CN114478955B - Preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber - Google Patents
Preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber Download PDFInfo
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- CN114478955B CN114478955B CN202011264674.4A CN202011264674A CN114478955B CN 114478955 B CN114478955 B CN 114478955B CN 202011264674 A CN202011264674 A CN 202011264674A CN 114478955 B CN114478955 B CN 114478955B
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- 238000009826 distribution Methods 0.000 title claims abstract description 113
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims description 50
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 259
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 130
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 87
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002667 nucleating agent Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 56
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 44
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007822 coupling agent Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 78
- 238000010438 heat treatment Methods 0.000 claims description 57
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 39
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 21
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 20
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- -1 methyl butyllithium Chemical compound 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 claims description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- FLFGMNFGOKXUQY-UHFFFAOYSA-L dichloro(propan-2-yl)alumane Chemical compound [Cl-].[Cl-].CC(C)[Al+2] FLFGMNFGOKXUQY-UHFFFAOYSA-L 0.000 claims description 2
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 claims description 2
- UUXZFMKOCRKVDG-UHFFFAOYSA-N methane;hydrofluoride Chemical compound C.F UUXZFMKOCRKVDG-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 class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 239000003607 modifier Substances 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- WXRBQHOKNRLOQI-UHFFFAOYSA-N dichloromethylaluminum Chemical compound [Al]C(Cl)Cl WXRBQHOKNRLOQI-UHFFFAOYSA-N 0.000 claims 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 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
- 229940050176 methyl chloride Drugs 0.000 claims 1
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 10
- WPUBUMYDZKJTBD-UHFFFAOYSA-N 1,5-dibromo-3,3-bis(2-bromoethyl)pentane Chemical compound BrCCC(CCBr)(CCBr)CCBr WPUBUMYDZKJTBD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 8
- 238000001125 extrusion Methods 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 239000005060 rubber Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 229910001220 stainless steel Inorganic materials 0.000 description 28
- 239000010935 stainless steel Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000005062 Polybutadiene Substances 0.000 description 24
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
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- 238000012360 testing method Methods 0.000 description 15
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- 238000005070 sampling Methods 0.000 description 12
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- PMSNDFUSQJHJER-UHFFFAOYSA-N 1,5-dichloro-3,3-bis(2-chloroethyl)pentane Chemical compound C(CCl)C(CCCl)(CCCl)CCCl PMSNDFUSQJHJER-UHFFFAOYSA-N 0.000 description 5
- 229920002367 Polyisobutene Polymers 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical group [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
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- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
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- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- 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
-
- 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
Abstract
The invention synthesizes the coupling agent 1, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and then couples with the reaction monomer from isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) to prepare the nucleating agent ([ - (DVB) SBR- (DVB) BR- (DVB) IR-bole) with wide-distribution quaternary four-arm comb star-shaped structure] n And Y), finally, under a catalytic system compounded by Lewis acid and protonic acid, using isobutene and isoprene as reaction monomers and a wide-distribution four-arm star-shaped nucleating agent, and adopting a first-arm and then-core method to carry out cationic polymerization to prepare the wide-distribution four-arm comb-shaped star-shaped branched butyl rubber. The nucleating agent prepared by variable temperature polymerization can increase the flexibility of a butyl rubber molecular chain segment while not damaging the regularity of the butyl rubber molecular chain, solves the problems of easy extrusion expansion and slow stress relaxation rate of the butyl rubber in the processing process, and has the characteristics of high stress relaxation rate and small extrusion expansion effect on the premise of keeping enough raw rubber strength and good air tightness of the butyl rubber.
Description
Technical Field
The invention relates to a preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing wide-distribution four-arm comb-shaped star-branched butyl rubber by using an isoprene/butadiene/styrene/Divinylbenzene (DVB) quaternary four-arm nucleating agent.
Background
Butyl Rubber (IIR) is known to be copolymerized from isobutylene and a small amount of isoprene by cationic polymerization. Butyl rubber has been industrialized by Exxon corporation in the united states in the 40 th century for over seventy years, and has been widely used in the fields of inner tubes, inner liners, curing bladder, medical plugs, etc. for manufacturing tires for vehicles because of its excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance, etc.
However, the molecular chain of butyl rubber mainly consists of single bonds of carbon and carbon, the number of double bonds is small, substituent methyl groups are symmetrically arranged, and the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesion, poor compatibility with other general rubber and the like exist, so that the butyl rubber is easy to excessively flow and deform in the processing process. How to achieve a balance of physical and mechanical properties and processability of butyl rubber has become a bottleneck in the preparation of high performance butyl rubber materials.
In recent years, researchers have found that star-branched butyl rubber with a unique four-dimensional network structure, which consists of a high molecular weight grafted structure and a low molecular weight linear structure, has excellent viscoelastic properties, high green strength and fast stress relaxation rate, can keep low melt viscosity in the processing process, can obtain a high molecular weight polymer, and realizes uniform balance of physical and mechanical properties and processing properties. The star-branched structure has therefore become one of the hot spots in the future butyl rubber research field.
