging agent into the reaction system in advance than the residual styrene and carboxylic acid monomers, specifically, adds the residual styrene and carboxylic acid monomers after the polymerization conversion rate of the polymerization reaction of the reactive anti-aging agent, conjugated diene and the first part of styrene reaches 10-20 percent. The addition sequence and the selection of the addition nodes are not only beneficial to maximally exerting the anti-aging effect of the reactive anti-aging agent on the polymer, but also beneficial to exerting the effects of various functional groups by adding the residual styrene and carboxylic acid monomers after the main chain is formed, so that the carboxyl poly-stable styrene-butadiene rubber with good wear resistance and high hardness is finally obtained.
In addition, in the process of preparing the carboxyl poly-stable styrene-butadiene 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 in batches is mainly used for adjusting the reaction speed and adjusting 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 invention is not limited to the termination mode of the reaction, and for example, the termination mode of the reaction can be selected from the common mode of adding the terminator to ensure that the polymerization conversion rate is 75-80 percent. After the reaction is terminated, a series of post-treatments can be performed on the reaction system to obtain the solid-phase carboxyl-group-polymerized styrene-butadiene 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 water content is below 0.5%, thereby preparing the carboxyl-group-containing poly-stable styrene-butadiene 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 activating agent and a dispersing agent into a reaction kettle containing water, stirring and dissolving, adding a reactive anti-aging agent monomer, a first part of styrene, a first part of molecular weight regulator and an electrolyte, performing nitrogen inflation-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 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. The carboxylic acid monomer is one or more selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride, and is specifically one or more selected from methacrylic acid, acrylic anhydride, itaconic acid, fumaric acid, maleic anhydride, aconitic acid, mesaconic acid, sinapic acid, undecylenic acid and angelic acid.
As described above, in the preparation process, styrene is added to the reaction system in two steps, wherein a first portion of styrene is added to the reaction system through the first raw material system and the remaining styrene is added to the reaction system through the second raw material system. In a specific embodiment, the mass of the first portion of styrene is not less than 60% of the total mass of styrene, and further, the mass of the first portion of styrene is 66 to 80% of the total mass of styrene. That is, styrene of not less than 60% by mass of the total styrene was used as the first portion of styrene, and the remaining not more than 40% of styrene was used as the remaining styrene, respectively. The inventors found that when the mass of the first portion of styrene is not less than 60% of the total mass of styrene, it is advantageous for styrene to be incorporated into the molecular main chain at the initial stage of formation of the polymer molecular main chain, and for uniformity of incorporation of styrene and siloxane into the main chain. The residual styrene is used for carrying out grafting reaction, so that the residual double bond structure on the conjugated diene molecular chain is opened, and the styrene monomer molecules are grafted to form more C-C single bond structures, thereby being beneficial to the heat resistance and stability of the polymer molecules.
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 partial emulsifier to the remaining emulsifier, as long as the function of supplementing the emulsifier and the function of forming the solubilized micelle can be achieved. The inventors found that when the mass of the first portion of the emulsifier is not less than 70% of the total mass of the emulsifier, more micelles are advantageously formed to serve as reaction sites for polymerization, increasing the reactivity.
The invention does not limit the adding amount of the molecular weight regulator of each part too much.
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 carboxyl-based poly-stable styrene-butadiene rubber.
In a specific embodiment, when the reaction monomer comprises 10-49% of styrene, 50-85% of conjugated diene, 0.5-2% of reactive anti-aging agent monomer and 0.1-20% of carboxylic acid monomer according to mass percentage, the carboxyl poly-stable styrene-butadiene rubber with good wear resistance and high hardness is obtained. Further, the reaction monomer comprises 14-46% of styrene, 50-82% of conjugated diene, 1.0-1.85% of reactive anti-aging agent monomer and 3.0-20% of carboxylic acid 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 carboxypoly-styrene-butadiene rubber obtained according to the preparation method of the first aspect. Generally, the carboxyl poly-stable styrene-butadiene 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 carboxyl poly-stable styrene-butadiene rubber obtained by the method has remarkable free radical resistance, high branching degree, excellent wear resistance and high hardness, can be used for a long time in a severe application environment, has extremely low damage rate or maintenance rate, and widens the application range of rubber products.
