CN114163585B - Preparation method of ultra-wide-distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber - Google Patents
Preparation method of ultra-wide-distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber Download PDFInfo
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- CN114163585B CN114163585B CN202010952094.8A CN202010952094A CN114163585B CN 114163585 B CN114163585 B CN 114163585B CN 202010952094 A CN202010952094 A CN 202010952094A CN 114163585 B CN114163585 B CN 114163585B
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- 238000009826 distribution Methods 0.000 title claims abstract description 97
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 224
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 187
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 144
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000005859 coupling reaction Methods 0.000 claims abstract description 70
- 239000002667 nucleating agent Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 44
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 239000007822 coupling agent Substances 0.000 claims abstract description 26
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 11
- 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 138
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 80
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 69
- 238000010438 heat treatment Methods 0.000 claims description 65
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 33
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000002140 halogenating effect Effects 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 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 4
- 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
- 229920001400 block copolymer Polymers 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
- 229920001519 homopolymer Polymers 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 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
- 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
- 238000010539 anionic addition polymerization reaction Methods 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
- 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
- 229940050176 methyl chloride Drugs 0.000 claims description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 abstract description 64
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 7
- 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
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000003003 spiro group Chemical group 0.000 abstract description 3
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 84
- 229910001220 stainless steel Inorganic materials 0.000 description 53
- 239000010935 stainless steel Substances 0.000 description 53
- 239000005062 Polybutadiene Substances 0.000 description 49
- 229910052786 argon Inorganic materials 0.000 description 42
- 239000004793 Polystyrene Substances 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000001112 coagulating effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 230000035882 stress Effects 0.000 description 7
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 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
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
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- 241001441571 Hiodontidae Species 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- WPUBUMYDZKJTBD-UHFFFAOYSA-N 1,5-dibromo-3,3-bis(2-bromoethyl)pentane Chemical compound BrCCC(CCBr)(CCBr)CCBr WPUBUMYDZKJTBD-UHFFFAOYSA-N 0.000 description 2
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 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
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- BGXXXYLRPIRDHJ-UHFFFAOYSA-N tetraethylmethane Chemical group CCC(CC)(CC)CC BGXXXYLRPIRDHJ-UHFFFAOYSA-N 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
- PMSNDFUSQJHJER-UHFFFAOYSA-N 1,5-dichloro-3,3-bis(2-chloroethyl)pentane Chemical compound C(CCl)C(CCCl)(CCCl)CCCl PMSNDFUSQJHJER-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
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-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
- 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
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 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
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 239000002131 composite material Chemical group 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000010552 living cationic polymerization reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 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
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—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
- 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
- C08F297/044—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 using a coupling agent
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber, which is specific to 3, 9-dioxy [5.5 ]]Carrying out halogenation reaction on spiro undecane to synthesize a novel coupling agent 1, 5-dihalogen-3, 3-bis (2-haloethyl) pentane with a linear long-chain symmetrical structure; then isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) are used as reaction monomers, alkyl lithium and organic peroxide are used as initiators, four kettles are used for reaction, temperature change and speed change polymerization are adopted, and then 1, 5-dihalogen-3, 3-bis (2-haloethyl) pentane coupling agent is used for coupling to prepare the quaternary four-hetero-arm star-shaped nucleating agent ([ PS- (DVB) BR ]] n [PS‑(DVB)IR‑] n Y[‑S(DVB)B/(S→(DVB)B)‑PS] n [‑(DVB)SBR‑] n ) The method comprises the steps of carrying out a first treatment on the surface of the Under the catalysis system of alkyl aluminum halide and protonic acid, the quaternary four-hetero-arm star-shaped nucleating agent, isobutene and isoprene adopt a first-arm-then-core method, and ultra-wide distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber is prepared through cationic polymerization. The preparation method has the characteristics of short process flow, controllable molecular weight, good product processing performance, suitability for industrial production and the like.
Description
Technical Field
The invention relates to a preparation method of ultra-wide-distribution four-hetero-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing ultra-wide-distribution four-hetero-arm comb-shaped star-branched butyl rubber by cationic polymerization of a quaternary four-hetero-arm nucleating agent synthesized by isoprene/butadiene/styrene/Divinylbenzene (DVB), isobutene and isoprene.
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 ℃ with 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. CN107793535a provides a butyl rubber having a molecular weight of 90 to 260 tens of thousands, log (MW) >6 and containing structural units derived from isobutylene, structural units derived from conjugated dienes, and optionally structural units derived from aryl olefins. CN200710129810.7 provides a first arm and then core method to synthesize linear butyl rubber, and then coupling with divinylbenzene to obtain star branched butyl rubber. Puskas et al synthesized an initiator tetra-cumyl alcohol having a four-arm structure using pyromellitic acid as the starting material, and then initiated isobutylene and isoprene copolymerization in an inert organic solvent at-120 to-50 ℃ using a tetra-cumyl alcohol/aluminum tetrachloride initiation system to synthesize star-branched butyl rubber having a bimodal molecular weight distribution (Catalysts for manufacture of IIR with bimodal molecular weight distribution: U.S. Pat. No. 5,94538 [ P ]. 1993-3-16.). Wieland et al synthesized a macroinitiator P (MMA-b-St-co-CMS) containing 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-stilbene (DPE) and initiated cationic polymerization of isobutylene and isoprene with this macroinitiator to successfully prepare a multi-arm star butyl rubber (Synthesis of new graft copolymers containing polyisobutylene by acombination of the 1,1-diphenylethylene techniqueand cationic polymerization [ J ]. Polymer Science: polymer Chemistry,2002, 40:3725-3733.). Hadjichristidis et al synthesized PI-PS-PBd four-arm copolymers by four-step coupling using CH3SiCl3 with strict control over the order of addition of the monomers and the degree of excess of the coupling agent (Iatrou H, hadjichristidis N. Synthesis a model 3-miktoarm star terpolymer [ J ]. Macromolecules,1992, 25:4649). Hadjchristids react with the silicon-chlorine group of p-chlorodimethylsilyl styrene by means of high vacuum technology to give a styrene-based polybutadiene macromer, which is then copolymerized with butadiene in the presence of random regulators to give active Comb-shaped polybutadiene, and finally with methyl silicon tetrachloride or silicon tetrachloride to give 3-or 4-arm Star-shaped Comb-shaped polybutadiene (KORTAAS G, IATROUH, LOHSE D J, et al well-Defined combs, star-Com b, and aldcom-on-Comb Polybutadienes by Anionic Polymerization and the Macrom onomerStrategy [ J ]. Macromolecules,2005,38 (12): 4996-5001). Huiqin A star-branched polymer with divinylbenzene as a core and polyisobutylene as an arm was synthesized by living cationic polymerization at-80℃using 2-chloro-2, 4-tetramethylpentane/titanium tetrachloride as an initiator system and methyl chloride/cyclohexane as a solvent ("preparation and characterization of star-branched polyisobutylene with divinylbenzene as a core", "synthetic rubber industry", synthetic rubber industry, 2008, 31 (5): 362-365 ").