In the prior art, the synthesis of star-branched butyl rubber is mainly prepared by adopting a method of a first-nucleus and then-arm method, a first-arm and then-nucleus method and a nucleus-arm simultaneous method. Such as: US5395885 discloses a star-branched polymer, which is synthesized by a method of first-arm-then-core method at-90 to-100 ℃ by taking polyisobutylene as an arm, polydivinylbenzene (PDVB) as a core, a complex of alkyl aluminum chloride and water as an initiator, and chloromethane as a diluent. CN88108392.57 discloses a star-shaped graft butyl rubber with comb structure prepared by using a hydrochloride polystyrene-isoprene copolymer as a polyfunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN101353403B discloses a method for preparing star-branched polyisobutylene or butyl rubber, which uses a polystyrene/isoprene block copolymer with a silicon-chlorine group at the end or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the end as a grafting agent for initiating cationic polymerization, and takes part in the cationic polymerization directly in a cationic polymerization system of a mixed solvent with a chloromethane/cyclohexane v ratio of 20-80/80-20 at the temperature of 0-100 ℃ to initiate cationic polymerization by the silicon-chlorine group, and takes part in grafting reaction by an unsaturated chain to prepare the star-branched polyisobutylene or butyl rubber product. CN01817708.5 provides a method of adding a multiolefin crosslinking agent such as divinylbenzene and a chain transfer agent (such as 2,4, 1-tetramethyl-1-pentene) to a mixture of isoolefin monomers and diolefin monomers, by which star-branched polymers are prepared. CN107793535 a provides a butyl rubber having a molecular weight of 90 to 260 tens of thousands, log (MW) >6 and contains structural units derived from isobutylene, structural units derived from conjugated dienes, and optionally structural units derived from aryl olefins. CN200710129810.7 provides a method for synthesizing linear butyl first by arm-first and core-later processesAnd (3) coupling the base rubber by using divinylbenzene to obtain the star-branched butyl rubber. Puskas et al synthesized tetra-cumyl alcohol as an initiator with a four-arm structure by using pyromellitic acid as a raw material, and then initiated isobutylene and isoprene copolymerization in an inert organic solvent at-120 to-50 ℃ by using a tetra-cumyl alcohol/aluminum tetrachloride initiation system to synthesize star-branched butyl rubber with bimodal molecular weight distribution (Catalysts for manufacture of IIR with bimodal molecular weight distribution:US,5194538[ P ]].1993-3-16.). Wieland et al synthesized a macroinitiator P (MMA-b-St-co-CMS) containing 4-chloromethylstyrene, styrene and methyl methacrylate quaternaries in the presence of 1, 2-stilbene (DPE) by a radical polymerization method, and initiated cationic polymerization of isobutylene and isoprene with the macroinitiator to thereby successfully prepare a multi-arm star butyl rubber (Synthesis of new graft copolymers containing polyisobutylene by acombination of the, 1-diphenylethylene techniqueand cationic polymerization [ J ] ]Polymer Science: polymer Chemistry,2002, 40: 3725-3733.). Hadjichristididis et al uses CH 3 SiCl 3 PI-PS-PBd four-arm copolymer (Iatrou H, hadjichristidis N.Synthesis of a model 3-miktoarm star terpolymer [ J ] was synthesized by four-step coupling with strict control of the order of addition of the monomers and the degree of excess of the coupling agent]Macromolecules,1992, 25:4649). Hadjchristids react with the silicon-chlorine group of p-chlorodimethylsilyl styrene by high vacuum technique to obtain styrene-based polybutadiene macromonomer, which is then copolymerized with butadiene in the presence of random regulator to obtain active Comb-shaped polybutadiene, and finally reacts with methyl silicon tetrachloride or silicon tetrachloride to obtain 3-arm or 4-arm Star-shaped Comb-shaped polybutadiene (KORTALAAS G, IATROUH, LOHSE D J, et al well-Defined Comb, star-Comb, and Comb-on-Comb Polybutadienes by Anionic Polymerization and the MacromonomerStrategy [ J)]Macromolecules,2005,38 (12): 4996-5001). Huiqin the preparation method comprises synthesizing a polymer with divinylbenzene as core and polyiso-benzene at-80deg.C by using 2-chloro-2, 4-tetramethylpentane/titanium tetrachloride as initiator system and chloromethane/cyclohexane as solvent and active positive ion polymerization Star branched polymers of butenes as arms ("preparation and characterization of star-branched polyisobutenes with divinylbenzene as core", "synthetic rubber industry", synthetic rubber industry, 2008, 31 (5): 362-365).
Disclosure of Invention
The invention aims to provide a preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber. The invention firstly takes alkyl lithium as initiator to be added at one time, the reaction monomer is composed of isoprene, 1, 3-butadiene and styrene, and a long chain segment [ -BR-IR-SBR [ -BR ] with wide vinyl distribution is synthesized by a variable temperature polymerization method] n Then coupling with a novel tetrahalide coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane to prepare the star copolymer [ -SBR-BR-IR ]] n Y, then polymerizing with Divinylbenzene (DVB) to obtain a wide-distribution four-arm star-shaped nucleating agent ([ - (DVB) SBR- (DVB) B R- (DVB) IR ]] n And Y), finally, under a catalytic system compounded by Lewis acid and protonic acid, using isobutene and isoprene as reaction monomers and a wide-distribution four-arm star-shaped nucleating agent, and adopting a first-arm and then-core method to carry out cationic polymerization to prepare the wide-distribution four-arm comb-shaped star-shaped branched butyl rubber. The method solves the problems of easy extrusion swelling and slow stress relaxation rate of the butyl rubber in the processing process, so that the wide-distribution four-arm comb-shaped star-branched butyl rubber has the characteristics of high stress relaxation rate and small extrusion swelling effect, has enough green rubber strength and good air tightness, and realizes the balance of physical and mechanical properties and processing properties of the butyl rubber.
The "%" of the invention refers to mass percent.
The preparation of the wide-distribution four-arm comb-shaped star-branched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: first in jacketed 4L, based on one hundred percent of the total mass of the reactants
In a stainless steel polymerization kettle, argon is introduced to replace 2-4 times, 100-200% of deionized water, 3, 9-dioxy [5.5] spiro undecane, a halogenating agent, 1-5% of a catalyst are sequentially added into the polymerization kettle, the temperature is raised to 50-80 ℃, after the reaction is carried out for 1-3 hours, 20-40% of aqueous solution of NaOH with the mass concentration of 10-20% is added to terminate the reaction, and finally 200-300% of chloromethane is added to extract, separate, wash and dry the reaction product to obtain the coupling agent 1, 5-dihalogen-3, 3-bis (2-haloethyl) pentane (the yield is 85-95%).
