CN114478957A - Preparation method of four-arm comb-shaped star-branched butyl rubber - Google Patents
Preparation method of four-arm comb-shaped star-branched butyl rubber Download PDFInfo
- Publication number
- CN114478957A CN114478957A CN202011274699.2A CN202011274699A CN114478957A CN 114478957 A CN114478957 A CN 114478957A CN 202011274699 A CN202011274699 A CN 202011274699A CN 114478957 A CN114478957 A CN 114478957A
- Authority
- CN
- China
- Prior art keywords
- arm
- star
- shaped
- comb
- 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.)
- Granted
Links
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 173
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 239000002667 nucleating agent Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 52
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 48
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007822 coupling agent Substances 0.000 claims abstract description 27
- -1 alkyl aluminum halide Chemical class 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 109
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 52
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 31
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 230000032683 aging Effects 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 229920001400 block copolymer Polymers 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
- 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
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229940050176 methyl chloride Drugs 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- YFIIENAGGCUHIQ-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptachloropropane Chemical compound ClC(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl YFIIENAGGCUHIQ-UHFFFAOYSA-N 0.000 claims description 2
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 claims description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010539 anionic addition polymerization reaction Methods 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
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 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
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 2
- 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
- UGFDIXXDKBKDSR-UHFFFAOYSA-N di(propan-2-yl)aluminum Chemical compound CC(C)[Al]C(C)C UGFDIXXDKBKDSR-UHFFFAOYSA-N 0.000 claims 1
- UKOVZLWSUZKTRL-UHFFFAOYSA-N naphthalid Chemical compound C1=CC(C(=O)OC2)=C3C2=CC=CC3=C1 UKOVZLWSUZKTRL-UHFFFAOYSA-N 0.000 claims 1
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 7
- 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 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 4
- 239000005060 rubber Substances 0.000 abstract description 4
- 125000003003 spiro group Chemical group 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 27
- 229910001220 stainless steel Inorganic materials 0.000 description 27
- 239000010935 stainless steel Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000012360 testing method Methods 0.000 description 25
- 239000005062 Polybutadiene Substances 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000035882 stress Effects 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000005049 silicon tetrachloride Substances 0.000 description 5
- 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 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 3
- 241001441571 Hiodontidae Species 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical group [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BMHYOFVQTZNPAG-UHFFFAOYSA-N 1,5-dibromo-3,3-diethylpentane Chemical compound BrCCC(CC)(CC)CCBr BMHYOFVQTZNPAG-UHFFFAOYSA-N 0.000 description 2
- KCNWHDKYRKZIGQ-UHFFFAOYSA-N CCC(CC)(CCCl)CCCl Chemical compound CCC(CC)(CCCl)CCCl KCNWHDKYRKZIGQ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- BGXXXYLRPIRDHJ-UHFFFAOYSA-N tetraethylmethane Chemical group CCC(CC)(CC)CC BGXXXYLRPIRDHJ-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- PMSNDFUSQJHJER-UHFFFAOYSA-N 1,5-dichloro-3,3-bis(2-chloroethyl)pentane Chemical compound C(CCl)C(CCCl)(CCCl)CCCl PMSNDFUSQJHJER-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 1
- QNTXHYILQCFXSN-UHFFFAOYSA-N 2-(4-chlorophenyl)ethenyl-dimethylsilane Chemical compound C[SiH](C)C=CC1=CC=C(Cl)C=C1 QNTXHYILQCFXSN-UHFFFAOYSA-N 0.000 description 1
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002131 composite material Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- ZYTJPPRBIGGXRO-UHFFFAOYSA-N propan-2-ylalumane Chemical compound C(C)(C)[AlH2] ZYTJPPRBIGGXRO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical group Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
Abstract
The invention firstly treats the 3, 9-dioxo [5.5]]The spiro undecane is halogenated to synthesize the coupling agent 1, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and then the coupling agent is coupled with the reaction monomers of styrene and butadiene to prepare the binary four-arm star polymer [ -SBR-BR-]nY, then [ -SBR-BR-]nY and divinylbenzene are used for synthesizing a binary four-arm comb-shaped star nucleating agent ([ - (DVB) SBR- (DVB) BR-]nY), and finally [ - (DVB) SBR- (DVB) BR-]nPreparing the four-arm comb-shaped star-branched butyl rubber from the Y, isobutene and isoprene through cationic polymerization by using a first-arm last-core method under a catalyst system compounded by alkyl aluminum halide and protonic acid. The method is characterized in thatOn the premise that the star-keeping branched butyl rubber has enough crude rubber strength and good air tightness, the problems of extrusion swelling and low stress relaxation rate of the butyl rubber in the processing process are solved, so that the four-arm comb-shaped star-shaped butyl rubber has good processability. The preparation method has the characteristics of controllable molecular weight and molecular structure, good product processability, suitability for industrial production and the like.
Description
Technical Field
The invention relates to a preparation method of four-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing four-arm comb-shaped star-branched butyl rubber by using a four-arm nucleating agent of butadiene/styrene/Divinylbenzene (DVB).
Background
It is known that Butyl Rubber (IIR) is produced by the cationic polymerization of isobutylene and a small amount of isoprene. Butyl rubber has been commercialized by Exxon corporation in the 40 th century for over seventy years since now, and has excellent properties such as airtightness, damping properties, thermal aging resistance, ozone resistance, and weather resistance, and thus it is widely used in the fields of manufacturing inner tubes, airtight layers, curing bladders, medical stoppers of tires for vehicles, and the like, and is one of the most important synthetic rubber products.
However, the molecular chain of the butyl rubber is mainly composed of carbon-carbon single bonds, the number of double bonds is small, and the substituent methyl groups are symmetrically arranged, so that the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesiveness, poor compatibility with other general rubbers and the like exist, and the butyl rubber is easy to excessively flow and deform in the processing process. Therefore, how to balance the physical and mechanical properties and the processability of the butyl rubber becomes a bottleneck for preparing high-performance butyl rubber materials.
