CN113831473B - Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber - Google Patents
Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber Download PDFInfo
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- CN113831473B CN113831473B CN202010591306.4A CN202010591306A CN113831473B CN 113831473 B CN113831473 B CN 113831473B CN 202010591306 A CN202010591306 A CN 202010591306A CN 113831473 B CN113831473 B CN 113831473B
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- Prior art keywords
- polymerization kettle
- molecular weight
- polymerization
- butadiene
- reaction
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- 238000009826 distribution Methods 0.000 title claims abstract description 102
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 250
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 160
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 136
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 87
- 238000005859 coupling reaction Methods 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 57
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-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 41
- 239000007822 coupling agent Substances 0.000 claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- -1 alkyl aluminum halide Chemical class 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 132
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 97
- 239000002174 Styrene-butadiene Substances 0.000 claims description 95
- 238000010438 heat treatment Methods 0.000 claims description 94
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 89
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 66
- 239000005062 Polybutadiene Substances 0.000 claims description 59
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000002140 halogenating effect Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 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
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012046 mixed solvent 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 238000013329 compounding Methods 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 compound 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 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
- 125000003003 spiro group Chemical group 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
- NEHMKBQYUWJMIP-OUBTZVSYSA-N chloromethane Chemical group Cl[13CH3] NEHMKBQYUWJMIP-OUBTZVSYSA-N 0.000 claims 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims 1
- WXRBQHOKNRLOQI-UHFFFAOYSA-N dichloromethylaluminum Chemical compound [Al]C(Cl)Cl WXRBQHOKNRLOQI-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 claims 1
- UUXZFMKOCRKVDG-UHFFFAOYSA-N methane;hydrofluoride Chemical compound C.F UUXZFMKOCRKVDG-UHFFFAOYSA-N 0.000 claims 1
- 239000003607 modifier Substances 0.000 claims 1
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 14
- 230000008878 coupling Effects 0.000 abstract description 11
- 238000010168 coupling process Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 80
- 229910001220 stainless steel Inorganic materials 0.000 description 55
- 239000010935 stainless steel Substances 0.000 description 55
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 53
- 239000004793 Polystyrene Substances 0.000 description 51
- 229910052786 argon Inorganic materials 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 229940050176 methyl chloride Drugs 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000002902 bimodal effect Effects 0.000 description 8
- WPUBUMYDZKJTBD-UHFFFAOYSA-N 1,5-dibromo-3,3-bis(2-bromoethyl)pentane Chemical compound BrCCC(CCBr)(CCBr)CCBr WPUBUMYDZKJTBD-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 5
- 229920002367 Polyisobutene Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241001441571 Hiodontidae Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical group [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- BGXXXYLRPIRDHJ-UHFFFAOYSA-N tetraethylmethane Chemical group CCC(CC)(CC)CC BGXXXYLRPIRDHJ-UHFFFAOYSA-N 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-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
- BQAZYKYBFAMHPG-UHFFFAOYSA-N 3,5-dimethylhex-2-ene Chemical compound CC=C(C)CC(C)C BQAZYKYBFAMHPG-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 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
- 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
- 238000000576 coating method 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
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 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
- 230000002522 swelling effect Effects 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
- 239000008096 xylene 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
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Abstract
The invention relates to a preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber, which utilizes binary reaction monomers of styrene and butadiene to prepare four chain segments with different wide vinyl content distribution and wide molecular weight distribution through four-kettle reaction and variable temperature polymerization, and prepares a binary four-hetero-arm star copolymer [ -B-SBR [ -5-dihalo-3-2-haloethyl) pentane with a four-hetero-arm star structure through coupling of a novel coupling agent 1, 5-dihalo-3, 3-bis (2-haloethyl) pentane synthesized] n [‑BR 1 ‑PS‑B‑] n Y[‑BR‑SBR 1 ‑B‑] n [‑PS 1 ‑B‑] n . The binary four-hetero-arm star-shaped copolymer is used as a grafting agent to prepare ultra-wide molecular weight distribution and hyperbranched butyl rubber by cationic polymerization with isobutene and isoprene under a catalytic system compounded by alkyl aluminum halide and protonic acid.
Description
Technical Field
The invention relates to a preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber, in particular to a method for preparing ultra-wide molecular weight distribution and hyperbranched butyl rubber by taking binary four-hetero-arm star-shaped copolymer synthesized by styrene and butadiene as a grafting agent and carrying out cationic polymerization on the binary four-hetero-arm star-shaped copolymer, isobutene and isoprene.
Background
Butyl Rubber (IIR) is known to be copolymerized from isobutylene and a small amount of isoprene by cationic polymerization. Butyl rubber has been industrialized by Exxon corporation in the united states in the 40 th century for over seventy years, and has been widely used in the fields of inner tubes, inner liners, curing bladder, medical plugs, etc. for manufacturing tires for vehicles because of its excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance, etc.
However, the molecular chain of butyl rubber mainly consists of single bonds of carbon and carbon, the number of double bonds is small, substituent methyl groups are symmetrically arranged, and the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesion, poor compatibility with other general rubber and the like exist, so that the butyl rubber is easy to excessively flow and deform in the processing process. How to achieve a balance of physical and mechanical properties and processability of butyl rubber has become a bottleneck in the preparation of high performance butyl rubber materials.
In recent years, researchers find that star-shaped highly branched butyl rubber with a unique three-dimensional network structure, which consists of a high molecular weight grafted structure and a low molecular weight linear structure, has excellent viscoelastic performance, high green strength and fast stress relaxation rate, can keep low melt viscosity in the processing process, can obtain a high molecular weight polymer, and realizes uniform balance of physical and mechanical properties and processing properties. The star-shaped hyperbranched structure has become one of the hot spots in the future butyl rubber research field.
