CN117801191A - Multi-copolymer, preparation method and application thereof, halogenated branched butyl rubber, and preparation method and application thereof - Google Patents
Multi-copolymer, preparation method and application thereof, halogenated branched butyl rubber, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117801191A CN117801191A CN202211173637.1A CN202211173637A CN117801191A CN 117801191 A CN117801191 A CN 117801191A CN 202211173637 A CN202211173637 A CN 202211173637A CN 117801191 A CN117801191 A CN 117801191A
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- butyl rubber
- polymerization
- formula
- halogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 229920001577 copolymer Polymers 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 150000001993 dienes Chemical class 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 117
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 104
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 55
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 53
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 24
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 22
- 229910052794 bromium Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- -1 hydrocarbyl monolithium compound Chemical class 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000003085 diluting agent Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 229920003244 diene elastomer Polymers 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 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
- 239000002253 acid Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 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
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 230000035939 shock Effects 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 230000000379 polymerizing effect Effects 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 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
- WXRBQHOKNRLOQI-UHFFFAOYSA-N dichloromethylaluminum Chemical compound [Al]C(Cl)Cl WXRBQHOKNRLOQI-UHFFFAOYSA-N 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
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 claims description 2
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 claims description 2
- UUXZFMKOCRKVDG-UHFFFAOYSA-N methane;hydrofluoride Chemical compound C.F UUXZFMKOCRKVDG-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000013016 damping Methods 0.000 abstract description 70
- 229920001971 elastomer Polymers 0.000 abstract description 12
- 239000005060 rubber Substances 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 27
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 26
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 19
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 229920005557 bromobutyl Polymers 0.000 description 12
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000003292 glue Substances 0.000 description 11
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 125000004185 ester group Chemical group 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000005070 sampling Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000012644 addition polymerization Methods 0.000 description 3
- 150000001350 alkyl halides Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- VTMSSJKVUVVWNJ-UHFFFAOYSA-N 1-ethenyl-4-(2-methylpropyl)benzene Chemical compound CC(C)CC1=CC=C(C=C)C=C1 VTMSSJKVUVVWNJ-UHFFFAOYSA-N 0.000 description 2
- YCJIHVHYPIKHLD-UHFFFAOYSA-N 1-ethenyl-4-(3-methylbutyl)benzene Chemical compound CC(C)CCC1=CC=C(C=C)C=C1 YCJIHVHYPIKHLD-UHFFFAOYSA-N 0.000 description 2
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 2
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 2
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- HHBCEKAWSILOOP-UHFFFAOYSA-N 1,3-dibromo-1,3,5-triazinane-2,4,6-trione Chemical compound BrN1C(=O)NC(=O)N(Br)C1=O HHBCEKAWSILOOP-UHFFFAOYSA-N 0.000 description 1
- USEGQJLHQSTGHW-UHFFFAOYSA-N 3-bromo-2-methylprop-1-ene Chemical group CC(=C)CBr USEGQJLHQSTGHW-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002757 inflammatory effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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Abstract
The invention relates to the technical field of rubber preparation, and discloses a multipolymer, a preparation method and application thereof, halogenated branched butyl rubber, and a preparation method and application thereof. The multipolymer comprises: a structural unit a, a structural unit B, and a structural unit C; wherein the structural unit A has a structure represented by formula (1), the structural unit B has a structure represented by formula (2), and the structural unit C has a structure represented by formula (3), wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 ‑C 10 Straight or branched alkyl of (a); x is halogen, n is any integer from 1 to 10; the terminal end of the multipolymer contains structural units derived from conjugated dienes. The invention utilizes the multipolymer as grafting agent to prepare the halogenated branched butyl rubber, improves the stability of the effective damping temperature range and damping performance of the halogenated branched butyl rubber,
Description
Technical Field
The invention relates to the technical field of rubber preparation, in particular to a multipolymer and a preparation method and application thereof, and halogenated branched butyl rubber and a preparation method and application thereof.