In recent years, researchers find that star-shaped branched butyl rubber with a unique four-dimensional net structure, which is composed of a high-molecular-weight graft structure and a low-molecular-weight linear structure, has excellent viscoelastic performance, high crude rubber strength and a fast stress relaxation rate, can keep low melt viscosity in the processing process, can obtain a high-molecular-weight polymer, and realizes the balance and unification of physical and mechanical properties and processing properties. Therefore, the star-branched structure has become one of the hot spots in the research field of future butyl rubber.
In the prior art, the star-branched butyl rubber is mainly prepared by a method of a first-nucleus-second-arm method, a first-arm-second-nucleus method and a nuclear-arm simultaneous method. Such as: US5395885 discloses a star-branched polyisobutylene-polydivinylbenzene polymer, which is synthesized by taking polyisobutylene as an arm, Polydivinylbenzene (PDVB) as a core, a complex of aluminium chloride and water as an initiator, and methyl chloride as a diluent through a first-arm-second-core method at-90 to-100 ℃. CN88108392.57 discloses a star-shaped grafted butyl rubber with a comb-shaped structure, which is prepared by using a hydrochloric acid polystyrene-isoprene copolymer as a multifunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN101353403B 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 terminal or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the terminal as a grafting initiating agent for positive ion polymerization, directly participates in the positive ion polymerization in a positive ion polymerization system of a mixed solvent with a ratio of methane chloride to cyclohexane v: v of 20-80/80-20 at the temperature of 0-100 ℃, and prepares a star-branched polyisobutylene or butyl rubber product by the participation of an unsaturated chain in a grafting reaction through the initiated positive ion polymerization of the silicon-chlorine group. CN01817708.5 provides a method of making star-branched polymers by adding a multiolefin cross-linking 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. CN107793535A provides a butyl rubber having a molecular weight of 90 to 260 ten thousand, Log (MW)>And contains structural units derived from isobutylene, structural units derived from a conjugated diene, and optionally structural units derived from an aryl olefin. CN200710129810.7 provides a method of synthesizing linear butyl rubber by a first arm and then core method, and then coupling the linear butyl rubber by divinylbenzene to obtain star-shaped branched butyl rubber. Puskas and the like adopt pyromellitic acid as a raw material to synthesize an initiator, namely the tetra-cumyl alcohol with a four-arm structure, and then adopt the tetra-cumyl alcoholThe base alcohol/aluminum tetrachloride initiation system initiates isobutylene and isoprene copolymerization in inert organic solvent under the condition of-120 to-50 ℃ to synthesize star branched butyl rubber (Catalysts for manufacturing efficiency of IIR with bi-modal molecular weight distribution: US, 5194538[ P ] with bimodal molecular weight distribution].1993-3-16.). Wieland et al successfully prepared a multi-arm star butyl rubber (J-styrene polymerization) by synthesizing a macroinitiator P (MMA-b-St-co-CMS) containing a quaternary element of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-Diphenylethylene (DPE) and then initiating cationic polymerization of isobutylene and isoprene using the macroinitiator]Polymer Science: polymer Chemistry, 2002, 40: 3725-3733.). Hadjichhritidis et al uses CH3SiCl3Synthesis of PI-PS-PBd four-arm copolymer (Iatrou H, Hadjichristis N.Synthesisof a model 3-miktoarm star polymer [ J ] by strictly controlling the order of addition of the monomers and overranging stepwise coupling of the coupling agent]Macromolecules,1992,25: 4649). Hadjrichists adopts high vacuum technique to obtain styrene polybutadiene macromonomer by reacting active polybutadiene lithium with silicon chloride group of p-chlorodimethylsilylstyrene, the macromonomer then copolymerizes with butadiene in the presence of random regulator to obtain active Comb polybutadiene, and finally reacts with methyl silicon tetrachloride or silicon tetrachloride to obtain 3-arm or 4-arm Star-shaped Comb polybutadiene (KOUTALAS G, IATROU H, LOHSE D J, et. well-Defined Comb, Star-Comb, and Comb-on-Comb polymers by Anionic Polymerization and the macromolecular Polymerization [ J ] of]Macromolecules,2005,38(12): 4996-. Gong Hui Qin et al synthesized a star-branched polymer (preparation and characterization of star-branched polyisobutylene with divinylbenzene as core; 2008, 31(5):362 and 365.) with divinylbenzene as core and polyisobutylene as arm at-80 deg.C by using 2-chloro-2, 4, 4-tetramethylpentane/titanium tetrachloride as initiator system and monochloromethane/cyclohexane as solvent and using active cationic polymerization.
Disclosure of Invention
The invention aims to provide a preparation method of four-arm comb-shaped star-branched butyl rubber. Firstly, carrying out halogenation reaction on 3, 9-dioxo [5.5] spiro undecane to synthesize a novel tetrahalide coupling agent; then taking styrene, butadiene and divinyl benzene (DVB) as reaction monomers, coupling by using a tetrahalide coupling agent, and grafting and polymerizing under the action of an initiator to obtain a four-arm comb-shaped star nucleating agent; finally, under a catalysis system compounded by Lewis acid and protonic acid, the four-arm comb-shaped star-shaped nucleating agent, isobutene and isoprene are subjected to cationic polymerization by adopting a first-arm last-core method to prepare the four-arm comb-shaped star-shaped branched butyl rubber. The method solves the problems of extrusion swelling and low stress relaxation rate of the butyl rubber during the processing on the premise of ensuring that the four-arm comb-shaped star-branched butyl rubber has certain crude rubber strength and good air tightness, so that the four-arm comb-shaped star-branched butyl rubber has good processability, and the balance of the physical and mechanical properties and the processability of the butyl rubber is realized.
All the percentages in the present invention are percentages by mass.
