CN114478956B - Preparation method of high-width-distribution three-hetero-arm comb-shaped star-shaped branched butyl rubber - Google Patents
Preparation method of high-width-distribution three-hetero-arm comb-shaped star-shaped branched butyl rubber Download PDFInfo
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- CN114478956B CN114478956B CN202011264675.9A CN202011264675A CN114478956B CN 114478956 B CN114478956 B CN 114478956B CN 202011264675 A CN202011264675 A CN 202011264675A CN 114478956 B CN114478956 B CN 114478956B
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- 238000009826 distribution Methods 0.000 title claims abstract description 87
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 172
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 163
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000005859 coupling reaction Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002667 nucleating agent Substances 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 39
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 28
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 102
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 64
- 238000010438 heat treatment Methods 0.000 claims description 63
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 52
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 239000003292 glue Substances 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- YFIIENAGGCUHIQ-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptachloropropane Chemical compound ClC(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl YFIIENAGGCUHIQ-UHFFFAOYSA-N 0.000 claims description 2
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 claims description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical group ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- FLFGMNFGOKXUQY-UHFFFAOYSA-L dichloro(propan-2-yl)alumane Chemical compound [Cl-].[Cl-].CC(C)[Al+2] FLFGMNFGOKXUQY-UHFFFAOYSA-L 0.000 claims description 2
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- WXRBQHOKNRLOQI-UHFFFAOYSA-N dichloromethylaluminum Chemical compound [Al]C(Cl)Cl WXRBQHOKNRLOQI-UHFFFAOYSA-N 0.000 claims 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 claims 1
- UUXZFMKOCRKVDG-UHFFFAOYSA-N methane;hydrofluoride Chemical compound C.F UUXZFMKOCRKVDG-UHFFFAOYSA-N 0.000 claims 1
- 229940050176 methyl chloride Drugs 0.000 claims 1
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 10
- 230000008878 coupling Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 150000001555 benzenes Chemical class 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000008094 contradictory effect Effects 0.000 abstract description 2
- 239000004793 Polystyrene Substances 0.000 description 66
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 58
- 229910001220 stainless steel Inorganic materials 0.000 description 40
- 239000010935 stainless steel Substances 0.000 description 40
- 229910052786 argon Inorganic materials 0.000 description 29
- 239000005062 Polybutadiene Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000005070 sampling Methods 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 8
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- 230000001112 coagulating effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical group [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
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- 241001441571 Hiodontidae Species 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
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- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- QNTXHYILQCFXSN-UHFFFAOYSA-N 2-(4-chlorophenyl)ethenyl-dimethylsilane Chemical compound C[SiH](C)C=CC1=CC=C(Cl)C=C1 QNTXHYILQCFXSN-UHFFFAOYSA-N 0.000 description 1
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 239000012986 chain transfer agent Substances 0.000 description 1
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- 229920000578 graft copolymer Polymers 0.000 description 1
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- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
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Abstract
The invention takes isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) as reaction monomers, takes alkyl lithium and organic peroxide as initiator, adopts three-kettle reaction, adopts variable temperature polymerization, and then prepares the quaternary three-hetero-arm star-shaped nucleating agent ([ (DVB) SBR) by coupling of trihalogenated benzene coupling agent] n Ph[‑(DVB)BR‑PS] n [‑(DVB)IR‑PS] n ) Finally, under the catalysis system of the quaternary three-hetero-arm star-shaped nucleating agent and the combination of the isobutene and the isoprene with the alkyl aluminum halide and the protonic acid, the three-hetero-arm comb-shaped star-shaped branched butyl rubber with high width distribution is prepared by adopting a first-arm and then-core method through cationic polymerization. The invention solves the problem of the contradictory relation between the processability and the physical and mechanical properties of the butyl rubber by the design of the quaternary three-hybrid-arm star-shaped structure, and realizes the optimal balance between the processability and the physical and mechanical properties of the butyl rubber.
Description
Technical Field
The invention relates to a preparation method of high-width-distribution three-hetero-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing high-width-distribution three-hetero-arm comb-shaped star-branched butyl rubber by using an isoprene/butadiene/styrene/Divinylbenzene (DVB) quaternary three-hetero-arm nucleating agent.
Background
Butyl Rubber (IIR) is known to be copolymerized from isobutylene and a small amount of isoprene by cationic polymerization. Butyl rubber has been industrialized by Exxon corporation in the united states in the 40 th century for over seventy years, and has been widely used in the fields of inner tubes, inner liners, curing bladder, medical plugs, etc. for manufacturing tires for vehicles because of its excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance, etc.
However, the molecular chain of butyl rubber mainly consists of single bonds of carbon and carbon, the number of double bonds is small, substituent methyl groups are symmetrically arranged, and the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesion, poor compatibility with other general rubber and the like exist, so that the butyl rubber is easy to excessively flow and deform in the processing process. How to achieve a balance of physical and mechanical properties and processability of butyl rubber has become a bottleneck in the preparation of high performance butyl rubber materials.
In recent years, researchers find that star-shaped highly branched butyl rubber with a unique three-dimensional network structure, which consists of a high molecular weight grafted structure and a low molecular weight linear structure, has excellent viscoelastic performance, high green strength and fast stress relaxation rate, can keep low melt viscosity in the processing process, can obtain a high molecular weight polymer, and realizes uniform balance of physical and mechanical properties and processing properties. The star-shaped hyperbranched structure has become one of the hot spots in the future butyl rubber research field.