Background
With the rapid development of modern science and technology, mechanical equipment tends to be high-frequency and high-speed in various fields such as high-speed rail, aerospace, naval vessels, mechanical engineering, automobiles, electronic appliances and the like, and a series of problems such as high-frequency vibration and noise are generated while convenience is brought to daily production and life. These problems accelerate fatigue damage to the mechanical structural materials, shortening their useful life. Therefore, vibration and noise reduction has become one of the challenges in today's society. Therefore, developing a high-efficiency damping material with excellent performance, improving the application effect of damping and shock absorption, and is important for improving the running environment of machinery and ensuring the health and safety of human beings.
Diene rubber is an unsaturated rubber containing two c=c double bonds, and main industrial products are butadiene rubber, isoprene rubber, butyl rubber and the like. Diene rubbers are widely used in various fields in daily production and living. However, the molecular chain of the butyl rubber has higher unsaturation degree, and the substituent methyl groups are symmetrically arranged, so that the molecular structure determines the unavoidable problems of poor ozone aging resistance, long vulcanization scorch time, low vulcanization speed, low damping performance and the like, and the butyl rubber cannot meet the increasingly diversified processing requirements and application scenes, thus becoming the bottleneck of expanding the application of the butyl rubber material.
Brominated butyl rubber (BIIR) is obtained by introducing bromine atoms into the molecular chain of butyl rubber (IIR) according to electrophilic substitution reaction under the action of molecular bromine. BIIR has excellent air tightness, good adhesiveness, high vulcanization speed, good thermal stability and corrosion resistance, and can be used in extreme environments such as strong corrosion or high temperature, in addition to IIR. Secondly, due to the introduction of bromine atoms, the polarity of molecular chains is increased, the relaxation resistance of chain segments is increased, the internal consumption is larger, and the damping rubber has excellent damping performance, so that the damping rubber is one of the most widely applied base damping rubbers.
In practical application, damping function is required to be achieved at the temperature ranging from minus 50 ℃ to +50 ℃, however, the effective damping function area (damping factor tan delta > 0.3) of the brominated butyl rubber is mainly concentrated at the low-temperature part, and the damping value is lower above 15 ℃, so that the use requirement of the wide-temperature-range damping material cannot be better met, and therefore, how to widen the effective damping function area of the butyl rubber above room temperature is one of research hot spots of the conventional rubber damping material.
CN112574333a discloses a bromination process of star-branched butyl rubber. The process comprises the following steps: a) Dissolving star-branched butyl rubber in aliphatic hydrocarbon to obtain a glue solution; b) Mixing the glue solution with ethanol serving as a branching agent capturing agent to obtain a mixed solution; c) Adding oxidant hydrogen peroxide and brominating agent Br into the above-mentioned mixed liquor 2 And the mole ratio of bromine element to unsaturated double bond in star branched butyl rubber is (0.75-2) l, and the brominated star branched butyl rubber is obtained by bromination reaction, final neutralization and product recovery.
CN106749816A discloses a process for preparing brominated butyl rubber. The method comprises the steps of firstly adopting normal alkane to dissolve butyl rubber, then taking specific organic bromides such as phenyl trimethyl tribromide, benzyl trimethyl tribromide and dibromoisocyanuric acid as brominating agents, and taking Br 2 Or HBr is used as a bromination accelerator to carry out bromination reaction in a solvent to obtain brominated butyl rubber.
Liao Mingyi et al (university of Dalian maritime university journal, 2008, 34 (2): 83-86) discloses a method for improving damping performance of butyl rubber (IIR) by adopting a stepwise method, taking IIR as a polymer network I, taking poly (styrene-methyl methacrylate) [ P (St-MMA) ] as a polymer network II, and preparing the butyl rubber/poly (styrene-methyl methacrylate) interpenetrating polymer network [ IIR/P (St-MMA) ] by graft polymerization to prepare the wide-temperature-range and high-damping butyl rubber material.