Specifically, the raw rubber of the carboxyl poly-stable styrene-butadiene rubber has the Mooney viscosity ML 100℃、1+4 -75, the combined styrene 18-42%, the Aldrich abrasion (cm 3/1.61 km) 0.136-0.269, the gel content below 3.0%, the Shore A hardness 75-88, the tear strength (KN\m) 49-68, the elongation at break 300-500%, the tensile strength 25-37 MPa and the 300% stretching stress 10-26 MPa.
The third aspect of the invention also provides a rubber product, the raw material of which is the carboxyl poly-stable styrene-butadiene rubber of the second aspect. Illustratively, the rubber article of the present invention is obtained by subjecting raw materials including a carboxypoly-styrene-butadiene 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 carboxyl poly-stable styrene-butadiene rubber, so that the rubber product has good wear resistance and high hardness, can improve the durability, reduces the production cost, and is particularly suitable for application environments with high requirements on the wear resistance and the hardness.
Hereinafter, the preparation method of the carboxyl-group-containing poly-styrene-butadiene rubber of the present invention will be described in detail 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; emulsifying agent AD (composite solution of disproportionated rosin potassium soap, synthetic fatty acid potassium soap and beta-sodium naphthalene sulfonate formaldehyde condensate); emulsifier AK (a composite solution of disproportionated rosin potassium soap, sodium dodecyl sulfate and beta-sodium naphthalene sulfonate formaldehyde condensate); emulsifier AH (composite 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
An activating agent: EDTA-4NA, EDTA-FENA and radix asparagi officinalis, wherein the mass ratio of EDTA-4NA, EDTA-FENA and radix asparagi officinalis is 4:3:2, EDTA-4NA, EDTA-FENA, the ratio of the total mass of the white block to the mass of water is 30:70;
Termination agent: sodium nitrite aqueous solution with mass concentration of 15+/-1%
Example 1
The preparation method of the carboxyl poly-stable styrene-butadiene rubber comprises the following steps:
1) 3500 ml of water, 1400 g of emulsifier AK and 10.5 g of activator are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 36.8 g of N- (4-anilinophenyl) acrylamide (NAPA) is added, 376 g of styrene, 4.8 g of tertiary dodecyl mercaptan, 5.8 g of potassium chloride and 0.5792 g of sodium hydrosulfite after nitrogen inflation-vacuum replacement are added, 1536.84 g of butadiene is then added, and after 30 minutes of stirring, 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 10-15%, adding 185 g of synthetic fatty acid potassium soap, 172.46 g of styrene, 115.8 g of acrylic acid and 12.8 g of tertiary dodecyl mercaptan into the mixture, and then continuing the reaction;
2) Adding 195 g of potassium oleate soap and 8.95 g of n-dodecyl mercaptan when the conversion rate reaches 45-50%, continuing to react, adding a terminator to stop the reaction after the conversion rate reaches 76-80%, flash evaporating and degassing, adding 1200 g of sodium chloride aqueous solution and 100 g of dilute sulfuric acid solution to coagulate, filtering and dehydrating, and drying at 95 ℃ until the water content is below 0.5%, thereby obtaining the carboxyl poly-stable styrene-butadiene rubber of the embodiment.