In the prior art, the synthesis of star-branched butyl rubber is mainly prepared by adopting a method of a first-nucleus and then-arm method, a first-arm and then-nucleus method and a nucleus-arm simultaneous method. Such as: US5395885 discloses a star-branched polymer, which is synthesized by a method of first-arm-then-core method at-90 to-100 ℃ by taking polyisobutylene as an arm, polydivinylbenzene (PDVB) as a core, a complex of alkyl aluminum chloride and water as an initiator, and chloromethane as a diluent. CN88108392.5 discloses a star-shaped graft butyl rubber with comb structure prepared by using a hydrochloride polystyrene-isoprene copolymer as a polyfunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN101353403B discloses a method for preparing star-branched polyisobutylene or butyl rubber, which uses a polystyrene/isoprene block copolymer with a silicon-chlorine group at the end or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the end as a grafting agent for initiating cationic polymerization, and takes part in the cationic polymerization directly in a cationic polymerization system of a mixed solvent with a chloromethane/cyclohexane v ratio of 20-80/80-20 at the temperature of 0-100 ℃ to initiate cationic polymerization by the silicon-chlorine group, and takes part in grafting reaction by an unsaturated chain to prepare the star-branched polyisobutylene or butyl rubber product. CN01817708.5 provides a method of adding a multiolefin crosslinking agent such as divinylbenzene and a chain transfer agent (such as 2,4, 1-tetramethyl-1-pentene) to a mixture of isoolefin monomers and diolefin monomers, by which star-branched polymers are prepared. CN107793535 a provides a butyl rubber having a molecular weight of 90 to 260 tens of thousands, log (MW) >6 and contains structural units derived from isobutylene, structural units derived from conjugated dienes, and optionally structural units derived from aryl olefins. CN200710129810.7 provides a method for synthesizing linear butyl rubber by arm-first and core-later processes, then coupling with divinylbenzene to obtain star-branchedButyl rubber. Puskas et al synthesized tetra-cumyl alcohol as an initiator with a four-arm structure by using pyromellitic acid as a raw material, and then initiated isobutylene and isoprene copolymerization in an inert organic solvent at-120 to-50 ℃ by using a tetra-cumyl alcohol/aluminum tetrachloride initiation system to synthesize star-branched butyl rubber with bimodal molecular weight distribution (Catalysts for manufacture of IIR with bimodal molecular weight distribution:US,5194538[ P ]].1993-3-16.). Wieland et al synthesized a macroinitiator P (MMA-b-St-co-CMS) containing 4-chloromethylstyrene, styrene and methyl methacrylate quaternaries in the presence of 1, 2-stilbene (DPE) by a radical polymerization method, and initiated cationic polymerization of isobutylene and isoprene with the macroinitiator to thereby successfully prepare a multi-arm star butyl rubber (Synthesis of new graft copolymers containing polyisobutylene by acombination of the, 1-diphenylethylene techniqueand cationic polymerization [ J ] ]Polymer Science: polymer Chemistry,2002, 40: 3725-3733.). Hadjichristididis et al uses CH 3 SiCl 3 PI-PS-PBd four-arm copolymer (Iatrou H, hadjichristidis N.Synthesis of a model 3-miktoarm star terpolymer [ J ] was synthesized by four-step coupling with strict control of the order of addition of the monomers and the degree of excess of the coupling agent]Macromolecules,1992, 25:4649). Hadjchristids react with the silicon-chlorine group of p-chlorodimethylsilyl styrene by high vacuum technique to obtain styrene-based polybutadiene macromonomer, which is then copolymerized with butadiene in the presence of random regulator to obtain active Comb-shaped polybutadiene, and finally reacts with methyl silicon tetrachloride or silicon tetrachloride to obtain 3-arm or 4-arm Star-shaped Comb-shaped polybutadiene (KORTALAAS G, IATROUH, LOHSE D J, et al, well-Defined Comb, star-Comb, and aldcom-on-Comb Polybutadienes by Anionic Polymerization and the MacromonomerStrategy [ J ]]Macromolecules,2005,38 (12): 4996-5001). Huiqin A star-branched polymer with divinylbenzene as core and polyisobutylene as arm (star with divinylbenzene as core) is synthesized by adopting 2-chloro-2, 4-tetramethylpentane/titanium tetrachloride as initiator system and chloromethane/cyclohexane as solvent and adopting active positive ion polymerization at-80 DEG C Preparation and characterization of branched polyisobutenes "," synthetic rubber industry ", synthetic rubber industry, 2008, 31 (5): 362-365".
Disclosure of Invention
The invention aims to provide a preparation method of high-width-distribution three-hetero-arm comb-shaped star-branched butyl rubber. The invention takes alkyl lithium and organic peroxide as initiator, isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) as reaction monomers, coupling agent trihalogenated benzene is used for coupling, a temperature-changing polymerization method is adopted for preparing quaternary three-hetero-arm star-shaped nucleating agent, and finally under a catalytic system compounded by Lewis acid and protonic acid, the quaternary three-hetero-arm star-shaped nucleating agent, isobutene and isoprene are subjected to cationic polymerization by adopting a first-arm and then-core method for preparing the high-width distribution three-hetero-arm comb-shaped star-shaped branched butyl rubber. The method solves the problems of easy extrusion swelling and slow stress relaxation rate of the butyl rubber in the processing process, so that the high-width-distribution three-hetero-arm comb-shaped star-shaped branched butyl rubber has the characteristics of sufficient green rubber strength and good air tightness, and also has the characteristics of fast stress relaxation rate and small extrusion swelling effect, and the balance of physical and mechanical properties and processing properties of the butyl rubber is realized.
The "%" of the invention refers to mass percent.
