CN116410428A - Preparation method of tri-hetero-arm all-secondary brominated branched butyl rubber - Google Patents
Preparation method of tri-hetero-arm all-secondary brominated branched butyl rubber Download PDFInfo
- Publication number
- CN116410428A CN116410428A CN202111647401.2A CN202111647401A CN116410428A CN 116410428 A CN116410428 A CN 116410428A CN 202111647401 A CN202111647401 A CN 202111647401A CN 116410428 A CN116410428 A CN 116410428A
- Authority
- CN
- China
- Prior art keywords
- arm
- brominated
- tri
- hetero
- butyl rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 72
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 180
- 238000006243 chemical reaction Methods 0.000 claims abstract description 163
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 157
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 114
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 102
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 238000003756 stirring Methods 0.000 claims abstract description 60
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000003085 diluting agent Substances 0.000 claims abstract description 19
- 238000007599 discharging Methods 0.000 claims abstract description 15
- 229920001400 block copolymer Polymers 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 90
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 82
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 82
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 80
- 229910001220 stainless steel Inorganic materials 0.000 claims description 62
- 239000010935 stainless steel Substances 0.000 claims description 62
- 238000010438 heat treatment Methods 0.000 claims description 59
- 239000000178 monomer Substances 0.000 claims description 59
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 42
- 229910052786 argon Inorganic materials 0.000 claims description 41
- 229920002521 macromolecule Polymers 0.000 claims description 39
- 238000005893 bromination reaction Methods 0.000 claims description 35
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 35
- 230000031709 bromination Effects 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 229920005557 bromobutyl Polymers 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 238000005859 coupling reaction Methods 0.000 claims description 21
- 238000009833 condensation Methods 0.000 claims description 20
- 230000005494 condensation Effects 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 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 17
- 230000008859 change Effects 0.000 claims description 17
- 239000003292 glue Substances 0.000 claims description 17
- YMOONIIMQBGTDU-UHFFFAOYSA-N 2-bromoethenylbenzene Chemical compound BrC=CC1=CC=CC=C1 YMOONIIMQBGTDU-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UWTUEMKLYAGTNQ-OWOJBTEDSA-N (e)-1,2-dibromoethene Chemical group Br\C=C\Br UWTUEMKLYAGTNQ-OWOJBTEDSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- -1 hydrocarbyl monolithium compound Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- 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
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-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
- 235000019400 benzoyl peroxide Nutrition 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
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 150000002894 organic compounds Chemical class 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
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 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
- 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
- 150000001451 organic peroxides Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- MCHYIMAQVBCMAP-UHFFFAOYSA-N [Li]C(C)CCC Chemical compound [Li]C(C)CCC MCHYIMAQVBCMAP-UHFFFAOYSA-N 0.000 claims 1
- ZEDXYOJKIFJKHK-UHFFFAOYSA-N [Li]CCCCC1=CC=CC=C1 Chemical compound [Li]CCCCC1=CC=CC=C1 ZEDXYOJKIFJKHK-UHFFFAOYSA-N 0.000 claims 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 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
- 238000004073 vulcanization Methods 0.000 abstract description 21
- 229920001971 elastomer Polymers 0.000 abstract description 11
- 239000005060 rubber Substances 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 31
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 125000001246 bromo group Chemical group Br* 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 229910052794 bromium Inorganic materials 0.000 description 15
- 238000005070 sampling Methods 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 11
- 230000035882 stress Effects 0.000 description 10
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
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- 239000006085 branching agent Substances 0.000 description 5
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- 241001441571 Hiodontidae Species 0.000 description 4
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical compound [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 3
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- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
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- HHBCEKAWSILOOP-UHFFFAOYSA-N 1,3-dibromo-1,3,5-triazinane-2,4,6-trione Chemical compound BrN1C(=O)NC(=O)N(Br)C1=O HHBCEKAWSILOOP-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
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
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- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
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- 229940050176 methyl chloride Drugs 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
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- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- C08F297/046—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 polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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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)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of tri-hetero-arm all-secondary brominated branched butyl rubber, which comprises the steps of adding a macromolecular tri-hetero-arm brominated grafting agent into a mixed solvent, and fully stirring until the macromolecular tri-hetero-arm brominated grafting agent is dissolved to obtain a mixed solution; cooling, sequentially adding a diluent, isobutene and isoprene into the mixed solution, fully stirring and mixing to obtain a polymerization reaction system, and cooling again; mixing and aging a diluent and a co-initiator, adding the mixture into a polymerization reaction system, fully stirring the mixture for reaction, adding a terminator, discharging, condensing, washing and drying to obtain the tri-hetero-arm all-secondary brominated branched butyl rubber; the macromolecular tri-hetero-arm brominated grafting agent is a tri-hetero-arm all-secondary brominated star-shaped block copolymer consisting of isoprene, 1, 3-butadiene, styrene and macromolecular composite brominating agent. The preparation method of the invention ensures that the butyl rubber maintains enough green rubber strength and good air tightness, and gives balance of physical and mechanical properties and vulcanization processability.
Description
Technical Field
The invention relates to a preparation method of tri-hetero-arm all-secondary brominated-branched butyl rubber, in particular to a method for preparing high-width molecular weight distribution brominated-branched butyl rubber by grafting modification of an isoprene/butadiene/styrene tri-hetero-arm star-shaped block copolymer with an all-secondary brominated structure.
Background
Butyl Rubber (IIR for short) is prepared from isobutylene and small amount of isoprene through cationic polymerization. The rubber has the characteristics of excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance and the like, is widely applied to the fields of manufacturing inner tubes, air barriers, vulcanization capsules and the like of vehicle tires, and becomes one of the most important synthetic rubber varieties. However, the molecular chain of the butyl rubber mainly consists of single bonds of carbon and carbon, has the defects of low unsaturation degree, symmetrical arrangement of substituent methyl groups, high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesion, poor compatibility with other general rubbers and the like, so that the butyl rubber is easy to excessively flow and deform in the processing process, and becomes a bottleneck for expanding application of the butyl rubber material.
At present, brominated butyl rubber (BIIR) is prepared by introducing bromine atoms into the molecular chain of butyl rubber (IIR) according to electrophilic substitution reaction under the action of molecular bromine. Compared with IIR, BIIR has the advantages that the polarity of molecular chains is increased, the adhesiveness with other rubber is improved due to the introduction of bromine atoms, the BIIR can be used together with unsaturated rubber such as natural rubber, styrene-butadiene rubber and the like at any ratio, and additional crosslinking points are generated, so that the activity of the original double bond is enhanced, the vulcanization performance of rubber materials is improved, the vulcanization speed is higher, and the vulcanization modes are more diversified; the heat resistance is also improved. Therefore, BIIR is gradually replacing IIR in the fields of industrial products such as radial tires, tubeless tires, medical sealing equipment, chemical equipment liners and the like, and has wide industrial application value and prospect.
In recent years, researchers have found a star-branched butyl rubber composed of a branched structure of high molecular weight and a linear structure of low molecular weight, which is brominated to give a brominated star-branched butyl rubber. The brominated star-branched butyl rubber has the characteristics of wide molecular weight distribution, excellent viscoelastic performance, high green rubber strength, high vulcanization speed, low melt viscosity, low processing energy consumption, low rubber discharge temperature, small shrinkage, long scorching time and the like because of the unique three-dimensional network branched structure and bromine atoms, and the balance and unification of the physical and mechanical properties and the processing properties of the brominated star-branched butyl rubber are realized. Brominated star-branched butyl rubber has therefore become one of the hot spots in the future butyl rubber research field.
CN112574333a provides a bromination process for star-branched butyl rubber, which comprises: a) Dissolving star-branched butyl rubber in aliphatic hydrocarbon to obtain a glue solution; b) Mixing the glue solution with ethanol serving as a branching agent capturing agent to obtain a mixed solution; c) Adding oxidant hydrogen peroxide and brominating agent Br into the above-mentioned mixed liquor 2 And the molar ratio of bromine element to unsaturated double bond in star branched butyl rubber is
And (3) carrying out bromination reaction, and finally neutralizing and recycling products to obtain the brominated star-branched butyl rubber. The technology can dissolve the residual branching agent in the star-branched butyl rubber before bromination, and prevent the branching agent from being combined with HBr byproducts generated in the bromination process, so that the neutralization efficiency is improved, and the isomerization conversion from a Type II secondary structure to a Type III primary structure is inhibited.