In the prior art, the synthesis of star-shaped hyperbranched butyl rubber is mainly prepared by adopting a method of a first nucleus and then arm method, a method of a first arm and then nucleus and a method of a simultaneous nuclear arm method. Such as: US5395885 discloses a star-shaped hyperbranched polymer, which is synthesized by a method of first-arm-then-core method under the condition of-90 ℃ to-100 ℃ by taking polyisobutylene as an arm, taking Polydivinylbenzene (PDVB) as a core, taking a complex of alkyl chloridizing aluminum and water as an initiator and taking chloromethane as a diluent. CN 107344982A discloses a process for producing butyl rubber with broad/bimodal molecular weight distribution, which comprises: in the first step, the molar ratio of isobutene to isoprene is 97:mixing 3 to 99:1 followed by mixing with a diluent (methyl chloride) to obtain a monomer stream, then mixing an initiator (aluminum chloride system and HCl/alkyl aluminum chloride complex) with the diluent (methyl chloride) to obtain an initiator stream, finally mixing the monomer stream and the initiator stream and feeding the mixed initiator stream into a first loop reactor zone, polymerizing at a temperature of-98 ℃ to-96 ℃ and a pressure of 0.3 to 0.4Mpa for 5 to 10 minutes to obtain a first portion of butyl rubber slurry; the second step, the first part of butyl rubber slurry is sent into a second loop reactor zone, and the butyl rubber slurry with broad/bimodal molecular weight distribution is finally obtained after polymerization reaction for 5-10min at the temperature of-92 ℃ to-90 ℃ and the pressure of 0.1 to 0.2 Mpa; and thirdly, contacting the butyl rubber slurry with the broad/bimodal molecular weight distribution with water, removing unreacted monomers and diluents to obtain colloidal particle water, and dehydrating and drying the colloidal particle water to obtain the butyl rubber with the broad/bimodal molecular weight distribution (Mw/Mn) of at least 5.0. CN1427851a discloses a process for preparing butyl rubber with a broad molecular weight distribution. The process uses a mixed catalyst system comprising a mixture of a major amount of internalized dialkylaluminum, a minor amount of monoalkylaluminum dihalide and a minor amount of aluminoxane to provide a broad distribution butyl rubber having a molecular weight distribution of greater than 3.5 and up to 7.6. CN 101353403B discloses a preparation method of star-shaped hyperbranched polyisobutene or butyl rubber, which adopts a polystyrene/isoprene segmented copolymer with a silicon-chlorine group at the end or a polystyrene/butadiene segmented copolymer with a silicon-chlorine group at the end as a grafting agent for initiating cationic polymerization, and directly participates in the cationic polymerization in a cationic polymerization system with a chloromethane/cyclohexane v ratio of 20-80/80-20 mixed solvent under the temperature condition of 0-minus 100 ℃, and prepares the star-shaped hyperbranched polyisobutene or butyl rubber product by initiating the cationic polymerization of the silicon-chlorine group and participating in the grafting reaction through an unsaturated chain. CN01817708.5 provides a method of adding a multiolefin crosslinking agent such as divinylbenzene and a chain transfer agent (such as 2,4, 1-trimethyl-1-pentene) to a mixture of isoolefin monomers and diolefin monomers by which star-shaped hyperbranched polymers are prepared. CN88108392.5 discloses the use of a hydrochloride polystyrene-isoprene copolymer as poly (styrene-isoprene) The functional group initiator or the polystyrene-butadiene or polystyrene-isoprene is used as a grafting agent to prepare the star-shaped grafted butyl rubber with a comb-shaped structure. 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. US3780002 proposes a complex initiator comprising a metal halide of group II or III of the periodic Table and a tetrahalide of a metal of group IV of the periodic Table, e.g. AlCl 3 With TiC1 4 For combined use, or by combining A1C1 3 With SnC1 4 The composite use makes each initiator independently initiate cationic polymerization, and the butyl rubber with the molecular weight distribution index Mw/Mn above 5.0 is synthesized under the conventional Ding Mou rubber polymerization condition.
CN101353386a discloses an initiating system for star-shaped hyperbranched polyisobutene or butyl rubber cationic polymerization, which consists of an initiating-grafting agent, a co-initiating agent and a nucleophilic reagent, and is used for initiating vinyl monomers to carry out homo-, block-and star-polymerization and graft copolymerization, and the obtained polymer shows obvious bimodal distribution. Puskas (Catalysts for manufacture of IIR with bimodal molecular weight distribution: U.S. Pat. No. 5,94538,1993-3-16.) uses trimesic acid as raw material to synthesize the initiator tricumyl alcohol with three-arm structure, and then uses the tricumyl alcohol/aluminum trichloride initiation system to initiate isobutene and isoprene copolymerization in inert organic solvent at-120 deg.C to-50 deg.C, thus synthesizing the star-shaped hyperbranched butyl rubber with bimodal molecular weight distribution. Wieland et al (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.) synthesized a macroinitiator P (MMA-b-St-co-CMS) containing a ternary of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-stilbene (DPE) by radical polymerization, and initiated cationic polymerization of isobutylene and isoprene with the macroinitiator to successfully prepare a multi-arm star butyl rubber. Wu Yibo et al (Davang S H, et al, skid resistant coatings for aircraft carrier decks [ J ]. Coat technology, 1980, 52 (671): 65-69.) Poly (isoprene-styrene) block copolymers were prepared by living anionic polymerization as grafting agents and star-shaped hyperbranched butyl rubber exhibiting a distinct bimodal appearance was prepared by living carbon cationic polymerization in the initiation system of 2-chloro-2, 4-trimethylpentane/titanium tetrachloride/proton scavenger.
Disclosure of Invention
The invention aims to provide a preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber. The invention firstly takes alkyl lithium as an initiator, hydrocarbon as a solvent, a reaction monomer is composed of styrene and butadiene, and the star-shaped copolymer with a binary tetrahetero-arm structure is prepared by adopting variable-temperature polymerization and coupling with a novel long-chain tetrahalide coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane. Finally, under the catalysis system of Lewis acid and protonic acid, the binary four-hetero-arm star-shaped copolymer is used as a grafting agent to carry out cationic polymerization with isobutene and isoprene to prepare the ultra-wide molecular weight distribution and hyperbranched butyl rubber. The method solves the problems of easy extrusion swelling and slow stress relaxation rate of the butyl rubber in the processing process, so that the ultra-wide molecular weight distribution and the hyperbranched butyl rubber can obtain excellent processability with fast stress relaxation rate and small extrusion swelling effect in the processing process, meanwhile, the butyl rubber is ensured to have enough green rubber strength and good air tightness, and the balance of physical and mechanical properties and processability is realized.
The "%" of the invention refers to mass percent.