The preparation of the three-hetero-arm comb-shaped star-branched butyl rubber with the high-width distribution is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: based on the total mass parts of reaction monomers, in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 2-3 times, sequentially adding 100-200% of solvent, 20-30% of 1, 3-butadiene and 0.01-0.5% of structure regulator into the polymerization kettle A, heating to 40 ℃, adding an initiator 1, reacting to perform variable-temperature polymerization, and gradually increasing the temperature from 40 ℃ to 60 ℃ within 40-60 min at a temperature increasing speed<1.3 ℃/min to form a BR chain segment with wide distribution, and sequentially adding 10% -20% of styrene and 0.05% -0.5% of structure regulator into the polymerization kettle A after the conversion rate of 1, 3-butadiene monomer reaches 100%, and reacting for 30-50 min to form the wide chain segmentDistributed PS-BR] n Segment, heating to 70-90 ℃ after complete conversion of monomer, adding coupling agent to perform coupling reaction for 50-70 min; simultaneously, in a 15L stainless steel polymerization kettle B, argon is introduced to replace the system for 2 to 3 times, 100 to 200 percent of solvent, 10 to 20 percent of isoprene and 0.05 to 0.5 percent of structure regulator are sequentially added, the temperature is increased to 50 ℃, an initiator 1 is added, the reaction is temperature-variable polymerization, the temperature is gradually increased from 50 ℃ to 70 ℃ within 30 to 50min, and the temperature-increasing speed is increased <1.2 ℃/min to form a wide-distribution IR chain segment, and sequentially adding 5-10% of styrene, 0.05-0.1% of structure regulator and 30-40 min to form a wide-distribution [ PS-IR ]] n A segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 50-70 min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 2 to 3 times, 100 to 200 percent of solvent, 25 to 30 percent of styrene, 20 to 30 percent of 1, 3-butadiene and 0.05 to 0.5 percent of structure regulator are sequentially added, the temperature is increased to 60 ℃, an initiator 1 is added, the reaction is temperature-variable polymerization, and the temperature is gradually increased from 60 ℃ to 80 ℃ within 40 to 60 minutes, and the temperature-increasing speed is increased<1.3 ℃/min to form a broad vinyl distribution [ -SBR ]] n Adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60-80 min; sequentially adding 5% -10% of Divinylbenzene (DVB) into a polymerization kettle A after the reaction is finished, heating to 85-95 ℃, adding an initiator 2, reacting for 50-70 min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hetero-arm star-shaped nucleating agent ([ - (DVB) SBR- ] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n )。
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle D with a jacket for 3-5 times, and sequentially adding 200% -300% of diluent/solvent V into the polymerization kettle by using the total mass portion of the reaction monomers: mixing 92-96% of isobutene and 3-5% of isoprene in a V ratio of 60-40/40-60 mixed solvent, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, mixing and aging 40-60% of diluent and 0.05-2.0% of co-initiator for 30-40 min at minus 95-minus 85 ℃, adding the mixture into the polymerization system together for stirring and reacting for 0.5-1.0 hr, mixing and dissolving 50-70% of solvent and 2.0-6.0% of nucleating agent obtained in the step (1) for 4.0-6.0 hr, aging for 40-60 min at minus 95-minus 85 ℃, adding the mixture into the polymerization system together for stirring and reacting for 6.0-7.0 hr, finally adding a terminator for discharging and agglomerating, washing and drying to obtain the three-hetero-arm star-shaped branched butyl rubber product with high and wide distribution.
The nucleating agent of the invention is a wide vinyl distribution quaternary three hetero-arm comb star copolymer containing isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) ([ - (DVB) SBR ] ] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n ) The structural general formula is shown in formula I:
wherein Ph is a benzene ring; DVB is divinylbenzene; BR is a butadiene wide distribution homopolymer segment, and the 1, 2-structure content of the BR is 10% -20%; IR is a homopolymer section with wide distribution of isoprene, and the 1, 2-structure content of the IR is 10% -15%; PS is a styrene homopolymer segment; SBR is a random segment of broad vinyl distribution of styrene and butadiene; the quaternary three-hetero-arm comb-like star-shaped copolymer has the styrene content of 30-40%, the butadiene content of 40-60% and the isoprene content of 10-20%; the quaternary three-hetero-arm comb-like star-shaped copolymer has a number average molecular weight (Mn) of 70000-90000 and a molecular weight distribution (Mw/Mn) of 11.21-13.61.
The coupling agent is one of 1,3, 5-benzene trichloride and 1,3, 5-benzene tribromide, preferably 1,3, 5-benzene trichloride. The amount of the coupling agent is determined by the amount of the initiator, and the molar ratio of the coupling agent to the organic lithium is 1.0-3.0.
The initiator 1 is a hydrocarbyl mono-lithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or a composite group of the above groups containing 1-20 carbon atoms. The hydrocarbyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the polymer being designed.
The initiator 2 is an organic peroxide selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, preferably dibenzoyl peroxide (BPO).
The structure regulator is a polar organic compound which generates solvation effect in a polymerization system, and can regulate the reactivity ratio of styrene and butadiene to enable the styrene and the butadiene to be randomly copolymerized. Such polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, preferably Tetrahydrofuran (THF).
The diluent is halogenated alkane, wherein halogen atoms in the halogenated alkane can be chlorine, bromine or fluorine; the number of carbon atoms in the halogenated alkane being C 1 -C 4 . The haloalkane is selected from one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably chloromethane.
The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene or ethylbenzene, preferably cyclohexane.
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from diethyl aluminum chloride, diisobutyl aluminum chloride, methyl aluminum dichloride, aluminum sesquioxide, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride, preferably aluminum sesquioxide. The protonic acid is selected from HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCl. Wherein the total addition amount of the co-initiator is 0.1-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1-0.5:1.
The terminator can be selected from one or more of methanol, ethanol and butanol.
The polymerization reactions of the present invention are all carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution processes are both carried out in a hydrocarbon solvent, which is a hydrocarbon solvent, including straight chain alkanes, aromatic hydrocarbons and cycloalkanes, selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention firstly takes isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) as reaction monomers, takes alkyl lithium and organic peroxide as initiators, adopts temperature-variable polymerization through three-kettle reaction, and then prepares the quaternary three-hetero-arm star-shaped nucleating agent ([ (DVB) SBR) with three-hetero-arm structure and wide vinyl distribution characteristics through coupling of trihalogenide benzene coupling agent ] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n ) Finally, under the catalysis system of the quaternary three-hetero-arm star-shaped nucleating agent and the combination of the isobutene and the isoprene with the alkyl aluminum halide and the protonic acid, the three-hetero-arm comb-shaped star-shaped branched butyl rubber with high width distribution is prepared by adopting a first-arm and then-core method through cationic polymerization.
The invention designs a quaternary three-hetero-arm star-shaped nucleating agent ([ (DVB) SBR) on a macromolecular chain by combining chain segments with three different microstructures on the macromolecular chain through a three-kettle feeding method, a temperature condition gradual change method and accurate control of the types and the dosage of coupling agents] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n ) The nucleating agent contains a three-hetero-arm structure, and the structure has different structural units on each arm, and the different lengths of chain segments can obviously increase the disorder of the whole butyl rubber macromolecule chain segments; meanwhile, the-BR-, -IR-and-SBR-chain segments in the nucleating agent are polymerized at variable temperature, and contain a large amount of vinyl groups which are widely distributed; it is for these two reasons that the butyl rubber is divided during the polymerization processThe disorder of the sub chain segments is increased, the regularity of the molecular chain is obviously destroyed, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic performance, the quick stress relaxation rate and the low extrusion swelling effect are realized, and the processability of the butyl rubber is improved; meanwhile, the PS-segment and the SBR-segment are utilized to contain a large amount of benzene rings, so that the decrease of strength and air tightness caused by the widening of the molecular weight distribution of the butyl rubber is avoided, and the high strength and good air tightness of the butyl rubber are ensured.