Example 2
The preparation method of the carboxyl poly-stable styrene-butadiene rubber comprises the following steps:
1) Adding 3500 ml of water, 1580 g of an emulsifier AD and 12.5 g of an activator into a 10-liter reaction kettle, dispersing and dissolving the mixture under stirring, adding 37.89 g of N- (benzoic acid-3, 5-di-tert-butylmethylparaben) maleimide, 442.5 g of styrene, 5.8 g of tert-dodecyl mercaptan, 12 g of potassium phosphate, adding 0.1992 g of sodium hydrosulfite after nitrogen inflation-vacuum replacement, adding 1473.68 g of isoprene, stirring for 30 minutes, adding 3.8526 g of dicumyl peroxide through a charging gun barrel, and controlling the temperature to 12+/-1 ℃ for reaction;
when the conversion rate reaches 15-20%, adding a mixture of 155 g of potassium oleate soap, 189.53 g of styrene, 148.0 g of methacrylic acid and 12.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) 45 g of potassium oleate soap and 3.95 g of n-dodecyl mercaptan are added when the conversion rate reaches 45-50%, the reaction is continued, a terminator is added to stop the reaction after the conversion rate reaches 75-79%, 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 the mixture is filtered and dehydrated and then dried at 95 ℃ until the water content is below 0.5%, so that the carboxyl-group poly-stable styrene-butadiene rubber of the embodiment is obtained.
Example 3
The preparation method of the carboxyl poly-stable styrene-butadiene rubber comprises the following steps:
1) 3500 ml of water, 1650 g of emulsifying agent AH and 10.8 g of activating agent are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 35.78 g of N- (4-phenylaminophenyl) Maleimide (MC), 315.9 g of styrene, 5.5 g of tertiary dodecyl mercaptan, 4.8 g of sodium pyrophosphate, and after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1684.21 g of butadiene is then added, after stirring for 30 minutes, 5.4897 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 12-18%, adding a mixture of 95 g of synthetic fatty acid potassium soap, 105.3 g of styrene, 208 g of acrylic anhydride and 10.5 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) Adding 100 g of emulsifier AD and 8.95 g of tertiary dodecyl mercaptan when the conversion rate reaches 45-50%, continuing to react, adding a terminator to stop the reaction after the conversion rate reaches 77-80%, flash evaporating and degassing, adding a mixed solution of 1200 g of sodium chloride aqueous solution and 150 g of dilute sulfuric acid solution for condensation, filtering and dehydrating, and drying at 95 ℃ until the water content is below 0.5%, thereby obtaining the carboxyl poly-stable styrene-butadiene rubber of the embodiment.
Example 4
The preparation method of the carboxyl poly-stable styrene-butadiene rubber comprises the following steps:
1) 3200 ml of water, 1650 g of synthetic fatty acid potassium soap solution and 9.8 g of activator are added into a 10-liter reaction kettle, 66.9 g of beta-naphthalene sulfonic acid sodium formaldehyde condensate solution is dispersed and dissolved under stirring, 31.8 g of N- (4-anilinophenyl) -2-hydroxyisobutyramide, 588 g of styrene, 6.8 g of tertiary dodecyl mercaptan, 12 g of potassium chloride are added, after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1368.45 g of butadiene is then added, 5.7 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, styrene 148.84 g, itaconic acid 168.5 g and tertiary dodecyl mercaptan 12 g when the conversion rate reaches 12-17%, and continuing to react after the mixture is added;
2) When the conversion rate reaches 45-50%, adding 120 g of potassium oleate soap and 8.95 g of n-dodecyl mercaptan, and then continuing to react; adding a terminator to terminate the reaction after the conversion rate reaches 75-79%, flash evaporating and degassing, adding a mixed solution of 1000 g of sodium chloride aqueous solution and 200 g of dilute sulfuric acid solution to coagulate, filtering and dehydrating, and drying at 95 ℃ until the water content is below 0.5%, thereby obtaining the carboxyl poly-stable styrene-butadiene rubber of the embodiment.
Example 5
The preparation method of the carboxyl poly-stable styrene-butadiene 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 activator are added into a 10-liter reaction kettle, 72.6 g of beta-naphthalene sulfonic acid sodium formaldehyde condensate solution is dispersed and dissolved under stirring, 37.5 g of N- (4-anilinophenyl) methacrylamide (NAPM), 620 g of styrene, 5.8 g of tertiary dodecyl mercaptan and 16 g of potassium chloride are added, after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1263.2 g of butadiene is then 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, 221.7 g of styrene, 50.9 g of fumaric acid, 20 g of maleic anhydride and 10.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 45-50%, 95 g of potassium oleate soap and 4.95 g of n-dodecyl mercaptan are added, the reaction is continued, after the conversion rate reaches 75-79%, a terminator is added to stop 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 to be condensed, and after filtration and dehydration, the mixture is dried at 95 ℃ until the water content is below 0.5%, so that the carboxyl-group poly-stable styrene-butadiene rubber of the embodiment is obtained.