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: based on the total mass parts of reaction monomers, firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 200-400% of solvent, 30-40% of 1, 3-butadiene, 0.05-0.1% of structure regulator and 1% of initiator into the polymerization kettle, carrying out variable-temperature polymerization, and gradually increasing the temperature from 40 ℃ to 60 ℃ within 40-60 min at the temperature increasing speed <1.3 ℃/min to form a wide-distribution BR chain segment, wherein the conversion rate of the 1, 3-butadiene monomer reaches 100%; then adding 20-30% of isoprene and 0.05-0.1% of structure regulator into the polymerization kettle in turn, and reacting to obtain variable-temperature polymerization, in 30-60 min, gradually raising the temperature from 60 ℃ to 75 ℃ and raising the temperature speed<1.0 ℃/min to form a wide-distribution IR chain segment, wherein the conversion rate of isoprene monomer reaches 100%; sequentially adding 20-30% of styrene, 10-20% of 1, 3-butadiene and 0.05-0.5% of structure regulator into a polymerization kettle, heating to 75-80 ℃ and reacting for 40-50 min to form a wide-distribution linear chain segment [ -SBR-BR-IR ]] n The method comprises the steps of carrying out a first treatment on the surface of the Finally, heating to 80-90 ℃, adding a coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane for coupling reaction for 80-100 min, sequentially adding 100-200% of solvent, 5-10% of Divinylbenzene (DVB) and 0.001-0.2% of initiator into a polymerization kettle after the reaction is finished, heating to 75-85 ℃, reacting for 40-60 min, and performing wet condensation and drying on the glue solution after the reaction is finished to obtain a nucleating agent ([ - (DVB) SBR- (DVB) BR- (DVB) IR) with a wide distribution and four-arm star structure] n Y)。
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3-5 times to replace the reaction monomer in total mass parts, and sequentially adding 200% -300% of diluent/solvent V into the polymerization kettle: mixing 93-97% of isobutene and 3-7% of isoprene in a V ratio of 60-40/40-60 mixed solvent, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, then mixing and aging 40-60% of diluent and 0.05-3.0% of co-initiator for 30-40 min at minus 95-minus 85 ℃, adding the mixture into the polymerization system together for stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 50-70% of solvent and 3.0-5.0% of nucleating agent obtained in the step (1) for 4.0-6.0 hr, aging for 40-60 min at minus 95-minus 85 ℃, adding the mixture into the polymerization system together for stirring and reacting for 5.0-7.0 hr, finally adding a terminator for discharging and agglomerating, washing and drying to obtain the wide-distribution four-arm comb-shaped star branched butyl rubber product.
The nucleating agent of the invention is a wide vinyl distribution quaternary four-arm comb star polymer ([ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n Y) has a structural general formula shown in formula I:
wherein Y is 3, 3-diethylpentane; DVB is divinylbenzene; IR is an isoprene homopolymer block, and the 1, 2-structure content of the block is 14% -19%; BR is a 1, 3-butadiene homopolymer block, and the 1, 2-structure content thereof is 15-20%; SBR is a styrene-butadiene random block copolymer, wherein the content of styrene is 20-30%, and the content of 1, 3-butadiene is 10-20%; the quaternary four-arm comb star polymer has number average molecular weight (Mn) of 60000-80000 and molecular weight distribution (Mw/Mn) of 7.35-8.68.
The halogenating agent is one of liquid chlorine and liquid bromine, preferably liquid bromine, the dosage of the halogenating agent depends on the dosage of 3, 9-dioxy [5.5] spiro-undecane, and the molar ratio of the dosage of the liquid bromine to the 3, 9-dioxy [5.5] spiro-undecane is 4.5-6.5.
The catalyst of the invention is HCl-CH 3 A mixed aqueous solution of OH, wherein the molar concentration of HCl is: 0.1 to 0.7mol/L.
The amount of the coupling agent is determined according to the amount of the initiator, and the molar ratio of the coupling agent to the organic lithium is 1.0-5.0.
The initiator 1 is a hydrocarbyl mono-lithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or a composite group of the above groups containing 1-20 carbon atoms. The hydrocarbyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the polymer being designed.
The initiator 2 is an organic peroxide selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, preferably dibenzoyl peroxide (BPO).
The structure regulator is a polar organic compound which generates solvation effect in a polymerization system, and can regulate the reactivity ratio of styrene and butadiene to enable the styrene and the butadiene to be randomly copolymerized. Such polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, preferably Tetrahydrofuran (THF).
The diluent is halogenated alkane, wherein halogen atoms in the halogenated alkane can be chlorine, bromine or fluorine; the number of carbon atoms in the halogenated alkane being C 1 -C 4 . The haloalkane is selected from one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably chloromethane.
The 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 sesquichloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloridePreferably, the aluminum sesquichloride ethyl chloride. The protonic acid is selected from HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCl. Wherein the total addition amount of the co-initiator is 0.1-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1-0.5:1.
The diluent is selected from one of methane chloride, methylene dichloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, and preferably is methane chloride.
The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene or ethylbenzene, preferably cyclohexane.
The terminator can be selected from one or more of methanol, ethanol and butanol.
The polymerization reactions of the present invention are all carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution processes are both carried out in a hydrocarbon solvent, which is a hydrocarbon solvent, including straight chain alkanes, aromatic hydrocarbons and cycloalkanes, selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention firstly aims at 3, 9-dioxy [5.5 ]]Carrying out halogenation reaction on spiro undecane to synthesize a novel coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane; then, alkyl lithium is used as an initiator to be added at one time, a reaction monomer is composed of isoprene, 1, 3-butadiene and styrene, and a long chain segment [ -SBR-BR-IR [ -BR-IR ]] n The method comprises the steps of carrying out a first treatment on the surface of the Then coupling with a novel coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) to prepare the ternary four-arm star polymer [ -SBR-BR-IR ]] n Y, and then synthesizing the wide-distribution quaternary four-arm comb-shaped star-shaped nucleating agent ([ - (DVB) SBR- (DVB) BR- (DVB) IR ] ] n Y); finally, isobutene and isoprene are subjected to a catalytic system compounded by alkyl aluminum halide and protonic acid, and a nucleating agent is utilized([-(DVB)SBR-(DVB)BR-(DVB)IR-] n Y) preparing the four-arm comb-shaped star-branched butyl rubber with wide molecular weight distribution through cationic polymerization by a first-arm and then-core method.