Although the effective damping temperature range of rubber can be widened to a certain extent by a blending method, a copolymerization method, an interpenetrating network polymer method and the like in the prior art, the damping performance of the rubber is improved, the methods still have certain limitations, and the problems of reduced mechanical performance, complex process, difficult actual operation, large addition amount, high cost, difficult removal of an organic solvent, environmental pollution and the like of the rubber material are caused.
Therefore, there is a need to develop a rubber material with wide effective damping temperature range, high damping performance and excellent mechanical properties, and the preparation method is easy to operate and pollution-free.
Disclosure of Invention
The invention aims to solve the problems that a rubber material in the prior art cannot have a wide effective damping temperature range, high damping performance and good mechanical property and is complicated to prepare and causes pollution, and provides a multipolymer and a preparation method and application thereof, halogenated branched butyl rubber and a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a multipolymer, wherein the multipolymer comprises: a structural unit a, a structural unit B, and a structural unit C; wherein the structural unit A has a structure represented by formula (1), the structural unit B has a structure represented by formula (2), the structural unit C has a structure represented by formula (3),
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 10 Straight or branched alkyl of (a); x is halogen, n is any integer from 1 to 10;
the terminal end of the multipolymer contains structural units derived from conjugated dienes.
The second aspect of the present invention provides a method for producing a multipolymer, wherein the method comprises: under the polymerization reaction condition, in the presence of an initiator, an optional structure regulator and an organic solvent, polymerizing a monomer shown in a formula (I), a monomer shown in a formula (II) and a monomer shown in a formula (III) to obtain a polymer solution;
Adding conjugated diene monomer into the polymer solution to carry out end-capping reaction to obtain the multipolymer;
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 10 Straight or branched alkyl of (a); x is halogen, and n is any integer from 1 to 10.
In a third aspect, the present invention provides a multipolymer obtainable by the process described above.
In a fourth aspect, the present invention provides the use of the aforementioned multipolymer as grafting agent in the preparation of diene rubber.
In a fifth aspect, the present invention provides a halogenated branched butyl rubber, wherein the halogenated branched butyl rubber comprises: structural units I from isobutene, structural units II from isoprene and structural units III from halogenated grafting agents; wherein the halogenated grafting agent is the multipolymer.
In a sixth aspect, the present invention provides a process for preparing the halogenated branched butyl rubber described above, wherein the process comprises: contacting isobutylene, isoprene and the multipolymer in the presence of a diluent, an organic solvent and a co-initiator for cationic polymerization to obtain the halogenated branched butyl rubber.
In a seventh aspect, the present invention provides a halogenated branched butyl rubber obtained by the aforementioned method of preparation.
In an eighth aspect the present invention provides the use of the halogenated branched butyl rubber described above in instrument and electrical shock absorbers.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
(1) The multipolymer provided by the invention combines p-alkylphenyl, p-haloalkylbenzene and ester group on a macromolecular chain to form an Interpenetrating Polymer Network (IPN), so that the p-alkylphenyl, halogen atom and ester group have the characteristics of high rigidity, high steric hindrance, high adsorption capacity and the like, when the multipolymer is used as a halogenated grafting agent for preparing halogenated branched butyl rubber, obvious synergistic effect can be generated in the aspect of widening the effective damping temperature range of the halogenated branched butyl rubber, the effective damping temperature range of the halogenated branched butyl rubber can be greatly widened, and the effective damping temperature range (tan delta is more than or equal to 0.3) exceeds the range of minus 50 ℃ to 62 ℃ can be prepared max Halogenated branched butyl rubber with wide temperature range and high damping of more than 1.9.
(2) The p-alkylphenyl, p-haloalkylbenzene and ester groups in the multipolymer are arranged on a molecular chain, so that superposition of a radical effect and a structural effect is generated, when the multipolymer is used as a halogenated grafting agent for preparing halogenated branched butyl rubber, not only is the damping performance of the halogenated branched butyl rubber reduced due to the expansion of the effective damping temperature range avoided, but also the problems of the mechanical property and the air tightness of the butyl rubber reduced due to the expansion of the molecular weight distribution caused by branching are avoided, and the tensile strength and the air tightness of the butyl rubber are improved.