Therefore, the invention organically combines the characteristics of the three-hetero-arm comb-shaped star structure with the characteristics of wide distribution and rigidity of various chain segments through the design of the quaternary three-hetero-arm star structure and cooperatively plays a role in solving the problem of the contradictory relation between the processability and the physical and mechanical properties of the butyl rubber, and finally realizes the optimal balance between the processability and the physical and mechanical properties of the butyl rubber.
Drawings
FIG. 1 is 1 # Comparative examples 1 samples and 2 # Comparison of GPC spectra of the samples of example 1.
Detailed Description
The following examples and comparative examples are given to illustrate the inventive effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial polymer grade, and are used after purification without other special requirements.
Raw material sources:
styrene, butadiene, polymer grade China petrochemical Co
Isobutene, isoprene, polymeric grade Zhejiang Xinhui New Material Co., ltd
N-butyllithium with purity of 98% Nanjing Tonglian chemical Co., ltd
1,3, 5-Trichlorobenzene purity 99% of Yangzhou sea chemical Co., ltd
Dibenzoyl peroxide (BPO), a lanzhou auxiliary plant
Sesquiethyl aluminum chloride with purity of 98% of carbofuran technology Co., ltd
Other reagents are commercial industrial products
The analysis and test method comprises the following steps:
determination of molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min -1 。
Measurement of stress relaxation: the measurement was carried out by using a GT-7080-S2 Mooney viscometer manufactured by Taiwan high-speed rail company.
The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.
Measurement of air tightness: an automatic air tightness tester is adopted to measure the air permeability number according to ISO 2782:1995,
the test gas is N 2 The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.
Determination of die swell ratio: RH2000 capillary rheometer manufactured by British Markov company
The temperature is 100 ℃, the length-diameter ratio is 16:1, and the shear rate is 10-1000S -1 Is measured in the interval of (2).
Tensile strength: the method in standard GB/T528-2009 is performed.
Example 1
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 200g of 1, 3-butadiene and 0.6g of THF into the polymerization kettle A, heating to 40 ℃, adding 30.5 mmol of n-butyllithium to start the reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 40 minutes at a heating rate of 0.5 ℃/min to form a wide-distribution BR chain segment, sequentially adding 100g of styrene and 0.8g of THF into the polymerization kettle A, and reacting for 30 minutes to form the wide-distribution [ PS-BR ]] n The chain segment is formed by a plurality of segments,then heating to 70 ℃, adding 230mmo of 11,3, 5-benzene trichloride, and carrying out coupling reaction for 50min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1000g of cyclohexane, 100g of isoprene and 0.5g of THF, heating to 50 ℃, adding 10.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.7 ℃/min to form a wide-distribution IR chain segment, sequentially adding 50g of styrene, 0.5g of THF and reacting for 30min to form a wide-distribution [ PS-IR ] ] n Adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 50min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 250g of styrene, 200g of 1, 3-butadiene and 0.7g of THF, heating to 60 ℃, adding 15.5mm & lt 1 & gt n-butyllithium to start the reaction, gradually heating from 60 ℃ to 80 ℃ within 40min at a heating rate of 0.5 ℃/min, and forming a wide-distribution chain segment [ -SBR ]] n After the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 60min; after the coupling reaction is finished, sequentially adding 50g of DVB into a polymerization kettle A, heating to 85 ℃, adding 0.13g of BPO, reacting for 50min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hetero-arm star-shaped nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n (Mn: 71000 and Mw/Mn: 11.23).
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 3 times, 320g of methyl chloride, 350g of cyclohexane, 276g of isobutene and 12g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 120g of methyl chloride, 2.7g of aluminum sesquichloride and 0.08g of HCl are mixed at minus 85 ℃ and aged for 30 minutes, then added into the polymerization system together and stirred and reacted for 0.5 hour, then 150g of cyclohexane and 10.0g of [ (DVB) SBR ] ] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n Stirring and dissolving for 4.0hr until completely dissolving, aging at-85deg.C for 40min, adding into polymerization system, stirring and reacting for 6.0hrAnd adding 260mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the high-width-distribution tri-hetero-arm comb-shaped star-shaped branched butyl rubber. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 2
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 2 times, sequentially adding 1300g of cyclohexane, 220g of 1, 3-butadiene and 0.7g of THF into the polymerization kettle A, heating to 40 ℃, adding 32.5 mmol of n-butyllithium to start the reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 40 minutes at a heating rate of 0.5 ℃/min to form a wide-distribution BR chain segment, sequentially adding 120g of styrene and 0.9g of THF into the polymerization kettle A, and reacting for 35 minutes to form the wide-distribution [ PS-BR ]] n Segment, then heating to 75 ℃, adding 250mmo of 11,3, 5-benzene trichloride, and carrying out coupling reaction for 55min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1200g of cyclohexane, 120g of isoprene and 0.6g of THF, heating to 50 ℃, adding 10.5 mmol 1 of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.7 ℃/min to form a wide-distribution IR chain segment, sequentially adding 60g of styrene, 0.6g of THF and reacting for 33min to form a wide-distribution [ PS-IR ] ] n Adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 55min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 260g of styrene, 230g of 1, 3-butadiene and 0.9g of THF, heating to 60 ℃, adding 15.5mm & lt 1 & gt of n-butyllithium to start reaction, gradually heating from 60 ℃ to 80 ℃ within 40min at a heating rate of 0.5 ℃/min, and forming a wide-distribution chain segment [ -SBR ]] n After the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 65min; after the coupling reaction is finished, 60g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 87 ℃, 0.21g of BPO is added, after the reaction is finished for 55min, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to prepare the quaternary three-hetero-arm star-shaped nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n (Mn is 76000 and Mw/Mn is 11.95).