The preparation of the ultra-wide molecular weight distribution and hyperbranched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) Preparation of grafting agent:
a, preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, introducing inert gas to replace for 2-4 times, sequentially adding 100-200% of deionized water, 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and 1-5% of catalyst into the polymerization kettle, heating to 50-80 ℃, reacting for 1-3 hours, adding 20-40% of NaOH aqueous solution with the mass concentration of 10-20% to terminate the reaction, and finally adding 200-300% of chloromethane to extract, separate, wash and dry to obtain the coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane (yield is 85-95%).
b, preparation of grafting agent: based on hundred percent of the total mass of reaction monomers, introducing inert gas into a 15L stainless steel polymerization kettle A with a jacket to replace a system for 3-5 times, sequentially adding 100-200% of solvent, 10-20% of styrene, 5-10% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator into the polymerization kettle, reacting for variable-temperature polymerization, gradually increasing the temperature from 50 ℃ to 80 ℃ within 60-90 min, continuously gradually increasing the temperature to form a SBR-chain segment with wide vinyl content distribution, wherein the conversion rate of the styrene and the 1, 3-butadiene monomer reaches 100%, and finally increasing the temperature to 80-90 ℃, and adding a coupling agent for coupling reaction for 60-90 min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing inert gas to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 10-20% of styrene, 5-10% of 1, 3-butadiene and 0.05-0.3% of structure regulator, heating to 50-60 ℃, adding an initiator, and reacting for 60-80 min to form the SBR 1 Segment, then sequentially adding 10-20% of 1, 3-butadiene and 0.05-0.2% of structure regulator into a polymerization kettle B, and reacting for 30-50 min to form the BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60-90 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing inert gas to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 10-20% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator into the polymerization kettle C, reacting for variable-temperature polymerization, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50-70 min, and continuously gradually changing the temperature rise to form BR with wide molecular weight distribution 1 A segment; then adding 5-10% of styrene and 0.05-0.2% of structure regulator into the polymerization kettle C in turn, reacting for 40-60 min to form-BR 1 PS-segment, to be polymerized after complete conversion of the monomersAdding the materials in the mixing kettle C into the polymerization kettle A, and carrying out coupling reaction for 60-90 min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing inert gas to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 5-10% of styrene, 0.05-0.2% of structure regulator and initiator into the polymerization kettle D, reacting for variable-temperature polymerization, gradually increasing the temperature from 40 ℃ to 80 ℃ within 60-90 min, and continuously gradually changing the temperature rise to form the PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 60-90 min; finally adding 3-5% of 1, 3-butadiene into a polymerization kettle A for end capping, reacting for 20-40 min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the binary four-hetero-arm star-shaped copolymer ([ -B-SBR ]] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n )。
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in hundred percent of the total mass of reaction monomers, introducing inert gas into a 4L stainless steel reaction kettle with a jacket for replacement for 3-5 times, adding 100-200 percent of diluent and solvent into the reaction kettle, and mixing the diluent and the solvent according to the ratio of V: v is 70-30: 30-70 of mixed solvent and 1-10% of grafting agent, stirring and dissolving for 10-30 min until the grafting agent is completely dissolved; then cooling to minus 75 ℃ to minus 85 ℃, adding 100 to 200 percent of diluent, 88 to 92 percent of isobutene and 1 to 4 percent of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to minus 100 ℃ to minus 90 ℃, then mixing and aging 30 to 50 percent of diluent and 0.05 to 3.0 percent of co-initiator for 20 to 30 minutes at minus 85 ℃ to minus 95 ℃, adding the mixture into the polymerization system together, stirring and reacting for 3.0 to 5.0 hours, discharging, condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product.
The grafting agent is a binary four-hetero-arm star-type copolymer synthesized by styrene and butadiene, and the structural general formula of the grafting agent is shown as formula I:
wherein Y is 3, 3-diethyl pentane; SBR is a styrene, butadiene random block copolymer with a broad vinyl content distribution; SBR (styrene butadiene rubber) 1 Is a styrene, butadiene random block copolymer; BR is a broad molecular weight distribution 1, 3-butadiene homopolymer; BR (BR) 1 1, 3-butadiene homopolymer with wide molecular weight distribution; PS is a styrene homopolymer; PS (PS) 1 Is a styrene homopolymer with wide molecular weight distribution; b is a capped butadiene, n=1 to 4; the content of 1, 3-butadiene in the binary four-arm star polymer is 25-40%, and the content of styrene is 60-75%; the binary four-hetero-arm star-type copolymer has a number average molecular weight (Mn) of 30000-70000 and a molecular weight distribution (Mw/Mn) of 14.5-18.2.
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 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 initiator is a hydrocarbyl mono-lithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or 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 amount of the coupling agent is determined according to the amount of the initiator, and the star polymer with the heteroarm structure is finally formed through gradual polymerization of excessive coupling agent, wherein the molar ratio of the amount of the coupling agent to the total organic lithium is 2.0-5.0.
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 sesquioxide, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride, preferably aluminum sesquioxide. The protonic acid is selected from HCI, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCI. Wherein the total addition amount of the co-initiator is 0.05-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01:1-0.1:1.
The polymerization reactions of the present invention are all carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution processes are both carried out in a hydrocarbon solvent, which is a hydrocarbon solvent, including straight chain alkanes, aromatic hydrocarbons and cycloalkanes, selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention firstly aims at 3, 9-dioxy [5.5 ]]The spirocycle undecane is halogenated to synthesize a novel coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, then styrene and butadiene reaction monomers are subjected to variable temperature polymerization to prepare four chain segments with different vinyl content distribution and wide molecular weight distribution, and binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ]] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n (see FIG. 1). The binary four-hetero-arm star-shaped copolymer is used as a grafting agent to prepare ultra-wide molecular weight distribution and hyperbranched butyl rubber (shown in figure 2) through cationic polymerization with isobutene and isoprene under a catalytic system compounded by alkyl aluminum halide and protonic acid.
The invention combines the long chain segments with four different microstructures on one macromolecular chain to form a four-hetero-arm star-shaped structure by a four-kettle feeding method and variable-temperature polymerization, thus the performances of different chain segments and the four-hetero-arm star-shaped structure can be organically combined together and cooperatively act, and BR is utilized 1 Segment and PS 1 The wide molecular weight distribution of the chain segments, the wide vinyl distribution in the SBR chain segments and the difference of reactivity ratio and steric hindrance effect of each chain segment in the four-hybrid-arm structure lead to the increase of disorder of the molecular chain segments and the deterioration of regularity of the molecular chains in the grafting polymerization process of the butyl rubber, the increase of flexibility of the chain segments and the obvious widening of the molecular weight distribution, so that the butyl rubber can obtain good viscoelastic performance and has rapid stress relaxation rate; meanwhile, the PS-segment and the SBR-segment are utilized to contain a large amount of benzene rings, so that the decrease of strength and air tightness caused by the widening of the molecular weight distribution of the butyl rubber is avoided, and the high strength and good air tightness of the butyl rubber are ensured.
The invention synthesizes the novel coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane to ensure that four kinds of [ -B-SBR ]] n 、[-BR 1 -PS-B-] n 、[-BR-SBR 1 -B-] n And [ -PS 1 -B-] n The long chain segment is coupled to design a binary four-hybrid-arm star-shaped structure, so that the problem of contradiction between poor processability and excellent air tightness of butyl rubber is solved, and the processability and physical and mechanical properties of the butyl rubber are optimally balanced. The preparation method provided by the invention has the characteristics of controllable process strips, stable product performance, suitability for industrial production and the like.