The preparation of the four-arm comb-shaped star-branched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) preparation of four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: based on the total mass parts of reactants, firstly 4L with a jacket
Introducing argon into a stainless steel polymerization kettle for 2-4 times of replacement, sequentially adding 100-200% of deionized water, 3, 9-dioxo [5.5] spiro undecane, a halogenating agent and 1-5% of a catalyst into the polymerization kettle, heating to 50-80 ℃, reacting for 1-3 hours, adding 20-40% of NaOH aqueous solution with the mass concentration of 10-20% to terminate the reaction, and finally adding 200-300% of monochloromethane to extract, separate, wash and dry to obtain the coupling agent 1, 5-dihalo-3, 3-bis (2-haloethyl) pentane (the yield is 85-95%).
b, preparation of a four-arm comb-shaped star nucleating agent: based on the total mass of the reaction monomersOne hundred percent, firstly introducing argon gas into a 15L stainless steel polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 200-400% of solvent, 30-50% of 1, 3-butadiene, 0.05-0.5% of structure regulator and 1% of initiator into the polymerization kettle, heating to 40-50 ℃, reacting for 40-60 min to form a BR chain segment, wherein the conversion rate of 1, 3-butadiene monomer reaches 100%; secondly, sequentially adding 30-60% of styrene, 10-20% of 1, 3-butadiene and 0.05-0.5% of structure regulator into a polymerization kettle, heating to 60-70 ℃, and reacting for 50-60 min to form a-BR-SBR-chain segment; heating to 80-90 ℃, adding a coupling agent for coupling reaction, wherein the reaction time is 70-90 min, sequentially adding 100-200% of solvent and 1-5% of Divinylbenzene (DVB) into a polymerization kettle after the reaction is finished, heating to 70-80 ℃, adding 0.01-0.1% of initiator 2, reacting for 50-70 min, treating the coupled reaction mixture with water after the reaction is finished, and condensing and drying a glue solution by a wet method to obtain the binary four-arm comb-shaped star nucleating agent ([ - (DVB) SBR- (DVB) BR-]nY)。
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: according to the total mass parts of reaction monomers, firstly introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3-5 times, and sequentially adding 200-300% of diluent/solvent V into the polymerization kettle: mixing a solvent mixture with a V ratio of 60-40/40-60, isobutene of 93-97% and isoprene of 3-7%, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then adding 40-60% of a diluent and 0.05-3.0% of a co-initiator into the polymerization system for mixing and aging for 30-40 min under the condition of-95 to-85 ℃, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 30-60% of the solvent and 1.0-2.0% of the nucleating agent with the four-arm star structure obtained in the step (1) for 3.0-5.0 hr, aging for 40-60 min under the condition of-95 to-85 ℃, adding the solvent and the nucleating agent with the four-arm star structure into the polymerization system for stirring and reacting for 3.0-6.0 hr, finally adding a terminator for discharging and coagulating, washing and drying to obtain the four-arm comb-like star-branched butyl rubber product.
The nucleating agent of the invention is [ -BR-SBR-]nBinary four-arm comb star polymer of block copolymer [ - (DVB) SBR- (DVB) BR-]nY, the structural general formula is shown as formula I:
wherein Y is 3, 3-diethylpentane; BR is a 1, 3-butadiene homopolymer block, and the 1, 2-structure content of the BR is 15-20%; SBR is a styrene and butadiene random block copolymer, wherein the content of styrene is 30-60 percent, and the content of 1, 3-butadiene is 10-20 percent; the number average molecular weight (Mn) of the binary four-arm star polymer is 40000-70000, and the molecular weight distribution (Mw/Mn) is 4.96-6.14.
The halogenating agent is one of liquid chlorine and liquid bromine, preferably liquid bromine, the dosage of the halogenating agent is determined according to the amount of the 3, 9-dioxo [5.5] spiroundecane, and the molar ratio of the dosage of the halogenating agent to the 3, 9-dioxo [5.5] spiroundecane is 4.5-6.5.
The catalyst of the invention is HCl-CH3A mixed aqueous solution of OH, wherein the molar concentration of HCl is: 0.1 to 0.7 mol/L.
The dosage of the coupling agent is determined according to the amount of the initiator, and the molar ratio of the dosage of the coupling agent to the organic lithium is 1.0-5.0.
The initiator 1 is an alkyl monolithium compound, namely RLi, wherein R is a saturated aliphatic alkyl, alicyclic alkyl, aromatic alkyl containing 1-20 carbon atoms or a composite group of the above groups. The alkyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and 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 dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, preferably dibenzoyl peroxide (BPO).
The structure regulator of the invention is a polar organic compound which generates solvation effect in a polymerization system and can regulate reactivity ratio of styrene and butadiene so that the styrene and the butadiene are 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), tetraethyl amine, 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 C1-C4. The alkyl halide is selected from one of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably methyl chloride.
The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene or ethylbenzene, preferably cyclohexane.
The co-initiator is prepared by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from the group consisting of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, isopropylaluminum dichloroide, dimethylaluminum chloride and ethylaluminum chloride, preferably ethylaluminum sesquichloride. The protonic acid is selected from HCl, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3Of (1), preferably HCl. Wherein the total addition amount of the coinitiator is 0.1-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05: 1-0.5: 1.
The terminator provided by the invention can be selected from one or more of methanol, ethanol and butanol.
