CN114478957B - Preparation method of four-arm comb-shaped star-branched butyl rubber - Google Patents
Preparation method of four-arm comb-shaped star-branched butyl rubber Download PDFInfo
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- CN114478957B CN114478957B CN202011274699.2A CN202011274699A CN114478957B CN 114478957 B CN114478957 B CN 114478957B CN 202011274699 A CN202011274699 A CN 202011274699A CN 114478957 B CN114478957 B CN 114478957B
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- Prior art keywords
- star
- shaped
- arm
- butyl rubber
- dvb
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- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 170
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002667 nucleating agent Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 47
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 46
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 23
- -1 alkyl aluminum halide Chemical class 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 105
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 52
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 33
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 26
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 18
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 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
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 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
- 238000005859 coupling reaction Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- YFIIENAGGCUHIQ-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptachloropropane Chemical compound ClC(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl YFIIENAGGCUHIQ-UHFFFAOYSA-N 0.000 claims description 2
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 claims description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-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
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- WXRBQHOKNRLOQI-UHFFFAOYSA-N dichloromethylaluminum Chemical compound [Al]C(Cl)Cl WXRBQHOKNRLOQI-UHFFFAOYSA-N 0.000 claims 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims 1
- UUXZFMKOCRKVDG-UHFFFAOYSA-N methane;hydrofluoride Chemical compound C.F UUXZFMKOCRKVDG-UHFFFAOYSA-N 0.000 claims 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 12
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 10
- WPUBUMYDZKJTBD-UHFFFAOYSA-N 1,5-dibromo-3,3-bis(2-bromoethyl)pentane Chemical compound BrCCC(CCBr)(CCBr)CCBr WPUBUMYDZKJTBD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 3
- 239000005060 rubber Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- 239000005062 Polybutadiene Substances 0.000 description 56
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 229910001220 stainless steel Inorganic materials 0.000 description 27
- 239000010935 stainless steel Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000005070 sampling Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002174 Styrene-butadiene Substances 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 229920002367 Polyisobutene Polymers 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical group [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 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 3
- 241001441571 Hiodontidae Species 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-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
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 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
- 238000000926 separation method Methods 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 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
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 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
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 230000001112 coagulating effect Effects 0.000 description 1
- 239000002131 composite material Chemical group 0.000 description 1
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- 238000013016 damping Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- 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
Abstract
The invention firstly aims at 3, 9-dioxy [5.5 ]]The spirocyclic undecane is halogenated to synthesize the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and then the coupling agent is coupled with the styrene and butadiene reaction monomer to prepare the binary four-arm star polymer [ -SBR-BR ]] n Y, then [ -SBR-BR ]] n Under the action of initiator, Y and divinylbenzene synthesize binary four-arm comb star-shaped nucleating agent ([ - (DVB) SBR- (DVB) BR ]] n Y), finally [ - (DVB) SBR- (DVB) BR-] n Under the catalysis system of the combination of alkyl aluminum halide and protonic acid, the Y, the isobutene and the isoprene are subjected to cationic polymerization by utilizing a first arm and then core method to prepare the four-arm comb-shaped star-shaped branched butyl rubber. On the premise of ensuring that the star-branched butyl rubber has enough rubber strength and good air tightness, the method solves the problems of easy extrusion swelling and low stress relaxation rate of the butyl rubber in the processing process, so that the four-arm comb-shaped star-shaped butyl rubber has good processability. The preparation method has the characteristics of controllable molecular weight and molecular structure, good product processing performance, suitability for industrial production and the like.
Description
Technical Field
The invention relates to a preparation method of four-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing four-arm comb-shaped star-branched butyl rubber by using a butadiene/styrene/Divinylbenzene (DVB) quaternary four-arm nucleating agent.
Background
Butyl Rubber (IIR) is known to be copolymerized from isobutylene and a small amount of isoprene by cationic polymerization. Butyl rubber has been industrialized by Exxon corporation in the united states in the 40 th century for over seventy years, and has been widely used in the fields of inner tubes, inner liners, curing bladder, medical plugs, etc. for manufacturing tires for vehicles because of its excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance, etc.
However, the molecular chain of butyl rubber mainly consists of single bonds of carbon and carbon, the number of double bonds is small, substituent methyl groups are symmetrically arranged, and the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesion, poor compatibility with other general rubber and the like exist, so that the butyl rubber is easy to excessively flow and deform in the processing process. How to achieve a balance of physical and mechanical properties and processability of butyl rubber has become a bottleneck in the preparation of high performance butyl rubber materials.
In recent years, researchers have found that star-branched butyl rubber with a unique four-dimensional network structure, which consists of a high molecular weight grafted structure and a low molecular weight linear structure, has excellent viscoelastic properties, 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-branched structure has therefore become one of the hot spots in the future butyl rubber research field.