Drawings
FIG. 1 is [ -B-SBR ]] n [-BR 1 -PS-B] n Y[BR-SBR 1 -B-] n [-PS 1 -B-] n And synthesizing a roadmap.
FIG. 2 is 1 # Sample of butyl rubber IIR301 with 2 # Comparison of GPC spectra of the samples of example 1.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions. The raw materials used in the examples are all industrial polymer grade, and are used after purification without other special requirements.
(1) The raw material sources are as follows:
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
Sesquiethyl aluminum chloride with purity of 98% of carbofuran technology Co., ltd
Other reagents are commercial industrial products
(2) The analytical test method comprises the following steps:
determination of molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min -1 。
Determination of mooney viscosity and stress relaxation: the measurement was carried out by using a Mooney viscometer model GT-7080-S2 manufactured by Taiwan high-speed rail company. The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.
Measurement of air tightness: an automatic air tightness tester is adopted to measure the air permeability number according to ISO 2782:1995, and 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.
Characterization of the degree of branching: degree of branching = polymer molecular weight after branching/polymer molecular weight before branching.
Example 1
(1) Preparation of grafting agent:
a, preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, argon is introduced for replacement for 3 times, 600g of deionized water and 58g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle]Spirocyclic undecane, 320g liquid bromine, 18g HCl-CH 3 OH solution (molar concentration of HCl: 0.7 mol/L), heating to 70 ℃, reacting for 3.0hr, adding 300g of 15% NaOH aqueous solution to terminate the reaction, finally adding 800g of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane (yield 93%).
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 1610g of cyclohexane, 160g of styrene, 80g of 1, 3-butadiene and 1.0g of THF into the polymerization kettle, heating to 50 ℃, adding 25.1 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 60 minutes, heating at a speed of 0.5 ℃/min, reacting for 60 minutes to form a SBR-chain segment with wide vinyl content distribution, then heating to 82 ℃, adding 220mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and performing coupling reaction for 60 minutes; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1630g cyclohexane, 165g styrene, 60g1, 3-butadiene and 1.0g THF, heating to 50 ℃, adding 30.1 mmol 1 n-butyllithium to start reaction, and reacting for 60min to form the-SBR 1 Segment, next, 160g of 1, 3-butadiene and 1.0g of THF are sequentially added into a polymerization kettle B to react for 30min to form the BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60min; at the same time at 15L of stainless steelIn a mixing kettle C, introducing argon to replace a system for 3 times, sequentially adding 1900g of cyclohexane, 155g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle C, heating to 40 ℃, adding 30.1 mmol of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting at a heating speed of 0.6 ℃/min for 50min to form BR with wide molecular weight distribution 1 A segment; then 160g of styrene and 1.0g of THF are added into the polymerization kettle C in sequence to react for 40min to form-BR 1 PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1550g of cyclohexane, 60g of styrene, 1.0g of THF into the polymerization kettle D, heating to 40 ℃, adding 15.5 mmol 1 of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 80 ℃ within 60min, and reacting at a heating speed of 0.7 ℃/min for 60min to form the PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 60min; finally, 46g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 20min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ]] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 30650, mw/Mn 14.9).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 650g of methyl chloride and 320g of cyclohexane into the polymerization kettle, [ -B-SBR ]] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n 7.5g of grafting agent, stirring and dissolving for 10min until the grafting agent is completely dissolved; then cooling to-75deg.C, sequentially adding methyl chloride 510g, isobutene 435g, isoprene 6g, stirring and mixing until the polymerization system temperature is reduced to-90deg.C, mixing methyl chloride 155g, aluminum sesquichloride 4.13g and HCl 0.082g at-85deg.C, aging for 20min, and adding into polymerization systemStirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 2
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 1720g of cyclohexane, 180g of styrene, 90g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle, heating to 50 ℃, adding 25.1 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 70min, heating to a speed of 0.5 ℃/min, reacting for 70min to form a SBR-chain segment with wide vinyl content distribution, then heating to 85 ℃, adding 240 mmol of 1, 5-dibromo-3, 3-bis (2-bromoethyl) pentane, and performing coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 1740g cyclohexane, 185g styrene, 85g1, 3-butadiene and 1.1g THF, heating to 50 ℃, adding 30.1 mmol 1 n-butyllithium to start reaction, and reacting for 65min to form the-SBR 1 Segment, then adding 195g of 1, 3-butadiene and 1.0g of THF into a polymerization kettle B in sequence, and reacting for 35min to form the BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 180g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle C, heating to 40 ℃, adding 30.1 mmol of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting at a heating speed of 0.6 ℃/min for 50min to form BR with wide molecular weight distribution 1 A segment; then 185g of styrene and 1.3g of THF are added into the polymerization kettle C in turn to react for 45min to form-BR 1 PS-chain segment, adding the material in the polymerization kettle C into the polymerization kettle A after the monomer is completely converted, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1650g of cyclohexane, 90g of styrene and 1.2g of THF are sequentially added into the polymerization kettle D, the temperature is raised to 40 ℃, and 17.5 mmol 1 of n-butyllithium is added for openingStarting reaction, gradually increasing the temperature from 40 ℃ to 80 ℃ within 60min, and reacting for 60min at the heating speed of 0.7 ℃/min to form the PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 70min; finally, 50g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 25min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ]] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 42650, mw/Mn 15.6).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 620g of methyl chloride and 350g of cyclohexane into the polymerization kettle, [ -B-SBR ] ]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent 15g, stirring and dissolving for 15min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 530g of methyl chloride, 447g of isobutene and 8g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 165g of methyl chloride, 4.83g of aluminum sesquichloride and 0.095g of HCl at-87 ℃ and aging for 20min, then adding the mixture into the polymerization system together and stirring and reacting for 3.5hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 3