CN112011019a discloses a preparation method of halogenated bimodal distribution star-branched butyl rubber, which adopts an anionic polymerization technology to synthesize a poly (styrene-conjugated diene) block polymer, and uses silicon tetrachloride for coupling to obtain a four-arm star-shaped block polymer; dissolving the copolymer, and continuously introducing HCl gas at the temperature of-20 to 0 ℃ for 3 to 12 hours to obtain a silicon-containing chlorine-containing functionalized four-arm star-shaped branching agent; dissolving a silicon-and chlorine-containing functionalized four-arm star-shaped branching agent in a solvent, adding isobutene and isoprene, reducing the temperature to below minus 60 ℃, mixing and ageing a main initiator and a co-initiator, adding the mixture into a system, polymerizing for 3-30 min under stirring, adding a terminator to terminate the reaction, steaming stuffing under reduced pressure, and vacuum drying a sample; and halogenating the mixture to obtain halogenated bimodal distribution star-branched butyl rubber. The bimodal distribution star-branched butyl rubber prepared by the method has the characteristics of small Mooney stress relaxation and lower intrinsic viscosity, and has good processability.
CN 101353403B discloses a preparation method of star-branched polyisobutylene or butyl rubber, which adopts 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 positive ion polymerization, and under the temperature condition of 0-minus 100 ℃, methyl chloride/cyclohexane v: the mixed solvent of the mixed solvent with the v ratio of 20-80/80-20 is directly involved in positive ion polymerization, the positive ion polymerization is initiated by a silicon-chlorine group, and the unsaturated chain is involved in the grafting reaction to prepare the star-branched polyisobutene or butyl rubber product.
CN 106749816A discloses a process for preparing brominated butyl rubber, which comprises dissolving butyl rubber with n-alkane, and using specific organic bromides such as phenyltrimethyl tribromide, benzyltrimethyl tribromide, and dibromoisocyanuric acid as brominating agent, and Br 2 Or HBr is used as a bromination accelerator to carry out bromination reaction in a solvent to obtain brominated butyl rubber. The method inhibits molecular rearrangement of secondary bromine in the brominated butyl rubber to form berth bromine, and improves the secondary bromine structure content in the brominated butyl rubber.
Wu Yibo et al (Davang S H, et al, skid resistant coatings for aircraft carrier decks [ J ]. Coat technology, 1980, 52 (671): 65-69.) disclose a poly (isoprene-styrene) block copolymer prepared by living anionic polymerization as grafting agent to produce star-branched butyl rubber exhibiting a distinct bimodal appearance by living carbon cationic polymerization in an initiating system of 2-chloro-2, 4-trimethylpentane/titanium tetrachloride/proton scavenger.
Synthetic rubber industry (2006, 29 (4):
a process for preparing brominated butyl rubber by dissolving butyl rubber (Polysar-301) in cycloalkane and brominating it with liquid bromine is disclosed, and the influence of residence time and reaction temp on Mooney viscosity, unsaturation, bromine content and microstructure of product is examined. The result shows that the Mooney viscosity and the unsaturation degree of the fiber are sharply reduced when the residence time is within 2min, and the change after the residence time exceeds 2min is not great; increasing the reaction temperature will decrease the Mooney viscosity with less effect on the unsaturation. Increasing the reaction temperature and extending the residence time not only favors an increase in the bromine content of the product, but also favors rearrangement of its molecular structure, i.e., the phenomenon of transition from the secondary allylic configuration to the more stable primary allylic configuration.
In the prior art, the molecular weight distribution of the brominated butyl rubber obtained by dissolving and brominating the star-branched butyl rubber or the butyl rubber is increased, the stress relaxation rate is increased, the vulcanization speed is increased, and the good processability is shown. However, these methods still have a certain limitation, hydrogen bromide is easily generated in the bromination process of butyl rubber to cause loss of other bromine, the utilization rate of bromine is reduced, and the isomerization of the rubber with a Type secondary structure in the brominated butyl rubber to a Type III primary structure is obvious, so that the processability of the brominated butyl rubber is affected, meanwhile, the hydrogen bromide corrosivity is strong, the quality of the brominated butyl rubber is poor, and in addition, the environmental pollution and the safety and health problems of people are easily caused.
Disclosure of Invention
The invention aims to provide a preparation method of tri-hetero-arm all-secondary brominated and branched butyl rubber. The preparation method uses a macromolecular compound brominating agent as a raw material, and the macromolecular compound brominating agent has reactivity; secondly, preparing a macromolecular tri-hetero-arm bromination grafting agent with wide distribution, a full-secondary bromine structure and a tri-hetero-arm structure by using a reaction monomer isoprene, styrene, butadiene, a macromolecular composite brominating agent and a coupling agent through three-kettle and variable-speed reaction; finally, preparing the tri-hetero-arm all-secondary brominated and branched butyl rubber by taking the macromolecular tri-hetero-arm brominated grafting agent, isobutene and isoprene as reaction monomers through cationic polymerization. According to the method, the Quan Zhong-position bromine-structured butyl rubber is prepared through the polyaddition reaction, so that rearrangement of a bromine structure is avoided, the problem of stability of the bromine structure in the brominated branched butyl rubber is solved, and the scorching safety and the vulcanizing efficiency in the vulcanizing process are greatly improved. Meanwhile, the high-width molecular weight distribution of the butyl rubber is realized, the problem of low stress relaxation rate of the butyl rubber in the processing process is well solved, the sufficient green rubber strength and good air tightness of the butyl rubber are also maintained, and the balance of the physical and mechanical properties and the processing properties of the butyl rubber is achieved.
Unless otherwise specified, "%" as used herein refers to mass percent.
In order to achieve the above purpose, the invention provides a preparation method of tri-hetero-arm all-secondary brominated and branched butyl rubber, which comprises the following steps:
s1: adding the macromolecule tri-hetero-arm brominated grafting agent into the mixed solvent, and fully stirring until the macromolecule tri-hetero-arm brominated grafting agent is completely dissolved to obtain a mixed solution;
s2: cooling, sequentially adding a diluent, isobutene and isoprene into the mixed solution in the step S1, fully stirring and mixing to obtain a polymerization reaction system, and cooling again;
s3: mixing and aging a diluent and a co-initiator, adding the mixture into a polymerization reaction system in the step S2, fully stirring and reacting, adding a terminator, discharging, condensing, washing and drying to obtain the tri-hetero-arm all-secondary brominated and branched butyl rubber;
the preparation method is characterized in that the macromolecular tri-hetero-arm brominated grafting agent is a tri-hetero-arm all-secondary brominated star-shaped block copolymer consisting of isoprene, 1, 3-butadiene, styrene and macromolecular composite brominating agent, and the structural general formula of the block copolymer is shown as formula I:
wherein: IR is an isoprene homopolymer block; SB is a random segment of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene; BR is a 1, 3-butadiene homopolymer segment; m and n are the number of repeating units, m is an integer not less than 1, and n is an integer not less than 1; the number average molecular weight (Mn) of the macromolecular tri-hetero-arm brominated grafting agent is 50000-70000, and the molecular weight distribution (Mw/Mn) is 11.53-13.12.
In the step S1, the mass ratio of the mixed solvent to the high-molecular tri-hetero-arm brominated grafting agent is 100-200: 5 to 10.
In the step S1, the mixed solvent comprises a diluent and a solvent, wherein the volume ratio of the diluent to the solvent is 70-30/30-70.
In the preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber, in the step S2, the temperature is reduced to be between-85 ℃ and-95 ℃.
In the preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber, in the step S2, the mass ratio of the diluent to the isobutene to the isoprene is 100-200: 80-90: 5 to 10.
In the step S2, the temperature is reduced again to-100 to-95 ℃.
In the preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber, in the step S3, the mass ratio of the diluent to the co-initiator to the terminator is 10-20: 0.2 to 0.6:3 to 7.
In the step S3, the aging temperature is between-95 ℃ and-85 ℃ and the aging time is between 60 min and 70min.
The preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber specifically comprises the following steps of:
a, preparing a macromolecular composite brominating agent: based on 100 parts by mass of the reactive brominating agent, firstly adding 200-300 parts of solvent, 70-80 parts of bromovinylbenzene, 20-30 parts of 1, 2-dibromoethylene and 0.2-0.5 part of molecular weight regulator into a reaction kettle after inert gas replacement in sequence, stirring, mixing and heating, adding 0.3-0.7 part of first initiator when the temperature of the reaction kettle reaches 70-80 ℃, and reacting for 4.0-6.0 hr, wherein the conversion rate of bromovinylbenzene reaches 100%; and then adding 1-5 parts of 1, 3-butadiene into the reaction kettle for end capping, reacting for 50-60 min until no free monomer exists, and washing and drying after the reaction is finished to obtain the macromolecular compound brominating agent.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: based on hundred percent of the total mass of the reaction monomers, firstly, sequentially adding 100 to 200 weight percent of solvent, 20 to 30 weight percent of isoprene, 0.2 to 0.5 weight percent of structure regulator and a second initiator into a reaction kettle A after inert gas replacement, heating to 60 to 70 ℃, reacting for 40 to 60 minutes to form an-IR-chain segment, then adding 20 to 30 weight percent of macromolecular composite brominating agent into the reaction kettle A, and reacting for 70 to 90 minutes until no free monomer exists; simultaneously adding 100-200wt% of solvent, 0.3wt% -0.6wt% of structure regulator and a second initiator into a reaction kettle B after inert gas replacement, heating to 70-80 ℃, stirring and mixing 15-20wt% of styrene and 20-30wt% of 1, 3-butadiene for 20-30 min, reacting to obtain variable-speed polymerization, adding the variable-speed polymerization into the reaction kettle B in a continuous injection mode, reacting within 60-80 min, wherein the initial feeding speed is higher than 7.0% of mixture/min, the feeding speed reduction range is determined according to the reaction time, forming a random and long gradual change section-SB/(S- & gtB) -chain segment, and then adding materials in the reaction kettle B into the reaction kettle A; simultaneously, in a 15L stainless steel reaction kettle C, introducing argon to replace a system for 2-4 times, sequentially adding 100-200 wt% of solvent, 10-20 wt% of 1, 3-butadiene and 0.1-0.3 wt% of structure regulator, heating to 40-50 ℃ by a second initiator, reacting for 40-60 min to form a-BR-chain segment until no free monomer exists, and then adding materials in the reaction kettle C into a reaction kettle A; and finally, heating the reaction kettle A to 80-90 ℃, adding a coupling agent for coupling reaction, treating the coupled reaction mixture with water after the reaction for 80-100 min, and performing wet condensation and drying on the glue solution to obtain the macromolecular tri-hetero-arm brominated grafting agent.
The preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber can be characterized in that the molecular weight regulator can be at least one of tertiary ten-carbon mercaptan, tertiary twelve-carbon mercaptan, tertiary fourteen-carbon mercaptan and tertiary sixteen-carbon mercaptan, and tertiary twelve-carbon mercaptan is preferred.
According to the preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber, the first initiator is an organic peroxide and is at least one selected from dicumyl peroxide (DCP), cumene hydroperoxide, benzoyl Peroxide (BPO) and di-tert-butyl peroxide, and preferably dicumyl peroxide (DCP).
According to the preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber, the structure regulator is a polar organic compound, a solvation effect is generated in a polymerization system, and the reactivity ratio of styrene and isoprene can be regulated, so that the styrene and the isoprene are randomly copolymerized. Such polar organic compound is selected from at least one of diethylene glycol dimethyl ether (DGE), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, preferably ethylene glycol dimethyl ether (DME).
The second initiator is a hydrocarbon-based mono-lithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a composite group of the above groups containing 1-20 carbon atoms. The hydrocarbon mono-lithium compound is at least one selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and dodecyllithium, preferably n-butyllithium. The amount of the second initiator added is determined by the molecular weight of the polymer being designed.
The coupling agent is at least one of 1,3, 5-benzene trichloride and 1,3, 5-benzene tribromide, preferably 1,3, 5-benzene trichloride. The dosage of the coupling agent is determined according to the amount of the second initiator, and the molar ratio of the coupling agent to the second initiator is 1:1-5:1.
In the preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber, the polymerization reaction is carried out in an oxygen-free and water-free environment, and preferably in an inert gas environment. The polymerization and dissolution processes are both carried out in hydrocarbon solvents, which are hydrocarbon solvents according to the present invention, including linear alkanes, aromatic hydrocarbons and cyclic alkanes, selected from at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably octane.
The invention relates to a preparation method of tri-hetero-arm all-secondary brominated branched butyl rubber, wherein the diluent is halogenated alkane, and 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 at least one selected from the group consisting of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably dichloromethane.
The invention relates to a preparation method of tri-hetero-arm all-secondary brominated branched butyl rubber, wherein a 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 HCI, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCI. The molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1-0.5:1.
The preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber can be used for example, but not limited to, at least one of methanol, ethanol and butanol.
The invention can be further described as follows:
in detail, the specific preparation process of the preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber comprises the following steps:
(1) Preparation of a macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: firstly, putting the reactive brominating agent with the mass of 100 parts into a 15L stainless steel reaction kettle with a jacket, introducing inert gas for replacement for 2-4 times, sequentially adding 200-300 parts of solvent, 70-80 parts of bromovinylbenzene, 20-30 parts of 1, 2-dibromoethylene and 0.2-0.5 part of molecular weight regulator into the reaction kettle, stirring, mixing and heating, adding 0.3-0.7 part of first initiator when the temperature of the reaction kettle reaches 70-80 ℃, and reacting for 4.0-6.0 hr, wherein the conversion rate of bromovinylic monomers reaches 100%; and then adding 1-5 parts of 1, 3-butadiene into the reaction kettle for end capping, reacting for 50-60 min until no free monomer exists, and washing and drying after the reaction is finished to prepare the macromolecular compound brominating agent.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle A with a jacket for replacement for 2-4 times, sequentially adding 100-200 wt% of solvent, 20-30 wt% of isoprene and 0.2-0.5 wt% of structure regulator into the reaction kettle A, heating to 60-70 ℃ by using a second initiator, reacting for 40-60 min to form an-IR-chain segment, and then adding 20-30% of macromolecular compound brominating agent into the reaction kettle A for reacting for 70-90 min until no free monomer exists; simultaneously, in a 15L stainless steel reaction kettle B, introducing argon to replace a system for 2-4 times, sequentially adding 100-200 wt% of solvent, 0.3-0.6 wt% of structure regulator, heating to 70-80 ℃, stirring and mixing 15-20 wt% of styrene and 20-30 wt% of 1, 3-butadiene for 20-30 min, reacting to obtain variable-speed polymerization, adding the variable-speed polymerization into the reaction kettle in a continuous injection mode, reacting within 60-80 min, and enabling the initial charging speed to be higher than 7.0% of mixture/min, wherein the charging speed reduction range is determined according to the reaction time, forming a random and long gradient-SB/(S- & gtB) -chain segment, and then adding materials in the reaction kettle B into the reaction kettle A; simultaneously, in a 15L stainless steel reaction kettle C, introducing argon to replace a system for 2-4 times, sequentially adding 100-200 wt% of solvent, 10-20 wt% of 1, 3-butadiene and 0.1-0.3 wt% of structure regulator, heating to 40-50 ℃ by a second initiator, reacting for 40-60 min to form a-BR-chain segment until no free monomer exists, and then adding materials in the reaction kettle C into a reaction kettle A; and finally, heating the reaction kettle A to 80-90 ℃, adding a coupling agent for coupling reaction, treating the coupled reaction mixture with water after the reaction for 80-100 min, and performing wet condensation and drying on the glue solution to obtain the macromolecular tri-hetero-arm brominated grafting agent.
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3-5 times, adding 100-200wt% of mixed solvent (the ratio of diluent/solvent V is 70-30/30-70) into the reaction, and stirring and dissolving 5-10wt% of macromolecule three-hetero-arm brominated grafting agent until the grafting agent is completely dissolved; then cooling to-85 to-95 ℃, sequentially adding 100 to 200 weight percent of diluent, 80 to 90 weight percent of isobutene and 5 to 10 weight percent of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-95 ℃, then mixing and aging for 60 to 70 minutes at-95 to-85 ℃ with 10 to 20 weight percent of diluent and 0.2 to 0.6 weight percent of co-initiator, adding the mixture into the polymerization system together for stirring and reacting for 6.0 to 8.0 hours, finally adding 3 to 7 weight percent of terminator, discharging and condensing, washing and drying to obtain the tri-hetero-arm all-secondary brominated and branched butyl rubber product.
The invention relates to a macromolecular tri-hetero-arm brominated grafting agent, which is a tri-hetero-arm all-secondary brominated star-shaped block copolymer composed of isoprene, 1, 3-butadiene, styrene and macromolecular composite brominating agent, and the structural general formula of the tri-hetero-arm all-secondary brominated star-shaped block copolymer is shown as formula I:
Wherein IR is an isoprene homopolymer block; SB is a random segment of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene; BR is a 1, 3-butadiene homopolymer segment; m and n are the number of repeating units. The number average molecular weight (Mn) of the macromolecular tri-hetero-arm brominated grafting agent is 50000-70000, and the molecular weight distribution (Mw/Mn) is 11.53-13.12.