The invention designs a wide-distribution quaternary four-arm comb-shaped star-shaped nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n The Y contains a four-arm comb-shaped star structure, the structure can widen the molecular weight distribution of the whole butyl rubber macromolecule on the premise of not damaging the molecular chain regularity of the single isobutene and isoprene copolymer, meanwhile, the-IR-and-BR-chain segments in the nucleating agent adopt variable temperature polymerization to cause the distribution of a certain amount of wide vinyl, the two aspects can obviously improve the flexibility of the butyl rubber macromolecule chain segment, so that the butyl rubber can obtain good viscoelastic performance, has a faster stress relaxation rate and a small extrusion swelling effect, and improves the processability of the butyl rubber; in addition, the SBR-chain segment in the nucleating agent contains a certain amount of benzene rings, so that the reduction of strength and air tightness caused by the improvement of the flexibility of the macromolecular chain segment of the butyl rubber is avoided, and the high strength and good air tightness of the butyl rubber are ensured. Therefore, the invention organically combines the characteristics of the four-arm comb star-shaped structure with the characteristics of wide distribution and rigidity of various chain segments and cooperatively plays roles, and the 'cooperative effect' solves the problems of slow stress relaxation and poor viscoelasticity of the butyl rubber in the processing process, solves the problems of strength and air tightness reduction caused by the widening of the molecular weight distribution of the butyl rubber, realizes the balance of the processability and the physical properties of the butyl rubber, and ensures that the performance of the butyl rubber is more comprehensively improved. The preparation method provided by the invention has the characteristics of controllable process conditions, stable product performance, suitability for industrial production and the like.
Drawings
FIG. 1 is 1 # Comparative examples 1 samples and 2 # Comparison of GPC spectra of the samples of example 1.
Detailed Description
The following examples and comparative examples are given to illustrate the inventive effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial polymer grade, and are used after purification without other special requirements.
Raw material sources:
styrene, butadiene, polymer grade China petrochemical Co
Isobutene, isoprene, polymeric grade Zhejiang Xinhui New Material Co., ltd
N-butyllithium with purity of 98% Nanjing Tonglian chemical Co., ltd
3, 9-Dioxo [5.5] spirocyclic undecane purity was 99% of Hubei ferry chemical Co.Ltd
Dibenzoyl peroxide (BPO), a lanzhou auxiliary plant
Sesquiethyl aluminum chloride with purity of 98% of carbofuran technology Co., ltd
Other reagents are commercial industrial products
The analysis and test method comprises the following steps:
determination of molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min -1 。
Measurement of stress relaxation: the measurement was carried out by using a GT-7080-S2 Mooney viscometer manufactured by Taiwan high-speed rail company.
The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.
Determination of die swell ratio: RH2000 capillary rheometer manufactured by British Markov company
The temperature is 100 ℃, the length-diameter ratio is 16:1, and the shear rate is 10-1000S -1 Is measured in the interval of (2).
Measurement of air tightness: an automatic air tightness tester is adopted to measure the air permeability number according to ISO 2782:1995,
the test gas is N 2 The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.
Tensile strength: the method in standard GB/T528-2009 is performed.
Example 1
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, argon is introduced for replacement for 3 times, 500g of deionized water, 48g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle]Spirocyclic undecane, 250g liquid bromine, 7g HCl-CH 3 OH solution (molar concentration of HCl: 0.3 mol/L), heating to 52 ℃, reacting for 1.8hr, adding 200g of 15% NaOH aqueous solution to terminate the reaction, finally adding 600g of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane (yield 87%).
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene and 0.8g of THF into the polymerization kettle, heating to 40 ℃, adding 27.1 mmol of n-butyllithium, starting to react, and gradually heating from 40 ℃ to 60 ℃ within 40min at a heating rate of 0.5 ℃/min to form a wide-distribution BR chain segment; then sequentially adding 200g of isoprene and 0.7g of THF into a polymerization kettle, gradually increasing the temperature from 60 ℃ to 75 ℃ within 30min, and forming a wide-distribution IR chain segment at a heating rate of 0.5 ℃/min; then 200g of styrene and 100g of 1, 3-butadiene, 1.5g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the mixture is reacted for 40min to form a linear chain segment [ -SBR-BR-IR ]] n The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 80 ℃, adding 22.5 mmol of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 80min to form [ -SBR-BR-IR ]] n Y; after the reaction is completed, 1000g of cyclohexane and 50g DVB,0.12g BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 40min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR [ -shaped structures with wide distribution and four arms and comb-shaped star structures are prepared ] n Y (Mn 61000, mw/Mn 7.38).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, and sequentially adding 320g of chloromethane and cyclohexane into the polymerization kettle340g,280g of isobutene and 9g of isoprene are stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 120g of methyl chloride, 2.1g of aluminum sesquichloride and 0.08g of HCl are mixed at minus 85 ℃ and aged for 30min, then 150g of cyclohexane and 9.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR-are added into the polymerization system together for stirring and reacting for 0.5hr] n Y, stirring and dissolving for 4.0hr until the nucleating agent is completely dissolved, aging at-85 ℃ for 40min, adding into a polymerization system together, stirring and reacting for 5.0hr, adding 200mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 2
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 2500g of cyclohexane, 320g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle, heating to 40 ℃, adding 29.2mm 1 of n-butyllithium, starting the reaction, and gradually heating from 40 ℃ to 60 ℃ within 40min at a heating rate of 0.5 ℃/min to form a wide-distribution BR chain segment; then 220g of isoprene and 1.1g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 30min, the temperature is gradually increased from 60 ℃ to 75 ℃, the heating speed is 0.5 ℃/min, and a wide-distribution IR chain segment is formed; then 220g of styrene and 120g of 1, 3-butadiene, 1.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the mixture is reacted for 42 minutes to form a linear chain segment [ -SBR-BR-IR ] ] n The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 80 ℃, adding 25.7mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 85min to form [ -SBR-BR-IR ]] n Y; after the reaction is completed, 1200g cyclohexane and 55g DVB,0.18g BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 45min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR [ -shaped structures with wide distribution and four arms and comb-shaped star structures are prepared] n Y (Mn 65000, mw/Mn 7.71).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 3 times, 330g of methyl chloride, 320g of cyclohexane, 282g of isobutene and 12g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 90 ℃, then 130g of methyl chloride, 2.5g of aluminum sesquichloride and 0.09g of HCl are mixed at minus 85 ℃ and aged for 32 minutes, then added into the polymerization system together and stirred and reacted for 0.6hr, then 160g of cyclohexane and 10.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR) are added into the polymerization system] n Y, stirring and dissolving for 4.5 hours until the nucleating agent is completely dissolved, then aging for 45 minutes at the temperature of minus 85 ℃, adding into a polymerization system together and stirring and reacting for 5.5 hours, adding 200mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 3