Example 6
The preparation method of the carboxyl poly-stable styrene-butadiene rubber comprises the following steps:
1) 3500 ml of water, 1550 g of emulsifying agent AH and 10.5 g of activating agent are added into a 10-liter reaction kettle, 11.5 g of N- (4-anilinophenyl) acrylamide (NAPA), 25.3 g of N- (4-anilinophenyl) methacrylamide (NAPM), 378 g of styrene, 4.8 g of tertiary dodecyl mercaptan, 15 g of potassium chloride, 0.5792 g of sodium dithionite is added after nitrogen aeration-vacuum displacement, 1536.84 g of butadiene is added, and after stirring for 30 minutes, hydrogen peroxide is added through a charging barrel 1.8558 G of alkane is reacted at the temperature of 12+/-1 ℃;
When the conversion rate reaches 10-15%, adding a mixture of 85 g of synthetic fatty acid potassium soap, 190.47 g of styrene, 50 g of aconitic acid, 55.8 g of mesaconic acid and 12.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 45-50%, 95 g of potassium oleate soap and 8.95 g of n-dodecyl mercaptan are added, the reaction is continued, after the conversion rate reaches 75-80%, a terminator is added to stop 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 to be condensed, and after filtration and dehydration, the mixture is dried at 95 ℃ until the water content is below 0.5%, so that the carboxyl-group poly-stable styrene-butadiene rubber of the embodiment is obtained.
Example 7
The preparation method of the carboxyl poly-stable styrene-butadiene rubber comprises the following steps:
1) 3500 ml of water, 1580 g of emulsifying agent AD and 12.8 g of activating agent 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), 461 g of styrene, 5.8 g of tert-dodecyl mercaptan, 10 g of potassium phosphate, and after nitrogen gas charging-vacuum replacement, 0.1992 g of sodium dithionite and 1473.68 g of isoprene are added, 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, 170.6 g of styrene, 85.6 g of sinapic acid, 62.8 g of undecylenic acid and 12.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) 45 g of potassium oleate soap and 3.95 g of n-dodecyl mercaptan are added when the conversion rate reaches 45-50%, the reaction is continued, a terminator is added to stop the reaction after the conversion rate reaches 76-79%, 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 the mixture is filtered and dehydrated and then dried at 95 ℃ until the water content is below 0.5%, so that the carboxyl-group poly-stable styrene-butadiene rubber of the embodiment is obtained.
Example 8
The preparation method of the carboxyl poly-stable styrene-butadiene rubber comprises the following steps:
1) 3500 ml of water, 1657 g of emulsifying agent AD and 10.8 g of activating agent are added into a 10-liter reaction kettle, the mixture is dispersed and dissolved under stirring, 35.98 g of N- (4-phenylaminophenyl) Maleimide (MC), 290.6 g of styrene, 5.5 g of tertiary dodecyl mercaptan, 3.2 g of ferrous sulfate, 2.8 g of sodium pyrophosphate solution, 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 is added through a charging gun barrel after stirring for 30 minutes, and hydrogen peroxide 1.2896 g is added for reaction at a temperature of 12+/-1 ℃;
When the conversion rate reaches 15-20%, adding a mixture of 85 g of synthetic fatty acid potassium soap, 130.6 g of styrene, 50 g of acrylic acid, 154.1 g of angelic acid and 10.5 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 45-50%, 102 g of emulsifier AK and 8.95 g of tertiary dodecyl mercaptan are added, the reaction is continued, after the conversion rate reaches 75-79%, 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 water content is below 0.5%, so that the carboxyl-group poly-stable styrene-butadiene rubber of the embodiment is obtained.