(3) The halogenated branched butyl rubber prepared by the invention is prepared by using the multipolymer as a grafting agent through addition polymerization instead of ion substitution, thus blocking the condition of isomerization of a halogen structure, improving the stability of effective damping temperature range and damping performance of the halogenated branched butyl rubber and widening the application range of the halogenated branched butyl rubber.
(4) In the preparation process of the halogenated branched butyl rubber, the invention has the characteristics of no emission of Volatile Organic Compounds (VOC) and byproducts (HBr), environment-friendly preparation method, short process flow, low production cost, suitability for industrial production and the like.
Drawings
FIG. 1 is a dynamic mechanical spectrum of the brominated branched butyl rubber product (curve # 1) prepared in example 11 of the present invention versus the existing brominated butyl rubber (BIIR) 2302 (curve # 2).
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a multipolymer, wherein the multipolymer comprises: a structural unit a, a structural unit B, and a structural unit C; wherein the structural unit A has a structure represented by formula (1), the structural unit B has a structure represented by formula (2), the structural unit C has a structure represented by formula (3),
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 10 Straight or branched alkyl of (a); x is halogen, n is any integer from 1 to 10;
the terminal end of the multipolymer contains structural units derived from conjugated dienes.
The multipolymer of the invention simultaneously comprises para-alkylphenyl, para-haloalkylbenzene and ester groups to form an Interpenetrating Polymer Network (IPN), so that the para-alkylphenyl, halogen atoms and ester groups have the characteristics of high rigidity, high steric hindrance, high adsorption capacity and the like, and the tail end of the multipolymer contains conjugated diene structural units, so that the multipolymer has high polymerization activity, can be used as a grafting agent for preparing branched diene rubber, and is particularly used for preparing halogenated branched diene rubber.
In the present invention, the C 1 -C 10 Examples of the straight-chain or branched alkyl group of (a) may be, for example, any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, 2-methylhexyl, 2-ethylhexyl, 1-methylheptyl, 2-methylheptyl, n-octyl, isooctyl, n-nonyl, isononyl and 3, 5-trimethylhexyl.
In the present invention, the value of n in the structure represented by formula (1) may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.
In some embodiments of the invention, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 6 Straight-chain or branched alkyl of (2), preferably hydrogen or C 1 -C 4 More preferably hydrogen, methyl or ethyl.
In some preferred embodiments of the invention, R 6 Is methyl.
In some preferred embodiments of the invention, X is selected from Cl and/or Br.
In some preferred embodiments of the invention, n is any integer from 1 to 5, preferably any integer from 1 to 3.
In some preferred embodiments of the invention, the conjugated diene is butadiene and/or isoprene.
In some preferred embodiments of the present invention, the structural unit represented by formula (1) may be a structural unit derived from p-bromomethylstyrene, the structural unit represented by formula (2) may be a structural unit derived from p-alkylstyrene, such as p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene or p-isopentylstyrene, and the structural unit represented by formula (3) may be a structural unit derived from an unsaturated acrylate, such as Methyl Methacrylate (MMA), ethyl methacrylate, butyl methacrylate or t-butyl methacrylate.
In the present invention, the multi-copolymer is a block copolymer or a random copolymer.
In some embodiments of the invention, wherein the mass ratio of building block a, building block B, building block C and building block from conjugated diene is 100:20-50:10-25:1-5, such as 100:20:25:1, 100:50:10:5, 100:30:15:2, 100:40:20:4, 100:25:12:3, and any value in the range of any two values set forth above, preferably 100:30-40:15-20:2-3. When the mass ratio of each structural unit in the multipolymer satisfies the above range, an effective damping temperature range (tan delta. Gtoreq.0.3) exceeding the range of-50 ℃ to 62 ℃ and a maximum damping factor tan delta max And the brominated and branched butyl rubber with wide temperature range and high damping with the tensile strength of 22MPa-24MPa is more than or equal to 1.9.