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 330g of methyl chloride, 330g of cyclohexane, 280g of isobutene and 15g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 140g of methyl chloride, 2.9g of aluminum sesquichloride and 0.09g of HCl are mixed at minus 85 ℃ and aged for 35 minutes, then added into the polymerization system together and stirred and reacted for 0.6hr, and then 160g of cyclohexane and 15.0g of [ (DVB) SBR ] ] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n Stirring and dissolving for 4.5hr until the mixture is completely dissolved, aging for 45min at-87 ℃, adding the mixture into a polymerization system together and stirring and reacting for 6.2hr, adding 280mL of methanol to terminate the reaction, discharging and condensing the mixture, washing the mixture, and drying the mixture to obtain the three-hetero-arm comb-shaped star-shaped branched butyl rubber with high and wide distribution. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 3
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 2 times, sequentially adding 1600g of cyclohexane, 240g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 35.1 mmol of n-butyllithium to start the reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 50min at a heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment, sequentially adding 150g of styrene and 1.1g of THF into the polymerization kettle A, and reacting for 40min to form the wide-distribution [ PS-BR ]] n Segment, then heating to 80 ℃, adding 260mmo11,3, 5-benzene trichloride, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1400g of cyclohexane, 140g of isoprene and 0.8g of THF, heating to 50 ℃, adding 12.1 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at a heating speed of 0.6 ℃/min to form a wide-distribution IR chain segment, sequentially adding 70g of styrene, 0.8g of THF and reacting for 36min to form a wide-distribution [ PS-IR ] ] n Chain segment, adding the materials in the polymerization kettle B into the polymerization after the monomers are completely convertedIn a mixing kettle A, carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 2 times, 1400g of cyclohexane, 270g of styrene, 260g of 1, 3-butadiene and 1.6g of THF are sequentially added, the temperature is raised to 60 ℃ and 17.2mm 1 of n-butyllithium is added to start the reaction, the temperature is gradually raised from 60 ℃ to 80 ℃ within 50min, the temperature raising speed is 0.4 ℃/min, and a chain segment [ -SBR [ -water-soluble) with wide distribution is formed] n After the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 70min; after the coupling reaction is finished, 70g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 90 ℃, 0.34g of BPO is added, after the reaction is finished for 60min, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to prepare the quaternary three-hetero-arm star-shaped nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n (Mn is 82000 and Mw/Mn is 12.55).
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 340g of methyl chloride, 310g of cyclohexane, 283g of isobutene and 19g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 95 ℃, then 150g of methyl chloride, 3.3g of aluminum sesquichloride and 0.13g of HCl are mixed at minus 90 ℃ and aged for 35 minutes, then added into the polymerization system together and stirred and reacted for 0.7hr, and then 180g of cyclohexane and 20.0g of [ (DVB) SBR ] ] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n Stirring and dissolving for 5.0hr until completely dissolving, aging at-90deg.C for 50min, adding into polymerization system together, stirring and reacting for 6.4hr, adding 300mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain the final product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 4
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: in a jacketed 15L stainless steel polymerizer A, the system was replaced 3 times by introducing argon, 1800g of cyclohexane, 270g of 1, 3-butadiene, 1.2g of THF were sequentially added to the polymerizer A, the temperature was raised to 40℃and 38.5 mmol of n-butyllithium was added to start the reaction within 50 minutes, and the temperature was raisedGradually increasing the temperature from 40 ℃ to 60 ℃ at a heating speed of 0.4 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 180g of styrene and 1.5g of THF into a polymerization kettle A, and reacting for 45min to form the wide-distribution [ PS-BR ]] n Segment, then heating to 85 ℃, adding 290mmo of 11,3, 5-benzene trichloride, and carrying out coupling reaction for 65min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1600g of cyclohexane, 180g of isoprene and 1.2g of THF, heating to 50 ℃, adding 14.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at a heating speed of 0.6 ℃/min to form a wide-distribution IR chain segment, sequentially adding 80g of styrene, 0.9g of THF and reacting for 38min to form a wide-distribution [ PS-IR ] ] n Adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 65min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1700g of cyclohexane, 280g of styrene, 270g of 1, 3-butadiene and 2.2g of THF, heating to 60 ℃, adding 19.1 mmol 1 of n-butyllithium to start reaction, gradually heating from 60 ℃ to 80 ℃ within 50min at a heating rate of 0.4 ℃/min, and forming a wide-distribution chain segment [ -SBR ]] n After the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 75min; after the coupling reaction is finished, 80g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 92 ℃, 0.45g of BPO is added, after the reaction is finished for 65min, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to prepare the quaternary three-hetero-arm star-shaped nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n (Mn is 86000 and Mw/Mn is 12.92).
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of methyl chloride, 300g of cyclohexane, 284 g of isobutene and 21g of isoprene are sequentially added into the polymerization kettle, and stirred and mixed until the temperature of a polymerization system is reduced to minus 95 ℃, then 160g of methyl chloride, 3.9g of aluminum sesquichloride and 0.26g of HCl are mixed at minus 93 ℃ and aged for 37 minutes, and then added into the polymerization system together and stirred for reaction for 0.8 hour, and then 190g of cyclohexane is added ，25.0g[(DVB)SBR-] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n Stirring and dissolving for 5.5hr until completely dissolving, aging at-90deg.C for 55min, adding into polymerization system together, stirring and reacting for 6.8hr, adding 330mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain the final product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 5
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 40.1 mmol of n-butyllithium to start the reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 60 minutes at a heating rate of 0.6 ℃/min to form a wide-distribution BR chain segment, sequentially adding 200g of styrene and 1.6g of THF into the polymerization kettle A, and reacting for 50 minutes to form the wide-distribution [ PS-BR ]] n Segment, then heating to 90 ℃, adding 310mmo11,3, 5-tribromide benzene, and carrying out coupling reaction for 70min; simultaneously, replacing a system in a 15L stainless steel polymerization kettle B for 3 times by introducing argon, sequentially adding 1800g of cyclohexane, 200g of isoprene and 1.5g of THF, heating to 50 ℃, adding 15.2 mmol 1 of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 50min at a heating speed of 0.4 ℃/min to form a wide-distribution IR chain segment, sequentially adding 100g of styrene, 1.0g of THF and reacting for 40min to form a wide-distribution [ PS-IR ] ] n Adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 3 times, 1900g of cyclohexane, 300g of styrene, 290g of 1, 3-butadiene and 2.6g of THF are sequentially added, the temperature is raised to 60 ℃ and 21.5mm & lt 1 & gt n-butyllithium is added to start the reaction, the temperature is gradually raised to 80 ℃ from 60 ℃ within 60min, the temperature raising speed is 0.5 ℃/min, and a chain segment [ -SBR ]] n After the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 80min; after the coupling reaction is completed, 100g DVB is added into the polymerization kettle A in turn, and 0.55g BPO is added after the temperature is raised to 95 DEG CAfter the reaction is carried out for 70min, the reaction mixture after the coupling is treated by water after the reaction is finished, and the glue solution is subjected to wet condensation and drying to prepare the quaternary three-hetero-arm star-shaped nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n (Mn of 89000 and Mw/Mn of 13.52).