Disclosure of Invention
The invention aims to provide a preparation method of ultra-wide-distribution three-hetero-arm comb-shaped star-branched butyl rubber. The preparation method of the invention takes alkyl lithium and organic peroxide as initiator, isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) as reaction monomers, and adopts a temperature-changing and speed-changing polymerization method to prepare the ultra-wide distribution quaternary four-hetero-arm star nucleating agent through coupling with novel long-chain tetrahalide coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane; finally, under the catalysis system of Lewis acid and protonic acid, the ultra-wide distribution quaternary four-hetero-arm star-shaped nucleating agent, isobutene and isoprene are subjected to cationic polymerization by adopting a first-arm and then-core method to prepare the ultra-wide distribution quaternary 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 ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber has the characteristics of high stress relaxation rate and small extrusion swelling effect, and simultaneously has enough green rubber strength and good air tightness, and the balance of the physical and mechanical properties and the processing properties of the butyl rubber is realized.
The "%" of the invention refers to mass percent.
The preparation of the ultra-wide distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
preparation of a quaternary four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: based on the total mass percent of reactants, firstly, introducing argon gas into a 4L stainless steel polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200% of deionized water, 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and 1-5% of catalyst into the polymerization kettle, heating to 50-80 ℃, reacting for 1-3 hours, adding 20-40% of NaOH aqueous solution with the mass concentration of 10-20% for stopping the reaction, and finally adding 200-300% of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane (the yield is 85-95%).
b, preparation of a quaternary four-hybrid-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, 10-20% 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 wide areaAnd sequentially adding 5% -10% of styrene, 0.01% -0.5% of structure regulator and the distributed BR chain segments into the polymerization kettle A, and reacting for 20-40 min to form the broad-distribution PS-BR-] n Segment, heating to 70-90 ℃ after complete conversion of monomer, adding coupling agent to perform coupling reaction for 40-60 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 0.01 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, then sequentially adding 5-10% of styrene and 0.01-0.5% of structure regulator into a polymerization kettle B, and reacting for 20-40 min to form a wide-distribution [ PS-IR ]]An n-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 40-60 min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace a system for 2 to 3 times, 100 to 200 percent of solvent, 0.01 to 0.5 percent of structure regulator and 70 to 80 ℃ are sequentially added, an initiator 1 is added, 10 to 20 percent of styrene and 5 to 10 percent of 1, 3-butadiene are stirred and mixed for 20 to 30 minutes, the reaction is carried out in a variable speed polymerization mode, the polymerization kettle is added in a continuous injection mode, the reaction is carried out within 50 to 60 minutes, and the initial feeding speed is increased >5.0% of mixture/min, the reduction of the feeding speed is determined according to the reaction time, a random and long gradual change section-SB/(S-B) -chain segment is formed, then 5-10% of styrene, 0.05-0.1% of structure regulator and 20-40 min of reaction are sequentially added into a polymerization kettle, and a random and gradual change [ PS-SB/(S-B) ] is formed] 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 50-70 min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 2 to 3 times, 100 to 200 percent of solvent, 10 to 20 percent of styrene, 5 to 10 percent of 1, 3-butadiene and 0.01 to 0.5 percent of structure regulator are sequentially added, the temperature is increased to 50 to 70 ℃, an initiator 1 is added, and the reaction is carried out for 30 to 40 minutes, thus forming [ -SBR [ -17 ]] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 40-60 min; after the coupling reaction is completed, the reaction mixture is then fed into a polymerization kettleSequentially adding 3% -7% of Divinylbenzene (DVB) into the A, heating to 70-80 ℃, adding 0.05% -1.0% of initiator 2, reacting for 50-70 min, treating the coupled reaction mixture with water after the reaction is finished, performing wet condensation on the glue solution, and drying to obtain the four-membered four-hetero-arm star-shaped nucleating agent ([ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n )。
(2) Preparation of ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3-4 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 92-98% of isobutene and 2-8% 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 ℃, then mixing and aging 40-60% of diluent and 0.05-3.0% 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, then mixing and dissolving 50-70% of solvent and 3.0-7.0% of nucleating agent obtained in the step (1) for 5.0-7.0 hr, aging for 30-40 min at minus 95-minus 85 ℃, adding the mixture into the polymerization system together for stirring and reacting for 5.0-7.0 hr, finally adding a terminator for discharging and agglomerating, washing and drying to obtain the four-hetero-arm comb-shaped star-shaped branched butyl rubber product.
The nucleating agent of the invention is a quaternary tetra-heteroarm star-shaped copolymer ([ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n ) The structural general formula is shown in formula I:
wherein Y is 3, 3-diethylpentane; DVB is divinylbenzene; BR is a butadiene homopolymer segment with wide vinyl distribution, and the 1, 2-structure content of BR is 15-20%; IR is a vinyl widely distributed isoprene homopolymer segment with a 1, 2-structure content of 5% -10%; SBR is a styrene, 1, 3-butadiene random block copolymer; PS is a styrene homopolymer segment; SB is a random segment of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene; the ultra-wide distribution quaternary four-hybrid arm star copolymer has the styrene content of 30-60%, the butadiene content of 20-30% and the isoprene content of 10-20%; the quaternary tetra-heteroarm star-shaped copolymer has the number average molecular weight (Mn) of 80000-100000 and the molecular weight distribution (Mw/Mn) of 14.23-16.72.
The halogenating agent is one of liquid chlorine and liquid bromine, preferably liquid bromine, the dosage of the halogenating agent depends on the dosage of 3, 9-dioxy [5.5] spiro-undecane, and the molar ratio of the dosage of the liquid bromine to the 3, 9-dioxy [5.5] spiro-undecane is 4.5-6.5.