Example 9
The preparation method of the carboxyl poly-stable styrene-butadiene 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 activator are added into a 10-liter reaction kettle, 72.6 g of beta-sodium naphthalene sulfonate formaldehyde condensate solution is dispersed and dissolved under stirring, 39.5 g of N- (4-anilinophenyl) methacrylamide (NAPM), 632 g of styrene, 5.8 g of tertiary dodecyl mercaptan, 12 g of potassium chloride, and after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1263.2 g of butadiene is then added, after stirring for 30 minutes, 8.95 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 15-18%, adding a mixture of 85 g of synthetic fatty acid potassium soap, 210.1 g of styrene, 20.8 g of methacrylic acid, 50g of mesaconic acid and 12.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 45-50%, 95 g of potassium oleate soap and 4.95 g of n-dodecyl mercaptan are added, the reaction is continued, after the conversion rate reaches 75-79%, a terminator is added to stop 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 to be condensed, and after filtration and dehydration, the mixture is dried at 95 ℃ until the water content is below 0.5%, so that the carboxyl-group poly-stable styrene-butadiene rubber of the embodiment is obtained.
Comparative example 1
Substantially the same procedure as in example 1 was followed except that the remaining styrene was added with the first feed system. The preparation method comprises the following steps:
1) 3500 ml of water, 1400 g of emulsifier AK and 10.5 g of activator are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 36.8 g of N- (4-anilinophenyl) acrylamide (NAPA), 548.46 g of styrene, 4.8 g of tertiary dodecyl mercaptan, 5.8 g of potassium chloride and after nitrogen gas 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 10-15%, adding 185 g of synthetic fatty acid potassium soap, 115.8 g of acrylic acid and 12.8 g of tertiary dodecyl mercaptan to continue the reaction;
2) When the conversion rate reaches 45-50%, 195 g of potassium oleate soap and 8.95 g of n-dodecyl mercaptan are added, the reaction is continued, after the conversion rate reaches 76-80%, a terminator is added to stop 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 to be condensed, and after filtration and dehydration, the mixture is dried at 95 ℃ until the water content is below 0.5%, so that the carboxyl-group poly-stable styrene-butadiene rubber of the comparative example is obtained.
Comparative example 2
Substantially the same as in example 2 was done, except that all of the monomer was added together with the first feed system. The preparation method comprises the following steps:
1) Adding 3500 ml of water into a 10-liter reaction kettle, adding 1650 g of emulsifier AH and 10.8 g of activator, dispersing and dissolving under stirring, adding 35.78 g of N- (4-phenylaminophenyl) Maleimide (MC), 421.2 g of styrene, 208 g of acrylic anhydride, 5.5 g of tertiary dodecyl mercaptan, 4.8 g of sodium pyrophosphate, adding 0.5792 g of sodium dithionite after nitrogen inflation-vacuum replacement, then adding 1684.21 g of butadiene, stirring for 30 minutes, adding 5.4897 g of dicumyl peroxide through a charging gun barrel, and controlling the temperature to 12+/-1 ℃ for reaction;
When the conversion rate reaches 12-18%, adding a mixture of 95 g of synthesized fatty acid potassium soap and 10.5 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) Adding 100 g of emulsifier AD and 8.95 g of tertiary dodecyl mercaptan when the conversion rate reaches 45-50%, continuing to react, adding a terminator to stop the reaction after the conversion rate reaches 77-80%, flash evaporating and degassing, adding a mixed solution of 1200 g of sodium chloride aqueous solution and 150 g of dilute sulfuric acid solution for condensation, filtering and dehydrating, and drying at 95 ℃ until the water content is below 0.5%, thus obtaining the carboxyl-group poly-stable styrene-butadiene rubber of the comparative example.