The polymerization reaction of the present invention is carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution are carried out in a hydrocarbon solvent, which is a hydrocarbon solvent including straight-chain alkanes, aromatic hydrocarbons and cycloalkanes, and is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention firstly treats 3, 9-dioxo [5.5]]The spiro undecane is halogenated to synthesize a novel coupling agent 1, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and then the coupling agent is coupled with reaction monomers of styrene and butadiene to prepare a binary four-arm star polymer [ -SBR-BR-]nY, then [ -SBR-BR-]nY and divinylbenzene are used for synthesizing a binary four-arm comb-shaped star nucleating agent ([ - (DVB) SBR- (DVB) BR-]nY), and finally [ - (DVB) SBR- (DVB) BR-]nAnd preparing the four-arm comb-shaped star-branched butyl rubber by cationic polymerization of Y, isobutene and isoprene by using a first-arm-second-core method under a catalyst system compounded by alkyl aluminum halide and protonic acid. The nucleating agent with the binary four-arm comb-like star-shaped structure is formed by combining two chain segments of different microstructures, namely SBR and BR, on a macromolecular chain by using a novel coupling agent, and the binary four-arm comb-like star-shaped structure increases the disorder of the whole macromolecular chain segment of butyl on the premise of not damaging the regularity of the molecular chain in the copolymerization of isobutene and isoprene, so that the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelasticity, the stress relaxation rate is high, the extrusion swelling effect is reduced, and the processing performance of the butyl rubber is improved. Meanwhile, the SBR chain segment contains a large number of benzene rings, so that the reduction of strength and airtightness caused by broadening of molecular weight distribution is avoided, and the high strength and good airtightness of the butyl rubber are ensured.
According to the invention, through the design of the binary four-arm comb-shaped star structure, the characteristics of the binary four-arm star structure and the performances of different chain segments are organically combined together and act synergistically, the problem of contradiction between the processability and the physical and mechanical performances of butyl rubber is solved, and the optimal balance between the processability and the physical and mechanical performances of butyl rubber is finally realized. The preparation method provided by the invention has the characteristics of controllable process conditions, stable product performance, suitability for industrial production and the like.
Drawings
FIG. 1 is 1#Comparative example 1 sample and 2#Comparison of the GPC spectra of the samples of example 1.
Detailed Description
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. All the raw materials used in the examples are of industrial polymerization grade, and are used after purification without other special requirements.
Firstly, raw material sources:
styrene, butadiene, Polymer grade, Petroleum Lanzhou petrochemical Co Ltd
Isobutene, isoprene, Polymer grade Zhejiang Credit New materials Co Ltd
N-butyl lithium, 98% purity Nanjing Tongtiang chemical Co., Ltd
3, 9-dioxo [5.5] spiroundecane of 99% purity from Hubei Ferry chemical Co., Ltd
Dibenzoyl peroxide (BPO), Lanzhou auxiliary plant
Aluminum sesquiethylate chloride, 98% pure Profenor technologies Ltd
Other reagents are all commercial products
The method comprises the following steps:
determination of the molecular weights and their distribution: the measurement was carried out by using 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation, USA. Taking polystyrene standard sample as calibration curve, tetrahydrofuran as mobile phase, column temperature of 40 deg.C, sample concentration of 1mg/ml, sample amount of 50 μ L, elution time of 40min, and flow rate of 1 ml/min-1。
Measurement of stress relaxation: the measurement was carried out by using a Mooney viscometer model GT-7080-S2 manufactured by Taiwan high-speed railway.
The Mooney relaxation time, determined with a large rotor at 125 ℃ C (1+8) according to the method of GB/T1232.1-2000, is 120 s.
Measurement of the extrusion swell ratio: using a capillary rheometer model RH2000 from Malvern, UK
At a temperature of 100 ℃, an aspect ratio of 16:1 and a shear rate of 10-1000S-1Is measured within the interval of (1).
Measurement of airtightness: the air permeability was determined using an automated air tightness tester according to ISO 2782:1995,
test gas is N2The test temperature is 23 ℃, and the test sample is a circular sea piece with the diameter of 8cm and the thickness of 1 mm.
Tensile strength: the method in standard GB/T528-2009 is executed.
Example 1
(1) Preparation of four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, introducing argon gas for 3 times of replacement, and adding 500g of deionized water and 48g of 3, 9-dioxygen [5.5] into the polymerization kettle in sequence]Spiroundecane, 250g of liquid bromine, 7g of HCl-CH3OH solution (HCl molar concentration: 0.3mol/L), heating to 52 ℃, reacting for 1.8hr, adding 200g NaOH aqueous solution with mass concentration of 15% to terminate the reaction, and finally adding 600g methane chloride to extract, separate, wash and dry to obtain the coupling agent 1, 5-dibromo-3, 3 bis (2-bromoethyl) pentane (yield 87%).
b, preparation of a four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene, 0.7g of THF and 22.3mmo1 n-butyllithium into a polymerization kettle, heating to 40 ℃, and reacting for 40min to form a BR chain segment; then, 300g of styrene, 100g of 1, 3-butadiene and 1.6g of THF are sequentially added into a polymerization kettle, the temperature is raised to 60 ℃, and the reaction is carried out for 50min to form a-BR-SBR-chain segment; then heating to 80 ℃, adding 20.1mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and reacting for 70min to form [ -SBR-BR-]nY; after the reaction is finished, sequentially adding 1000g of cyclohexane, 25g of DVB and 0.06g of BPO into a polymerization kettle, heating to 70 ℃, after the reaction is carried out for 50min, carrying out wet condensation and drying on the glue solution to obtain the nucleating agent [ - (DVB) SBR- (DVB) BR-]nY (Mn 41000, Mw/Mn 4.98).