The catalyst of the invention is HCl-CH 3 A mixed aqueous solution of OH, wherein the molar concentration of HCl is: 0.1 to 0.7mol/L.
The amount of the coupling agent is determined according to the amount of the initiator, and the molar ratio of the coupling agent to the organic lithium is 1.0-5.0.
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 is C1-C4. 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 aims at 3, 9-dioxy [5.5 ]]Halogenating spiro undecane to synthesize a novel coupling agent 1, 5-o with linear long-chain symmetrical structureDihalo-3, 3-bis (2-haloethyl) pentane; then isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) are used as reaction monomers, alkyl lithium and organic peroxide are used as initiators, four kettles are used for reaction, temperature change and speed change polymerization are adopted, and then 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane coupling agent is used for coupling to prepare the quaternary four-hetero-arm star-shaped nucleating agent ([ PS- (DVB) BR) with the characteristics of four hetero-arm structure, wide vinyl distribution, random and long gradient sections] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n ) Finally, under the catalysis system of alkyl aluminum halide and protonic acid, the quaternary three-hetero-arm star-shaped nucleating agent, isobutene and isoprene adopt a first-arm and then-core method, and ultra-wide distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber is prepared through cationic polymerization.
The invention designs a four-hybrid-arm star-shaped nucleating agent ([ PS- (DVB) BR- ] with ultra-wide distribution by combining chain segments with four different microstructures on a macromolecular chain through a four-kettle feeding method, a reaction temperature and a feeding speed condition gradual change method and the use of a novel coupling agent with a linear long-chain symmetrical structure] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n ) Y, the nucleating agent contains a four hetero-arm structure, and the structure is different in structural units on each arm and different in chain segment length; in addition, the-BR-, -IR-chain segments in the nucleating agent are all polymerized at variable temperature, and contain a large amount of vinyl groups which are widely distributed; the chain segment of the SB/(S-B) adopts variable speed polymerization, so that the chain segment has certain randomness and gradual change; the reason for the three aspects is that the disorder of a molecular chain segment is obviously increased, the regularity of the molecular chain is obviously destroyed, the flexibility of the molecular chain segment is obviously improved, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic performance, the butyl rubber has fast stress relaxation rate and small extrusion swelling effect, and the processability of the butyl rubber is improved; meanwhile, the nucleating agent contains a large amount of benzene rings in the-PS-and-SBR-chain segments, and the strength and air tightness reduction caused by the widening of the molecular weight distribution of the butyl rubber are avoided by utilizing the characteristics of the barrier property and rigidity of the benzene rings The high strength and good air tightness of butyl rubber are ensured. Thus, the first and second substrates are bonded together,
the invention organically combines the characteristics of four-hybrid-arm star-shaped structure and the characteristics of wide distribution, randomness, gradual change, barrier property and rigidity of various chain segments through the synthesis of the novel coupling agent with the linear long-chain symmetrical structure and the design of the quaternary four-hybrid-arm star-shaped structure, and solves the problem of contradiction relation between the processability and the physical and mechanical properties of butyl rubber by synergistic effect, and finally realizes the optimal balance between the processability and the physical and mechanical properties of the butyl rubber.
Drawings
FIG. 1:1 # 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.
(1) The raw material sources are as follows:
other reagents are commercial industrial products
(2) The analytical 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 Mooney viscometer model GT-7080-S2 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.
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).
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.
Tensile strength: the method in standard GB/T528-2009 is performed.
Example 1
(1) Preparation of a quaternary four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, argon is introduced for replacement for 3 times, 600g of deionized water and 58g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle ]Spirocyclic undecane, 320g liquid bromine, 18g HCl-CH 3 OH solution (molar concentration of HCl: 0.7 mol/L), heating to 70 ℃, reacting for 3.0hr, adding 300g of 15% NaOH aqueous solution to terminate the reaction, finally adding 800g of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane (yield 93%).
b, preparation of a quaternary four-hybrid-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, 100g of 1, 3-butadiene and 0.5g of THF into the polymerization kettle A, heating to 40 ℃, adding 33.5 mmol of n-butyllithium to start the reaction, reacting in 40min, gradually increasing the temperature from 40 ℃ to 60 ℃ at a heating rate of 0.6 ℃/min to form a wide-distribution BR chain segment, sequentially adding 50g of styrene and 0.6g of THF into the polymerization kettle A, reacting for 20min to form a wide-distribution PS-BR [ (polystyrene) -BR ]] n Segment, then heating to 70 ℃, adding 260mmo11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 40min; simultaneously, in a 15L stainless steel polymerization kettle B, argon is introduced to replace the system for 2 times, and 1000g of rings are sequentially addedHexane, 100g of isoprene, 0.6g of THF, heating to 50 ℃ and adding 13.5mm 1 of n-butyllithium to start reaction, gradually heating from 50 ℃ to 70 ℃ within 30min at a heating speed of 0.8 ℃/min to form a wide-distribution IR chain segment, then sequentially adding 50g of styrene, 0.6g of THF into a polymerization kettle B, and reacting for 20min to form a wide-distribution PS-IR (polystyrene-styrene) material ] 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 40min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 2 times, sequentially adding 1000g of cyclohexane and 1.9g of THF, heating to 70 ℃, adding 16.5 mmol 1 of n-butyllithium to start reaction, stirring and mixing 100g of styrene and 50g of 1, 3-butadiene for 20min, and within 50min, reducing the feeding speed by 2g of mixture per minute at the initial feeding speed of 10g of mixture/min to form a random and long gradient-SB/(S-B) -chain segment; then sequentially adding 50g of styrene and 0.6g of THF into a polymerization kettle C for reacting for 20min to form broad-distribution random and gradual [ PS-SB/(S-B) ]] 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 50min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 2 times, 1000g of cyclohexane, 100g of styrene, 50g of 1, 3-butadiene and 1.2g of THF are sequentially added, the temperature is raised to 50 ℃,17.5 mmol 1 of n-butyllithium is added to react for 30min, and [ -SBR [ -17 mmol 1 ] is formed] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 40min; after the coupling reaction is finished, sequentially adding 30g of DVB into a polymerization kettle A, heating to 70 ℃, adding 0.11g 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 four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n (Mn is 82000 and Mw/Mn is 14.23).