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3000g of cyclohexane, 350g of 1, 3-butadiene and 1.3g of THF into the polymerization kettle, heating to 40 ℃, adding 32.2mm 1 of n-butyllithium, starting the reaction, and gradually heating from 40 ℃ to 60 ℃ within 50min at a heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment; then 240g of isoprene and 1.5g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 40min, the temperature is gradually increased from 60 ℃ to 75 ℃, the heating speed is 0.4 ℃/min, and a wide-distribution IR chain segment is formed; then 240g of styrene and 140g of 1, 3-butadiene, 2.3g of THF are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃ and the reaction is carried out for 45min, thus forming a linear chain segment [ -SBR-BR-IR ]] n The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 85 ℃, adding 27.2 mmol of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 90min to form [ -SBR-BR-IR ]] n Y; after the reaction is completed, 1400g of cyclohexane, 60g DVB,0.24g BPO and the temperature are sequentially added into a polymerization kettle, and the temperature is raised to 80 ℃ for reaction After 50min, the glue solution is subjected to wet condensation and drying to prepare the nucleating agent with a wide-distribution four-arm comb-shaped star-shaped structure [ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n Y (Mn 72000, mw/Mn 7.92).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 340g of methyl chloride, 310g of cyclohexane, 284g of isobutene and 14g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 95 ℃, then 150g of methyl chloride, 3.2g of aluminum sesquichloride and 0.13g of HCl are mixed at minus 90 ℃ and aged for 34 minutes, then added into the polymerization system together and stirred for reaction for 0.7hr, and then 170g of cyclohexane and 11.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR) are added into the polymerization system] n Y, stirring and dissolving for 5.0hr until the nucleating agent is completely dissolved, aging at-90 ℃ for 50min, adding into a polymerization system together, stirring and reacting for 6.0hr, adding 230mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 4
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: as in example 1.
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3300g of cyclohexane, 370g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle, heating to 40 ℃, adding 33.2mm 1 of n-butyllithium, starting the reaction, and gradually heating from 40 ℃ to 60 ℃ within 50min at a heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment; then 260g of isoprene and 1.9g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 40min, the temperature is gradually increased from 60 ℃ to 75 ℃, the heating speed is 0.4 ℃/min, and a wide-distribution IR chain segment is formed; then 260g of styrene and 150g of 1, 3-butadiene, 2.5g of THF are added into the polymerization kettle in turn, the temperature is raised to 77 ℃ and the reaction is carried out for 47min, thus forming a linear chain segment [ -SBR-BR-IR ]] n The method comprises the steps of carrying out a first treatment on the surface of the Subsequently, the temperature was raised to 85℃and 29.5mm o1 was added1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and reacting for 93min to form [ -SBR-BR-IR ]] n Y; after the reaction is completed, 1600g of cyclohexane and 70g DVB,0.31g BPO are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after the reaction is carried out for 53min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR [ -shaped structures with wide distribution and four arms and comb-shaped star structures are prepared ] n Y (Mn 74000, mw/Mn 8.19).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of methyl chloride, 300g of cyclohexane, 284 g of isobutene and 16g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 95 ℃, then 160g of methyl chloride, 3.7g of aluminum sesquichloride and 0.26g of HCl are mixed at minus 90 ℃ and aged for 36min, then added into the polymerization system together and stirred for reaction for 0.8hr, and then 180g of cyclohexane and 12.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR) are added into the polymerization system] n Y, stirring and dissolving for 6.0hr until the nucleating agent is completely dissolved, aging for 53min at-90 ℃, adding the nucleating agent and the polymerization system together, stirring and reacting for 6.2hr, adding 260mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 5
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, argon is introduced for replacement for 4 times, 600g of deionized water and 65g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle ]Spirocyclic undecane, 290g liquid chlorine, 15g HCl-CH 3 OH solution (molar concentration of HCl: 0.7 mol/L), heating to 85 ℃, reacting for 4.0hr, adding 300g of aqueous solution of NaOH with mass concentration of 20% to terminate the reaction, finally adding 900g of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dichloro-3, 3-di (2-chloroethyl) pentane (yield 93%).
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacementSequentially adding 3700g of cyclohexane, 390g of 1, 3-butadiene and 2.1g of THF into a polymerization kettle for 3 times, heating to 40 ℃, adding 35.6mmo1 of n-butyllithium, starting to react, gradually heating from 40 ℃ to 60 ℃ within 60 minutes, and forming a wide-distribution BR chain segment at a heating rate of 0.6 ℃/min; then 280g of isoprene and 2.3g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 60min, the temperature is gradually increased from 60 ℃ to 75 ℃, the heating speed is 0.3 ℃/min, and a wide-distribution IR chain segment is formed; then 280g of styrene and 180g of 1, 3-butadiene and 3.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃ and the reaction is carried out for 49min, thus forming a wide-distribution linear chain segment [ -SBR-BR-IR ]] n The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 85 ℃, adding 30.2 mmol of 1, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 96min to form [ -SBR-BR-IR ] ] n Y; after the reaction is completed, 1800g of cyclohexane and 80g DVB,0.37g BPO are sequentially added into a polymerization kettle, the temperature is raised to 83 ℃, after the reaction is carried out for 55min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR [ -shaped structures with wide distribution and four arms and comb-shaped star structures are prepared] n Y (Mn 77000, mw/Mn 8.31).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 360g of methyl chloride, 280g of cyclohexane, 289g of isobutene and 18g of isoprene are sequentially added into the polymerization kettle, and stirred and mixed until the temperature of the polymerization system is reduced to minus 100 ℃, then 180g of methyl chloride, 4.9g of aluminum sesquichloride and 0.35g of HCl are mixed at minus 95 ℃ and aged for 37 minutes, then added into the polymerization system together and stirred and reacted for 0.9hr, and then 190g of cyclohexane and 14.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR) are added] n Y, stirring and dissolving for 5.5 hours until the grafting agent is completely dissolved, then aging for 57 minutes at the temperature of minus 95 ℃, adding into a polymerization system together and stirring and reacting for 6.5 hours, adding 300mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the wide-distribution four-arm comb-shaped star-shaped branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 6
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 5.