In the prior art, the synthesis of star-branched butyl rubber is mainly prepared by adopting a method of a first-nucleus and then-arm method, a first-arm and then-nucleus method and a nucleus-arm simultaneous method. Such as: US5395885 discloses a star-branched polymer, which is synthesized by a method of first-arm-then-core method at-90 to-100 ℃ by taking polyisobutylene as an arm, polydivinylbenzene (PDVB) as a core, a complex of alkyl aluminum chloride and water as an initiator, and chloromethane as a diluent. CN88108392.57 discloses a star-shaped graft butyl rubber with comb structure prepared by using a hydrochloride polystyrene-isoprene copolymer as a polyfunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN101353403B discloses a method for preparing star-branched polyisobutylene or butyl rubber, which uses a polystyrene/isoprene block copolymer with a silicon-chlorine group at the end or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the end as a grafting agent for initiating cationic polymerization, and takes part in the cationic polymerization directly in a cationic polymerization system of a mixed solvent with a chloromethane/cyclohexane v ratio of 20-80/80-20 at the temperature of 0-100 ℃ to initiate cationic polymerization by the silicon-chlorine group, and takes part in grafting reaction by an unsaturated chain to prepare the star-branched polyisobutylene or butyl rubber product. CN01817708.5 provides a method of adding a multiolefin crosslinking agent such as divinylbenzene and a chain transfer agent (such as 2,4, 1-tetramethyl-1-pentene) to a mixture of isoolefin monomers and diolefin monomers, by which star-branched polymers are prepared. CN107793535 a provides a butyl rubber having a molecular weight of 90 to 260 tens of thousands, log (MW) >6 and contains structural units derived from isobutylene, structural units derived from conjugated diene, and optionally structural units derived from aryl olefin. 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 tetra-cumyl alcohol as an initiator with a four-arm structure by using pyromellitic acid as a raw material, and then initiated isobutylene and isoprene copolymerization in an inert organic solvent at-120 to-50 ℃ by using a tetra-cumyl alcohol/aluminum tetrachloride initiation system to synthesize star-branched butyl rubber with bimodal molecular weight distribution (Catalysts for manufacture of IIR with bimodal molecular weight distribution:US,5194538[ P ]].1993-3-16.). Wieland et al synthesized a macroinitiator P (MMA-b-St-co-CMS) containing 4-chloromethylstyrene, styrene and methyl methacrylate quaternaries in the presence of 1, 2-stilbene (DPE) by a radical polymerization method, and initiated cationic polymerization of isobutylene and isoprene with the macroinitiator to thereby successfully prepare a multi-arm star butyl rubber (Synthesis of new graft copolymers containing polyisobutylene by acombination of the, 1-diphenylethylene techniqueand cationic polymerization [ J ] ]Polymer Science: polymer Chemistry,2002, 40: 3725-3733.). Hadjichristididis et al uses CH 3 SiCl 3 PI-PS-PBd four-arm copolymer (Iatrou H, hadjichristidis N.Synthesis of a model 3-miktoarm star terpolymer [ J ] was synthesized by four-step coupling with strict control of the order of addition of the monomers and the degree of excess of the coupling agent]Macromolecules,1992, 25:4649). Hadjchristids react with the silicon-chlorine group of p-chlorodimethylsilyl styrene by high vacuum technique to obtain styrene-based polybutadiene macromonomer, which is then copolymerized with butadiene in the presence of random regulator to obtain active Comb-shaped polybutadiene, and finally reacts with methyl silicon tetrachloride or silicon tetrachloride to obtain 3-arm or 4-arm Star-shaped Comb-shaped polybutadiene (KORTALAAS G, IATROUH, LOHSE D J, et al well-Defined Comb, star-Comb, and Comb-on-Comb Polybutadienes by Anionic Polymerization and the MacromonomerStrategy [ J)]Macromolecules,2005,38 (12): 4996-5001). Huiqin the method adopts 2-chloro-2, 4-tetramethylpentane/titanium tetrachloride as initiator system and methane chloride/cyclohexane as solvent, adopts active positiveIonic polymerization Star branched polymers with divinylbenzene as core and polyisobutene as arms were synthesized at-80 ℃ ("preparation and characterization of Star branched polyisobutenes with divinylbenzene as core", "synthetic rubber industry", synthetic rubber industry, 2008, 31 (5): 362-365.).