(2) Preparation of ultra-wide distribution four-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, 310g of chloromethane, 370g of cyclohexane, 276g of isobutene and 6g of isoprene are added into the polymerization kettle in sequence, and the mixture is stirred and mixed until the temperature of a polymerization system is reduced to minus 90 DEG CThen 120g of methyl chloride, 2.8g of sesquiethyl aluminum chloride and 0.09g of HCl are mixed at the temperature of minus 85 ℃ and then aged for 30min, and then added into a polymerization system together to be stirred and reacted for 0.5hr, and then 160g of cyclohexane and 9.0g of [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n Stirring and dissolving for 5.0hr until completely dissolving, aging at-85deg.C for 30min, adding into polymerization system together, stirring and reacting for 5.0hr, adding 300mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain ultra-wide distribution four-hetero-arm comb-like star-shaped branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 2
(1) Preparation of a quaternary four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of a quaternary four-hybrid-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, 130g of 1, 3-butadiene and 0.7g of THF into the polymerization kettle A, heating to 40 ℃, adding 34.6mmo1 of n-butyllithium to start the reaction, reacting in 40min, gradually increasing the temperature from 40 ℃ to 60 ℃ at a heating rate of 0.6 ℃/min to form a wide-distribution BR chain segment, sequentially adding 60g of styrene and 0.9g of THF into the polymerization kettle A, and reacting for 25min to form a wide-distribution PS-BR [ (polystyrene) -BR ] ] n Segment, then heating to 75 ℃, adding 280mmo11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 45min; 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 0.8g of THF, heating to 50 ℃, adding 14.5 mmol 1 of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.8 ℃/min to form a wide-distribution IR chain segment, sequentially adding 70g of styrene, 0.9g of THF and reacting for 26min 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 45min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 2 times, 1300g of cyclohexane and 2 g of cyclohexane are sequentially added3g of THF, heating to 70 ℃, adding 18.5 mmol 1 of n-butyllithium to start reaction, stirring and mixing 130g of styrene and 60g of 1, 3-butadiene for 20min, and within 50min, reducing the feeding speed by 3g of mixture per minute at the initial feeding speed of 11g of mixture per min to form a random and long transition segment-SB/(S-B) -chain segment; then 60g of styrene and 0.8g of THF are sequentially added into a polymerization kettle C to react for 25min to form broad distribution of random and gradual [ PS-SB/(S-B) ] ] 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 55min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 2 times, 1200g of cyclohexane, 130g of styrene, 60g of 1, 3-butadiene and 1.5g of THF are sequentially added, the temperature is raised to 55 ℃, 18.5mm mu 1 of n-butyllithium is added to react for 32min, and [ -SBR [ -17 m ] is formed] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 45min; after the coupling reaction is finished, 40g of DVB is added into a polymerization kettle A in turn, after the temperature is raised to 72 ℃, 0.14g 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 four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n (Mn 85000, mw/Mn 14.89).
(2) Preparation of ultra-wide distribution four-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, 350g of cyclohexane, 280g of isobutene and 10g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 90 ℃, then 140g of methyl chloride, 3.1g of aluminum sesquichloride and 0.11g of HCl are mixed at minus 87 ℃ and aged for 32 minutes, then added into the polymerization system together and stirred and reacted for 0.6hr, and then 170g of cyclohexane and 12.0g of [ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n Stirring and dissolving for 5.5hr until completely dissolving, aging at-87 deg.C for 33min, adding into polymerization system together, stirring and reacting for 5.5hr, adding 320mL methanol to terminate reaction, discharging and coagulating, washingAnd drying to obtain the ultra-wide-distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 3
(1) Preparation of a quaternary four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of a quaternary four-hybrid-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 1500g of cyclohexane, 150g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle A, heating to 40 ℃ and adding 36.6mmo1 of n-butyllithium to start the reaction, reacting in 50min, gradually increasing the temperature from 40 ℃ to 60 ℃ at a heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment, sequentially adding 70g of styrene and 1.2g of THF into the polymerization kettle A, reacting for 30min to form a wide-distribution [ PS-BR ]] n Segment, then heating to 80 ℃, adding 300mmo11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 50min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 1400g of cyclohexane, 140g of isoprene and 0.9g of THF, heating to 50 ℃, adding 16.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at the heating rate of 0.5 ℃/min to form a wide-distribution IR chain segment, sequentially adding 80g of styrene, 1.3g of THF and reacting for 31min to form a wide-distribution [ PS-IR ] ]n chain segments, 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 a system for 3 times, sequentially adding 1500g of cyclohexane and 2.5g of THF, heating to 75 ℃, adding 20.5 mmol of n-butyllithium to start reaction, stirring and mixing 150g of styrene and 80g of 1, 3-butadiene for 25min, and within 55min, reducing the feeding speed by 2g of mixture per minute at an initial feeding speed of 13g of mixture/min to form a random and long gradient-SB/(S-B) -chain segment; then 70g of styrene and 1.1g of THF are sequentially added into a polymerization kettle C to react for 30min, thus forming random and gradual [ PS-SB/(S-B) ]] n Chain segment, adding the material in the polymerization kettle C into the polymerization kettle A after the monomer is completely converted, and coupling reaction60min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1400g of cyclohexane, 150g of styrene, 80g of 1, 3-butadiene and 1.9g of THF are sequentially added, the temperature is raised to 60 ℃, and 20.5 mmol 1 of n-butyllithium is added to react for 35min to form [ -SBR [ -17 ]] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 50min; after the coupling reaction is finished, sequentially adding 50g of DVB into a polymerization kettle A, heating to 75 ℃, adding 0.21g of BPO, reacting for 60min, 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 four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n (Mn of 89000 and Mw/Mn of 15.39).