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of methyl chloride, 280g of cyclohexane, 288g of isobutene and 24g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 95 ℃, then 180g of methyl chloride, 4.6g of aluminum sesquichloride and 0.33g of HCl are mixed at minus 95 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred for 1.0hr, and then 200g of cyclohexane and 30.0g of [ (DVB) SBR ] ] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n Stirring and dissolving for 6.0hr until completely dissolving, aging at-90deg.C for 60min, adding into polymerization system together, stirring and reacting for 7.0hr, adding 400mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain the final product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 1
Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 1 except that: no nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS] n The method comprises the following steps: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 320g of methyl chloride, 350g of cyclohexane, 276g of isobutene and 12g of isoprene are sequentially added into the polymerization kettle, stirring and mixing are carried out until the temperature of a polymerization system is reduced to minus 90 ℃, then 120g of methyl chloride, 2.7g of aluminum sesquichloride and 0.08g of HCl are mixed at minus 85 ℃ and then aged for 30 minutes, the mixture is added into the polymerization system together and stirred for 0.5 hour, 260mL of methanol is added to terminate the reaction, finally, discharging, condensing, washing and drying are carried out, and the high-width-distribution three-hetero-arm comb-shaped star-branched butyl rubber is obtained. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: other conditions were the same as in example 2 except that: the 1, 3-butadiene in the polymerizer A does not adopt variable temperature polymerization, and reacts at the constant temperature of 40 ℃, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 2 times, sequentially adding 1300g of cyclohexane, 220g of 1, 3-butadiene and 0.7g of THF into the polymerization kettle A, heating to 40 ℃, adding 32.5 mmol 1 of n-butyllithium to start reaction, and reacting for 40min to form BR 1 Segment, then sequentially adding 120g of styrene and 0.9g of THF into a polymerization kettle A, reacting for 35min to form wide-distribution [ PS-BR ] 1 -] n Segment, then heating to 75 ℃, adding 250mmo of 11,3, 5-benzene trichloride, and carrying out coupling reaction for 55min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1200g of cyclohexane, 120g of isoprene and 0.6g of THF, heating to 50 ℃, adding 10.5 mmol 1 of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.7 ℃/min to form a wide-distribution IR chain segment, sequentially adding 60g of styrene, 0.6g of THF and reacting for 33min to form a wide-distribution [ PS-IR ]] n Adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 55min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 260g of styrene, 230g of 1, 3-butadiene and 0.9g of THF, heating to 60 ℃, adding 15.5mm & lt 1 & gt of n-butyllithium to start reaction, gradually heating from 60 ℃ to 80 ℃ within 40min at a heating rate of 0.5 ℃/min, and forming a wide-distribution chain segment [ -SBR ] ] n After the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 65min; after the coupling reaction is finished, 60g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 87 ℃, 0.21g of BPO is added, after the reaction is finished for 55min, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to prepare the quaternary three-hetero-arm star-shaped nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR 1 -PS] n [-(DVB)IR-PS] n (Mn 72000, mw/Mn 9.15).
(2) Three height and width distributionsPreparation of heteroarm comb-shaped star-branched butyl rubber: other conditions were the same as in example 2 except that: no nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS]But with the addition of nucleating agents [ (DVB) SBR ]] n Ph[-(DVB)BR 1 -PS] n [-(DVB)IR-PS] n The method comprises the following steps: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 330g of methyl chloride, 330g of cyclohexane, 280g of isobutene and 15g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 140g of methyl chloride, 2.9g of aluminum sesquichloride and 0.09g of HCl are mixed at minus 85 ℃ and aged for 35 minutes, then added into the polymerization system together and stirred and reacted for 0.6hr, and then 160g of cyclohexane and 15.0g of [ (DVB) SBR ]] n Ph[-(DVB)BR 1 -PS] n [-(DVB)IR-PS] n Stirring and dissolving for 4.5hr until the mixture is completely dissolved, aging for 45min at-87 ℃, adding the mixture into a polymerization system together and stirring and reacting for 6.2hr, adding 280mL of methanol to terminate the reaction, discharging and condensing the mixture, washing the mixture, and drying the mixture to obtain the three-hetero-arm comb-shaped star-shaped branched butyl rubber with high and wide distribution. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: other conditions were the same as in example 3 except that: in the temperature-changing polymerization of isoprene in the polymerization kettle B, the temperature rising speed is 1.5 ℃/min, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 2 times, sequentially adding 1600g of cyclohexane, 240g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 35.1 mmol of n-butyllithium to start the reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 50min at a heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment, sequentially adding 150g of styrene and 1.1g of THF into the polymerization kettle A, and reacting for 40min to form the wide-distribution [ PS-BR ]] n Segment, then heating to 80 ℃, adding 260mmo11,3, 5-benzene trichloride, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle B, argon is introduced to replace the system for 2 times, 1400g of cyclohexane, 140g of isoprene and 0.8g of THF are sequentially added, and the temperature is raised toThe reaction was started by adding 12.1 mmol of n-butyllithium at 50deg.C, and the temperature was gradually increased from 50deg.C to 70deg.C at a rate of 1.5 ℃/min over 40min to form a broad distribution of IR 1 Segment, then sequentially adding 70g of styrene and 0.8g of THF into a polymerization kettle B, and reacting for 36min to form wide-distribution [ PS-IR ] 1 -] n Adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 2 times, 1400g of cyclohexane, 270g of styrene, 260g of 1, 3-butadiene and 1.6g of THF are sequentially added, the temperature is raised to 60 ℃ and 17.2mm 1 of n-butyllithium is added to start the reaction, the temperature is gradually raised from 60 ℃ to 80 ℃ within 50min, the temperature raising speed is 0.4 ℃/min, and a chain segment [ -SBR [ -water-soluble) with wide distribution is formed] n After the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 70min; after the coupling reaction is finished, 70g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 90 ℃, 0.34g of BPO is added, after the reaction is finished for 60min, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to prepare the quaternary three-hetero-arm star-shaped nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR 1 -PS] n (Mn is 81000, mw/Mn is 9.75).