Firstly, carrying out free radical polymerization on 1, 2-dibromoethylene and bromovinylbenzene to generate a macromolecular compound brominating agent with anionic reactivity; secondly, isoprene, styrene, 1, 3-butadiene and a macromolecular compound brominating agent form a reaction monomer, and finally a macromolecular tri-hetero-arm brominating grafting agent is prepared by coupling a trihalobenzene coupling agent through a three-kettle reaction and variable-temperature polymerization process; finally, a high molecular tri-hetero-arm brominated grafting agent, isobutene and isoprene are used as reaction monomers, and the tri-hetero-arm brominated and branched butyl rubber with a full-secondary bromine structure and high-wide molecular weight distribution is prepared through cationic polymerization.
The high polymer tri-hetero-arm brominated grafting agent solves the problem of easy rearrangement of a bromine structure in brominated branched butyl rubber, ensures the stability of a secondary bromine structure, ensures the scorching safety of the butyl rubber, accelerates the vulcanization speed, increases the vulcanization degree and improves the vulcanization efficiency. Secondly, the macromolecular tri-hetero-arm brominated grafting agent adopts a three-kettle polymerization and variable-speed polymerization process to obtain a tri-hetero-arm star-shaped branched structure and a highly random and gradual chain segment-SB/(S-B) -, the structural characteristics are that the disorder of a molecular chain segment is increased in the grafting polymerization process of butyl rubber, the regularity of the molecular chain is obviously destroyed, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic performance, the stress relaxation rate is high, and the processability of the butyl rubber is improved; finally, the-SB/(S-B) -chain segment in the macromolecular tri-hetero-arm bromination grafting agent and the macromolecular composite bromination agent contain a certain amount of benzene rings, and the benzene rings have the characteristics of high rigidity and high steric hindrance, so that the reduction of strength and air tightness caused by the widening of the molecular weight distribution of the butyl rubber can be avoided, and the high strength and good air tightness of the butyl rubber are ensured.
Therefore, the polymer tri-hetero-arm brominated grafting agent organically combines a Quan Zhong-position bromine structure, a tri-hetero-arm star-shaped branching structure and an SB/(S-B) chain segment and cooperatively plays a role, so that the balance of vulcanization characteristics, processability, strength and air tightness of the butyl rubber is realized, and the performance of the butyl rubber is more comprehensively improved. The preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber has the characteristics of short process flow, controllable bromine structure, safety, environmental protection, suitability for industrial production and the like.
In summary, the invention has the following beneficial effects:
1. the polymer tri-hetero-arm brominated grafting agent adopts free radical polymerization and anion polymerization instead of ionic substitution reaction in the prior art, thereby avoiding bromine structure rearrangement in brominated and branched butyl rubber, improving the stability of all-secondary-position bromine structures in brominated and branched butyl rubber, solving the problem of easy rearrangement of bromine structures in tri-hetero-arm all-secondary-position brominated and branched butyl rubber, ensuring the stability of all-secondary-position bromine structures, ensuring the scorching safety of butyl rubber, accelerating the vulcanization speed, increasing the vulcanization degree and improving the vulcanization efficiency.
2. The macromolecular bromination grafting agent of the invention uses the organic brominating agent containing unsaturated double bond to generate macromolecular brominating agent by first free radical polymerization, then takes part in anion reaction, does not generate HBr in the whole reaction process, avoids the loss of other bromine, increases the reaction degree of the organic brominating agent, and improves the utilization ratio of bromine element in brominated branched butyl rubber.
3. The macromolecular brominating agent of the invention can not generate by-product HBr in the whole reaction process, reduces harm to human and environment, omits the process of alkali washing and recycling of by-product HBr, shortens the process flow and reduces the production cost.
4. The macromolecular tri-hetero-arm brominated grafting agent adopts a three-kettle polymerization and variable-speed polymerization process to obtain a tri-hetero-arm star-shaped branched structure and a highly random and gradual chain segment-SB/(S-B) -, the structural characteristics are that the disorder of a molecular chain segment is increased in the grafting polymerization process of butyl rubber, the regularity of the molecular chain is obviously destroyed, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic performance, the stress relaxation rate is high, the processability of the butyl rubber is improved, the strength and air tightness reduction caused by the widening of the molecular weight distribution of the butyl rubber can be avoided, the butyl rubber is ensured to have high strength and good air tightness, and the vulcanization characteristic and the processability of the butyl rubber and the balance of the strength and the air tightness are realized.
5. The polymer three-hetero-arm bromination grafting agent is a novel safe and environment-friendly compound without emission of atmospheric pollutants (VOC) and byproducts HBr, and has the characteristics of environment-friendly preparation method, short process flow, stable bromine structure, excellent processability, suitability for industrial production and the like.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
(1) The raw material sources are as follows:
styrene, 1, 3-butadiene, polymer grade chinese petroleum lanzhou petrochemical company;
isobutene, isoprene, polymeric grade Zhejiang Xinhui New Material Co., ltd;
bromovinylbenzene, a polymer grade Shanghai susceptance chemical Co., ltd;
1, 2-dibromoethylene, a polymer grade Shanghai chemical Co., ltd;
dicumyl peroxide (DCP), a lanzhou auxiliary plant;
n-butyllithium with purity of 98%, nanjing Tonglian chemical Co., ltd;
1,3, 5-benzene trichloride has a purity of 99%, which is a chemical industry company of sea, yangzhou;
The purity of the sesquiethyl aluminum chloride is 98%, and the carbofuran science and technology Co., ltd;
the other reagents are all commercial products.
(2) The analytical test method comprises the following steps:
and measuring bromine content, namely weighing 10mg of sample, and carrying out thermal degradation on the sample in a nitrogen atmosphere with the flow rate of 50mL/min by adopting a Q600 type TG/DTG thermal gravimetric analyzer at the heating rate of 10 ℃/min. The first stage of thermal degradation is to remove bromine from a bromine-containing unit of a sample to form HBr, and then reversely calculate the bromine content (X) in the sample by the percentage of the removed HBr, wherein the calculation formula is as follows:
wherein: y is the percentage of the sample at 220 ℃;79.904 the relative atomic mass of bromine; 1.008 is the relative atomic mass of hydrogen.
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 。
Determination of mooney stress relaxation: the measurement was carried out by using a high-speed rail GT-7080S2 type Mooney viscosimeter, with reference to GB/T1232.1-2000, under 125 ℃ (1+8) conditions using a large rotor. Measurement of stress relaxation after the end of the mooney viscosity test, the rotor was stopped rapidly (within 0.1 seconds) and the decay of the mooney viscosity number was recorded over time. The stress relaxation behavior of the rubber was expressed by t80[ time taken for torque to decay by 80% (remaining 20%) and X30 (percentage of torque remaining after the rotor stopped for 30 s) taking the torque after the rotor stopped (within 0.1 seconds) as 100%.
Vulcanization characteristics: according to GB/T16584-1996.