Disclosure of Invention
The invention aims to provide a preparation method of four-arm comb-shaped star-branched butyl rubber. Firstly, carrying out halogenation reaction on 3, 9-dioxy [5.5] spiro undecane to synthesize a novel tetrahalide coupling agent; then using styrene, butadiene and Divinylbenzene (DVB) as reaction monomers, coupling by tetrahalide coupling agents, and grafting and polymerizing under the action of an initiator to obtain a four-arm comb-shaped star-shaped nucleating agent; finally, under the catalysis system of Lewis acid and protonic acid, the four-arm comb-shaped star-shaped nucleating agent, isobutene and isoprene are subjected to cationic polymerization by adopting a first-arm and then-core method to prepare the four-arm comb-shaped star-shaped branched butyl rubber. The method solves the problems of extrusion swelling and slow stress relaxation rate of the butyl rubber in the processing process on the premise of ensuring that the four-arm comb-shaped star-branched butyl rubber has certain raw rubber strength and good air tightness, so that the four-arm comb-shaped star-branched butyl rubber has good processability, 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 four-arm comb-shaped star-branched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) Preparation of a four-arm comb star-shaped nucleating agent:
a, preparation of a coupling agent: based on the total mass of reactants, the method comprises the steps of firstly adding 4L of a jacket
In a stainless steel polymerization kettle, argon is introduced to replace 2-4 times, 100-200% of deionized water, 3, 9-dioxy [5.5] spiro undecane, a halogenating agent, 1-5% of a catalyst are sequentially added into the polymerization kettle, the temperature is raised to 50-80 ℃, after the reaction is carried out for 1-3 hours, 20-40% of aqueous solution of NaOH with the mass concentration of 10-20% is added to terminate the reaction, and finally 200-300% of chloromethane is added to extract, separate, wash and dry the reaction product to obtain the coupling agent 1, 5-dihalogen-3, 3-bis (2-haloethyl) pentane (the yield is 85-95%).
b, preparation of a four-arm comb star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 200-400% of solvent, 30-50% of 1, 3-butadiene, 0.05-0.5% of structure regulator and 1% of initiator into the polymerization kettle, heating to 40-50 ℃ for reaction for 40-60 min to form BR chain segments, wherein the conversion rate of the 1, 3-butadiene monomer reaches 100%; sequentially adding 30% -60% of styrene, 10% -20% of 1, 3-butadiene and 0.05% -0.5% of structure regulator into a polymerization kettle, heating to 60-70 ℃ and reacting for 50-60 min to form a-BR-SBR-chain segment; then heating to 80-90 ℃, adding a coupling agent for coupling reaction for 70-90 min, sequentially adding 100-200% of solvent into a polymerization kettle after the reaction is completed, heating to 70-80 ℃, adding 0.01-0.1% of initiator 2 into the polymerization kettle, reacting for 50-70 min, treating the coupled reaction mixture with water after the reaction is completed, performing wet condensation and drying on the glue solution to obtain the binary four-arm comb star-shaped nucleating agent ([ - (DVB) SBR- (DVB) BR-) ] n Y)。
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3-5 times to replace the reaction monomer in total mass parts, and sequentially adding 200% -300% of diluent/solvent V into the polymerization kettle: mixing 93-97% of isobutene and 3-7% of isoprene in a V ratio of 60-40/40-60 mixed solvent, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, mixing and aging 40-60% of diluent and 0.05-3.0% 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, mixing and dissolving 30-60% of solvent and 1.0-2.0% of nucleating agent with a four-arm star structure obtained in the step (1) for 3.0-5.0 hr, aging the mixture at minus 95-minus 85 ℃ for 40.0-6.0 hr, adding a terminator for discharging and agglomerating, washing and drying to obtain the four-arm comb-shaped branched butyl rubber product.
The nucleating agent of the invention is a nucleating agent containing [ -BR-SBR ]] n Binary four-arm comb star polymer [ - (DVB) SBR- (DVB) BR ]] n Y has a structural general formula shown in formula I:
Wherein Y is 3, 3-diethylpentane; BR is a 1, 3-butadiene homopolymer block, and the 1, 2-structure content thereof is 15-20%; SBR is a styrene-butadiene random block copolymer, wherein the content of styrene is 30-60%, and the content of 1, 3-butadiene is 10-20%; the binary four-arm star polymer has a number average molecular weight (Mn) of 40000-70000 and a molecular weight distribution (Mw/Mn) of 4.96-6.14.
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 halogenating agent 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), tetraethylamine, preferably Tetrahydrofuran (THF).
The diluent is halogenated alkane, wherein halogen atoms in the halogenated alkane can be chlorine, bromine or fluorine; the number of carbon atoms in the halogenated alkane being C 1 -C 4 . The haloalkane is selected from one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably chloromethane.
The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene or ethylbenzene, preferably cyclohexane.
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from diethyl aluminum chloride, diisobutyl aluminum chloride, methyl aluminum dichloride, aluminum sesquioxide, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride, preferably aluminum sesquioxide. The protonic acid is selected from HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCl. Wherein the total addition amount of the co-initiator is 0.1-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1-0.5:1.
The terminator can be selected from one or more of methanol, ethanol and butanol.