The above ratio can be determined by infrared spectrum and nuclear magnetic resonance method, or according to the preparation feeding relationship.
In some preferred embodiments of the invention, the mass percent of halogen in the multipolymer is 2.5-5.5%, such as 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, and any value within the range of any two values recited above, preferably 4-5%. When the mass percentage of halogen in the multipolymer satisfies the above range, the damping property and vulcanization processability of the butyl rubber can be improved. In the invention, a Q600 type TG/DTG thermogravimetric analyzer is adopted to measure the halogen content.
In some embodiments of the invention, the multipolymer has a number average molecular weight (Mn) of 2.5 to 6 thousand g/mol, for example 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, and any value in the range of any two values recited above, preferably 4 to 5.
In some preferred embodiments of the invention, the molecular weight distribution index (Mw/Mn) of the multipolymer is in the range of 1.2 to 2, such as 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, and any value in the range of any two values recited above, preferably 1.45 to 1.95.
In the present invention, both the number average molecular weight and the molecular weight distribution index were tested by gel chromatography.
In some embodiments of the present invention, the apparent viscosity of the multipolymer is 8-40cps at 25 ℃.
In the present invention, the apparent viscosity of the multipolymer at 25℃was measured using an Ubbelohde viscometer according to GB/T10247-2008.
The second aspect of the present invention provides a method for producing a multipolymer, wherein the method comprises: under the polymerization reaction condition, in the presence of an initiator, an optional structure regulator and an organic solvent, polymerizing a monomer shown in a formula (I), a monomer shown in a formula (II) and a monomer shown in a formula (III) to obtain a polymer solution;
Adding conjugated diene monomer into the polymer solution to carry out end-capping reaction to obtain the multipolymer;
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 10 Straight or branched alkyl of (a); x is halogen, and n is any integer from 1 to 10.
The preparation method has the characteristics of complete reaction, no byproduct generation, stable structure of the prepared multipolymer and regular molecular chain arrangement.
In some embodiments of the invention, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 6 Straight-chain or branched alkyl of (2), preferably hydrogen or C 1 -C 4 More preferably hydrogen, methyl or ethyl.
In some preferred embodiments of the invention, R 6 Is methyl.
In some preferred embodiments of the invention, X is selected from Cl and/or Br.
In some preferred embodiments of the invention, n is any integer from 1 to 5, preferably any integer from 1 to 3.
C according to the second aspect of the invention 1 -C 10 Examples of straight or branched alkyl groups of (a) are as described above in the first aspect of the invention and are not described here again.
In some embodiments, the monomer of formula (I) is p-bromomethylstyrene, the monomer of formula (II) is p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene, or p-isopentylstyrene, and the monomer of formula (III) is Methyl Methacrylate (MMA), ethyl methacrylate, butyl methacrylate, or t-butyl methacrylate.
In some embodiments of the invention, wherein the conjugated diene is butadiene and/or isoprene.
In some preferred embodiments of the present invention, the mass ratio of the monomer of formula (I), the monomer of formula (II), the monomer of formula (III) and the conjugated diene is from 100:20 to 50:10 to 25:1 to 5, for example from 100:20:25:1, 100:50:10:5, 100:30:15:2, 100:40:20:4, 100:25:12:3, and any value in the range of any two values mentioned above, preferably from 100:30 to 40:15 to 20:2 to 3. In the present invention, a monomer represented by the formula (I) and a monomer represented by the formula (II)The mass ratio of the monomer to the monomer shown in the formula (III) to the conjugated diene is controlled within a specific range, so that an effective damping temperature range (tan delta is more than or equal to 0.3) exceeding the range of minus 50 ℃ to 62 ℃ can be obtained; maximum damping factor tan delta max Butyl rubber of 1.9 or more.
In some preferred embodiments of the invention, the polymerization is carried out under a protective atmosphere, preferably an inert atmosphere.