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 macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of octane, 700g of bromovinylbenzene, 300g of 1, 2-dibromoethylene and 2.0g of tertiary dodecyl mercaptan into the reaction kettle, stirring, mixing and heating, adding 3.0g of DCP when the temperature of the reaction kettle reaches 70 ℃, and reacting for 4.0hr; then adding 10g of 1, 3-butadiene into a polymerization kettle for end capping, reacting for 50min until no free monomer exists, washing and drying after the reaction is finished, and obtaining the macromolecular compound brominating agent.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 2 times, sequentially adding 1000g of octane, 200g of isoprene and 2.0g of DME into the polymerization kettle, heating to 60 ℃, adding 11.3mmo1 of n-butyllithium to start reaction for 40min to form an-IR-chain segment, then adding 200g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 70min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1000g of octane and 3.0g DME,15.1mmo1 n-butyllithium, heating to 70 ℃, adding 200g of styrene and 300g of 1, 3-butadiene, stirring and mixing for 30min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within 60min of reaction time, wherein the feeding speed is reduced by 6g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 2 times, sequentially adding 1000g of heptane, 100g of 1, 3-butadiene and 1.0g of DME, heating to 40 ℃, adding 5.5 mmol of n-butyllithium to start reaction for 40min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 80 ℃, 35.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 80min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent (Mn is 52000, mw/Mn is 11.53).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 350g of methylene dichloride, 150g of hexane and 25.0g of macromolecule three-hetero-arm brominated grafting agent are added into the polymerization kettle, stirring and dissolving are carried out for 70min until the macromolecule three-hetero-arm brominated grafting agent is completely dissolved, then, when the temperature is reduced to minus 85 ℃, 500g of methylene dichloride, 450g of isobutene and 25.0g of isoprene are sequentially added, stirring and mixing are carried out until the temperature of a polymerization system is reduced to minus 90 ℃, then 50g of methylene dichloride, 1.52g of aluminum sesquichloride and 0.027g of HCl are mixed and aged for 60min at minus 85 ℃, then, the mixture is added into the polymerization system together, stirring and reacting are carried out for 6.0hr, finally, 15g of ethanol is added, and finally, discharging and condensing, washing and drying are carried out, thus obtaining the three-hetero-arm all-secondary brominated 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 macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing nitrogen for 2 times for replacement, sequentially adding 2100g of octane, 720g of bromovinylbenzene, 280g of 1, 2-dibromoethylene and 2.5g of tertiary dodecyl mercaptan into the reaction kettle, stirring, mixing and heating, adding 3.5g of DCP when the temperature of the reaction kettle reaches 72 ℃, and reacting for 4.5hr; and then adding 20g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 52min until no free monomer exists, and washing and drying after the reaction is finished to obtain the macromolecular compound brominating agent.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 2 times, sequentially adding 1100g of octane, 220g of isoprene and 3.0g of DME into the polymerization kettle, heating to 62 ℃, adding 12.1 mmol of n-butyllithium to start reaction for 45min to form an-IR-chain segment, then adding 220g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 75min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1100g of octane and 3.5g DME,16.9mmo1 n-butyllithium, heating to 72 ℃, stirring and mixing 190g of styrene and 280g of 1, 3-butadiene for 28min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within a reaction time of 60min, wherein the feeding speed is reduced by 6g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 2 times, sequentially adding 1100g of heptane, 110g of 1, 3-butadiene and 1.3g of DME, heating to 45 ℃, adding 6.8mmo1 of n-butyllithium to start reacting for 43min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 83 ℃, 40.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 82min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent (Mn is 55000, mw/Mn is 11.87).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 320g of methylene dichloride, 180g of hexane and 30.0g of macromolecule three-hetero-arm brominated grafting agent are added into the polymerization kettle, stirring and dissolving are carried out for 75min until the macromolecule three-hetero-arm brominated grafting agent is completely dissolved, then, when the temperature is reduced to minus 87 ℃, 600g of methylene dichloride, 440g of isobutene and 30.0g of isoprene are sequentially added, stirring and mixing are carried out until the temperature of a polymerization system is reduced to minus 92 ℃, then, 60g of methylene dichloride, 1.78g of aluminum sesquichloride and 0.035g of HCl are mixed and aged for 62min at minus 87 ℃, then, the mixture is added into the polymerization system together, stirring and reacting are carried out for 6.4hr, finally, 20g of ethanol is added, and finally, discharging and condensing, washing and drying are carried out, thus obtaining the three-hetero-arm all-secondary brominated 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 macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 2300g of octane, 260g of bromovinylbenzene, 260g of 1, 2-dibromoethylene and 3.0g of tertiary dodecyl mercaptan into the reaction kettle, stirring, mixing and heating, adding 4.0g of DCP when the temperature of the reaction kettle reaches 74 ℃, and reacting for 5.0hr; then adding 30g of 1, 3-butadiene into a polymerization kettle for end capping, reacting for 54min until no free monomer exists, and washing and drying after the reaction is finished to obtain the macromolecular compound brominating agent.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 3 times, sequentially adding 1400g of octane, 250g of isoprene and 3.5g of DME into the polymerization kettle, heating to 65 ℃, adding 14.2 mmol 1 of n-butyllithium to start reaction for 50min to form an-IR-chain segment, then adding 240g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 80min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1300g of octane and 4.0g DME,18.1mmo1 n-butyllithium, heating to 75 ℃, stirring and mixing 180g of styrene and 260g of 1, 3-butadiene for 26min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within a reaction time of 70min, wherein the feeding speed is reduced by 4g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 3 times, sequentially adding 1300g of heptane, 140g of 1, 3-butadiene and 1.7g of DME, heating to 45 ℃, adding 7.5 mmol of n-butyllithium to start reacting for 48min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 85 ℃, 50.7mmo11,3, 5-benzene trichloride is added for reaction for 88min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the high polymer tri-hetero-arm brominated grafting agent (Mn is 60000 and Mw/Mn is 12.27).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 300g of methylene dichloride, 200g of hexane and 35.0g of macromolecule three-hetero-arm brominated grafting agent are added into the polymerization kettle, stirring and dissolving are carried out for 78min until the macromolecule three-hetero-arm brominated grafting agent is completely dissolved, then, when the temperature is reduced to minus 90 ℃, 700g of methylene dichloride, 430g of isobutene and 35.0g of isoprene are sequentially added, stirring and mixing are carried out until the temperature of a polymerization system is reduced to minus 95 ℃, then, 70g of methylene dichloride, 2.18g of aluminum sesquichloride and 0.047g of HCl are mixed and aged for 64min at minus 90 ℃, then, the mixture is added into the polymerization system together, stirring and reacting are carried out for 6.8hr, finally, 24g of ethanol is added, and finally, discharging and condensing, washing and drying are carried out, thus obtaining the three-hetero-arm all-secondary brominated 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 macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, sequentially adding 2500g of octane, 760g of bromovinylbenzene, 240g of 1, 2-dibromoethylene and 3.5g of tertiary dodecyl mercaptan into the reaction kettle, stirring, mixing and heating, adding 5.0g of DCP when the temperature of the reaction kettle reaches 76 ℃, and reacting for 5.3 hours; then adding 40g of 1, 3-butadiene into a polymerization kettle for end capping, reacting for 56min until no free monomer exists, and washing and drying after the reaction is finished to obtain the macromolecular compound brominating agent.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 3 times, sequentially adding 1600g of octane, 260g of isoprene and 4.0g of DME into the polymerization kettle, heating to 66 ℃, adding 16.8mmo1 of n-butyllithium to start reaction for 53min to form an-IR-chain segment, then adding 260g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 83min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1500g of octane and 4.5g DME,19.7mmo1 n-butyllithium, heating to 76 ℃, stirring and mixing 170g of styrene and 240g of 1, 3-butadiene for 24min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within a reaction time of 70min, wherein the feeding speed is reduced by 4g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 3 times, sequentially adding 1600g of heptane, 160g of 1, 3-butadiene and 2.0g of DME, heating to 47 ℃, adding 8.6mmo1 of n-butyllithium to start reacting for 52min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 87 ℃, 60.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 92min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent (Mn is 63000 and Mw/Mn is 12.58).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 300g of methylene dichloride, 700g of hexane and 40.0g of macromolecule three-hetero-arm brominated grafting agent are added into the polymerization kettle, stirring and dissolving are carried out for 80 minutes until the macromolecule three-hetero-arm brominated grafting agent is completely dissolved, then, when the temperature is reduced to minus 92 ℃, 800g of methylene dichloride, 420g of isobutene and 40.0g of isoprene are sequentially added, stirring and mixing are carried out until the temperature of a polymerization system is reduced to minus 96 ℃, then, 80g of methylene dichloride, 2.35g of aluminum sesquichloride and 0.058g of HCl are mixed and aged for 66 minutes at minus 92 ℃, then, the mixture is added into the polymerization system together, stirred and reacted for 7.0 hours, finally, 28g of ethanol is added, and finally, the three-hetero-arm all-secondary brominated branched butyl rubber product is obtained after discharging condensation, washing and drying. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 5