Comparative example 3
The preparation process was substantially identical to that of example 3, except that no acrylic anhydride was added when the conversion was 12 to 18%, and that acrylic anhydride was added when the conversion was 45 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 activating agent are added into a 10-liter reaction kettle, dispersed and dissolved under stirring, 35.78 g of N- (4-phenylaminophenyl) Maleimide (MC), 315.9 g of styrene, 5.5 g of tertiary dodecyl mercaptan, 4.8 g of sodium pyrophosphate, and after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1684.21 g of butadiene is then added, after stirring for 30 minutes, 5.4897 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 12-18%, adding a mixture of 95 g of synthetic fatty acid potassium soap, 105.3 g of styrene and 10.5 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) Adding 100 g of emulsifier AD, 208 g of acrylic anhydride and 8.95 g of tertiary dodecyl mercaptan when the conversion rate reaches 45-50%, continuing to react, adding a terminator to stop the reaction after the conversion rate reaches 77-80%, flash evaporating and degassing, adding 1200 g of sodium chloride aqueous solution and 150 g of dilute sulfuric acid solution to coagulate, filtering and dehydrating, and drying at 95 ℃ until the water content is below 0.5%, thus obtaining the carboxyl poly (styrene-butadiene rubber) of the comparative example.
Comparative example 4
The preparation process was substantially identical to that of example 4, except that styrene was not added when the conversion was 12 to 17% and was added when the conversion was 45 to 50%. The preparation method comprises the following steps:
1) 3200 ml of water, 1650 g of synthetic fatty acid potassium soap solution and 9.8 g of activator are added into a 10-liter reaction kettle, 66.9 g of beta-naphthalene sulfonic acid sodium formaldehyde condensate solution is dispersed and dissolved under stirring, 31.8 g of N- (4-anilinophenyl) -2-hydroxyisobutyramide, 588 g of styrene, 6.8 g of tertiary dodecyl mercaptan, 12 g of potassium chloride are added, after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1368.45 g of butadiene is then added, 5.7 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, itaconic acid 168.5 g and tert-dodecyl mercaptan 12 g when the conversion rate reaches 12-17%, and continuing to react after the mixture is added;
2) When the conversion rate reaches 45-50%, 120 g of potassium oleate soap, 148.84 g of styrene and 8.95 g of n-dodecyl mercaptan are added for continuous reaction, after the conversion rate reaches 75-79%, 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 mixed solution condensation, and after filtration and dehydration, the mixture is dried at 95 ℃ until the water content is below 0.5%, and the carboxyl poly-stable styrene-butadiene rubber of the comparative example is obtained.
Comparative example 5
Substantially the same as in example 5 was conducted, except that the second raw material system (synthetic fatty acid potassium soap, styrene, fumaric acid, maleic anhydride, t-dodecyl mercaptan) was added at a conversion of 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 activator are added into a 10-liter reaction kettle, 72.6 g of beta-naphthalene sulfonic acid sodium formaldehyde condensate solution is dispersed and dissolved under stirring, 37.5 g of N- (4-anilinophenyl) methacrylamide (NAPM), 620 g of styrene, 5.8 g of tertiary dodecyl mercaptan and 16 g of potassium chloride are added, after nitrogen aeration-vacuum displacement, 0.5792 g of sodium dithionite is added, 1263.2 g of butadiene is then 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, 221.7 g of styrene, 50.9 g of fumaric acid, 20 g of maleic anhydride and 10.8 g of tertiary dodecyl mercaptan, and continuing the reaction;
2) When the conversion rate reaches 45-50%, 95 g of potassium oleate soap and 4.95 g of n-dodecyl mercaptan are added, the reaction is continued, after the conversion rate reaches 75-79%, a terminator is added to stop 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 to be condensed, and after filtration and dehydration, the mixture is dried at 95 ℃ until the water content is below 0.5%, so that the carboxyl-group poly-stable styrene-butadiene rubber of the comparative example is obtained.