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1920g of cyclohexane, 200g of styrene, 100g of 1, 3-butadiene and 1.3g of THF into the polymerization kettle, heating to 50 ℃, adding 27.5mm of 1-n-butyllithium to start the reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 80 minutes, and reacting for 80 minutes at a heating speed of 0.4 ℃/min to form the wide vinyl containingThe distributed-SBR-chain segment is heated to 85 ℃, 270mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added, and the coupling reaction is carried out for 75min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1900g of cyclohexane, 195g of styrene, 92g of 1, 3-butadiene and 1.3g of THF, heating to 55 ℃, adding 31.5 mmol 1 of n-butyllithium to start reaction, and reacting for 70min to form the-SBR 1 Segment, then 210g of 1, 3-butadiene and 1.2g of THF are added into a polymerization kettle B in sequence to react for 40min to form the BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 75min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 2000g of cyclohexane, 195g of 1, 3-butadiene and 1.4g of THF into the polymerization kettle C, heating to 40 ℃, adding 30.1 mmol of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 70 ℃ within 60min, and reacting at a heating speed of 0.5 ℃/min for 60min to form BR with wide molecular weight distribution 1 A segment; then adding 205g of styrene and 1.5g of THF into a polymerization kettle C in sequence to react for 50min to form-BR 1 PS-chain segment, adding the material in the polymerization kettle C into the polymerization kettle A after the monomer is completely converted, and carrying out coupling reaction for 75min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1860g cyclohexane, 105g styrene and 1.4g THF into the polymerization kettle D, heating to 40 ℃, adding 19.7mmo1 n-butyllithium to start the reaction, gradually heating from 40 ℃ to 80 ℃ within 80min, and reacting for 80min at a heating rate of 0.5 ℃/min to form the PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 75min; finally, 60g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 30min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ]] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 51650, mw/Mn 16.5).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: head partFirstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 590g of methyl chloride and 390g of cyclohexane into the polymerization kettle, [ -B-SBR ]]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent 22g, stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-80 ℃, then adding 540g of methyl chloride, 453g of isobutene and 11g of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 175g of methyl chloride, 5.23g of aluminum sesquichloride and 0.105g of HCl at-87 ℃ and aging for 25min, then adding the mixture into the polymerization system together and stirring and reacting for 4.0hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 4
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 2120g of cyclohexane, 230g of styrene, 110g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle, heating to 50 ℃, adding 29.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 80 minutes, heating to a speed of 0.4 ℃/min, reacting for 80 minutes to form a SBR-chain segment with wide vinyl content distribution, then heating to 85 ℃, adding 310mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and performing coupling reaction for 80 minutes; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 2100g of cyclohexane, 215g of styrene, 106g of 1, 3-butadiene and 1.5g of THF, heating to 60 ℃, adding 32.5mm 1 of n-butyllithium to start reaction, and reacting for 75min to form the-SBR 1 Chain segment, then 225g of 1, 3-butadiene and 1.4g of THF are added into a polymerization kettle B in sequence to react for 45min to form the-BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 80min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 3 times, 2200g of cyclohexane, 205g of 1, 3-butadiene and 1.6g of THF are sequentially added into the polymerization kettle C, and the temperature is raised to 40 DEG C 30.1mm 1 n-butyllithium is added to start the reaction, the temperature is gradually increased from 40 ℃ to 70 ℃ within 60min, the heating speed is 0.5 ℃/min, and the reaction is carried out for 60min, thus forming BR with wide molecular weight distribution 1 A segment; then 224g of styrene and 1.7g of THF are added into the polymerization kettle C in sequence to react for 55min to form-BR 1 PS-chain segment, adding the material in the polymerization kettle C into the polymerization kettle A after the monomer is completely converted, and carrying out coupling reaction for 80min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 2060g of cyclohexane, 119g of styrene and 1.6g of THF into the polymerization kettle D, heating to 40 ℃, adding 19.7mmo1 of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 80 ℃ within 80min, and reacting for 80min at a heating rate of 0.5 ℃/min to form the PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 80min; finally adding 65g of 1, 3-butadiene into a polymerization kettle A for end capping, reacting for 35min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, condensing the glue solution by wet method, and drying to obtain binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ]] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 60230, mw/Mn 17.3).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 480g of methyl chloride and 410g of cyclohexane into the polymerization kettle, [ -B-SBR ]]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent 30g, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-83 ℃, sequentially adding 540g of methyl chloride, 462g of isobutene and 13g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 186g of methyl chloride, 5.89g of aluminum sesquichloride and 0.235g of HCl at-90 ℃ and aging for 25min, then adding the mixture into the polymerization system together and stirring and reacting for 4.5hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 5
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 2350g of cyclohexane, 250g of styrene, 130g of 1, 3-butadiene and 1.7g of THF into the polymerization kettle, heating to 50 ℃, adding 29.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 90 minutes, heating at a speed of 0.3 ℃/min, reacting for 90 minutes to form a SBR-chain segment with wide vinyl content distribution, then heating to 90 ℃, adding 370 mmol of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and performing coupling reaction for 90 minutes; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 2400g of cyclohexane, 245g of styrene, 130g of 1, 3-butadiene and 1.9g of THF, heating to 60 ℃, adding 35.6mmo1 of n-butyllithium to start reaction, and reacting for 80min to form the-SBR 1 Segment, 250g of 1, 3-butadiene and 1.7g of THF are sequentially added into a polymerization kettle B to react for 50min to form the BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 90min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 3 times, sequentially adding 2400g of cyclohexane, 236g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle C, heating to 40 ℃, adding 30.1 mmol of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 70 ℃ within 70min, and reacting at a heating speed of 0.5 ℃/min for 70min to form BR with wide molecular weight distribution 1 A segment; then 260g of styrene and 1.9g of THF are added into the polymerization kettle C in sequence to react for 60min to form-BR 1 PS-chain segment, adding the material in the polymerization kettle C into the polymerization kettle A after the monomer is completely converted, and carrying out coupling reaction for 90min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace a system for 3 times, sequentially adding 2230g of cyclohexane, 135g of styrene and 1.8g of THF into the polymerization kettle D, heating to 40 ℃, adding 21.5mm of n-butyllithium to start reaction, gradually heating from 40 ℃ to 80 ℃ within 90min, and reacting for 90min at a heating rate of 0.5 ℃/min to form PS with wide molecular weight distribution 1 -a segment; after complete conversion of the monomersAdding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 90min; finally, 70g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 40min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ]] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 68360, mw/Mn 18.1).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 430g of methyl chloride and 550g of cyclohexane into the polymerization kettle, [ -B-SBR ]]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]45g of grafting agent, stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, adding 540g of methyl chloride, 475g of isobutene and 16g of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methyl chloride, 6.23g of aluminum sesquichloride and 0.365g of HCl at-95 ℃ and aging for 30min, then adding the mixture into the polymerization system together and stirring and reacting for 5.0hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 1