(1) Preparation of a macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 2700g of octane, 780g of bromovinylbenzene, 220g of 1, 2-dibromoethylene and 4.0g of tertiary dodecyl mercaptan into the reaction kettle, stirring, mixing and heating, and adding 6.0g of DCP when the temperature of the reaction kettle reaches 78 ℃ for reaction for 5.7hr; then adding 45g of 1, 3-butadiene into a polymerization kettle for end capping, reacting for 58min until no free monomer exists, and washing and drying after the reaction is finished to obtain the macromolecular compound brominating agent.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 1800g of octane, 280g of isoprene and 4.5g of DME into the polymerization kettle, heating to 68 ℃, adding 17.5 mmol 1 of n-butyllithium to start reaction for 57min to form an-IR-chain segment, then adding 280g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 86min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 1700g of octane and 5.0g DME,21.5mmo1 n-butyllithium, heating to 78 ℃, stirring and mixing 160g of styrene and 220g of 1, 3-butadiene for 22min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within a reaction time of 80min, wherein the feeding speed is reduced by 2g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 4 times, sequentially adding 1800g of heptane, 180g of 1, 3-butadiene and 2.6g of DME, heating to 49 ℃, adding 9.5 mmol 1 of n-butyllithium to start reacting for 57min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 89 ℃, 80.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 95min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent (Mn is 67000 and Mw/Mn is 12.89).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 500g of dichloromethane and 500g of hexane are added into the polymerization kettle, 45.0g of macromolecule tri-hetero-arm brominated grafting agent is stirred and dissolved for 84min until the macromolecule tri-hetero-arm brominated grafting agent is completely dissolved, then 900g of dichloromethane, 410g of isobutene and 45.0g of isoprene are sequentially added when the temperature is reduced to minus 94 ℃, stirred and mixed until the temperature of a polymerization system is reduced to minus 98 ℃, then 90g of dichloromethane, 2.63g of sesquiethyl aluminum chloride and 0.072g of HCl are mixed and aged for 68min at minus 94 ℃, and then added into the polymerization system together for stirring and reacting for 7.5hr, finally 30g of ethanol is added, and finally, the tri-hetero-arm all-secondary brominated branched butyl rubber product is obtained after discharging coagulation, washing and drying. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 6
(1) Preparation of a macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 300g of octane, 800g of bromovinylbenzene, 200g of 1, 2-dibromoethylene and 5.0g of tertiary dodecyl mercaptan into the reaction kettle, stirring, mixing and heating, and adding 7.0g of DCP when the temperature of the reaction kettle reaches 80 ℃ for reaction for 6.0hr; and then 50g of 1, 3-butadiene is added into the polymerization kettle for end capping, the reaction is carried out for 60min until no free monomer exists, and the macromolecular compound brominating agent is obtained after washing and drying after the reaction is completed.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 2000g of octane, 300g of isoprene and 5.0g of DME into the polymerization kettle, heating to 70 ℃, adding 18.6mmo1 of n-butyllithium to start reaction for 60min to form an-IR-chain segment, then adding 300g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 90min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 2000g of octane and 6.0g DME,22.6mmo1 n-butyllithium, heating to 80 ℃, stirring and mixing 150g of styrene and 200g of 1, 3-butadiene for 20min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within 80min of reaction time, wherein the feeding speed is reduced by 2g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 4 times, sequentially adding 2000g of heptane, 200g of 1, 3-butadiene and 3.0g of DME, heating to 50 ℃, adding 10.6mmo1 of n-butyllithium to start reacting for 60min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 90 ℃, 100.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 100min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent (Mn is 69000 and Mw/Mn is 13.12).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 300g of methylene dichloride, 700g of hexane and 50.0g of macromolecule three-hetero-arm brominated grafting agent are added into the polymerization kettle, stirring and dissolving are carried out for 90min until the macromolecule three-hetero-arm brominated grafting agent is completely dissolved, then, when the temperature is reduced to minus 95 ℃, 1000g of methylene dichloride, 400g of isobutene and 50.0g of isoprene are sequentially added, stirring and mixing are carried out until the temperature of a polymerization system is reduced to minus 100 ℃, then, 100g of methylene dichloride, 2.85g of aluminum sesquichloride and 0.085g of HCl are mixed and aged for 70min at minus 95 ℃, then, the mixture is added into the polymerization system together, stirring and reacting are carried out for 8.0hr, finally, 35g of ethanol is added, and finally, discharging and condensing, washing and drying are carried out, thus obtaining the three-hetero-arm all-secondary brominated branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 1
(1) Preparation of a macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: other conditions were the same as in example 1 except that: no bromovinylbenzene is added in the preparation process of the macromolecular compound brominating agent, namely: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of octane, 300g of 1, 2-dibromoethylene and 2.0g of tertiary dodecyl mercaptan into the reaction kettle, stirring, mixing and heating, adding 3.0g of DCP when the temperature of the reaction kettle reaches 70 ℃, and reacting for 4.0hr; then adding 10g of 1, 3-butadiene into a polymerization kettle for end capping, reacting for 50min until no free monomer exists, and washing and drying after the reaction is finished to obtain the macromolecular compound brominating agent-1.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: other conditions were the same as in example 1 except that: the preparation process of the macromolecular tri-hetero-arm cloth bromination grafting agent does not add a macromolecular compound brominating agent, but adds a macromolecular compound brominating agent-1, namely: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 2 times, sequentially adding 1000g of octane, 200g of isoprene and 2.0g of DME into the polymerization kettle, heating to 60 ℃, adding 11.3mmo1 of n-butyllithium to start reaction for 40min to form an-IR-chain segment, then adding 200g of macromolecular compound brominating agent-1 into the polymerization kettle A, and reacting for 70min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1000g of octane and 3.0g DME,15.1mmo1 n-butyllithium, heating to 70 ℃, adding 200g of styrene and 300g of 1, 3-butadiene, stirring and mixing for 30min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within 60min of reaction time, wherein the feeding speed is reduced by 6g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 2 times, sequentially adding 1000g of heptane, 100g of 1, 3-butadiene and 1.0g of DME, heating to 40 ℃, adding 5.5 mmol 1 of n-butyllithium to start reaction for 40min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 80 ℃, 35.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 80min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent-1 (Mn is 41000, mw/Mn is 9.12).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: other conditions were the same as in example 1 except that: the preparation process of the tri-hetero-arm all-secondary brominated butyl rubber does not add a macromolecular tri-hetero-arm brominated grafting agent, but adds macromolecular tri-hetero-arm brominated grafting agent-1, and the addition amount is 25g, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 350g of methylene dichloride and 150g of hexane are added into the polymerization kettle, 25.0g of high polymer three hetero-arm bromination grafting agent-1 is stirred and dissolved for 70min until the mixture is completely dissolved, then, when the temperature is reduced to minus 85 ℃, 500g of methylene dichloride, 450g of isobutene and 25.0g of isoprene are sequentially added, and stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 50g of methylene dichloride, 1.52g of aluminum sesquichloride and 0.027g of HCl are mixed and aged for 60min at minus 85 ℃, and then, the mixture is added into the polymerization system together to be stirred and reacted for 6.0hr, finally, 15g of ethanol is added, and then, the mixture is subjected to discharging condensation, washing and drying to obtain the three hetero-arm all-secondary brominated branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
(1) Preparation of a macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: as in example 2.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: other conditions were the same as in example 2 except that: the adding amount of the macromolecular compound brominating agent in the preparation of the macromolecular tri-hetero-arm brominating grafting agent is 100g, namely: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 2 times, sequentially adding 1100g of octane, 220g of isoprene and 3.0g of DME into the polymerization kettle, heating to 62 ℃, adding 12.1 mmol of n-butyllithium to start reaction for 45min to form an-IR-chain segment, then adding 100g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 75min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1100g of octane and 3.5g DME,16.9mmo1 n-butyllithium, heating to 72 ℃, stirring and mixing 190g of styrene and 280g of 1, 3-butadiene for 28min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within a reaction time of 60min, wherein the feeding speed is reduced by 6g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 2 times, sequentially adding 1100g of heptane, 110g of 1, 3-butadiene and 1.3g of DME, heating to 45 ℃, adding 6.8mmo1 of n-butyllithium to start reacting for 43min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 83 ℃, 40.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 82min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent-2 (Mn is 52000, and Mw/Mn is 10.95).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: other conditions were the same as in example 2 except that: the preparation process of the tri-hetero-arm all-secondary brominated butyl rubber does not add a macromolecular tri-hetero-arm brominated grafting agent, but adds macromolecular tri-hetero-arm brominated grafting agent-2, and the addition amount is 30.0g, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 320g of methylene dichloride and 180g of hexane are added into the polymerization kettle, 30.0g of high polymer three-hetero-arm bromination grafting agent-2 is stirred and dissolved for 75min until the mixture is completely dissolved, then, when the temperature is reduced to minus 87 ℃, 600g of methylene dichloride, 440g of isobutene and 30.0g of isoprene are sequentially added, and stirred and mixed until the temperature of a polymerization system is reduced to minus 92 ℃, then, 60g of methylene dichloride, 1.78g of aluminum sesquichloride and 0.035g of HCl are mixed and aged for 62min under the condition of minus 87 ℃, and then, the mixture is added into the polymerization system together for stirring and reacting for 6.4hr, finally, 20g of ethanol is added, and then, the three-hetero-arm all-secondary brominated and branched butyl rubber product is obtained after discharging condensation, washing and drying. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