(2) Preparation of ultra-wide distribution four-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, 330g of cyclohexane, 284g of isobutene and 14g 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, 3.5g of aluminum sesquichloride and 0.15g 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 16.0g of [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)S BR-] n Stirring and dissolving for 6.0hr until completely dissolving, aging at-90deg.C for 35min, adding into polymerization system together, stirring and reacting for 6.0hr, adding 350mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain ultra-wide distribution four-hetero-arm comb-like star-shaped branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 4
(1) Preparation of a quaternary four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of a quaternary four-hybrid-arm star-shaped nucleating agent: in a 15L stainless steel polymerizer A with a jacket, introducing argon to replace the system for 3 times, and sequentially adding the components into the polymerizer A 1800g of cyclohexane, 170g of 1, 3-butadiene and 1.2g of THF are added, the temperature is raised to 40 ℃ and 38.6mmo1 of n-butyllithium is added for starting the reaction, the reaction is carried out within 50min, the temperature is gradually raised to 60 ℃ from 40 ℃ and the temperature raising speed is 0.4 ℃/min, a wide-distribution BR chain segment is formed, then 90g of styrene and 1.6g of THF are sequentially added into a polymerization kettle A, and after the reaction is carried out for 35min, the wide-distribution PS-BR-17-one-pot is formed] n Segment, then heating to 85 ℃, adding 320mmo11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 55min; 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 1.3g of THF, heating to 50 ℃, adding 18.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at a heating speed of 0.5 ℃/min to form a wide-distribution IR chain segment, sequentially adding 90g of styrene, 1.7g of THF and reacting for 36min to form a wide-distribution [ PS-IR ]]n chain segments, 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 a system for 3 times, sequentially adding 1700g of cyclohexane, 2.7g of THF, heating to 75 ℃, adding 23.5 mmol of n-butyllithium to start reaction, stirring and mixing 170g of styrene and 90g of 1, 3-butadiene for 27min, and within 55min, reducing the feeding speed by 2g of mixture per minute at an initial feeding speed of 13g of mixture/min to form a random and long gradient-SB/(S-B) -chain segment; then adding 90g of styrene and 1.4g of THF into a polymerization kettle C in sequence to react for 35min to form broad-distribution random and gradual [ PS-SB/(S-B) ] ] 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 65min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1600g of cyclohexane, 170g of styrene, 90g of 1, 3-butadiene and 2.2g of THF are sequentially added, the temperature is raised to 65 ℃, 23.5mm mu 1 of n-butyllithium is added for reaction for 38min, and [ -SBR [ -17 ]] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 55min; after the coupling reaction is finished, 60g of DVB is added into a polymerization kettle A in sequence, 0.32g of BPO is added after the temperature is raised to 77 ℃, after the reaction is finished for 65min, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet methodCondensing and drying to obtain the quaternary four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n (Mn is 93000 and Mw/Mn is 16.12).
(2) Preparation of ultra-wide distribution four-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, 360g of methyl chloride, 310g of cyclohexane, 290g of isobutene and 20g of isoprene are sequentially added into the polymerization kettle, and stirred and mixed until the temperature of the polymerization system is reduced to-97 ℃, then 170g of methyl chloride, 4.1g of aluminum sesquichloride and 0.26g of HCl are mixed at-95 ℃ and aged for 37 minutes, and then added into the polymerization system together to be stirred and reacted for 0.8hr, and then 200g of cyclohexane and 19.0g of [ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n Stirring and dissolving for 6.5hr until completely dissolving, aging at-95deg.C for 38min, adding into polymerization system together, stirring and reacting for 6.5hr, adding 400mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 5
(1) Preparation of a quaternary four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, argon is introduced for replacement for 4 times, 600g of deionized water and 60g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle]Spirocyclic undecane, 280g liquid chlorine, 14g HCl-CH 3 OH solution (molar concentration of HCl: 0.7 mol/L), heating to 85 ℃, reacting for 4.0hr, adding 300g of aqueous solution of NaOH with mass concentration of 20% to terminate the reaction, finally adding 920g of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dichloro-3, 3-di (2-chloroethyl) pentane (yield 91%).
b, preparation of a quaternary four-hybrid-arm star-shaped nucleating agent: in a jacketed 15L stainless steel polymerizer A, the system was replaced 3 times by introducing argon, 2000g of cyclohexane, 200g of 1, 3-butadiene, 1.5g of THF were sequentially added to the polymerizer A, and the temperature was raised to 40℃and 40.6m was added The mo1 n-butyllithium starts to react, the temperature is gradually increased from 40 ℃ to 60 ℃ within 60min, the temperature rising speed is 0.5 ℃/min, a wide-distribution BR chain segment is formed, then 100g of styrene and 1.8g of THF are sequentially added into a polymerization kettle A, and after 40min of reaction, a wide-distribution [ PS-BR ]] n Segment, then heating to 90 ℃, adding 340mmo11, 5-dichloro-3, 3-di (2-chloroethyl) pentane, and carrying out coupling reaction for 60min; 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 19.5 mmol 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, 1.9g of THF and reacting for 40min to form a wide-distribution [ PS-IR ]]n chain segments, 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, introducing argon to replace a system for 3 times, sequentially adding 1900g of cyclohexane and 3.1g of THF, heating to 80 ℃, adding 25.5 mmol 1 of n-butyllithium to start reaction, stirring and mixing 200g of styrene and 100g of 1, 3-butadiene for 30min, and within 60min, reducing the feeding speed by 3g of mixture per minute at the initial feeding speed of 14g of mixture/min to form a random and long gradient-SB/(S-B) -chain segment; then adding 100g of styrene and 1.8g of THF into a polymerization kettle C in sequence to react for 40min to form broad-distribution random and gradual [ PS-SB/(S-B) ] ] 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 70min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1600g of cyclohexane, 170g of styrene, 90g of 1, 3-butadiene and 2.2g of THF are sequentially added, the temperature is raised to 65 ℃, 24.5mm mu 1 of n-butyllithium is added for reaction for 40min, and [ -SBR [ -17 ]] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60min; after the coupling reaction is finished, 70g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 80 ℃, 0.45g 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 four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n (Mn is 100000, mw/Mn is 16.72).