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: other conditions were the same as in example 1 except that: in the polymerization kettle A, the SBR-chain segment does not adopt variable temperature polymerization, and reacts at the constant temperature of 50 ℃, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1610g of cyclohexane, 160g of styrene, 80g of 1, 3-butadiene and 1.0g of THF into the polymerization kettle, heating to 50 ℃, adding 25.1mm 1 of n-butyllithium to start reaction, and reacting for 60min to form the-SBR 2 Segment, followed by heating to 82℃and adding 220mmo1, 5-dibromo-3, 3-bis (2-bromoethyl) pentane for coupling reactionThe time should be 60min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1630g cyclohexane, 165g styrene, 60g 1, 3-butadiene and 1.0g THF, heating to 50 ℃, adding 30.1 mmol 1 n-butyllithium to start reaction, and reacting for 60min to form the-SBR 1 Segment, then adding 160g of 1, 3-butadiene and 1.0g of THF into a polymerization kettle B in sequence, and reacting for 30min to form the BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1900g of cyclohexane, 155g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle C, heating to 40 ℃, adding 30.1 mmol of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting at a heating speed of 0.6 ℃/min for 50min to form BR with wide molecular weight distribution 1 A segment; then 160g of styrene and 1.0g of THF are added into the polymerization kettle C in sequence to react for 40min to form-BR 1 PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1550g of cyclohexane, 60g of styrene and 1.0g of THF into the polymerization kettle D, heating to 40 ℃, adding 15.5 mmol 1 of n-butyllithium to start reaction, gradually heating from 40 ℃ to 80 ℃ within 60min, and reacting at a heating speed of 0.7 ℃/min for 60min to form the PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 60min; finally, 46g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 20min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is subjected to wet condensation and drying to prepare the binary four-hetero-arm star-shaped copolymer [ -B-SBR 2 -] n [-BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 29850, mw/Mn 8.5).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 1 except that: during the synthesis process, no [ -B-SBR ] ]n[-BR1-PS-B-]n Y[-BR-SBR1-B-]n[-PS1-B-]n grafting agent, instead [ -B-SBR 2- ]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 650g of methyl chloride and 320g of cyclohexane into the polymerization kettle, and adding [ (-B-SBR) 2- ]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent 7.5g, stirring and dissolving for 10min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 510g of methyl chloride, 435g of isobutene and 6g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 155g of methyl chloride, 4.13g of aluminum sesquichloride and 0.082g of HCl at-85 ℃, aging for 20min, adding the mixture into the polymerization system together, stirring and reacting for 3.0hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 2.
b, preparation of grafting agent: other conditions were the same as in example 2 except that: BR in polymerizer C 1 The chain segment does not adopt variable temperature polymerization, and reacts at the constant temperature of 40 ℃, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 1720g of cyclohexane, 180g of styrene, 90g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle, heating to 50 ℃, adding 25.1 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 70min, heating to a speed of 0.5 ℃/min, reacting for 70min to form a SBR-chain segment with wide vinyl content distribution, then heating to 85 ℃, adding 240 mmol of 1, 5-dibromo-3, 3-bis (2-bromoethyl) pentane, and performing coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 1740g cyclohexane, 185g styrene, 85g 1, 3-butadiene and 1.1g THF, heating to 50 ℃, adding 30.1 mmol 1 n-butyllithium to start reaction, and reacting for 65min to form the-SBR 1 Segment, and then sequentially adding the segments into a polymerization kettle B195g of 1, 3-butadiene, 1.0g of THF, reacted for 35min to form-BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 180g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle C, heating to 40 ℃, adding 30.1 mmol of n-butyllithium to start the reaction, and reacting for 50min to form BR with wide molecular weight distribution 2 A segment; then 185g of styrene and 1.3g of THF are added into the polymerization kettle C in turn to react for 45min to form-BR 2 PS-chain segment, adding the material in the polymerization kettle C into the polymerization kettle A after the monomer is completely converted, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1650g of cyclohexane, 90g of styrene and 1.2g of THF into the polymerization kettle D, heating to 40 ℃, adding 17.5 mmol 1 of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 80 ℃ within 60min, and reacting at a heating speed of 0.7 ℃/min for 60min to form the PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 70min; finally, 50g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 25min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ] ] n [-BR 2 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 40350, mw/Mn 7.6).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 2 except that: during the synthesis process, no [ -B-SBR ]]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent, instead [ -B-SBR ]] n [-BR 2 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 620g of methyl chloride and 350g of cyclohexane into the polymerization kettle, [ -B-SBR ]] n [-BR 2 -PS-B-] n Y[-BR-SBR 1 -B-] n [-PS 1 -B-] n 15g of grafting agent, stirring and dissolving for 15min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 530g of methyl chloride, 447g of isobutene and 8g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 165g of methyl chloride, 4.83g of aluminum sesquichloride and 0.095g of HCl at-87 ℃ and aging for 20min, then adding the mixture into the polymerization system together and stirring and reacting for 3.5hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched 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 grafting agent:
a, preparation of a coupling agent: same as in example 3.
b, preparation of grafting agent: other conditions were the same as in example 3 except that: the three-kettle polymerization is adopted, namely the materials in the polymerization kettle D are added into the polymerization kettle C for reaction, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 1920g of cyclohexane, 200g of styrene, 100g of 1, 3-butadiene and 1.3g of THF into the polymerization kettle, heating to 50 ℃, adding 27.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 80 minutes, heating at a speed of 0.4 ℃/min, reacting for 80 minutes to form a SBR-chain segment with wide vinyl content distribution, then heating to 85 ℃, adding 270mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and performing coupling reaction for 75 minutes; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1900g of cyclohexane, 195g of styrene, 92g of 1, 3-butadiene and 1.3g of THF, heating to 55 ℃, adding 31.5 mmol 1 of n-butyllithium to start reaction, and reacting for 70min to form the-SBR 1 Segment, then 210g of 1, 3-butadiene and 1.2g of THF are added into a polymerization kettle B in sequence to react for 40min to form the BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 75min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, and sequentially adding 2000g of cyclohexane and 195g of 1, 3-butyl into the polymerization kettle CDiene and 1.4g THF are heated to 40 ℃, 30.1 mmol of n-butyllithium is added to start the reaction, the temperature is gradually increased from 40 ℃ to 70 ℃ within 60min, the heating speed is 0.5 ℃/min, the reaction is carried out for 60min, and BR with wide molecular weight distribution is formed 1 A segment; then adding 205g of styrene and 1.5g of THF into a polymerization kettle C in sequence to react for 50min to form-BR 1 PS-chain segment, then sequentially adding 1860g cyclohexane, 105g styrene and 1.4g THF into a polymerization kettle C, heating to 40 ℃, adding 19.7mmo1 n-butyllithium to start reaction, gradually heating from 40 ℃ to 80 ℃ within 80min, and reacting for 80min at a heating speed of 0.5 ℃/min to form PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 75min; finally, 60g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 30min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ] ] n [-PS 1 -BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n Grafting agent (Mn 49620, mw/Mn 11.2).