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 4000g of cyclohexane, 400g of 1, 3-butadiene and 2.9g of THF into the polymerization kettle, heating to 40 ℃, adding 37.5mm & lt 1 & gt n-butyllithium for starting reaction, gradually heating from 40 ℃ to 60 ℃ within 60 minutes, and heating at a speed of 0.6 ℃/min to form a wide-distribution BR chain segment; then 300g of isoprene and 3.3g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 60min, the temperature is gradually increased from 60 ℃ to 75 ℃, the heating speed is 0.3 ℃/min, and a wide-distribution IR chain segment is formed; then 300g of styrene and 200g of 1, 3-butadiene, 4.3g of THF are added into a polymerization kettle in turn, the temperature is raised to 80 ℃ and the reaction is carried out for 50min, thus forming a linear chain segment [ -SBR-BR-IR ]] n The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 90 ℃, adding 32.5 mmol of 1, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 100min to form [ -SBR-BR-IR ]] n Y; after the reaction is completed, 2000g of cyclohexane and 90g DVB,0.45g BPO are sequentially added into a polymerization kettle, the temperature is raised to 85 ℃, after the reaction is carried out for 60min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR [ -and [ -a broad-distribution four-arm comb-shaped star-shaped structure ] is prepared ] n Y (Mn 79000, mw/Mn 8.62).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 340g of methyl chloride, 270g of cyclohexane, 29 g of isobutene and 20g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 100 ℃, then 180g of methyl chloride, 5.2g of aluminum sesquichloride and 0.42g of HCl are mixed at minus 95 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred and reacted for 1.0hr, then 200g of cyclohexane and 15.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR) are added into the polymerization system] n Y, stirring and dissolving for 6.0hr until the grafting agent is completely dissolved, aging at-95 ℃ for 60min, adding into a polymerization system together, stirring and reacting for 7.0hr, adding 350mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling analysis: standard samples were prepared and the test performance is shown in table 1.
Comparative example 1
Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 1 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR ] ] n Y is: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 320g of methyl chloride, 340g of cyclohexane, 280g of isobutene and 9g of isoprene are sequentially added into the polymerization kettle, the mixture is stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 120g of methyl chloride, 2.1g of aluminum sesquichloride and 0.08g of HCl are mixed and aged for 30 minutes at minus 85 ℃, then the mixture is added into the polymerization system together to be stirred and reacted for 0.5 hour, 200mL of methanol is added to terminate the reaction, finally, the mixture is discharged and condensed, washed and dried, and the wide-distribution four-arm comb-shaped star-branched butyl rubber product is obtained. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent: other conditions were the same as in example 2 except that: 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added in the synthesis process, but a conventional coupling agent silicon tetrachloride (SiCl is added 4 ) The method comprises the following steps: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 2500g of cyclohexane, 320g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle, heating to 40 ℃, adding 29.2mm 1 of n-butyllithium, starting the reaction, and gradually heating from 40 ℃ to 60 ℃ within 40min at a heating rate of 0.5 ℃/min to form a wide-distribution BR chain segment; then 220g of isoprene and 1.1g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 30min, the temperature is gradually increased from 60 ℃ to 75 ℃, the heating speed is 0.5 ℃/min, and a wide-distribution IR chain segment is formed; then 220g of styrene and 120g of 1, 3-butadiene, 1.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the mixture is reacted for 42 minutes to form a linear chain segment [ -SBR-BR-IR ] ] n The method comprises the steps of carrying out a first treatment on the surface of the Subsequently, the temperature was raised to 80℃and 25.7mmo1 SiCl was added 4 Reacting for 85min to form [ -SBR-BR-IR ]] n Si; after the reaction is completed, 1200g cyclohexane, 55 g are added into the polymerization kettle in turngDVB,0.18g BPO, heating to 75 ℃, reacting for 45min, wet condensing and drying the glue solution to obtain the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n Si (Mn 61000, mw/Mn 5.87).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 2 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n Y, instead, nucleating agents [ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n Si, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 3 times, 330g of methyl chloride, 320g of cyclohexane, 282g of isobutene and 12g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 90 ℃, then 130g of methyl chloride, 2.5g of aluminum sesquichloride and 0.09g of HCl are mixed at minus 85 ℃ and aged for 32 minutes, then added into the polymerization system together and stirred and reacted for 0.6hr, then 160g of cyclohexane and 10.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR) are added into the polymerization system ] n Stirring and dissolving Si for 4.5hr until the nucleating agent is completely dissolved, aging at-85deg.C for 45min, adding into a polymerization system together, stirring and reacting for 5.5hr, adding 200mL methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain wide-distribution four-arm comb-like star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 3.
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: other conditions were the same as in example 3 except that: 1, 3-butadiene does not adopt variable temperature polymerization, and reacts at the constant temperature of 40 ℃, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, argon is introduced for replacement for 3 times, 3000g of cyclohexane, 350g of 1, 3-butadiene and 1.3g of THF are sequentially added into the polymerization kettle, the temperature is raised to 40 ℃, 32.2mm 1 of n-butyllithium is added for starting the reaction, the reaction is carried out for 50min, and BR is formed 1 A segment; then 240g of isoprene, 1.5g of THF were added into the polymerization vessel in sequence, and reacted inGradually increasing the temperature from 60 ℃ to 75 ℃ within 40min, wherein the temperature increasing speed is 0.4 ℃/min, and forming a wide-distribution IR chain segment; then 240g of styrene and 140g of 1, 3-butadiene, 2.3g of THF are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 45min, thus forming a wide-distribution linear chain segment [ -SBR-BR 1 -IR-] n The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 85 ℃, adding 27.2 mmol of 1, 5-dibromo-3, 3 di (2-bromoethyl) pentane, reacting for 90min to form [ -SBR-BR 1 -IR-] n Y; after the reaction is completed, 1400g cyclohexane, 60g DVB,0.24g BPO and then heating to 80 ℃ are sequentially added into a polymerization kettle, after the reaction is carried out for 50min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR with wide-distribution four-arm comb-shaped star-shaped structure is prepared 1 -(DVB)IR-] n Y (Mn is 70000, mw/Mn is 6.52).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 3 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n Y, instead of adding nucleating agents [ - (DVB) SBR- (DVB) BR 1 -(DVB)IR-] n Y is: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 340g of methyl chloride, 310g of cyclohexane, 284g of isobutene and 14g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 95 ℃, then 150g of methyl chloride, 3.2g of aluminum sesquichloride and 0.13g of HCl are mixed at minus 90 ℃ and aged for 34 minutes, then added into the polymerization system together and stirred and reacted for 0.7hr, and then 170g of cyclohexane and 11.0g [ - (DVB) SBR- (DVB) BR are added 1 -(DVB)IR-] n Y, stirring and dissolving for 5.0hr until the nucleating agent is completely dissolved, aging at-90 ℃ for 50min, adding into a polymerization system together, stirring and reacting for 6.0hr, adding 230mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 4
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 4.