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, nitrogen gas is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, 310g of methane chloride, 330g of cyclohexane, 279g of isobutene and 9g of isoprene are sequentially added into a polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to-90 ℃, and then 120g of methane chloride and 1.9g of aluminum sesquiethylate chloride are addedg and HCl0.07g are mixed at-85 ℃ and then aged for 30min, then added into the polymerization system together and stirred for reaction for 0.5hr, then 100g cyclohexane, 3.1g [ - (DVB) SBR- (DVB) BR-]nAnd Y, stirring and dissolving for 3.0hr until the grafting agent is completely dissolved, aging at-85 ℃ for 40min, adding the materials into a polymerization system, stirring and reacting for 3.0hr, adding 150mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Preparation of four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b, preparation of a four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2600g of cyclohexane, 340g of 1, 3-butadiene, 1.5g of THF and 23.2mmo1 n-butyllithium into a polymerization kettle, heating to 42 ℃, and reacting for 44min to form a BR chain segment; then, sequentially adding 360g of styrene, 130g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle, heating to 63 ℃, and reacting for 52min to form a-BR-SBR-chain segment; then heating to 82 ℃, adding 23.5mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and reacting for 75min to form [ -SBR-BR-]nY; after the reaction is finished, 1200g of cyclohexane, 30g of DVB and 0.09g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 72 ℃, after the reaction is carried out for 55min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR-]nY (Mn 48000, Mw/Mn 5.17).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 320g of methane chloride, 310g of cyclohexane, 283g of isobutene and 11g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then adding 130g of methane chloride, 2.2g of aluminum sesquiethylate chloride and 0.09g of HCl into the polymerization system after mixing at-87 ℃ and aging for 32min, stirring and reacting for 0.6hr, and then adding 120g of cyclohexane, 3.7g of [ - (DVB) SBR- (DVB) BR-]nY, stirringStirring and dissolving for 4.0hr until the grafting agent is completely dissolved, then aging for 45min at-88 ℃, adding the mixture into a polymerization system, stirring and reacting for 3.5hr, adding 170mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b, preparation of a four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3000g of cyclohexane, 400g of 1, 3-butadiene, 2.1g of THF and 25.6mmo1 n-butyllithium into a polymerization kettle, heating to 44 ℃, and reacting for 47min to form a BR chain segment; then, 400g of styrene, 150g of 1, 3-butadiene and 2.7g of THF are sequentially added into a polymerization kettle, the temperature is raised to 65 ℃, and the reaction is carried out for 54min to form a-BR-SBR-chain segment; then heating to 85 ℃, adding 26.5mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and reacting for 80min to form [ -SBR-BR-]nY; after the reaction is finished, 1400g of cyclohexane, 32g of DVB and 0.11g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 58min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR-]nY (Mn 53000, Mw/Mn 5.42).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 330g of methane chloride, 300g of cyclohexane, 286g of isobutene and 13g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 140g of methane chloride, 2.9g of sesquiethylaluminum chloride and 0.12g of HCl into the polymerization system after mixing at-87 ℃ and aging for 34min, stirring and reacting for 0.7hr, and then adding 140g of cyclohexane, 4.2g of [ - (DVB) SBR- (DVB) BR-]nY, stirring to dissolve for 4.5hr until the grafting agent is completely dissolved, aging at-90 deg.C for 50min, adding into the polymerization system, stirring to react for 4.0hr, adding 180mL methanol to terminate the reaction, and dischargingCoagulating, washing and drying the material to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Preparation of four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b, preparation of a four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3300g of cyclohexane, 430g of 1, 3-butadiene, 2.5g of THF and 26.6mm of 1 n-butyllithium into a polymerization kettle, heating to 46 ℃, and reacting for 52min to form a BR chain segment; then, 470g of styrene, 170g of 1, 3-butadiene and 3.1g of THF are sequentially added into a polymerization kettle, the temperature is raised to 67 ℃, and the reaction is carried out for 56min to form a-BR-SBR-chain segment; then the temperature is raised to 85 ℃, 27.8 mmols 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane is added for reaction for 83min, and [ -SBR-BR-]nY; after the reaction is finished, 1600g of cyclohexane, 38g of DVB and 0.25g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, after the reaction is carried out for 61min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR-]nY (Mn of 58000, Mw/Mn of 5.67).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, adding 340g of methane chloride, 290g of cyclohexane, 289g of isobutene and 15g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 150g of methane chloride, 3.2g of aluminum sesquiethylate chloride and 0.21g of HCl into the polymerization system after mixing at-87 ℃ and aging for 36min, stirring and reacting for 0.8hr, then adding 150g of cyclohexane, 5.1g of [ - (DVB) SBR- (DVB) BR-]nAnd Y, stirring and dissolving for 5.0hr until the grafting agent is completely dissolved, aging at-90 ℃ for 52min, adding the materials into a polymerization system, stirring and reacting for 4.5hr, adding 200mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Preparation of four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, introducing argon for 4 times of replacement, and adding 550g of deionized water and 55g of 3, 9-dioxygen [5.5] into the polymerization kettle in sequence]Spiroundecane, 280g of liquid chlorine, 10g of HCl-CH3OH solution (HCl molar concentration: 0.7mol/L), heating to 80 deg.C, reacting for 3.0hr, adding 250g NaOH aqueous solution with mass concentration of 20% to terminate the reaction, and finally adding 800g methane chloride to extract, separate, wash and dry to obtain the coupling agent 1, 5-dichloro-3, 3 bis (2-chloroethyl) pentane (yield 91%).
b, preparation of a four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 3500g of cyclohexane, 460g of 1, 3-butadiene, 2.9g of THF and 28.1mm of 1 n-butyllithium into the polymerization kettle, heating to 48 ℃, and reacting for 57min to form a BR chain segment; then, 510g of styrene, 190g of 1, 3-butadiene and 3.8g of THF are sequentially added into a polymerization kettle, the temperature is raised to 68 ℃, and the reaction is carried out for 58min to form a-BR-SBR-chain segment; then heating to 87 ℃, adding 29.1mmo11, 5-dichloro-3, 3 bis (2-chloroethyl) pentane, reacting for 85min to form [ -SBR-BR-]nY; after the reaction is finished, 1800g of cyclohexane, 42g of DVB and 0.31g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 79 ℃, after the reaction is carried out for 65min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR-]nY (Mn of 63000, Mw/Mn of 5.85).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 350g of methane chloride, 280g of cyclohexane, 290g of isobutene and 18g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-98 ℃, then mixing 170g of methane chloride, 4.1g of aluminum sesquiethylate chloride and 0.35g of HCl at-90 ℃, aging for 38min, adding into the polymerization system together, stirring and reacting for 0.9hr, and then adding 170g of cyclohexane, 5.6g of [ - (DVB) SBR- (DVB) BR-]nY, stirring to dissolve for 5.5hr until the grafting agent is completely dissolved, aging at-93 deg.C for 56min, addingStirring and reacting in a polymerization system for 5.0hr, adding 230mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) Preparation of a four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 5.