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 3 except that: during the synthesis process, no [ -B-SBR ]]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent, instead [ -B-SBR ]] n [-PS 1 -BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n Grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 590g of chloromethane and 390g of cyclohexane are added into the polymerization kettle, [ -B-SBR ]] n [-PS 1 -BR 1 -PS-B-] n Y[-BR-SBR 1 -B-] n 22g of grafting agent, stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-80 ℃, adding 540g of methyl chloride, 453g of isobutene and 11g of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 175g of methyl chloride, 5.23g of aluminum sesquichloride and 0.105g of HCl at-87 ℃ and aging for 25minAnd then adding the materials into a polymerization system together for stirring reaction for 4.0hr, discharging, condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched 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 grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: other conditions were the same as in example 4 except that: the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added in the synthesis process, but the conventional coupling agent silicon tetrachloride is added, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 2120g of cyclohexane, 230g of styrene, 110g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle, heating to 50 ℃, adding 29.5 mmol of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 80 minutes, heating to a speed of 0.4 ℃/min, reacting for 80 minutes to form a SBR-chain segment with wide vinyl content distribution, then heating to 85 ℃, adding 310mmo of 1 silicon tetrachloride, and performing coupling reaction for 80 minutes; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 2100g of cyclohexane, 215g of styrene, 106g of 1, 3-butadiene and 1.5g of THF, heating to 60 ℃, adding 32.5 mmol 1 of n-butyllithium to start reaction, and reacting for 75min to form the-SBR 1 Chain segment, then 225g of 1, 3-butadiene and 1.4g of THF are sequentially added into a polymerization kettle B to react for 45min to form the-BR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 80min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 2200g of cyclohexane, 205g of 1, 3-butadiene and 1.6g of THF into the polymerization kettle C, heating to 40 ℃, adding 30.1 mmol of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 70 ℃ within 60min, and reacting at a heating speed of 0.5 ℃/min for 60min to form BR with wide molecular weight distribution 1 A segment; then 224g of styrene and 1.7g of THF are sequentially added into a polymerization kettle C to react for 55min to form-BR 1 PS-chain segment, adding the material in the polymerization kettle C into the polymerization kettle A after the monomer is completely converted, and carrying out coupling reaction for 80min; at the same timeIn a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 2060g cyclohexane, 119g styrene and 1.6g THF into the polymerization kettle D, heating to 40 ℃, adding 19.7mmo1 n-butyllithium to start reaction, gradually heating from 40 ℃ to 80 ℃ within 80min, and reacting for 80min at a heating rate of 0.5 ℃/min to form the PS with wide molecular weight distribution 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 80min; finally, 65g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 35min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the binary four-hetero-arm star-shaped copolymer [ -B-SBR [ -A ]] n [-BR 1 -PS-B-] n Y 1 [-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 58620, mw/Mn 8.1).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 4 except that: during the synthesis process, no [ -B-SBR ]]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent, instead [ -B-SBR ]]n[-BR 1 -PS-B-]n Y 1 [-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 480g of methyl chloride and 410g of cyclohexane into the polymerization kettle, [ -B-SBR ]]n[-BR 1 -PS-B-]n Y 1 [-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent 30g, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-83 ℃, sequentially adding 540g of methyl chloride, 462g of isobutene and 13g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 186g of methyl chloride, 5.89g of aluminum sesquichloride and 0.235g of HCl at-90 ℃ and aging for 25min, then adding the mixture into the polymerization system together and stirring and reacting for 4.5hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched 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 grafting agent: other conditions were the same as in example 5 except that: the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added in the synthesis process, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 2350g of cyclohexane, 250g of styrene, 130g of 1, 3-butadiene and 1.7g of THF into the polymerization kettle, heating to 50 ℃, adding 29.5 mmol 1 of n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 90min, heating at a speed of 0.3 ℃/min, reacting for 90min to form a SBR-chain segment with wide vinyl content distribution, simultaneously in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 2400g of cyclohexane, 245g of styrene, 130g of 1, 3-butadiene and 1.9g of THF, heating to 60 ℃, adding 35.6 mmol 1 of n-butyllithium to start reaction, and reacting for 80min to form the SBR 1 Segment, 250g of 1, 3-butadiene and 1.7g of THF are sequentially added into a polymerization kettle B to react for 50min to form the BR-SBR 1 -a segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and reacting for 90min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace a system for 3 times, sequentially adding 2400g of cyclohexane, 236g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle C, heating to 40 ℃, adding 30.1 mmol of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 70 ℃ within 70min, and reacting at a heating speed of 0.5 ℃/min for 70min to form BR with wide molecular weight distribution 1 A segment; then 260g of styrene and 1.9g of THF are added into the polymerization kettle C in sequence to react for 60min to form-BR 1 PS-chain segment, after the monomer is completely converted, adding the material in the polymerization kettle C into the polymerization kettle A, and reacting for 90min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace a system for 3 times, sequentially adding 2230g of cyclohexane, 135g of styrene and 1.8g of THF into the polymerization kettle D, heating to 40 ℃, adding 21.5mm of n-butyllithium to start reaction, gradually heating from 40 ℃ to 80 ℃ within 90min, and reacting for 90min at a heating rate of 0.5 ℃/min to form PS with wide molecular weight distribution 1 -a segment; after the monomers are completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and reacting for 90min; finally, 70g of 1, 3-butadiene is added into the polymerization kettle A for end capping, and the reaction is completed after 40min until no free monomer existsThen the coupled reaction mixture is treated by water, the glue solution is subjected to wet condensation and drying, and the binary four-hetero-arm star-shaped copolymer [ -B-SBR ]] n [-BR 1 -PS-B-] n [-BR-SBR 1 -B-] n [-PS 1 -B-] n Grafting agent (Mn 59120, mw/Mn 5.3).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 5 except that: during the synthesis process, no [ -B-SBR ] ]n[-BR 1 -PS-B-]n Y[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent, instead [ -B-SBR ]]n[-BR 1 -PS-B-]n[-BR-SBR 1 -B-]n[-PS 1 -B-]n grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 430g of methyl chloride and 550g of cyclohexane into the polymerization kettle, [ -B-SBR ]]n[-BR 1 -PS-B-]n[-BR-SBR 1 -B-]n[-PS 1 -B-]45g of grafting agent, stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, adding 540g of methyl chloride, 475g of isobutene and 16g of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methyl chloride, 6.23g of aluminum sesquichloride and 0.365g of HCl at-95 ℃ and aging for 30min, then adding the mixture into the polymerization system together and stirring and reacting for 5.0hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 ultra-broad molecular weight distribution, hyperbranched butyl rubber Properties
As can be seen from table 1: the ultra-wide molecular weight distribution and ultra-wide molecular weight distribution of the ultra-wide molecular weight distribution butyl rubber disclosed by the invention has the advantages of small Mooney relaxation area, good air tightness and high tensile strength, and shows that the ultra-wide molecular weight distribution and ultra-wide molecular weight distribution butyl rubber has good processability while maintaining excellent physical and mechanical properties.