The polymerization reactions of the present invention are all carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution processes are both carried out in a hydrocarbon solvent, which is a hydrocarbon solvent, including straight chain alkanes, aromatic hydrocarbons and cycloalkanes, selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention firstly aims at 3, 9-dioxy [5.5 ] ]The spirocyclic undecane is subjected to halogenation reaction to synthesize a novel coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and then the novel coupling agent is coupled with styrene and butadiene reaction monomers to prepare a binary four-arm star polymer [ -SBR-BR ]] n Y, then [ -SBR-BR ]] n Under the action of initiator, Y and divinylbenzene synthesize binary four-arm comb star-shaped nucleating agent ([ - (DVB) SBR- (DVB) BR ]] n Y), finally [ - (DVB) SBR- (DVB) BR-] n Under the catalysis system of the combination of alkyl aluminum halide and protonic acid, the Y, the isobutene and the isoprene are subjected to cationic polymerization by utilizing a first arm and then core method to prepare the four-arm comb-shaped star-shaped branched butyl rubber. The invention combines two chain segments with different microstructures, namely SBR-, -BR-on a macromolecular chain to form a nucleating agent with a binary four-arm comb-shaped star structure, and the binary four-arm comb-shaped star structure increases the disorder of the whole macromolecular chain segment of butyl on the premise of not damaging the regularity of the molecular chain in the copolymerization of isobutene and isoprene, so that the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic performance, the quick stress relaxation rate is ensured, the extrusion swelling effect is reduced, and the processability of the butyl rubber is improved. Meanwhile, the SBR-chain segment contains a large amount of benzene rings, so that the reduction of strength and air tightness caused by the widening of molecular weight distribution is avoided, and the high strength and good air tightness of the butyl rubber are ensured.
According to the invention, through the design of the binary four-arm comb-shaped star-shaped structure, the characteristics of the binary four-arm star-shaped structure and the performances of different chain segments are organically combined together and synergistically acted, the problem of the contradictory relation between the processability and the physical and mechanical properties of the butyl rubber is solved, and the optimal balance between the processability and the physical and mechanical properties of the butyl rubber is finally realized. The preparation method provided by the invention has the characteristics of controllable process conditions, stable product performance, suitability for industrial production and the like.
Drawings
FIG. 1 is 1 # Comparative examples 1 samples and 2 # Comparison of GPC spectra of the samples of example 1.
Detailed Description
The following examples and comparative examples are given to illustrate the inventive effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial polymer grade, and are used after purification without other special requirements.
Raw material sources:
styrene, butadiene, polymer grade China petrochemical Co
Isobutene, isoprene, polymeric grade Zhejiang Xinhui New Material Co., ltd
N-butyllithium with purity of 98% Nanjing Tonglian chemical Co., ltd
3, 9-Dioxo [5.5] spirocyclic undecane purity was 99% of Hubei ferry chemical Co.Ltd
Dibenzoyl peroxide (BPO), a lanzhou auxiliary plant
Sesquiethyl aluminum chloride with purity of 98% of carbofuran technology Co., ltd
Other reagents are commercial industrial products
The analysis and test method comprises the following steps:
determination of molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min -1 。
Measurement of stress relaxation: the measurement was carried out by using a GT-7080-S2 Mooney viscometer manufactured by Taiwan high-speed rail company.
The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.
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 four-arm comb 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, 500g of deionized water, 48g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle]Spirocyclic undecane, 250g liquid bromine, 7g HCl-CH 3 OH solution (molar concentration of HCl: 0.3 mol/L), heating to 52 ℃, reacting for 1.8hr, adding 200g of 15% NaOH aqueous solution to terminate the reaction, finally adding 600g of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane (yield 87%).
b, preparation of a four-arm comb star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene and 0.7g THF,22.3mmo1 n-butyllithium into the polymerization kettle, heating to 40 ℃, and reacting for 40min to form BR chain segments; then 300g of styrene and 100g of 1, 3-butadiene, 1.6g of THF are sequentially added into the polymerization kettle, the temperature is raised to 60 ℃, and the reaction is carried out for 50min, so that a-BR-SBR-chain segment is formed; then heating to 80 ℃, adding 20.1 mmol of 1, 5-dibromo-3, 3 di (2-bromoethyl) pentane, reacting for 70min to form [ -SBR-BR ] ] n Y; after the reaction is completed, 1000g of cyclohexane and 25g DVB,0.06g BPO are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃, after the reaction is carried out for 50min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR [ -17 ] with the four-arm comb-shaped star-shaped structure is prepared] n Y (Mn: 41000, mw/Mn: 4.98).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 3 times, 310g of methyl chloride, 330g of cyclohexane, 279g of isobutene and 9g 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 120g of methyl chloride, 1.9g of aluminum sesquichloride and 0.07g of HCl are mixed at minus 85 ℃ and aged for 30 minutes, then added into the polymerization system together and stirred and reacted for 0.5 hour, then 100g of cyclohexane and 3.1g of [ - (DVB) SBR- (DVB) BR [ ] are added into the polymerization system] n And Y, stirring and dissolving for 3.0hr until the grafting agent is completely dissolved, aging for 40min at the temperature of minus 85 ℃, adding into a polymerization system together and stirring for 3.0hr, adding 150mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the four-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 2