b, preparation of a four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacing for 4 times, sequentially adding 4000g of cyclohexane, 500g of 1, 3-butadiene, 3.3g of THF and 30.1mmo1 n-butyl lithium into a polymerization kettle, heating to 50 ℃, and reacting for 60min to form a BR chain segment; then, sequentially adding 600g of styrene, 200g of 1, 3-butadiene and 4.5g of THF into a polymerization kettle, heating to 70 ℃, and reacting for 60min to form a-BR-SBR-chain segment; then heating to 90 deg.C, adding 32.0mmo 11, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 90min to form [ -SBR-BR-]nY; after the reaction is finished, 2000g of cyclohexane, 50g of DVB and 0.42g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after the reaction is carried out for 70min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR-]nY (Mn of 69000, Mw/Mn of 6.12).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, sequentially adding 360g of methane chloride, 270g of cyclohexane, 291g of isobutene and 20g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then adding 180g of methane chloride, 4.9g of aluminum sesquiethylate chloride and 0.42g of HCl into the polymerization system after mixing at-95 ℃ and aging for 40min, stirring and reacting for 1.0hr, and then adding 180g of cyclohexane, 6.0g of [ - (DVB) SBR- (DVB) BR-]nAnd Y, stirring and dissolving for 6.0hr until the grafting agent is completely dissolved, aging at-95 ℃ for 60min, adding the materials into a polymerization system, stirring and reacting for 6.0hr, adding 270mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: system for makingThe test performance of the standard sample is shown in Table 1.
Comparative example 1
Preparation of four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 1 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR-]nY, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 310g of methane chloride, 330g of cyclohexane, 279g of isobutene and 9g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 120g of methane chloride, 1.9g of aluminum sesquiethylate chloride and 0.07g of HCl at-85 ℃, aging for 30min, adding the mixture into the polymerization system together, stirring and reacting for 0.5hr, adding 150mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of four-arm comb-shaped star nucleating agent: the other conditions were the same as in example 2 except that: in the synthesis process, 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added, but a conventional coupling agent of silicon tetrachloride (SiCl) is added4) Namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2600g of cyclohexane, 340g of 1, 3-butadiene, 1.5g of THF and 23.2mmo1 n-butyllithium into a polymerization kettle, heating to 42 ℃, and reacting for 44min to form a BR chain segment; then, sequentially adding 360g of styrene, 130g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle, heating to 63 ℃, and reacting for 52min to form a-BR-SBR-chain segment; subsequently, the temperature was increased to 82 ℃ and 23.5mmo1 SiCl was added4Reacting for 75min to form [ -SBR-BR-]nY; after the reaction is finished, 1200g of cyclohexane, 30g of DVB and 0.09g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 72 ℃, after the reaction is carried out for 55min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR-]nSi (Mn 45000, Mw/Mn 4.35).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 2 except that: in the synthetic processAdding nucleating agent [ - (DVB) SBR- (DVB) BR-]nY, but adding a nucleating agent [ - (DVB) SBR- (DVB) BR-]nSi, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 320g of methane chloride, 310g of cyclohexane, 283g of isobutene and 11g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then adding 130g of methane chloride, 2.2g of aluminum sesquiethylate chloride and 0.09g of HCl into the polymerization system after mixing at-87 ℃ and aging for 32min, stirring and reacting for 0.6hr, and then adding 120g of cyclohexane, 3.7g of [ - (DVB) SBR- (DVB) BR-]nAnd Si, stirring and dissolving for 4.0hr until the grafting agent is completely dissolved, aging at-88 ℃ for 45min, adding the materials into a polymerization system, stirring and reacting for 3.5hr, adding 170mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparation of four-arm comb-shaped star nucleating agent: the other conditions were the same as in example 3 except that: no coupling agent 1, 5-dibromo-3, 3 bis (2-bromoethyl) pentane was added, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3000g of cyclohexane, 400g of 1, 3-butadiene, 2.1g of THF and 25.6mmo1 n-butyllithium into a polymerization kettle, heating to 44 ℃, and reacting for 47min to form a BR chain segment; then 400g of styrene, 150g of 1, 3-butadiene and 2.7g of THF are sequentially added into a polymerization kettle, the temperature is raised to 65 ℃, and the reaction is carried out for 54min to form a chain segment [ -SBR-BR-]n(ii) a After the reaction is finished, 1400g of cyclohexane, 32g of DVB and 0.11g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 58min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR-]n(Mn of 50000 and Mw/Mn of 2.21).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 3 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR-]nY, but adding a nucleating agent [ - (DVB) SBR- (DVB) BR-]nNamely: firstly, with a clampIntroducing nitrogen into a 4L stainless steel reaction kettle for 4 times of replacement, sequentially adding 330g of methane chloride, 300g of cyclohexane, 286g of isobutene and 13g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 140g of methane chloride, 2.9g of aluminum sesquiethyl chloride and 0.12g of HCl at-87 ℃, aging for 34min, adding into the polymerization system together, stirring and reacting for 0.7hr, and then adding 140g of cyclohexane, 4.2g of [ - (DVB) SBR- (DVB) BR-]nStirring and dissolving for 4.5hr until the grafting agent is completely dissolved, then aging for 50min at-90 ℃, adding the mixture into a polymerization system, stirring and reacting for 4.0hr, adding 180mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
(1) Preparation of four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 4.