(2) Preparation of ultra-wide distribution four-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, 380g of chloromethane, 300g of cyclohexane, 254 g of isobutene and 24g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 100 ℃, then 180g of chloromethane, 5.2g of sesquiethylaluminum chloride and 0.37g of HCl are mixed at minus 95 ℃ and aged for 40min, then added into the polymerization system together and stirred for reaction for 1.0hr, and then 220g of cyclohexane and 21.0g of [ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n Stirring and dissolving for 7.0hr until completely dissolving, aging at-95deg.C for 40min, adding into polymerization system together, stirring and reacting for 7.0hr, adding 450mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 1
Preparation of ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 1 except that: no nucleating agent (PS- (DVB) BR) is added in the synthesis process] n [PS-(DVB)IR-] n Y
[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] 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, 310g of methyl chloride, 370g of cyclohexane, 276g of isobutene and 6g 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, 2.8g of aluminum sesquichloride and 0.09g of HCl are mixed at minus 85 ℃ and then aged for 30 minutes, then the mixture is added into the polymerization system together and stirred for 0.5 hour, then 300mL of methanol is added to terminate the reaction, finally, discharging, condensing, washing and drying are carried out, and the ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber product 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 four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 2.
b, preparation of a quaternary four-hybrid-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, 130g of 1, 3-butadiene and 0.7g of THF into the polymerization kettle A, heating to 40 ℃ and adding 34.6mmo1 of n-butyllithium to start the reaction, reacting for 40min to form a BR1 chain segment, sequentially adding 60g of styrene, 0.9g of THF into the polymerization kettle A, reacting for 25min to form a broad-distribution [ PS-BR1 ]]n segment, then heating to 75 ℃, adding 280mmo11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 45min; 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 0.8g of THF, heating to 50 ℃, adding 14.5 mmol 1 of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.8 ℃/min to form a wide-distribution IR chain segment, sequentially adding 70g of styrene, 0.9g of THF and reacting for 26min 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 45min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 2 times, sequentially adding 1300g of cyclohexane and 2.3g of THF, heating to 70 ℃, adding 18.5mm 1 of n-butyllithium to start reaction, stirring and mixing 130g of styrene and 60g of 1, 3-butadiene for 20min, and within 50min, reducing the feeding speed by 3g of mixture per minute at the initial feeding speed of 11g of mixture per min to form a random and long gradient-SB/(S-B) -chain segment; then 60g of styrene and 0.8g of THF are sequentially added into a polymerization kettle C to react for 25min to form broad distribution of random and gradual [ PS-SB/(S-B) ]] 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 55min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 2 times1200g cyclohexane, 130g styrene, 60g1, 3-butadiene, 1.5g THF are added in sequence, the temperature is raised to 55 ℃, 18.5 mmol 1 n-butyllithium is added for reaction for 32min, and [ -SBR [ -17 mmol ] is formed] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 45min; after the coupling reaction is finished, 40g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 72 ℃, 0.14g 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 four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR1 ] ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n (Mn is 83000, mw/Mn is 13.23).
(2) Preparation of ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 2 except that: no nucleating agent (PS- (DVB) BR) is added in the synthesis process]n[PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n But the nucleating agent PS- (DVB) BR1-] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] 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, 350g of cyclohexane, 280g of isobutene and 10g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 90 ℃, then 140g of methyl chloride, 3.1g of aluminum sesquichloride and 0.11g of HCl are mixed at minus 87 ℃ and aged for 32 minutes, then added into the polymerization system together and stirred and reacted for 0.6hr, and then 170g of cyclohexane and 12.0g of [ PS- (DVB) BR1 ]] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n Stirring and dissolving for 5.5hr until completely dissolving, aging at-87 deg.C for 33min, adding into polymerization system together, stirring and reacting for 5.5hr, adding 320mL methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
(1) Quaternary four-hybrid-arm star-shaped nucleating agent Is prepared from the following steps: other conditions were the same as in example 3 except that: 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added in the synthesis process, but a conventional coupling agent silicon tetrachloride (SiCl is added 4 ) The method comprises the following steps: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1500g of cyclohexane, 150g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle A, heating to 40 ℃ and adding 36.6mmo1 of n-butyllithium to start the reaction, reacting in 50min, gradually increasing the temperature from 40 ℃ to 60 ℃ at a heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment, sequentially adding 70g of styrene and 1.2g of THF into the polymerization kettle A, reacting for 30min to form a wide-distribution [ PS-BR ]] n Segment, then raise the temperature to 80 ℃, add 300mmo1 SiCl 4 Coupling reaction for 50min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 1400g of cyclohexane, 140g of isoprene and 0.9g of THF, heating to 50 ℃, adding 16.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at the heating rate of 0.5 ℃/min to form a wide-distribution IR chain segment, sequentially adding 80g of styrene, 1.3g of THF and reacting for 31min 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 a system for 3 times, sequentially adding 1500g of cyclohexane and 2.5g of THF, heating to 75 ℃, adding 20.5 mmol of n-butyllithium to start reaction, stirring and mixing 150g of styrene and 80g of 1, 3-butadiene for 25min, and within 55min, reducing the feeding speed by 2g of mixture per minute at an initial feeding speed of 13g of mixture/min to form a random and long gradient-SB/(S-B) -chain segment; then 70g of styrene and 1.1g of THF are sequentially added into a polymerization kettle C to react for 30min, thus forming random and gradual [ PS-SB/(S-B) ]] 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 60min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1400g of cyclohexane, 150g of styrene, 80g of 1, 3-butadiene and 1.9g of THF are sequentially added, the temperature is raised to 60 ℃, and 20.5 mmol 1 of n-butyllithium is added to react for 35min to form [ -SBR [ -17 ]] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 50min; after the coupling reaction is finished, sequentially adding 50g of DVB into a polymerization kettle A, heating to 75 ℃, adding 0.21g of BPO, reacting for 60min, 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 four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Si[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n (Mn 85000, mw/Mn 10.12).
(2) Preparation of ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 2 except that: no nucleating agent (PS- (DVB) BR) is added in the synthesis process] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n But to add nucleation [ PS- (DVB) BR1 ]] n [PS-(DVB)IR-]nSi[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 340g of methyl chloride, 330g of cyclohexane, 284g of isobutene and 14g 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, 3.5g of aluminum sesquichloride and 0.15g 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 16.0g of [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Si[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n Stirring and dissolving for 6.0hr until completely dissolving, aging at-90deg.C for 35min, adding into polymerization system together, stirring and reacting for 6.0hr, adding 350mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain ultra-wide distribution four-hetero-arm comb-like star-shaped branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 4
(1) Preparation of a quaternary four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 4.