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 activating agent are added into a 10-liter reaction kettle, 11.5 g of N- (4-anilinophenyl) acrylamide (NAPA), 25.3 g of N- (4-anilinophenyl) methacrylamide (NAPM), 378 g of styrene, 4.8 g of tertiary dodecyl mercaptan, 15 g of potassium chloride, 0.5792 g of sodium dithionite is added after nitrogen aeration-vacuum displacement, 1536.84 g of butadiene is added, and after stirring for 30 minutes, hydrogen peroxide is added through a charging barrel 1.8558 G of alkane is reacted at the temperature of 12+/-1 ℃;
When the conversion rate reaches 10-15%, 85 g of synthetic fatty acid potassium soap, 190.47 g of styrene, 50 g of aconitic acid, 55.8 g of mesaconic acid, 95 g of potassium oleate soap, 8.95 g of n-dodecyl mercaptan and 12.8 g of tert-dodecyl mercaptan are added, the mixture is reacted continuously, after the conversion rate reaches 75-80%, a terminator is added to terminate 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 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 carboxyl poly-stable styrene-butadiene rubber of the comparative example.
Test examples
The following method was used to examine the relevant parameters of the carboxy-polymerized styrene-butadiene rubber of all examples and comparative examples, and the results are shown in tables 1 and 2.
Mooney viscosity: standard measurements of section 1 were performed with a disc shear viscometer with reference to GB/T1232.1-2000 unvulcanized rubber;
Acle abrasion: the abrasion resistance of the vulcanized rubber is measured by an acle abrasion tester and is measured by referring to the standard of GB/T1689-2014 vulcanized rubber abrasion resistance;
combining with styrene: reference to standard spectrophotometric measurements of GB/T13646-2013 rubber in combination with styrene content determination;
shore A hardness: reference is made to GB/T531.1 part 1 of the test method for indentation hardness of vulcanized rubber or thermoplastic rubber: standard measurement of Shore hardness measurement;
Gel content: reference SH/T1050-2014 standard determination of gel content of synthetic raw rubber;
Elongation at break and tensile strength are determined by reference to the standard of GBT 6037-1985 vulcanized rubber for high temperature tensile strength and elongation at break;
300% stress at definite elongation: reference is made to the standard measurement of tensile stress strain properties of GB/T528-2009 vulcanizates or thermoplastic rubbers.
TABLE 1
TABLE 2
In tables 1 and 2, ". Gtoreq". Gtoreq.in the elongation at break (%) "means a range of" not lower than the present value and not higher than the present value +9 units "; "not less than" in tensile strength (MPa) means a range of "not less than the present value and not more than +0.09 units" in the present value; 25min, 35min, 50min refer to the vulcanization time of the test sample.
From tables 1 and 2, it can be seen that:
1. Compared with the comparative example, the acle abrasion in the example is lower, and the Shore A hardness is higher, so that the carboxyl poly-stable styrene-butadiene rubber obtained by the preparation method has excellent performances in the aspects of wear resistance, hardness and the like;
2. The carboxypoly-styrene-butadiene rubber in the examples clearly has more excellent performance in terms of physical and mechanical strength than the comparative examples;
3. As is clear from comparative example 1 and comparative example 1, since the addition of the additional styrene in comparative example 1 is advanced, the effect of embedding acrylic acid in the polybutadiene main chain is affected, and the acrylic acid grafted on the polymer main chain is less, which affects the performance of the resultant;
as is clear from comparative example 2 and comparative example 2, the control sequence of polymerization reaction is changed because the reactive monomer is not added in batches in comparative example 2, the polymerization reaction is in disordered self-polymerization, the reactive anti-aging agent, the styrene and the carboxylic acid monomer have a racing effect on isoprene, the distribution of the reactive anti-aging agent on a polymer main chain is affected, the molecular weight of the generated reactant is smaller, the generated reactant is a mixture of various polymers, and the performance of the processed polymer is obviously deteriorated;
As can be seen from the comparison example 3 and the comparison example 3, the carboxylic acid monomer in the comparison example 3 is added into the reaction system too late, the emulsion particles of the poly-stable styrene-butadiene rubber with larger particle size are formed by the early reaction, the carboxylic acid monomer loses the best opportunity of embedding into the molecular main chain of the polymer, the reaction is mainly grafted on the molecular surface of the poly-stable styrene-butadiene rubber formed in the early stage, and the functional group distribution on the molecular chain is alternately worse, so that the performance of the product is affected;