b, preparation of a four-arm comb-shaped star nucleating agent: the other conditions were the same as in example 4 except that: 1, 3-butadiene is not added in the synthesis process, and a-BR-chain segment is not formed, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3300g of cyclohexane, 2.5g of THF and 26.6mmo1 n-butyllithium into the polymerization kettle, and heating to 46 ℃; then, 470g of styrene, 170g of 1, 3-butadiene and 3.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 67 ℃, and the reaction is carried out for 56min, so as to form a-SBR-chain segment; then the temperature is raised to 85 ℃, 27.8 mmols 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added for reaction for 83min, and [ -SBR-]nY; after the reaction is finished, 1600g of cyclohexane, 38g of DVB and 0.25g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, after the reaction is carried out for 61min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR-]nY (Mn of 46000, Mw/Mn of 4.57).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 4 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR-]nY is but addThe nucleating agent [ - (DVB) SBR-]nY, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, adding 340g of methane chloride, 290g of cyclohexane, 289g of isobutene and 15g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 150g of methane chloride, 3.2g of aluminum sesquiethylate chloride and 0.21g of HCl into the polymerization system after mixing at-87 ℃ and aging for 36min, stirring and reacting for 0.8hr, then adding 150g of cyclohexane, 5.1g of [ - (DVB) SBR- (DVB) BR-]nAnd Y, stirring and dissolving for 5.0hr until the grafting agent is completely dissolved, aging at-90 ℃ for 52min, adding the materials into a polymerization system, stirring and reacting for 4.5hr, adding 200mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 5
(1) Preparation of four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 5.
b, preparation of a four-arm comb-shaped star nucleating agent: the other conditions were the same as in example 5 except that: during the synthesis, no styrene and 1, 3-butadiene were added, and no-SBR-segment was formed, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 3500g of cyclohexane, 460g of 1, 3-butadiene, 2.9g of THF and 28.1mm of 1 n-butyllithium into the polymerization kettle, heating to 48 ℃, and reacting for 57min to form a BR chain segment; then heating to 87 ℃, adding 29.1mmo11, 5-dichloro-3, 3 bis (2-chloroethyl) pentane, reacting for 85min to form [ -SBR-BR-]nY; after the reaction is finished, 1800g of cyclohexane, 42g of DVB and 0.31g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 79 ℃, after the reaction is carried out for 65min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) BR-]nY (Mn 41000, Mw/Mn 4.73).
(2) Preparation of four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 5 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR-]nY, but adding nucleationAgent [ - (DVB) BR-]nY, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 350g of methane chloride, 280g of cyclohexane, 290g of isobutene and 18g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-98 ℃, then mixing 170g of methane chloride, 4.1g of aluminum sesquiethylate chloride and 0.35g of HCl at-90 ℃, aging for 38min, adding into the polymerization system together, stirring and reacting for 0.9hr, then adding 170g of cyclohexane, 5.6g of [ - (DVB) BR-]nAnd Y, stirring and dissolving for 5.5 hours until the grafting agent is completely dissolved, aging at-93 ℃ for 56min, adding the materials into a polymerization system, stirring and reacting for 5.0 hours, adding 230mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 6
Preparation of four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 6 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR-]nY, but the nucleating agent DVB was added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, sequentially adding 360g of methane chloride, 270g of cyclohexane, 291g of isobutene and 20g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then mixing 180g of methane chloride, 4.9g of aluminum sesquiethyl chloride and 0.42g of HCl at-95 ℃, aging for 40min, adding into the polymerization system together, stirring and reacting for 1.0hr, then stirring and dissolving 180g of cyclohexane and 6.0g of DVB for 6.0hr until a grafting agent is completely dissolved, aging for 60min at-95 ℃, adding into the polymerization system together, stirring and reacting for 6.0hr, adding 270mL of methanol to terminate the reaction, finally discharging, washing, and drying to obtain a four-arm comb-shaped branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of four-arm comb-like Star-branched butyl rubber
As can be seen from Table 1: the four-arm comb-shaped star-branched butyl rubber has high tensile strength, good air tightness, lower Mooney relaxation area and good processability (the smaller the area under a stress relaxation curve is, the lower the mixing processing energy consumption is).
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (19)
1. A preparation method of four-arm comb-shaped star-branched butyl rubber comprises the following steps:
(1) styrene, 1, 3-butadiene and divinylbenzene are taken as reaction monomers, 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane is taken as a coupling agent, and the four-arm pectinate star-shaped nucleating agent is prepared by utilizing a method of combining temperature-changing and speed-changing polymerization, anionic polymerization and free radical polymerization;
(2) carrying out cationic polymerization on isobutene and isoprene serving as reaction monomers in the presence of the four-arm comb-shaped star nucleating agent to prepare the four-arm comb-shaped star-branched butyl rubber;
the wide-distribution four-arm comb-shaped star nucleating agent is characterized in that the structural general formula of the wide-distribution four-arm comb-shaped star nucleating agent is shown as a formula I:
wherein BR is a 1, 3-butadiene homopolymer block, and the 1, 2-structure content of BR is 15-20%; SBR is a styrene and butadiene random block copolymer, wherein the content of styrene is 30-60%, and the content of 1, 3-butadiene is 10-20%; the number average molecular weight of the four-arm star-shaped nucleating agent is 40000-70000, and the ratio of the weight average molecular weight to the number average molecular weight is 4.96-6.14.