b, preparation of a quaternary four-hybrid-arm star-shaped nucleating agent: other conditionsThe same as in example 4, except that: only adopting A, B and C three kettles for polymerization, the polymerization kettle D 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, 170g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle A, heating to 40 ℃, adding 38.6mmo1 of n-butyllithium to start the reaction, reacting in 50min, gradually increasing the temperature from 40 ℃ to 60 ℃ at a heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment, sequentially adding 90g of styrene and 1.6g of THF into the polymerization kettle A, and reacting for 35min to form a wide-distribution [ PS-BR ]] n Segment, then heating to 85 ℃, adding 320mmo11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 55min; 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 1.3g of THF, heating to 50 ℃, adding 18.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at a heating speed of 0.5 ℃/min to form a wide-distribution IR chain segment, sequentially adding 90g of styrene, 1.7g of THF and reacting for 36min 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 a system for 3 times, sequentially adding 1700g of cyclohexane, 2.7g of THF, heating to 75 ℃, adding 23.5 mmol of n-butyllithium to start reaction, stirring and mixing 170g of styrene and 90g of 1, 3-butadiene for 27min, and within 55min, reducing the feeding speed by 2g of mixture per minute at an initial feeding speed of 13g of mixture/min to form a random and long gradient-SB/(S-B) -chain segment; then adding 90g of styrene and 1.4g of THF into a polymerization kettle C in sequence to react for 35min to form broad-distribution random and gradual [ PS-SB/(S-B) ]] 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 65min; after the coupling reaction is finished, 60g of DVB is added into a polymerization kettle A in turn, after the temperature is raised to 77 ℃, 0.32g 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 four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n (Mn is 82000 and Mw/Mn is 8.63).
(2) Preparation of ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 4 except that: no nucleating agent (PS- (DVB) BR) is added in the synthesis process ] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n But to add nucleation [ PS- (DVB) BR ]]n[PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-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, 360g of methyl chloride, 310g of cyclohexane, 290g of isobutene and 20g of isoprene are sequentially added into the polymerization kettle, and stirred and mixed until the temperature of the polymerization system is reduced to-97 ℃, then 170g of methyl chloride, 4.1g of aluminum sesquichloride and 0.26g of HCl are mixed at-95 ℃ and aged for 37 minutes, and then added into the polymerization system together to be stirred and reacted for 0.8hr, and then 200g of cyclohexane and 19.0g of [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n Stirring and dissolving for 6.5hr until completely dissolving, aging at-95deg.C for 38min, adding into polymerization system together, stirring and reacting for 6.5hr, adding 400mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber 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 four-hybrid-arm star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 5.
b, preparation of a quaternary four-hybrid-arm star-shaped nucleating agent: other conditions were the same as in example 5 except that: the polymerization kettle C does not adopt variable speed polymerization, and the mixture of the styrene and the 1, 3-butadiene is discontinuously injected into the polymerization kettle, but is added at one time, namely: in a 15L stainless steel polymerizer A with a jacket, argon is introduced to replace the system for 3 times, 2000g of cyclohexane, 200g of 1, 3-butadiene and 1.5g of THF are sequentially added into the polymerizer A, the temperature is raised to 40 ℃ and 40.6mmo1 of n-butyllithium is added to start the reaction, the reaction is carried out within 60 minutes, and the temperature is changed from 40 Gradually heating to 60 ℃ at a heating speed of 0.5 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 100g of styrene and 1.8g of THF into a polymerization kettle A, and reacting for 40min to form the wide-distribution [ PS-BR ]] n Segment, then heating to 90 ℃, adding 340mmo11, 5-dichloro-3, 3-di (2-chloroethyl) pentane, and carrying out coupling reaction for 60min; 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 19.5 mmol 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, 1.9g of THF and reacting for 40min to form a wide-distribution [ PS-IR ]]n chain segments, 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, introducing argon to replace a system for 3 times, sequentially adding 1900g of cyclohexane and 3.1g of THF, heating to 80 ℃, adding 25.5 mmol 1 of n-butyllithium to start reaction, stirring and mixing 200g of styrene and 100g of 1, 3-butadiene for 30min, adding the mixture into the polymerization kettle C at one time, and reacting for 60min to form an-SBR 1-chain segment; then adding 100g of styrene and 1.8g of THF into a polymerization kettle C in sequence to react for 40min to form [ PS-SBR1 ] ] 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 70min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1600g of cyclohexane, 170g of styrene, 90g of 1, 3-butadiene and 2.2g of THF are sequentially added, the temperature is raised to 65 ℃, 24.5mm mu 1 of n-butyllithium is added for reaction for 40min, and [ -SBR [ -17 ]] n Adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60min; after the coupling reaction is finished, 70g of DVB is sequentially added into a polymerization kettle A, after the temperature is raised to 80 ℃, 0.45g 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 four-hetero-arm star-shaped nucleating agent [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-(DVB)SBR1-PS] n [-(DVB)SBR-] n (Mn is 91000 and Mw/Mn is 10.56).
(2) Ultra-wide-distribution four-hetero-arm comb-shaped star-shaped branched butyl rubberIs prepared from the following steps: other conditions were the same as in example 5 except that: no nucleating agent (PS- (DVB) BR) is added in the synthesis process] n [PS-(DVB)IR-] n Y[-S(DVB)B/(S→(DVB)B)-PS] n [-(DVB)SBR-] n But to add nucleation [ PS- (DVB) BR ]] n [PS-(DVB)IR-] n Y[-(DVB)SBR1-PS]n[-(DVB)SBR-] 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, 380g of chloromethane, 300g of cyclohexane, 254 g of isobutene and 24g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 100 ℃, then 180g of chloromethane, 5.2g of sesquiethylaluminum chloride and 0.37g of HCl are mixed at minus 95 ℃ and aged for 40min, then added into the polymerization system together and stirred for reaction for 1.0hr, and then 220g of cyclohexane and 21.0g of [ PS- (DVB) BR ] ] n [PS-(DVB)IR-] n Y[-(DVB)SBR1-PS] n [-(DVB)SBR-] n Stirring and dissolving for 7.0hr until completely dissolving, aging at-95deg.C for 40min, adding into polymerization system together, stirring and reacting for 7.0hr, adding 450mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 ultra-wide distribution four heteroarm comb-like Star branched butyl rubber Performance
As can be seen from table 1: the ultra-wide-distribution four-hetero-arm comb-shaped star-branched butyl rubber has high tensile strength, good air tightness, small 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).