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 3 except that: no nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS]But with the addition of nucleating agents [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR 1 -PS] n The method comprises the following steps: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 340g of methyl chloride, 310g of cyclohexane, 283g of isobutene and 19g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 95 ℃, then 150g of methyl chloride, 3.3g of aluminum sesquichloride and 0.13g of HCl are mixed at minus 90 ℃ and aged for 35 minutes, then added into the polymerization system together and stirred and reacted for 0.7hr, and then 180g of cyclohexane and 20.0g of [ (DVB) SBR ] ] n Ph[-(DVB)BR-PS] n [-(DVB)IR 1 -PS] n Stirring and dissolving for 5.0hrCompletely dissolving, aging at-90deg.C for 50min, adding into polymerization system, stirring for 6.4hr, adding 300mL methanol to stop reaction, discharging, coagulating, washing, and drying to obtain three hetero-arm comb-like star-branched butyl rubber with high width distribution. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 4
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: other conditions were the same as in example 4 except that: only adopts two kettles A and B for polymerization, the polymerization kettle C does not participate in the reaction, and no-SBR-chain segment is formed, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 270g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle A, heating to 40 ℃, adding 38.5 mmol of n-butyllithium to start the reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 50min at a heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment, sequentially adding 180g of styrene and 1.5g of THF into the polymerization kettle A, and reacting for 45min to form the wide-distribution [ PS-BR ]] n Segment, then heating to 85 ℃, adding 290mmo of 11,3, 5-benzene trichloride, and carrying out coupling reaction for 65min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1600g of cyclohexane, 180g of isoprene and 1.2g of THF, heating to 50 ℃, adding 14.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at a heating speed of 0.6 ℃/min to form a wide-distribution IR chain segment, sequentially adding 80g of styrene, 0.9g of THF and reacting for 38min to form a wide-distribution [ PS-IR ] ] n Adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 65min; after the coupling reaction is completed, 80g of DVB is added into a polymerization kettle A in turn, after the temperature is raised to 92 ℃, 0.45g of BPO is added, after the reaction is completed for 65min, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to prepare the quaternary three-hetero-arm star-shaped nucleating agent [ - (DVB) BR-PS] n Ph[-(DVB)IR-PS] n (Mn 72000, mw/Mn 6.92).
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 4, except thatThe method comprises the following steps: no nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS]But rather, a nucleating agent [ - (DVB) BR-PS is added] n Ph[-(DVB)IR-PS] n The method comprises the following steps: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of methyl chloride, 300g of cyclohexane, 284 g of isobutene and 21g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 95 ℃, then 160g of methyl chloride, 3.9g of aluminum sesquichloride and 0.26g of HCl are mixed at minus 93 ℃ and aged for 37 minutes, then added into the polymerization system together and stirred and reacted for 0.8hr, and then 190g of cyclohexane and 25.0g [ - (DVB) BR-PS are added] n Ph[-(DVB)IR-PS] n Stirring and dissolving for 5.5hr until completely dissolving, aging at-90deg.C for 55min, adding into polymerization system together, stirring and reacting for 6.8hr, adding 330mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain the final product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 5
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: other conditions were the same as in example 5 except that: during the synthesis, not 1,3, 5-tribromide benzene is added, but methyl silicon trichloride (CH 3 SiCl 3 ) The method comprises the following steps: other conditions were the same as in example 5 except that: the single kettle A is adopted for polymerization, namely monomer materials in a polymerization kettle B and a polymerization kettle C are sequentially added into the polymerization kettle A for reaction in two times, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 40.1 mmol of n-butyllithium to start the reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 60 minutes at a heating rate of 0.6 ℃/min to form a wide-distribution BR chain segment, sequentially adding 200g of styrene and 1.6g of THF into the polymerization kettle A, and reacting for 50 minutes to form the wide-distribution [ PS-BR ]] n Segment, then raise the temperature to 90 ℃, add 310mmo1 CH 3 SiCl 3 Coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle B, argon is introduced to replace the system for 3 times, and the steps are sequentially carried out1800g cyclohexane, 200g isoprene, 1.5g THF are added, the temperature is raised to 50 ℃ and 15.2 mmol 1 n-butyllithium is added to start the reaction, the temperature is gradually raised from 50 ℃ to 70 ℃ within 50min, the temperature raising speed is 0.4 ℃/min, a wide-distribution IR chain segment is formed, then 100g styrene, 1.0g THF and a wide-distribution PS-IR (polystyrene-IR) are sequentially added into a polymerization kettle B, and the reaction is carried out for 40min, thus forming the wide-distribution PS-IR (polystyrene-IR) ] n Adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 3 times, 1900g of cyclohexane, 300g of styrene, 290g of 1, 3-butadiene and 2.6g of THF are sequentially added, the temperature is raised to 60 ℃ and 21.5mm & lt 1 & gt n-butyllithium is added to start the reaction, the temperature is gradually raised to 80 ℃ from 60 ℃ within 60min, the temperature raising speed is 0.5 ℃/min, and a chain segment [ -SBR ]] n After the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 80min; after the coupling reaction is finished, 100g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 95 ℃, 0.55g of BPO is added, after the reaction is finished for 70min, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to prepare the quaternary three-hetero-arm star-shaped nucleating agent [ (DVB) SBR ]] n CH 3 Si[-(DVB)BR-PS] n [-(DVB)IR-PS] n (Mn is 83000, mw/Mn is 8.92).