2. The method of claim 1, wherein the specific manufacturing process comprises the steps of:
(1) preparation of four-arm comb-shaped star nucleating agent: based on the total mass parts of reaction monomers, firstly, sequentially adding a solvent, 30-50% of 1, 3-butadiene, 0.05-0.5% of a structure regulator and 1% of an initiator into a polymerization kettle, heating to 40-50 ℃, and reacting until the conversion rate of the 1, 3-butadiene monomer reaches 100%; secondly, sequentially adding 30-60% of styrene, 10-20% of 1, 3-butadiene and 0.05-0.5% of structure regulator into the polymerization kettle, heating to 60-70 ℃, and reacting for 50-60 min; heating to 80-90 ℃, adding a 1, 5-dihalo-3, 3-di (2-haloethyl) pentane coupling agent for coupling reaction, wherein the reaction time is 70-90 min, after the reaction is finished, sequentially adding a solvent and 1-5% of divinylbenzene into a polymerization kettle, heating to 70-80 ℃, adding 0.01-0.1% of an initiator 2, after the reaction is finished, treating the coupled reaction mixture with water, and performing wet condensation and drying on a glue solution to prepare the four-arm comb-shaped star-shaped nucleating agent;
(2) preparation of four-arm comb-shaped star-branched butyl rubber: firstly, sequentially adding a diluent/solvent mixed solvent with the volume ratio of 60-40/40-60, isobutene with the volume ratio of 93-97 and isoprene with the volume ratio of 3-7% into a polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, adding 0.05-3.0% of the diluent and a co-initiator into the polymerization system under the condition of-95 to-85 ℃, mixing and aging, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 30-60% of the solvent and 1.0-2.0% of a four-arm star-shaped nucleating agent for 3.0-5.0 hr, aging under the condition of-95 to-85 ℃, adding into the polymerization kettle, stirring and reacting for 3.0-6.0 hr, finally adding a terminator, discharging and coagulating, washing and drying to obtain a four-arm comb-shaped branched butyl rubber product;
the polymerization reaction is carried out in an oxygen-free and water-free environment.
3. The method of claim 2, wherein the initiator 1 is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, cyclohexyllithium, and dodecyllithium.
4. The process of claim 3 wherein said initiator 1 is n-butyllithium.
5. The method of claim 2 wherein said initiator 2 is an organic peroxide selected from the group consisting of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-t-butyl peroxide.
6. The method of claim 5, wherein said initiator 2 is dibenzoyl peroxide.
7. The method of claim 2, 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 tetraethyl amine.
8. The method of claim 7, wherein said structure modifier is tetrahydrofuran.
9. The method of claim 2, wherein the co-initiator is a combination of an alkyl aluminum halide and a protonic acid, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1 to 0.5: 1.
10. The method of claim 9 wherein the alkyl aluminum halide is selected from at least one of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, diisopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride.
11. The method of claim 10 wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.
12. The method according to claim 9, wherein the protic acid is selected from the group consisting of HCl, HF, HBr, H2SO4、H2CO3、H3PO4Or HNO3One kind of (1).
13. The method of claim 12, wherein the protic acid is HCl.
14. The method of claim 2, wherein the diluent is selected from the group consisting of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
15. The method of claim 14, wherein the diluent is methyl chloride.
16. The method of claim 2, wherein the solvent is selected from the group consisting of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
17. The method of claim 16, wherein the solvent is cyclohexane.
18. The method of claim 2, wherein the terminating agent is selected from one or more of methanol, ethanol, butanol.
19. The method of claim 2, wherein steps (1) and (2) are performed in an inert gas environment.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3985830A (en) * | 1974-07-15 | 1976-10-12 | The University Of Akron | Star polymers and process for the preparation thereof |
| US20050192408A1 (en) * | 2001-10-04 | 2005-09-01 | Bridggestone Corporation | Nano-particle preparation and applications |
| US20050209408A1 (en) * | 2004-03-17 | 2005-09-22 | Lee Hyung-Jae | Star-shaped polymer, multiple star polymer and their preparation methods |
| US20060167187A1 (en) * | 2002-10-28 | 2006-07-27 | Basf Aktiengesellschaft | Method for the anionic polymerisation of high-impact polystyrene |
| WO2008078814A1 (en) * | 2006-12-27 | 2008-07-03 | Jsr Corporation | Method for producing modified conjugated diene polymer, modified conjugated diene polymer, and rubber composition |
| CN102453214A (en) * | 2010-10-28 | 2012-05-16 | 中国石油化工股份有限公司 | Terpolymer as well as preparation method and application thereof |
| CN103030756A (en) * | 2011-10-10 | 2013-04-10 | 中国石油化工股份有限公司 | Styrene-butadiene copolymer as well as preparation and applications thereof |
-
2020
- 2020-11-12 CN CN202011274699.2A patent/CN114478957B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3985830A (en) * | 1974-07-15 | 1976-10-12 | The University Of Akron | Star polymers and process for the preparation thereof |
| US3985830B1 (en) * | 1974-07-15 | 1998-03-03 | Univ Akron | Star polymers and process for the preparation thereof |
| US20050192408A1 (en) * | 2001-10-04 | 2005-09-01 | Bridggestone Corporation | Nano-particle preparation and applications |
| US20060167187A1 (en) * | 2002-10-28 | 2006-07-27 | Basf Aktiengesellschaft | Method for the anionic polymerisation of high-impact polystyrene |
| US20050209408A1 (en) * | 2004-03-17 | 2005-09-22 | Lee Hyung-Jae | Star-shaped polymer, multiple star polymer and their preparation methods |
| WO2008078814A1 (en) * | 2006-12-27 | 2008-07-03 | Jsr Corporation | Method for producing modified conjugated diene polymer, modified conjugated diene polymer, and rubber composition |
| CN102453214A (en) * | 2010-10-28 | 2012-05-16 | 中国石油化工股份有限公司 | Terpolymer as well as preparation method and application thereof |
| CN103030756A (en) * | 2011-10-10 | 2013-04-10 | 中国石油化工股份有限公司 | Styrene-butadiene copolymer as well as preparation and applications thereof |
Non-Patent Citations (4)
| Title |
|---|
| 刘海峰: "星形多官能团大分子接枝合成异丁烯系聚合物", 中国优秀硕士学位论文全文数据库 工程科技I辑 * |
| 刘海峰等: "利用阴离子与阳离子聚合技术合成星型支化丁基橡胶", 2005年全国高分子学术论文报告会 * |
| 刘海峰等: "星形多官能团大分子接枝合成支化聚异丁烯的研究", 高分子材料科学与工程 * |
| 赵锦波: "线形丁基橡胶新型引发剂体系的研究以及星形支化丁基橡胶的合成", 中国优秀硕士学位论文全文数据库 工程科技I辑 * |
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