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: other conditions were the same as in example 4 except that: in the variable temperature polymerization of 1, 3-butadiene, the temperature rising speed is 1.6 ℃/min, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, argon is introduced for replacement for 3 times, 3300g of cyclohexane, 370g of 1, 3-butadiene and 1.5g of THF are sequentially added into the polymerization kettle, 33.2mm 1 of n-butyllithium is added when the temperature is raised to 40 ℃, the reaction starts within 50min, the temperature is gradually raised to 60 ℃ from 40 ℃ and the temperature raising speed is 1.6 ℃/min, and wide-distribution BR is formed 2 A segment; then 260g of isoprene and 1.9g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 40min, the temperature is gradually increased from 60 ℃ to 75 ℃, the heating speed is 0.4 ℃/min, and a wide-distribution IR chain segment is formed; then 260g of styrene and 150g of 1, 3-butadiene, 2.5g of THF are added into the polymerization kettle in turn, the temperature is raised to 77 ℃ and the reaction is carried out for 47min, thus forming a linear chain segment [ -SBR-BR with wide distribution 2 -IR-] n The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 85 ℃, adding 29.5 mmol of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 93min to form [ -SBR-BR 2 -IR-] n Y; after the reaction is completed, 1600g cyclohexane, 70g DVB,0.31g BPO and the temperature are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after the reaction is carried out for 53min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR with a wide-distribution four-arm comb-shaped star-shaped structure is prepared 2 -(DVB)IR-] n Y (Mn: 71000, mw/Mn: 6.23).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 4 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n Y, instead of adding nucleating agents [ - (DVB) SBR- (DVB) BR 2 -(DVB)IR-] n Y is: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of methyl chloride, 300g of cyclohexane, 284 g of isobutene and 16g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 95 ℃, then 160g of methyl chloride, 3.7g of aluminum sesquichloride and 0.26g of HCl are mixed at minus 90 ℃ and aged for 36 minutes, and then added into the polymerization system together to be stirred and reacted for 0.8hr, and then 180g of cyclohexane and 12.0g of [ - (D)VB)SBR-(DVB)BR 2 -(DVB)IR-] n Y, stirring and dissolving for 6.0hr until the nucleating agent is completely dissolved, aging for 53min at-90 ℃, adding the nucleating agent and the polymerization system together, stirring and reacting for 6.2hr, adding 260mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 5
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 5.
b, preparation of a four-arm comb star-shaped nucleating agent: other conditions were the same as in example 5 except that: isoprene does not adopt variable temperature polymerization, and reacts at the constant temperature of 70 ℃, namely: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3700g of cyclohexane, 390g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle, heating to 40 ℃, adding 35.6mmo1 of n-butyllithium, starting to react, and gradually heating from 40 ℃ to 60 ℃ within 60 minutes at a heating rate of 0.6 ℃/min to form a wide-distribution BR chain segment; then 280g of isoprene, 2.3g of THF are added into the polymerization kettle in sequence, and the temperature is raised to 70 ℃ to react for 60min to form IR 1 A segment; then 280g of styrene and 180g of 1, 3-butadiene and 3.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃ and the reaction is carried out for 49min, thus forming a wide-distribution linear chain segment [ -SBR-BR-IR 1 -] n The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 85 ℃, adding 30.2 mmol of 1, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 96min to form [ -SBR-BR-IR 1 -] n Y; after the reaction is completed, 1800g cyclohexane, 80g DVB,0.37g BPO and the temperature are sequentially added into a polymerization kettle, the temperature is raised to 83 ℃, after the reaction is carried out for 55min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR with wide-distribution four-arm comb-shaped star-shaped structure is prepared 1 -] n Y (Mn 73000, mw/Mn 6.71).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 5 except that: no nucleating agent [ - (DVB) SBR- (DVB) is added in the synthesis process)BR-(DVB)IR-] n Y, instead of adding nucleating agents [ - (DVB) SBR- (DVB) BR- (DVB) IR 1 -] n Y is: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 360g of methyl chloride, 280g of cyclohexane, 289g of isobutene and 18g of isoprene are sequentially added into the polymerization kettle, and stirred and mixed until the temperature of the polymerization system is reduced to minus 100 ℃, then 180g of methyl chloride, 4.9g of aluminum sesquichloride and 0.35g of HCl are mixed at minus 95 ℃ and aged for 37 minutes, then added into the polymerization system together and stirred and reacted for 0.9hr, and then 190g of cyclohexane and 14.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR are added 1 -] n Y, stirring and dissolving for 5.5 hours until the grafting agent is completely dissolved, then aging for 57 minutes at the temperature of minus 95 ℃, adding into a polymerization system together and stirring and reacting for 6.5 hours, adding 300mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the wide-distribution four-arm comb-shaped star-shaped branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 6
(1) Preparation of a wide-distribution four-arm comb-shaped star-shaped nucleating agent:
a, preparation of a coupling agent: same as in example 6.