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.
Claims (13)
1. The preparation method of the ultra-wide molecular weight distribution hyperbranched butyl rubber is characterized by comprising the following steps of:
(1) Preparation of grafting agent:
a, preparation of a coupling agent: firstly, adding 100% -200% of deionized water, 3, 9-dioxygen [5.5] spiro undecane, a halogenating agent and 1% -5% of a catalyst into a polymerization kettle in turn under the inert gas atmosphere, heating to 50-80 ℃, reacting for 1-3 hr, adding 20% -40% of 10% -20% NaOH aqueous solution with the mass concentration to terminate the reaction, and finally adding 200% -300% of chloromethane to extract, separate, wash and dry to obtain a coupling agent;
b, preparation of grafting agent: sequentially adding 100-200% of solvent, 10-20% of styrene, 5-10% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator into a polymerization kettle A in an inert gas atmosphere, wherein the reaction is variable-temperature polymerization, gradually increasing the temperature from 50 ℃ to 80 ℃ within 60-90 min, then increasing the temperature to 80-90 ℃ and adding a coupling agent for coupling reaction for 60-90 min; simultaneously, in a polymerization kettle B, under the atmosphere of inert gas, sequentially adding 100% -200% of solvent, 10% -20% of styrene, 5% -10% of 1, 3-butadiene and 0.05% -0.3% of structure regulator, heating to 50-60 ℃, adding an initiator, reacting for 60-80 min, sequentially adding 10% -20% of 1, 3-butadiene and 0.05% -0.2% of structure regulator into the polymerization kettle B, and reacting for 30-50 min; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60-90 min; simultaneously, in a polymerization kettle C, under the atmosphere of inert gas, sequentially adding 100% -200% of solvent, 10% -20% of 1, 3-butadiene, 0.05% -0.3% of structure regulator and initiator into the polymerization kettle C, wherein the reaction is temperature-variable polymerization, and the temperature is gradually increased from 40 ℃ to 70 ℃ within 50-70 min; sequentially adding 5-10% of styrene and 0.05-0.2% of structure regulator into a polymerization kettle C, reacting for 40-60 min, adding materials in the polymerization kettle C into a polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60-90 min; simultaneously, in a polymerization kettle D, under the atmosphere of inert gas, sequentially adding 100% -200% of solvent, 5% -10% of styrene, 0.05% -0.2% of structure regulator and initiator into the polymerization kettle D, reacting to obtain temperature-variable polymerization, and gradually increasing the temperature from 40 ℃ to 80 ℃ within 60-90 min; after the monomer is completely converted, adding the materials in the polymerization kettle D into the polymerization kettle A, and carrying out coupling reaction for 60-90 min; finally adding 3% -5% of 1, 3-butadiene into the polymerization kettle A for end capping, reacting until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain a grafting agent;
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, adding 100% -200% of diluent and solvent into a polymerization kettle in an inert gas atmosphere according to the volume ratio of 70-30: 30-70 of mixed solvent and 1-10% of grafting agent, and stirring and dissolving for 10-30 min until the grafting agent is completely dissolved; then cooling to-75 to-85 ℃, sequentially adding 100-200% of diluent, 88-92% of isobutene and 1-4% of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then mixing and ageing 30-50% of diluent and 0.05-3.0% of co-initiator at-85 to-95 ℃ for 20-30 min, adding the mixture into the polymerization system together, stirring and reacting for 3.0-5.0 hr, discharging, condensing, washing and drying to obtain ultra-wide molecular weight distribution hyperbranched butyl rubber products;
wherein the initiator is selected from one of n-butyllithium, sec-butyllithium, methyl butyllithium, phenyl butyllithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium; the coupling agent is 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, and the molar ratio of the coupling agent to the initiator is 2.0-5.0; the co-initiator is formed by compounding alkyl aluminum halide and protonic acid, wherein the molar ratio of protonic acid to alkyl aluminum halide is 0.01:1-0.1:1.
2. The method according to claim 1, wherein the grafting agent is a binary four-arm star copolymer synthesized by styrene and butadiene, and the structural general formula of the grafting agent is shown in formula I:
wherein, SBR is a styrene and butadiene random block copolymer segment with wide vinyl content distribution; SBR (styrene butadiene rubber) 1 Is a styrene, butadiene random block copolymer block; BR is a broad molecular weight distribution 1, 3-butadiene homopolymer segment; BR (BR) 1 1, 3-butadiene homopolymer segments of broad molecular weight distribution; PS is a styrene homopolymer segment; PS (PS) 1 A styrene homopolymer segment having a broad molecular weight distribution; b is a blocked butadiene segment, n=1.
3. The method of claim 2, wherein the binary four-arm star polymer has a 1, 3-butadiene content of 25% to 40% and a styrene content of 60% to 75%.
4. The method according to claim 2, wherein the binary four-arm star polymer has a number average molecular weight of 30000 to 70000 and a ratio of weight average molecular weight to number average molecular weight of 14.5 to 18.2.
5. The method of claim 1, wherein the halogenating agent is one of liquid chlorine and liquid bromine.
6. The method of claim 1, wherein the halogenating agent is liquid bromine and the molar ratio of liquid bromine usage to 3, 9-dioxo [5.5] spirocyclic undecane usage is 4.5-6.5.
7. The process according to claim 1, wherein the catalyst is HCl-CH 3 And mixed aqueous solution of OH, wherein the molar concentration of HCl is 0.1-0.7 mol/L.
8. The method of claim 1, wherein the structure modifier is selected from one of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
9. The method according to claim 1, wherein the diluent is a halogenated alkane, wherein halogen atoms in the halogenated alkane are chlorine, bromine or fluorine, and the number of carbon atoms in the halogenated alkane is 1 to 4.
10. The method according to claim 9, wherein the haloalkane is selected from one of methane chloride, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, methane monofluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
11. The method according to claim 10, wherein the haloalkane is chloromethane.
12. 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.
13. The method of claim 1, wherein the protic acid is selected from HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 One of them.
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| CN102924840A (en) * | 2012-10-09 | 2013-02-13 | 大连理工大学 | Method for preparing ABS resin from phenylethylene-butadiene-isoprene terpolymer composite latex by emulsion grafting |
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