(1) Preparation of a macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: same as in example 3.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: other conditions were the same as in example 3 except that: the preparation process of the macromolecular tri-hetero-arm bromination grafting agent does not add macromolecular compound brominating agent, but adds bromovinylbenzene, the adding amount is 240g, namely: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 3 times, sequentially adding 1400g of octane, 250g of isoprene, 3.5g of DME, heating to 65 ℃, adding 14.2 mmol 1 of n-butyllithium for reaction for 50min to form an-IR-chain segment, then adding 240g of bromovinylbenzene into the polymerization kettle A, and reacting for 80min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1300g of octane and 4.0g DME,18.1mmo1 n-butyllithium, heating to 75 ℃, stirring and mixing 180g of styrene and 260g of 1, 3-butadiene for 26min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within a reaction time of 70min, wherein the feeding speed is reduced by 4g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 3 times, sequentially adding 1300g of heptane, 140g of 1, 3-butadiene and 1.7g of DME, heating to 45 ℃, adding 7.5 mmol of n-butyllithium to start reacting for 48min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 85 ℃, 50.7mmo11,3, 5-benzene trichloride is added for reaction for 88min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent-3 (Mn is 42000, mw/Mn is 9.51).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: other conditions were the same as in example 3 except that: the preparation process of the tri-hetero-arm brominated butyl rubber does not add a macromolecular tri-hetero-arm brominated grafting agent, but adds macromolecular tri-hetero-arm brominated grafting agent-3, the addition amount of which is 35.0g, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 300g of methylene dichloride and 200g of hexane are added into the polymerization kettle, 35.0g of high-molecular tri-hetero-arm bromination grafting agent-3 is stirred and dissolved for 78min until the mixture is completely dissolved, then 700g of methylene dichloride, 430g of isobutene and 35.0g of isoprene are sequentially added when the temperature is reduced to minus 90 ℃, the mixture is stirred and mixed until the temperature of a polymerization system is reduced to minus 95 ℃, then 70g of methylene dichloride, 2.18g of aluminum sesquichloride and 0.047g of HCl are mixed and aged for 64min at minus 90 ℃, and then the mixture is added into the polymerization system together for stirring and reacting for 6.8hr, finally, after 24g of ethanol is added, the mixture is subjected to discharging condensation, washing and drying, and the tri-hetero-arm all-secondary brominated and branched butyl rubber product is obtained. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 4
(1) Preparation of a macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: same as in example 4.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: other conditions were the same as in example 4 except that: the preparation process of the macromolecular tri-hetero-arm bromination grafting agent does not add macromolecular compound brominating agent, but adds 1, 2-dibromoethylene, the adding amount is 260g, namely: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 3 times, sequentially adding 1600g of octane, 260g of isoprene and 4.0g of DME into the polymerization kettle, heating to 66 ℃, adding 16.8mmo1 of n-butyllithium to start reaction for 53min to form an-IR-chain segment, then adding 260g of 1, 2-dibromoethylene into the polymerization kettle A, and reacting for 83min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1500g of octane and 4.5g DME,19.7mmo1 n-butyllithium, heating to 76 ℃, stirring and mixing 170g of styrene and 240g of 1, 3-butadiene for 24min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within a reaction time of 70min, wherein the feeding speed is reduced by 4g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 3 times, sequentially adding 1600g of heptane, 160g of 1, 3-butadiene and 2.0g of DME, heating to 47 ℃, adding 8.6mmo1 of n-butyllithium to start reacting for 52min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 87 ℃, 60.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 92min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent-4 (Mn is 43000, mw/Mn is 9.28).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: other conditions were the same as in example 4 except that: the preparation process of the tri-hetero-arm all-secondary brominated butyl rubber does not add a macromolecular tri-hetero-arm brominated grafting agent, but adds macromolecular tri-hetero-arm brominated grafting agent-4, the addition amount of which is 40.0g, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 300g of methylene dichloride and 700g of hexane are added into the polymerization kettle, 40.0g of high polymer three hetero-arm bromination grafting agent-4 is stirred and dissolved for 80min until the mixture is completely dissolved, then, when the temperature is reduced to minus 92 ℃, 800g of methylene dichloride, 420g of isobutene and 40.0g of isoprene are sequentially added, and stirred and mixed until the temperature of a polymerization system is reduced to minus 96 ℃, then, 80g of methylene dichloride, 2.35g of aluminum sesquichloride and 0.058g of HCl are mixed and aged for 66min at minus 92 ℃, and then, the mixture is added into the polymerization system together for stirring and reacting for 7.0hr, finally, 28g of ethanol is added, and then, the three hetero-arm all-secondary brominated and branched butyl rubber product is obtained after discharging coagulation, washing and drying. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 5
(1) Preparation of a macromolecular tri-hetero-arm brominated grafting agent:
a, preparing a macromolecular composite brominating agent: same as in example 5.
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: other conditions were the same as in example 5 except that: in the preparation process of the macromolecular tri-hetero-arm brominated grafting agent, variable-speed polymerization is not adopted in a polymerization kettle B, namely: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 1800g of octane, 280g of isoprene and 4.5g of DME into the polymerization kettle, heating to 68 ℃, adding 17.5 mmol 1 of n-butyllithium to start reaction for 57min to form an-IR-chain segment, then adding 280g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 86min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 1700g of octane and 5.0g DME,21.5mmo1 n-butyllithium, heating to 78 ℃, stirring and mixing 160g of styrene and 220g of 1, 3-butadiene for 22min, adding the mixture into the polymerization kettle B together to react for 80min to form an-SBR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 4 times, sequentially adding 1800g of heptane, 180g of 1, 3-butadiene and 2.6g of DME, heating to 49 ℃, adding 9.5 mmol 1 of n-butyllithium to start reacting for 57min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the temperature of the polymerization kettle A is raised to 89 ℃, 80.5 mmol of 11,3, 5-benzene trichloride is added for reaction for 95min, then the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the macromolecular tri-hetero-arm brominated grafting agent-5 (Mn is 65000, mw/Mn is 8.21).
(2) Preparation of Tri-arm all-secondary brominated branched butyl rubber: other conditions were the same as in example 4 except that: the preparation process of the tri-hetero-arm all-secondary brominated butyl rubber does not add a macromolecular tri-hetero-arm brominated grafting agent, but adds macromolecular tri-hetero-arm brominated grafting agent-5, the addition amount of which is 45.0g, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 500g of dichloromethane and 500g of hexane are added into the polymerization kettle, 45.0g of high polymer three-hetero-arm bromination grafting agent is stirred and dissolved for 84min until the high polymer three-hetero-arm bromination grafting agent is completely dissolved, then 900g of dichloromethane, 410g of isobutene and 45.0g of isoprene are sequentially added when the temperature is reduced to minus 94 ℃, the mixture is stirred and mixed until the temperature of a polymerization system is reduced to minus 98 ℃, then 90g of dichloromethane, 2.63g of aluminum sesquichloride and 0.072g of HCl are mixed and aged for 68min at minus 94 ℃, and then the mixture is added into the polymerization system together for stirring and reacting for 7.5hr, and finally 30g of ethanol is added, and then the three-hetero-arm all-secondary brominated and branched butyl rubber product is obtained after discharging condensation, washing and drying. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 6
(1) Preparation of a high molecular brominated grafting agent:
a, preparing a macromolecular composite brominating agent: same as in example 6.
b, preparing a high molecular brominated grafting agent: other conditions were the same as in example 6 except that: the preparation process of the polymer brominated grafting agent does not add 1,3, 5-benzene trichloride for coupling, namely: firstly, in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 2000g of octane, 300g of isoprene and 5.0g of DME into the polymerization kettle, heating to 70 ℃, adding 18.6mmo1 of n-butyllithium to start reaction for 60min to form an-IR-chain segment, then adding 300g of macromolecular composite brominating agent into the polymerization kettle A, and reacting for 90min until no free monomer exists; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 2000g of octane and 6.0g DME,22.6mmo1 n-butyllithium, heating to 80 ℃, stirring and mixing 150g of styrene and 200g of 1, 3-butadiene for 20min, injecting the mixture into the reaction kettle at an initial feeding speed of 70g of mixture/min within 80min of reaction time, wherein the feeding speed is reduced by 2g of mixture per minute, forming a random and long gradual change section-SB/(S-B) -chain segment until no free monomer exists, and then adding the materials in the polymerization kettle B into the polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 4 times, sequentially adding 2000g of heptane, 200g of 1, 3-butadiene and 3.0g of DME, heating to 50 ℃, adding 10.6mmo1 of n-butyllithium to start reacting for 60min to form a-BR-chain segment until no free monomer exists, and then adding materials in the polymerization kettle C into a polymerization kettle A; finally, the polymerization kettle A is heated to 90 ℃, then the reaction mixture after coupling is treated by water, the glue solution is subjected to wet condensation and drying, and the polymer brominated grafting agent-6 (Mn is 64000, mw/Mn is 5.23) is obtained, and the polymer brominated wide-distribution grafting agent-6 has no three-arm star-shaped branching structure.
(2) Preparation of brominated branched butyl rubber at position Quan Zhong: other conditions were the same as in example 6 except that: the preparation process of Quan Zhong-position brominated branched butyl rubber does not add a macromolecular tri-hetero-arm brominated grafting agent, but adds macromolecular brominated grafting agent-6, the adding amount is 50.0g, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 300g of methylene dichloride, 700g of hexane and 50.0g of high molecular brominated grafting agent are added into the polymerization kettle, stirring and dissolving are carried out for 90min until the high molecular brominated grafting agent is completely dissolved, then 1000g of methylene dichloride, 400g of isobutene and 50.0g of isoprene are sequentially added when the temperature is reduced to minus 95 ℃, stirring and mixing are carried out until the temperature of a polymerization system is reduced to minus 100 ℃, then 100g of methylene dichloride, 2.85g of aluminum sesquichloride and 0.085g of HCl are mixed and aged for 70min at minus 95 ℃, then the mixture is added into the polymerization system together, stirring and reacting are carried out for 8.0hr, finally 35g of ethanol is added, and then the mixture is discharged, condensed, washed and dried, thus obtaining the all-secondary brominated branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 Properties of Tri-arm all-para-brominated branched butyl rubber
Note that: t is t 10 Reflecting the scorch safety window size for the scorch time; t is t 90 The positive vulcanization time reflects the vulcanization speed.