(1) Preparation of a four-arm comb star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of a four-arm comb star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 2600g of cyclohexane, 340g of 1, 3-butadiene and 1.5g THF,23.2mmo1 n-butyllithium into the polymerization kettle, heating to 42 ℃, and reacting for 44min to form a BR chain segment; then adding 360g of styrene and 130g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle in sequence, heating to 63 ℃, and reacting for 52min to form a-BR-SBR-chain segment; then heating to 82 ℃, adding 23.5 mmol of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 75min to form [ -SBR-BR ]] n Y; after the reaction is completed, 1200g cyclohexane and 30g DVB,0.09g BPO are sequentially added into a polymerization kettle, the temperature is raised to 72 ℃, after the reaction is carried out for 55min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR [ -17 ] with a four-arm comb-shaped star-shaped structure is prepared] n Y (Mn 48000, mw/Mn 5.17).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times, and sequentially adding methyl chloride into the polymerization kettle320g of alkane, 310g of cyclohexane, 283g of isobutene and 11g of isoprene are stirred and mixed until the temperature of a polymerization system is reduced to minus 93 ℃, 130g of methyl chloride, 2.2g of aluminum sesquichloride and 0.09g of HCl are mixed at minus 87 ℃ and then aged for 32 minutes, and then added into the polymerization system together for stirring and reacting for 0.6 hour, and then 120g of cyclohexane and 3.7g [ - (DVB) SBR- (DVB) BR [ -17 ] ] n Y, stirring and dissolving for 4.0hr until the grafting agent is completely dissolved, aging for 45min at-88 ℃, adding into a polymerization system together, stirring and reacting for 3.5hr, adding 170mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the four-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 3
(1) Preparation of a four-arm comb star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of a four-arm comb star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3000g of cyclohexane, 400g of 1, 3-butadiene and 2.1g THF,25.6mmo1 n-butyllithium into the polymerization kettle, heating to 44 ℃, and reacting for 47min to form a BR chain segment; then sequentially adding 400g of styrene and 150g of 1, 3-butadiene and 2.7g of THF into a polymerization kettle, heating to 65 ℃, and reacting for 54min to form a-BR-SBR-chain segment; then heating to 85 ℃, adding 26.5 mmol of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 80min to form [ -SBR-BR ]] n Y; after the reaction is completed, 1400g of cyclohexane and 32g DVB,0.11g BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 58min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR [ -17 ] with the four-arm comb star-shaped structure is prepared ] n Y (Mn 53000, mw/Mn 5.42).
(2) Preparation of four-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, 330g of methyl chloride, 300g of cyclohexane, 284 g of isobutene and 13g of isoprene are added into the polymerization kettle in sequence, and stirred and mixed until the temperature of a polymerization system is reduced to minus 95 ℃, then 140g of methyl chloride, 2.9g of aluminum sesquichloride and 0.12g of HCl are added into the polymerization kettleMixing at-87 deg.C, aging for 34min, adding into polymerization system, stirring for 0.7hr, adding 140g cyclohexane, 4.2g [ - (DVB) SBR- (DVB) BR [ (R) BR ]] n Y, stirring and dissolving for 4.5 hours until the grafting agent is completely dissolved, then aging for 50 minutes at the temperature of minus 90 ℃, adding into a polymerization system together and stirring and reacting for 4.0 hours, adding 180mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the four-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 4
(1) Preparation of a four-arm comb star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of a four-arm comb star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3300g of cyclohexane, 430g of 1, 3-butadiene and 2.5g THF,26.6mmo1 n-butyllithium into the polymerization kettle, heating to 46 ℃, and reacting for 52min to form BR chain segments; then 470g of styrene and 170g of 1, 3-butadiene, 3.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 67 ℃, and the reaction is carried out for 56min, so that a-BR-SBR-chain segment is formed; then heating to 85 ℃, adding 27.8mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 83min to form [ -SBR-BR ] ] n Y; after the reaction is completed, 1600g of cyclohexane and 38g DVB,0.25g BPO are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, after the reaction is carried out for 61min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR [ -17 ] with a four-arm comb-shaped star-shaped structure is prepared] n Y (Mn is 58000 and Mw/Mn is 5.67).