b, preparing a wide-distribution four-arm comb star-shaped nucleating agent: other conditions were the same as in example 6 except that: styrene and 1, 3-butadiene are not added in the synthesis process, and an-SBR-chain segment is not formed, namely: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 4000g of cyclohexane, 400g of 1, 3-butadiene and 2.9g of THF into the polymerization kettle, heating to 40 ℃, adding 37.5mm & lt 1 & gt n-butyllithium for starting reaction, gradually heating from 40 ℃ to 60 ℃ within 60 minutes, and heating at a speed of 0.6 ℃/min to form a wide-distribution BR chain segment; then 300g of isoprene and 3.3g of THF are sequentially added into a polymerization kettle, the temperature is gradually increased from 60 ℃ to 75 ℃ within 60min, the heating speed is 0.3 ℃/min, and the wide distribution [ -BR-IR ]] n A segment; then heating to 90 ℃, adding 32.5 mmol of 1, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 100min to form [ -BR-IR ]] n Y; after the reaction is completed, 2000g cyclohexane and 90g DVB are added into the polymerization kettle in turn0.45g of BPO, heating to 85 ℃, reacting for 60min, and then performing wet condensation and drying on the glue solution to obtain the nucleating agent [ - (DVB) BR- (DVB) IR [ (radial) IR ] ] n Y (Mn 57000, mw/Mn 5.62).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 6 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR ]] n Y, instead of adding nucleating agents [ - (DVB) BR- (DVB) IR ]] n Y is: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 340g of methyl chloride, 270g of cyclohexane, 29 g of isobutene and 20g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 100 ℃, then 180g of methyl chloride, 5.2g of aluminum sesquichloride and 0.42g of HCL are mixed at minus 95 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred for 1.0hr, then 200g of cyclohexane and 15.0g of [ - (DVB) BR- (DVB) IR [ (infrared radiation) are added into the mixture] n Y, stirring and dissolving for 6.0hr until the grafting agent is completely dissolved, aging at-95 ℃ for 60min, adding into a polymerization system together, stirring and reacting for 7.0hr, adding 350mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 Performance of widely distributed four-arm comb-like Star branched butyl rubber
As can be seen from table 1: the wide-distribution four-arm comb-shaped star-branched butyl rubber provided by the invention has high tensile strength, good air tightness, low Mooney relaxation area and good processability (the smaller the area under a stress relaxation curve is, the lower the energy consumption for mixing processing is).
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (16)
1. A preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber comprises the following steps:
(1) Preparation of a four-arm comb star-shaped nucleating agent: based on the total mass of the reaction monomers as one hundred percent, firstly, sequentially adding a solvent, 30% -40% of 1, 3-butadiene and 0.05% -0.1% of a structure regulator into a polymerization kettle, wherein the reaction is temperature-variable polymerization, the temperature is gradually increased from 40 ℃ to 60 ℃, and the heating speed is less than 1.3 ℃/min until the conversion rate of the 1, 3-butadiene monomers reaches 100%; then adding 20-30% of isoprene into the polymerization kettle in sequence, gradually increasing the temperature from 60 ℃ to 75 ℃ with the temperature increasing speed of <1.0 ℃/min until the isoprene monomer conversion rate reaches 100%; sequentially adding 20-30% of styrene, 10-20% of 1, 3-butadiene and 0.05-0.5% of structure regulator into a polymerization kettle, heating to 75-80 ℃ and reacting for 40-50 min; finally, heating to 80-90 ℃, adding a 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane coupling agent for coupling reaction, sequentially adding a solvent, 5-10% of divinylbenzene and 0.001-0.2% of an initiator into a polymerization kettle after the reaction is finished, heating to 75-85 ℃, and carrying out wet condensation and drying on the glue solution after the reaction is finished to obtain the four-arm comb-shaped star-shaped nucleating agent;
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: adding a mixed solvent consisting of a diluent and a solvent into a polymerization kettle in sequence, wherein the volume ratio of the diluent to the solvent is 60-40/40-60, the isobutene is 93-97%, the isoprene is 3-7%, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, mixing and ageing the diluent and 0.05-3.0% of a co-initiator at minus 95-minus 85 ℃ for 30-40 min, adding the mixed diluent and aged mixture into the polymerization system together for stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 3.0-5.0% of a four-arm comb star-shaped nucleating agent and the solvent for 4.0-6.0 hr, ageing the mixed solution at minus 95-minus 85 ℃ for 40-60 min, adding the mixed solution into the polymerization kettle together for stirring and reacting for 5.0-7.0 hr, discharging and agglomerating the comb-shaped terminator, washing and drying to obtain a four-arm star-shaped branched butyl rubber product;
wherein, the steps (1) and (2) are carried out in an anaerobic and anhydrous environment;
the initiator 1 is selected from one of n-butyllithium, sec-butyllithium, methyl butyllithium, phenyl butyllithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium;
the initiator 2 is an organic peroxide, and is selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide;
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid.
2. The process according to claim 1, wherein the initiator 1 is n-butyllithium.
3. The method according to claim 1, wherein the initiator 2 is dibenzoyl peroxide.
4. The method of claim 1, wherein the structure modifier is selected from the group consisting of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
5. The method of claim 4, wherein the structure modifier is tetrahydrofuran.
6. The method of claim 1, wherein the molar ratio of the protic acid to the alkyl aluminum halide is between 0.05:1 and 0.5:1.
7. The method of claim 1, wherein the alkyl aluminum halide is selected from at least one of diethyl aluminum monochloride, diisobutyl aluminum monochloride, dichloromethyl aluminum, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride, and ethyl aluminum chloride.
8. The method of claim 7 wherein said alkyl aluminum halide is aluminum sesquichloride.
9. The method of claim 1, wherein said protonic acid is selected from the group consisting of HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 Or HNO (HNO) 3 One of them.
10. The method of claim 9, wherein the protic acid is HCl.
11. The method of claim 1, wherein the diluent is selected from the group consisting of methane chloride, methylene chloride, carbon tetrachloride, ethylene dichloride, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
12. The method of claim 11, wherein the diluent is methyl chloride.
13. The method of claim 1, wherein the solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
14. The method of claim 13, wherein the solvent is cyclohexane.
15. The method of claim 1, wherein the terminator is selected from one or more of methanol, ethanol, butanol.
16. The method of claim 1, wherein steps (1) and (2) are both performed in an inert gas atmosphere.
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