As can be seen from table 1: the brominated and branched butyl rubber has high molecular weight distribution, high vulcanization speed and short Mooney stress relaxation time, and has good processing and vulcanization characteristics, and meanwhile, high tensile strength and good air tightness are maintained.
The above examples are exemplary examples listed for the purpose of describing the technical solution of the present invention in detail, the present invention is subject to the protection scope of the claims and the summary of the invention, and is not limited by the embodiments, and the simple substitution or modification of the present invention is still within the protection scope of the present invention.
Claims (12)
1. A method for preparing a tri-hetero-arm all-secondary brominated and branched butyl rubber, comprising the following steps:
s1: adding the macromolecule tri-hetero-arm brominated grafting agent into the mixed solvent, and fully stirring until the macromolecule tri-hetero-arm brominated grafting agent is completely dissolved to obtain a mixed solution;
s2: cooling, sequentially adding a diluent, isobutene and isoprene into the mixed solution in the step S1, fully stirring and mixing to obtain a polymerization reaction system, and cooling again;
s3: mixing and aging a diluent and a co-initiator, adding the mixture into a polymerization reaction system in the step S2, fully stirring and reacting, adding a terminator, discharging, condensing, washing and drying to obtain the tri-hetero-arm all-secondary brominated and branched butyl rubber;
The preparation method is characterized in that the macromolecular tri-hetero-arm brominated grafting agent is a tri-hetero-arm all-secondary brominated star-shaped block copolymer consisting of isoprene, 1, 3-butadiene, styrene and macromolecular composite brominating agent, and the structural general formula of the block copolymer is shown as formula I:
wherein: IR is an isoprene homopolymer block; SB is a random segment of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene; BR is a 1, 3-butadiene homopolymer segment; m and n are the number of repeating units, m is an integer not less than 1, and n is an integer not less than 1; the number average molecular weight (Mn) of the macromolecular tri-hetero-arm brominated grafting agent is 50000-70000, and the molecular weight distribution (Mw/Mn) is 11.53-13.12.
2. The preparation method of the tri-hetero-arm all-secondary brominated butyl rubber according to claim 1, wherein in the step S1, the mass ratio of the mixed solvent to the high-molecular tri-hetero-arm brominated grafting agent is 100-200: 5 to 10; in the step S1, the mixed solvent comprises a diluent and a solvent, wherein the volume ratio of the diluent to the solvent is 70-30/30-70.
3. The preparation method of the tri-arm all-secondary brominated and branched butyl rubber according to claim 1, wherein in the step S2, the temperature is reduced to-85 to-95 ℃, and the temperature is reduced again to-100 to-95 ℃.
4. The preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber according to claim 1, wherein in the step S2, the mass ratio of the diluent, the isobutene and the isoprene is 100-200: 80-90: 5 to 10.
5. The preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber according to claim 1, wherein in the step S3, the mass ratio of the diluent to the co-initiator to the terminator is 10-20: 0.2 to 0.6:3 to 7.
6. The preparation method of the tri-hetero-arm all-secondary brominated and branched butyl rubber according to claim 1, which is characterized by specifically comprising the following steps:
a, preparing a macromolecular composite brominating agent: based on 100 parts by mass of the reactive brominating agent, firstly adding 200-300 parts of solvent, 70-80 parts of bromovinylbenzene, 20-30 parts of 1, 2-dibromoethylene and 0.2-0.5 part of molecular weight regulator into a reaction kettle after inert gas replacement in sequence, stirring, mixing and heating, adding 0.3-0.7 part of first initiator when the temperature of the reaction kettle reaches 70-80 ℃, and reacting for 4.0-6.0 hr, wherein the conversion rate of bromovinylbenzene reaches 100%; then adding 1-5 parts of 1, 3-butadiene into the reaction kettle for end capping, reacting for 50-60 min until no free monomer exists, and washing and drying after the reaction is completed to obtain the macromolecular compound brominating agent;
b, preparing a macromolecular tri-hetero-arm bromination grafting agent: based on hundred percent of the total mass of the reaction monomers, firstly, sequentially adding 100 to 200 weight percent of solvent, 20 to 30 weight percent of isoprene, 0.2 to 0.5 weight percent of structure regulator and a second initiator into a reaction kettle A after inert gas replacement, heating to 60 to 70 ℃, reacting for 40 to 60 minutes to form an-IR-chain segment, then adding 20 to 30 weight percent of macromolecular composite brominating agent into the reaction kettle A, and reacting for 70 to 90 minutes until no free monomer exists; simultaneously adding 100-200wt% of solvent, 0.3wt% -0.6wt% of structure regulator and a second initiator into a reaction kettle B after inert gas replacement, heating to 70-80 ℃, stirring and mixing 15-20wt% of styrene and 20-30wt% of 1, 3-butadiene for 20-30 min, reacting to obtain variable-speed polymerization, adding the variable-speed polymerization into the reaction kettle B in a continuous injection mode, reacting within 60-80 min, wherein the initial feeding speed is higher than 7.0% of mixture/min, the feeding speed reduction range is determined according to the reaction time, forming a random and long gradual change section-SB/(S- & gtB) -chain segment, and then adding materials in the reaction kettle B into the reaction kettle A; simultaneously, in a 15L stainless steel reaction kettle C, introducing argon to replace a system for 2-4 times, sequentially adding 100-200 wt% of solvent, 10-20 wt% of 1, 3-butadiene and 0.1-0.3 wt% of structure regulator, heating to 40-50 ℃ by a second initiator, reacting for 40-60 min to form a-BR-chain segment until no free monomer exists, and then adding materials in the reaction kettle C into a reaction kettle A; and finally, heating the reaction kettle A to 80-90 ℃, adding a coupling agent for coupling reaction, treating the coupled reaction mixture with water after the reaction for 80-100 min, and performing wet condensation and drying on the glue solution to obtain the macromolecular tri-hetero-arm brominated grafting agent.
7. The process for preparing a tri-arm all-secondary brominated butyl rubber according to claim 6, wherein the molecular weight regulator is at least one selected from the group consisting of tertiary ten-carbon mercaptan, tertiary twelve-carbon mercaptan, tertiary fourteen-carbon mercaptan, tertiary sixteen-carbon mercaptan, preferably tertiary twelve-carbon mercaptan;
the first initiator is an organic peroxide, and is at least one selected from dicumyl peroxide (DCP), cumene hydroperoxide, benzoyl Peroxide (BPO) and di-tert-butyl peroxide, preferably dicumyl peroxide (DCP);
the structure regulator is a polar organic compound and is at least one selected from diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME) and triethylamine, and preferably ethylene glycol dimethyl ether (DME);
the second initiator is a hydrocarbyl monolithium compound RLi, and is at least one selected from n-butyl lithium, sec-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium, and preferably n-butyl lithium.
8. The method for preparing the tri-arm all-secondary brominated and branched butyl rubber according to claim 6, wherein the coupling agent is at least one of 1,3, 5-benzene trichloride and 1,3, 5-benzene tribromide, preferably 1,3, 5-benzene trichloride; the molar ratio of the coupling agent to the second initiator is 1:1-5:1.
9. The process for the preparation of a tri-arm all-secondary brominated butyl rubber according to claim 2 or 6, characterized in that the solvent is selected from at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably octane.
10. The method for preparing the tri-arm full-secondary brominated butyl rubber according to claim 1, wherein the diluent is halogenated alkane, and at least one selected from chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane is preferably dichloromethane.
11. The method for preparing the tri-hetero-arm all-secondary brominated and branched butyl rubber according to claim 1, wherein the co-initiator is composed of alkyl aluminum halide and protonic acid in a compounding ratio; the alkyl aluminum halide is at least one selected from diethyl aluminum chloride, diisobutyl aluminum chloride, dichloromethyl aluminum, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride, preferably sesquiethyl aluminum chloride; the protonic acid is selected from HCI, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCI; the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1-0.5:1.
12. The method for preparing the tri-arm all-secondary brominated and branched butyl rubber according to claim 1, wherein the terminator is at least one of methanol, ethanol and butanol.
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