(2) Preparation of four-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, 290g of cyclohexane, 289g of isobutene and 15g 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, 3.2g of aluminum sesquichloride and 0.21g of HCl are mixed at minus 87 ℃ and aged for 36min, then added into the polymerization system together and stirred for reaction for 0.8hr, and then 150g of cyclohexane and 5.1g of [ - (DVB) SBR- (DVB) BR [ ]] n Y, stirring and dissolving for 5.0hrAfter the grafting agent is completely dissolved, aging for 52min at the temperature of minus 90 ℃, adding the grafting agent into a polymerization system together, stirring and reacting for 4.5hr, adding 200mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the four-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 four-arm comb 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, 550g of deionized water and 55g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle]Spirocyclic undecane, 280g liquid chlorine, 10g HCl-CH 3 OH solution (molar concentration of HCl: 0.7 mol/L), heating to 80 ℃, reacting for 3.0hr, adding 250g of aqueous solution of NaOH with mass concentration of 20% to terminate the reaction, finally adding 800g 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 four-arm comb star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 3500g of cyclohexane, 460g of 1, 3-butadiene and 2.9g THF,28.1mmo1 n-butyllithium into the polymerization kettle, heating to 48 ℃, and reacting for 57min to form a BR chain segment; then 510g of styrene and 190g of 1, 3-butadiene and 3.8g of THF are added into the polymerization kettle in sequence, the temperature is raised to 68 ℃ and the reaction is carried out for 58 minutes, so that a-BR-SBR-chain segment is formed; then heating to 87 ℃, adding 29.1 mmol of 1, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 85min to form [ -SBR-BR ] ] n Y; after the reaction is completed, 1800g of cyclohexane and 42g DVB,0.31g BPO are sequentially added into a polymerization kettle, the temperature is raised to 79 ℃, after the reaction is carried out for 65min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR [ -17 ] with a four-arm comb-shaped star-shaped structure is prepared] n Y (Mn 63000, mw/Mn 5.85).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of chloromethane, 280g of cyclohexane, 290g of isobutene and 18g of isoprene are added into the polymerization kettle in sequence, and stirred and mixed until the temperature of a polymerization system is reduced170g of methyl chloride, 4.1g of aluminum sesquichloride and 0.35g of HCl are mixed at the temperature of minus 90 ℃ and then aged for 38min, and then added into a polymerization system together for stirring reaction for 0.9hr, and then 170g of cyclohexane and 5.6g of [ - (DVB) SBR- (DVB) BR [ (R) BR ]] n Y, stirring and dissolving for 5.5 hours until the grafting agent is completely dissolved, then aging for 56 minutes at the temperature of minus 93 ℃, adding the mixture into a polymerization system together and stirring and reacting for 5.0 hours, adding 230mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the four-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 6
(1) Preparation of a four-arm comb star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 5.
b, preparation of a four-arm comb star-shaped nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 4000g of cyclohexane, 500g of 1, 3-butadiene and 3.3g THF,30.1mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, and reacting for 60min to form BR chain segments; then 600g of styrene and 200g of 1, 3-butadiene and 4.5g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃ and the reaction is carried out for 60min, so that a-BR-SBR-chain segment is formed; then heating to 90 ℃, adding 32.0 mmol of 1, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 90min to form [ -SBR-BR ]] n Y; after the reaction is completed, 2000g of cyclohexane and 50g DVB,0.42g BPO are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after the reaction is carried out for 70min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR [ -17 ] with a four-arm comb-shaped star-shaped structure is prepared] n Y (Mn 69000, mw/Mn 6.12).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 360g of methyl chloride, 270g of cyclohexane, 107 g of isobutene and 20g of isoprene are sequentially added into the polymerization kettle, and are stirred and mixed until the temperature of a polymerization system is reduced to minus 100 ℃, then 180g of methyl chloride, 4.9g of aluminum sesquichloride and 0.42g of HCl are mixed at minus 95 ℃ and aged for 40 minutes, and then are added into the polymerization system together for stirring and reacting for 1.0hr, and then the mixture is stirred and mixed with 180g of cyclohexane, 6.0g [ - (DVB) SBR- (DVB) BR ]] n Y, stirring and dissolving for 6.0hr until the grafting agent is completely dissolved, aging at-95 ℃ for 60min, adding into a polymerization system together, stirring and reacting for 6.0hr, adding 270mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the four-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 four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 1 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR ]] n Y is: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 310g of methyl chloride, 330g of cyclohexane, 279g of isobutene and 9g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 120g of methyl chloride, 1.9g of aluminum sesquichloride and 0.07g of HCL are mixed at minus 85 ℃ and aged for 30 minutes, then the mixture is added into the polymerization system together to be stirred and reacted for 0.5 hour, then 150mL of methanol is added to terminate the reaction, finally, the mixture is discharged and condensed, washed and dried, and the four-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 four-arm comb star-shaped nucleating agent: other