Claims (20)
1. A preparation method of ultra-wide distribution four-arm comb-shaped star-branched butyl rubber comprises the following steps:
(1) Styrene, 1, 3-butadiene, isoprene and divinylbenzene are used as reaction monomers, 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane is used as a coupling agent, and a quaternary four-arm star-shaped nucleating agent is prepared by a method of combining variable temperature and variable speed polymerization, anion polymerization and free radical polymerization;
(2) Carrying out cationic polymerization on isobutene and isoprene serving as reaction monomers at the temperature of minus 95 to minus 85 ℃ in the presence of a quaternary four-arm star nucleating agent to prepare ultra-wide distribution four-arm comb-shaped star-branched butyl rubber; the quaternary four-arm star-shaped nucleating agent is characterized in that the structural general formula of the quaternary four-arm star-shaped nucleating agent is shown as formula I:
wherein BR is a butadiene homopolymer section with wide vinyl distribution, IR is an isoprene homopolymer section with wide vinyl distribution, SBR is a styrene and 1, 3-butadiene random block copolymer section, PS is a styrene homopolymer section, SB is a random polymerization section of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene;
the number average molecular weight of the quaternary four-arm star-shaped nucleating agent is 80000-100000, and the ratio of the weight average molecular weight to the number average molecular weight is 14.23-16.72;
the preparation process comprises the following steps:
(1) Preparation of a quaternary four-arm star-shaped nucleating agent: firstly, sequentially adding a solvent, 10-20% of 1, 3-butadiene and 0.01-0.5% of a structure regulator into a polymerization kettle A, heating to 40 ℃, adding an initiator 1, reacting to perform variable-temperature polymerization, gradually heating to 60 ℃ from 40 ℃ within 40-60 min, sequentially adding 5-10% of styrene and 0.01-0.5% of a structure regulator into the polymerization kettle A, heating to 70-90 ℃ after the monomers are completely converted, and adding a coupling agent 1, 5-dihalogen-3, 3-bis (2-haloethyl) pentane for coupling reaction for 40-60 min; simultaneously, sequentially adding a solvent, 10% -20% of isoprene and 0.01% -0.5% of structure regulator into a polymerization kettle B, heating to 50 ℃, adding an initiator 1, reacting to obtain variable-temperature polymerization, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30-50 min, sequentially adding 5% -10% of styrene and 0.01% -0.5% of structure regulator into the polymerization kettle B, adding materials in the polymerization kettle B into the polymerization kettle A after complete conversion of monomers, and performing coupling reaction for 40-60 min; simultaneously, sequentially adding a solvent and 0.01-0.5% of a structure regulator into a polymerization kettle C, heating to 70-80 ℃, adding an initiator 1, stirring and mixing 10-20% of styrene and 5-10% of 1, 3-butadiene for 20-30 min, then adding the mixture into the polymerization kettle C in a continuous injection mode, wherein the initial feeding speed is more than 5.0% of the mixture/min, the feeding speed is gradually reduced, the reduction range is determined according to the reaction time, and the reaction is completed within 50-60 min; sequentially adding 5-10% of styrene and 0.05-0.1% of structure regulator into the polymerization kettle C, 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 50-70 min; simultaneously, sequentially adding a solvent, 10% -20% of styrene, 5% -10% of 1, 3-butadiene and 0.01% -0.5% of a structure regulator into a polymerization kettle D, heating to 50-70 ℃, adding an initiator 1, and adding materials in the polymerization kettle D into the polymerization kettle A for coupling reaction after the monomers are completely converted; sequentially adding 3% -7% of divinylbenzene into a polymerization kettle A after the coupling reaction is finished, heating to 70-80 ℃, adding 0.05% -1.0% of initiator 2, 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 four-arm star-shaped nucleating agent;
(2) Preparation of ultra-wide distribution four-arm comb-shaped star-branched butyl rubber: firstly, sequentially adding a diluent/solvent volume ratio of 60-40/40-60 mixed solvent, 92-98% of isobutene and 2-8% of isoprene into a polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, then adding the diluent and 0.05-3.0% of co-initiator into the polymerization kettle for reaction after mixing and aging at minus 95-minus 85 ℃, then mixing and dissolving 3.0-7.0% of solvent and quaternary four-arm star-shaped nucleating agent for 5.0-7.0 hr, aging for 30-40 min at minus 95-minus 85 ℃, adding the mixture into the polymerization kettle for reaction, adding a terminator for discharging and condensing after the reaction is finished, washing, and drying to obtain ultra-wide distribution four-arm star-shaped branched butyl rubber;
wherein, the polymerization reactions in the step (1) and the step (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 and di-tert-butyl peroxide;
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid, and the molar ratio of protonic acid to alkyl aluminum halide is 0.05:1-0.5:1.
2. The method of claim 1, wherein the BR stage 1, 2-structure content is 15% to 20%.
3. The method of claim 1, wherein the IR segment 1, 2-structure content is from 5% to 10%.
4. The method of claim 1, wherein the quaternary four-arm star-shaped nucleating agent comprises 30% -60% of styrene, 20% -30% of 1, 3-butadiene and 10% -20% of isoprene.
5. The method of claim 1, wherein the halogenating agent is one of liquid chlorine and liquid bromine.
6. The method of claim 5, wherein the halogenating agent is liquid bromine.
7. The process according to claim 1, wherein the initiator 1 is n-butyllithium.
8. The process according to claim 1, wherein the initiator 2 is dibenzoyl peroxide.
9. 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.
10. The method of claim 9, wherein the structure modifier is tetrahydrofuran.
11. 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.
12. The method of claim 11, wherein the alkyl aluminum halide is aluminum sesquichloride.
13. The method of claim 1, wherein the protic acid is selected from HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 One of them.
14. The method of claim 13, wherein the protic acid is HCl.
15. The method of claim 1, wherein the diluent is selected from one of methane chloride, methylene chloride, carbon tetrachloride, ethylene dichloride, tetrachloropropane, heptachloropropane, methane monofluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
16. The method of claim 15, wherein the diluent is methyl chloride.
17. The method of claim 1, wherein the solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
18. The method of claim 17, wherein the solvent is cyclohexane.
19. The method of claim 1, wherein the terminator is selected from at least one of methanol, ethanol, and butanol.
20. The method of claim 1, wherein steps (1) and (2) are carried out in an inert gas atmosphere.
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| CN109134765A (en) * | 2017-06-28 | 2019-01-04 | 北京化工大学 | A kind of polyisobutene and the graft copolymer of polyisoprene and preparation method thereof |
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