In some preferred embodiments of the invention, the initiator is a hydrocarbyl monolithium compound, preferably RLi, wherein R is selected from C 1 -C 20 Saturated aliphatic hydrocarbon radicals, C 3 -C 20 Alicyclic hydrocarbon group and C 6 -C 20 At least one of the aromatic hydrocarbon groups of (a).
In some preferred embodiments of the present invention, the initiator is selected from at least one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, and dodecyllithium. In the present invention, the above-mentioned initiator is selected so that each monomer is anionically polymerized to form a block copolymer, thereby achieving the superposition of the "structural effect" and the "radical effect".
In some preferred embodiments of the invention, the initiator is used in an amount of 16 to 30mmo1, preferably 18 to 25mmo1, relative to 1000g of the monomer of formula (I). Too little initiator causes the molecular weight of the prepared multipolymer to be reduced, and the wide temperature range and damping performance of butyl rubber can be affected when the multipolymer is applied, so that the modification effect can not be achieved; too much initiator leads to broadening of molecular weight distribution of the prepared multipolymer, resulting in deterioration of air tightness and mechanical strength of butyl rubber.
In some preferred embodiments of the invention, the structure-modifying agent is a polar organic compound.
The structure regulator is a polar organic compound, can generate solvation effect in a polymerization system, and can regulate the reactivity ratio of p-alkylstyrene and isoprene so as to realize block copolymerization of the p-alkylstyrene and isoprene.
In some preferred embodiments of the present invention, the structure modifier is selected from at least one of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
In some preferred embodiments of the present invention, the organic solvent is a hydrocarbon solvent, preferably at least one of linear alkanes, aromatic hydrocarbons, and cycloalkanes, and more preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
In some embodiments, the polymerization conditions include: the polymerization temperature is 50 to 80 ℃, for example 50 ℃, 60 ℃, 70 ℃, 80 ℃, and any value within the range of any two values mentioned above. The polymerization reaction temperature is too low, so that the reactivity is reduced, the reaction rate is slow, the reaction is incomplete, and the wide temperature range and high damping modification effect of the butyl rubber can not be achieved when the butyl rubber is applied; the polymerization reaction temperature is too high, so that the reaction activity is increased, the reaction rate is increased, the molecular structure is not orderly arranged, and the strength and the air tightness of the butyl rubber are reduced when the butyl rubber is applied.
The polymerization time is 220-270min, such as 220min, 230min, 240min, 250min, 260min, 270min, and any value within the range of any two values mentioned above. The polymerization reaction time is too short, and the wide temperature range and high damping modification effect of the butyl rubber can not be achieved when the butyl rubber is applied; the polymerization reaction time is too long, so that the energy consumption is too high, and obvious effects can not appear in the aspects of wide temperature range and high damping modification degree of the butyl rubber during application.
In some preferred embodiments of the invention, the capping reaction temperature is in the range of 60-90 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, and any value in the range of any two values recited above, preferably 70-80 ℃. The end-capping reaction temperature is too low, so that the end capping is incomplete, the reactive points are reduced, the grafting rate is reduced, and the butyl rubber has poor wide temperature range and damping performance modification effect when in use; the end capping reaction temperature is too high, so that conjugated diene is easy to self-polymerize and cannot play a role in end capping. The blocking reaction time is 10-45min, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, preferably 20-30min. The end-capping reaction time is too short, so that the end capping is incomplete, the reactive points are reduced, and the wide temperature range and high damping modification effect of the butyl rubber can not be achieved during application; the end-capping reaction time is too long, so that the flexibility of the prepared multipolymer chain segment is increased, and the damping performance and mechanical strength of the butyl rubber can be damaged during application.