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 5 except that: no nucleating agent [ (DVB) SBR ]] n Ph[-(DVB)BR-PS] n [-(DVB)IR-PS]But with the addition of nucleating agents [ (DVB) SBR ]] n CH 3 Si[-(DVB)BR-PS] n [-(DVB)IR-PS] n The method comprises the following steps: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of methyl chloride, 280g of cyclohexane, 288g of isobutene and 24g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 95 ℃, then 180g of methyl chloride, 4.6g of aluminum sesquichloride and 0.33g of HCl are mixed at minus 95 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred for 1.0hr, and then 200g of cyclohexane and 30.0g of [ (DVB) SBR ] ] n CH 3 Si[-(DVB)BR-PS] n [-(DVB)IR-PS] n Stirring and dissolving for 6.0hr until completely dissolving, aging at-90deg.C for 60min, adding into polymerization system together, stirring and reacting for 7.0hr, adding 400mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain the final product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 Performance of high-width distributed three heteroarm comb-like Star branched butyl rubber
As can be seen from table 1: the high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber has high tensile strength, good air tightness, low Mooney relaxation area and low extrusion expansion ratio, and good processability (the smaller the area under a stress relaxation curve is, the lower the energy consumption for mixing processing is).
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (18)
1. A preparation method of an aspect-width-distributed three-hetero-arm comb-shaped star-branched butyl rubber comprises the following steps:
(1) Preparation of a quaternary three-hetero-arm star-shaped nucleating agent: sequentially adding a solvent, 20-30% of 1, 3-butadiene and 0.01-0.5% of a structure regulator into a polymerization kettle A by the total mass parts of reaction monomers, heating to 40 ℃, adding an initiator 1, reacting to change temperature, gradually increasing the temperature from 40 ℃ to 60 ℃ within 40-60 min, heating at a rate of less than 1.3 ℃/min, sequentially adding 10-20% of styrene and 0.05-0.5% of the structure regulator into the polymerization kettle A after the conversion rate of the 1, 3-butadiene monomers reaches 100%, heating to 70-90 ℃ after the monomers are completely converted, and adding a coupling agent for coupling reaction for 50-70 min; simultaneously, sequentially adding a solvent, 10% -20% of isoprene and 0.05% -0.5% of structure regulator into a polymerization kettle B, heating to 50 ℃, adding an initiator 1, reacting to obtain temperature-variable polymerization, gradually heating from 50 ℃ to 70 ℃, heating at a speed of less than 1.2 ℃/min, sequentially adding 5% -10% of styrene and 0.05% -0.1% of structure regulator into the polymerization kettle B after the conversion rate of isoprene monomers reaches 100%, adding materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 50-70 min; simultaneously, sequentially adding 25-30% of solvent, 20-30% of styrene and 0.05-0.5% of structure regulator into a polymerization kettle C, heating to 60 ℃, adding an initiator 1, gradually increasing the temperature from 60 ℃ to 80 ℃ for reaction, adding materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60-80 min, wherein the temperature is gradually increased to 80 ℃ from 60 ℃ at a heating rate of <1.3 ℃/min; sequentially adding 5% -10% of divinylbenzene into a polymerization kettle A after the reaction is finished, heating to 85-95 ℃, adding an initiator 2, reacting for 50-70 min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to prepare the quaternary three-hetero-arm star-shaped nucleating agent;
(2) Preparation of high-width distribution three-hetero-arm comb-shaped star-branched butyl rubber: based on the total mass of reaction monomers, firstly, sequentially adding 200-300% of diluent/solvent volume ratio of 60-40/40-60 mixed solvent, 92-96% of isobutene and 3-5% of isoprene into a reaction kettle, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, mixing and ageing for 30-40 min at minus 95-minus 85 ℃, adding the diluent and 0.05-2.0% of co-initiator into the reaction kettle together for stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 2.0-6.0% of solvent and 2.0% of quaternary three-hetero-arm star-shaped nucleating agent for 4.0-6.0 hr, ageing for 40-60 min at minus 95-minus 85 ℃, adding the mixed solvent into the reaction kettle together for stirring and reacting for 6.0-7.0 hr, finally adding a terminator for discharging and agglomerating, washing and drying to obtain a high-wide-distribution three-hetero-arm star-shaped branched butyl rubber product;
wherein, the steps (1) and (2) are carried out in an anaerobic and anhydrous environment;
the initiator 1 is selected from one of n-butyllithium, sec-butyllithium, methyl butyllithium, phenyl butyllithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium;
the initiator 2 is an organic peroxide, and is selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide or di-tert-butyl peroxide;
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid, and the coupling agent is one of 1,3, 5-benzene trichloride and 1,3, 5-benzene tribromide.
2. The process according to claim 1, wherein the molar ratio of the coupling agent to the initiator 1 is from 1.0 to 3.0.
3. The method of claim 1, wherein the coupling agent is 1,3, 5-trichlorobenzene.
4. The process according to claim 1, wherein the initiator 1 is n-butyllithium.
5. The method according to claim 1, wherein the initiator 2 is dibenzoyl peroxide.
6. The method of claim 1, wherein the structure modifier is selected from the group consisting of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
7. The method of claim 6, wherein the structure modifier is tetrahydrofuran.
8. The method of claim 1, wherein the molar ratio of the protic acid to the alkyl aluminum halide is between 0.05:1 and 0.5:1.
9. The method of claim 1, wherein the alkyl aluminum halide is selected from at least one of diethyl aluminum monochloride, diisobutyl aluminum monochloride, dichloromethyl aluminum, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride, and ethyl aluminum chloride.
10. The method of claim 9, wherein the alkyl aluminum halide is aluminum sesquichloride.
11. The method of claim 1, wherein said protonic acid is selected from the group consisting of HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 Or HNO (HNO) 3 One of them.
12. The method of claim 11, wherein the protic acid is HCl.
13. The method of claim 1, wherein the diluent is selected from the group consisting of methane chloride, methylene chloride, carbon tetrachloride, ethylene dichloride, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
14. The method of claim 13, wherein the diluent is methyl chloride.
15. The method of claim 1, wherein the solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
16. The method of claim 15, wherein the solvent is cyclohexane.
17. The method of claim 1, wherein the terminator is selected from one or more of methanol, ethanol, butanol.
18. The method of claim 1, wherein steps (1) and (2) are both performed in an inert gas atmosphere.
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