conditions were the same as in example 2 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: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 2600g of cyclohexane, 340g of 1, 3-butadiene and 1.5g THF,23.2mmo1 n-butyllithium into the polymerization kettle, heating to 42 ℃, and reacting for 44min to form a BR chain segment; then adding 360g of styrene and 130g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle in sequence, heating to 63 ℃, and reacting for 52min to form a-BR-SBR-chain segment; subsequently, the temperature was raised to 82℃and 23.5mm 1 SiCl was added 4 Reacting for 75min to form [ -SBR-BR ]] n Y; after the reaction is completed, 1200g of cyclohexane, 30g DVB,0.09g BPO, is added into the polymerization kettle in turnHeating to 72 deg.c, reacting for 55min, wet coagulating and stoving to obtain nucleating agent with four-arm comb star structure] n Si (Mn 45000, mw/Mn 4.35).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 2 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR ] ] n Y, instead, nucleating agents [ - (DVB) SBR- (DVB) BR ]] n Si, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 3 times, 320g of chloromethane, 310g of cyclohexane, 283g of isobutene and 11g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 93 ℃, then 130g of chloromethane, 2.2g of sesquiethylaluminum chloride and 0.09g 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, then 120g of cyclohexane and 3.7g of [ - (DVB) SBR- (DVB) BR [ ] are added into the polymerization system] n Stirring and dissolving Si for 4.0hr until the grafting agent is completely dissolved, aging at-88 ℃ for 45min, adding the mixture into a polymerization system together, stirring and reacting for 3.5hr, adding 170mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the four-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) Preparation of a four-arm comb star-shaped nucleating agent: other conditions were the same as in example 3 except that: no coupling agent 1, 5-dibromo-3, 3-bis (2-bromoethyl) pentane was added, namely: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3000g of cyclohexane, 400g of 1, 3-butadiene and 2.1g THF,25.6mmo1 n-butyllithium into the polymerization kettle, heating to 44 ℃, and reacting for 47min to form a BR chain segment; then sequentially adding 400g of styrene and 150g of 1, 3-butadiene and 2.7g of THF into a polymerization kettle, heating to 65 ℃, and reacting for 54min to form chain segments [ -SBR-BR ] ] n The method comprises the steps of carrying out a first treatment on the surface of the After the reaction is completed, 1400g of cyclohexane and 32g DVB,0.11g BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 58min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR [ ] with a four-arm comb-like star-shaped structure is prepared(DVB)BR-] n (Mn: 50000 and Mw/Mn: 2.21).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 3 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR ]] n Y, instead, nucleating agents [ - (DVB) SBR- (DVB) BR ]] 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, 330g of methyl chloride, 300g of cyclohexane, 284 g of isobutene and 13g 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 140g of methyl chloride, 2.9g of aluminum sesquichloride and 0.12g of HCl are mixed at minus 87 ℃ and aged for 34 minutes, then added into the polymerization system together and stirred and reacted for 0.7hr, and then 140g of cyclohexane and 4.2g of [ - (DVB) SBR- (DVB) BR [ ] F ]] n Stirring and dissolving for 4.5hr until the grafting agent is completely dissolved, aging at-90 ℃ for 50min, adding into a polymerization system together, stirring and reacting for 4.0hr, adding 180mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the four-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 4
(1) Preparation of a four-arm comb star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 4.
b, preparation of a four-arm comb star-shaped nucleating agent: other conditions were the same as in example 4 except that: 1, 3-butadiene is not added in the synthesis process, and a-BR-chain segment is not formed, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 3300g of cyclohexane, 2.5g THF,26.6mmo1 n-butyllithium into the polymerization kettle, and heating to 46 ℃; then 470g of styrene and 170g of 1, 3-butadiene, 3.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 67 ℃, and the reaction is carried out for 56min, so that a-SBR-chain segment is formed; then heating to 85 ℃, adding 27.8mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 83min to form [ -SBR ]] n Y; after the reaction is completed, 1600g of cyclohexane, 38g DVB,0.25g BPO and 77 ℃ are sequentially added into a polymerization kettle, and after the reaction is carried out for 61min, the glue solution is subjected to wet methodCondensing and drying to obtain nucleating agent [ - (DVB) SBR [ - (DVB) SBR ]] n Y (Mn of 46000, mw/Mn of 4.57).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 4 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR ] ] n Y, instead of adding nucleating agents [ - (DVB) SBR ]] n Y is: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 340g of methyl chloride, 290g of cyclohexane, 289g of isobutene and 15g 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, 3.2g of aluminum sesquichloride and 0.21g of HCl are mixed at minus 87 ℃ and aged for 36min, then added into the polymerization system together and stirred for reaction for 0.8hr, and then 150g of cyclohexane and 5.1g of [ - (DVB) SBR- (DVB) BR [ ]] n Y, stirring and dissolving for 5.0hr until the grafting agent is completely dissolved, aging at-90 ℃ for 52min, adding into a polymerization system together, stirring and reacting for 4.5hr, adding 200mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the four-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 four-arm comb star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 5.