As can be seen from the comparison example 4 and the comparison example 4, since the addition of the additional styrene is delayed, the molecular main chain formed in the early stage is carboxyl poly-stable styrene-butadiene rubber particles, the particle size is larger, the additional styrene is added when the conversion rate reaches 40-45%, the reaction effect of grafting and embedding the styrene with the large particle size is not as good as that of grafting and embedding the styrene with the small particle size when the styrene is added when the conversion rate reaches 12-17%; the distribution of styrene on the molecular chain also affects the properties of the final product by changing the timing and sequence of addition;
As can be seen from comparative example 5 and comparative example 5, since the particle size of the main chain molecules in which butadiene, styrene and NAPM are intercalated formed earlier in comparative example 5 is too large, the uniformity of grafting and blocking reactions of additional styrene, fumaric acid and maleic anhydride on the main chain is affected, the branching degree of the formed multipolymer molecules is relatively smaller than that of the multipolymer molecules in which styrene and carboxylic acid are added when the conversion rate reaches 15-20%, and the intercalation bonding effect of the styrene and the carboxylic acid is poor, and the performance of the final product is affected;
As is clear from the comparison between the comparative example 6 and the comparative example 6, the potassium oleate and the n-dodecyl mercaptan are not added in the conversion rate of 45-50%, so that no solubilised micelle is generated in the later stage of the reaction, the unreacted monomer and the molecular weight regulator are affected to diffuse into the generated micelle again, the molecular weight of the product is small and branched less, the effect required by the invention is not achieved, the potassium oleate and the molecular weight regulator are added in the conversion rate of 10-15%, the active points of the formed reactive micelle are excessive in the early stage of the reaction, and the molecular structure and the molecular weight of the final product are affected, so that the performance is obviously deteriorated.
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 carboxyl poly-stable styrene-butadiene 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 10-20%;
2) When the polymerization conversion rate is 45-50%, adding a third raw material system to perform a third emulsion polymerization reaction;
3) Terminating the reaction when the polymerization conversion rate is 75-80%, so as to obtain the carboxyl poly-stable styrene-butadiene rubber;
Wherein the first raw material system at least comprises a reactive antioxidant monomer, conjugated diene, a first part of styrene, a first part of emulsifier and a first part of molecular weight regulator;
The second raw material system at least comprises residual styrene, carboxylic acid monomers, a second part of emulsifying agent and a second part of molecular weight regulator;
the third feed system comprises at least a residual emulsifier and a residual molecular weight regulator.
2. The method of claim 1, wherein the mass of the first portion of emulsifier is no less than 70% of the total mass of emulsifier; and/or the number of the groups of groups,
The mass of the first portion of styrene is not less than 60% of the total mass of styrene.
3. The preparation process according to claim 1 or 2, wherein the reaction temperature is 5 to 30 ℃.
4. The method according to any one of claims 1 to 3, wherein the reactive monomer comprises 10 to 49% by mass of styrene, 50 to 85% by mass of conjugated diene, 0.5 to 2% by mass of reactive anti-aging agent monomer and 0.1 to 20% by mass of carboxylic acid monomer.
5. The preparation method of claim 4, wherein the reactive monomer comprises, by mass, 14-46% of styrene, 50-82% of conjugated diene, 1.0-1.85% of reactive anti-aging agent monomer, and 3.0-20% of carboxylic acid 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 carboxyl-group-containing poly-styrene-butadiene rubber is obtained by sequentially performing coagulation treatment, filtration treatment and dehydration treatment on the reaction system after termination of the reaction.
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 carboxyl-based poly-styrene-butadiene rubber, characterized in that it is obtained by the preparation process according to any one of claims 1 to 8.
10. A rubber product, characterized in that the raw material of the rubber product comprises the carboxyl-group-containing poly-stable styrene-butadiene rubber as defined in claim 9.
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