b, preparation of a four-arm comb star-shaped nucleating agent: other conditions were the same as in example 5 except that: styrene and 1, 3-butadiene are not added in the synthesis process, and no-SBR-chain segment is formed, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 3500g of cyclohexane, 460g of 1, 3-butadiene and 2.9g THF,28.1mmo1 n-butyllithium into the polymerization kettle, heating to 48 ℃, and reacting for 57min to form a BR chain segment; then heating to 87 ℃, adding 29.1 mmol of 11, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 85min to form [ -SBR-BR ] ] n Y; after the reaction is completed, 1800g of cyclohexane, 42g DVB,0.31g BPO and 79 ℃ are sequentially added into a polymerization kettle, and after the reaction is completed for 65min, the glue solution is subjected to wet condensationDrying to obtain nucleating agent [ - (DVB) BR [ (DVB) BR ]] n Y (Mn: 41000, mw/Mn: 4.73).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 5 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR ]] n Y, instead, nucleating agents [ - (DVB) BR ]] n Y is: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of methyl chloride, 280g of cyclohexane, 290g of isobutene and 18g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 98 ℃, then 170g of methyl chloride, 4.1g of aluminum sesquichloride and 0.35g of HCl are mixed at minus 90 ℃ and aged for 38 minutes, then added into the polymerization system together and stirred and reacted for 0.9hr, and then 170g of cyclohexane and 5.6g [ - (DVB) BR [ (digital video broadcasting) are added into the polymerization system] n Y, stirring and dissolving for 5.5 hours until the grafting agent is completely dissolved, then aging for 56 minutes at the temperature of minus 93 ℃, adding the mixture into a polymerization system together and stirring and reacting for 5.0 hours, adding 230mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the four-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 6
Preparation of four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 6 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR ]] n Y, instead, the nucleating agent DVB is added, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen to replace for 5 times, sequentially adding 360g of methyl chloride, 270g of cyclohexane, 270g of isobutene and 20g of isoprene into the polymerization kettle, stirring and mixing until the temperature of the polymerization system is reduced to minus 100 ℃, then adding 180g of methyl chloride, 4.9g of aluminum sesquichloride and 0.42g of HCl into the polymerization system after mixing and aging for 40min at minus 95 ℃ and stirring and reacting for 1.0hr, then adding 180g of cyclohexane, 6.0g of DVB, stirring and dissolving for 6.0hr until the grafting agent is completely dissolved, aging for 60min at minus 95 ℃, adding 270mL of methanol to terminate the reaction after adding into the polymerization system and stirring and reacting for 6.0hr, finally discharging and flocculating, washing and dryingObtaining the four-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 Properties of four-arm comb-like Star branched butyl rubber
As can be seen from table 1: the four-arm comb-shaped star-branched butyl rubber provided by the invention has high tensile strength, good air tightness, low Mooney relaxation area and good processability (the smaller the area under a stress relaxation curve is, the lower the energy consumption for mixing processing is).
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (16)
1. A preparation method of four-arm comb-shaped star-branched butyl rubber comprises the following steps:
(1) Preparation of a four-arm comb star-shaped nucleating agent: based on the total mass part of the reaction monomers as one hundred percent, firstly, sequentially adding a solvent, 30-50% of 1, 3-butadiene and 0.05-0.5% of a structure regulator into a polymerization kettle, heating an initiator 1 to 40-50 ℃ and reacting until the conversion rate of the 1, 3-butadiene monomers reaches 100%; sequentially adding 30-60% of styrene, 10-20% of 1, 3-butadiene and 0.05-0.5% of structure regulator into a polymerization kettle, heating to 60-70 ℃ and reacting for 50-60 min; then heating to 80-90 ℃, adding a 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane coupling agent for coupling reaction for 70-90 min, sequentially adding a solvent, 1-5% of divinylbenzene and 0.01-0.1% of initiator 2 into a polymerization kettle after the reaction is finished, treating the coupled reaction mixture by water after the reaction is finished, and carrying out wet condensation and drying on glue solution to obtain the four-arm comb-shaped star-shaped nucleating agent;
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, adding a diluent/solvent volume ratio of 60-40/40-60 percent, 93-97 percent of isobutene and 3-7 percent of isoprene into a polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, adding 0.05-3.0 percent of diluent and co-initiator into the polymerization system for stirring and reacting for 0.5-1.0 hr after mixing and aging at minus 95-minus 85 ℃, then adding 30-60 percent of solvent and 1.0-2.0 percent of four-arm star-shaped nucleating agent for mixing and dissolving for 3.0-5.0 hr, aging at minus 95-minus 85 ℃ and adding the mixture into the polymerization kettle for stirring and reacting for 3.0-6.0 hr, finally adding terminator for discharging and condensing, washing and drying to obtain the four-arm star-shaped branched butyl rubber product;
wherein, the steps (1) and (2) are carried out in an anaerobic and anhydrous environment;
the initiator 1 is selected from one of n-butyllithium, sec-butyllithium, methyl butyllithium, phenyl butyllithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium;
the initiator 2 is an organic peroxide, and is selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide;
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid.
2. The process according to claim 1, wherein the initiator 1 is n-butyllithium.
3. The method according to claim 1, wherein the initiator 2 is dibenzoyl peroxide.
4. 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 tetraethylamine.
5. The method of claim 4, wherein the structure modifier is tetrahydrofuran.
6. The method of claim 1, wherein the molar ratio of the protic acid to the alkyl aluminum halide is between 0.05:1 and 0.5:1.
7. The method of claim 6, 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.
8. The method of claim 7 wherein said alkyl aluminum halide is aluminum sesquichloride.
9. The method of claim 6, wherein said protonic acid is selected from the group consisting of HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 Or HNO (HNO) 3 One of them.
10. The method of claim 9, wherein the protic acid is HCl.
11. The method of claim 1, wherein the diluent is selected from the group consisting of methane chloride, methylene chloride, carbon tetrachloride, ethylene dichloride, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
12. The method of claim 11, wherein the diluent is methyl chloride.
13. The method of claim 1, wherein the solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
14. The method of claim 13, wherein the solvent is cyclohexane.
15. The method of claim 1, wherein the terminator is selected from one or more of methanol, ethanol, butanol.
16. The method of claim 1, wherein steps (1) and (2) are both performed in an inert gas atmosphere.
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