In some embodiments of the invention, the method comprises the steps of:
(1) Mixing a monomer shown in a formula (I), a structure regulator, a solvent and an initiator to perform a first polymerization reaction to obtain a first polymerization product;
(2) Adding a monomer shown in a formula (II) and a structure regulator into the first polymerization product to be mixed for a second polymerization reaction, so as to obtain a second polymerization product;
(3) Adding a monomer shown in a formula (III) and a structure regulator into the second polymerization product to carry out mixing to generate a third polymerization reaction, so as to obtain a third polymerization product;
(4) And adding conjugated diene into the third polymerization product to carry out end-capping reaction, so as to obtain the multipolymer.
In the preparation method, the anionic polymerization method is adopted to prepare the multiblock multipolymer, and the multipolymer has the characteristics of controllable structure, stable bromine structure, high isotacticity, complete reaction, no byproducts and the like, and can bring the effects of wide applicable temperature range, high damping property, excellent mechanical strength and vulcanization processability of the halogenated branched diene rubber.
In some preferred embodiments of the invention, the mass ratio of monomer of formula (I) to structure modifier in step (1) is from 100:0.5 to 0.7, e.g. 100:0.5, 100:0.6, 100:0.7, and any value in the range of any two values mentioned above. By controlling the mass ratio of the monomer represented by the formula (I) to the structure-controlling agent within the above-mentioned range, a block polymer having high isotacticity can be produced.
In some preferred embodiments of the invention, the mass ratio of monomer of formula (II) to structure modifier in step (2) is from 30 to 40:0.3 to 0.5, e.g. 30:0.3, 35:0.35, 40:0.5, and any value in the range of any two values mentioned above. By controlling the mass ratio of the monomer represented by the formula (II) to the structure-controlling agent within the above-mentioned range, a block polymer having high isotacticity can be produced.
In some preferred embodiments of the invention, the mass ratio of monomer of formula (III) to structure modifier in step (3) is from 15 to 20:0.2 to 0.3, e.g. 15:0.2, 18:0.25:20:0.3, and any value in the range of any two values mentioned above. By controlling the mass ratio of the monomer represented by the formula (III) to the structure-adjusting agent within the above-mentioned range, a block polymer having high isotacticity can be produced.
In some embodiments of the invention, the first polymerization temperature is in the range of 40-80 ℃, such as 40 ℃, 45 ℃, 55 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, and any value in the range of any two values recited above, preferably 50-60 ℃. Too low a first polymerization temperature may result in too low bromine content; the first polymerization temperature is too high to destroy the bromine structure. The first polymerization time is 80 to 150min, for example 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, and any value within the range of any two values mentioned above, preferably 100 to 120min. Too short a first polymerization time may result in a lower molecular weight and lower bromine content; the first polymerization reaction time is too long, the molecular weight change is not obvious, and the modification effect is not obvious.
In some preferred embodiments of the invention, the second polymerization temperature is 60-90 ℃, e.g., 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, and any value within the range of any two values recited above, preferably 70-80 ℃. Too low a second polymerization temperature may result in too low a benzene ring structure content, resulting in reduced strength and airtightness; the second polymerization reaction temperature is too high, and the damping modification effect is not obvious. The second polymerization time is 50 to 80min, for example, 50min, 55min, 60min, 65min, 70min, 75min, 80min, and any value in the range of any two values mentioned above, preferably 60 to 70min. The second polymerization reaction time is too short, so that the molecular weight is reduced, the benzene ring structure is reduced, and the damping increase amplitude is small; the second polymerization reaction time is too long, the energy consumption is high, the benzene ring structure is not obviously changed, and the damping increase amplitude is not obviously changed.
In some preferred embodiments of the invention, the third polymerization temperature is 60-90 ℃, e.g., 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, and any value within the range of any two values recited above, preferably 70-80 ℃. The third polymerization reaction temperature is too low, which can lead to too low content of polar group ester groups and narrow damping temperature range of butyl rubber during application; the temperature of the third polymerization reaction is too high, and the applicable temperature range of the butyl rubber is not obviously widened during application. The third polymerization time is 30-60min, for example 30min, 35min, 40min, 45min, 50min, 55min, 60min, and any value in the range of any two values mentioned above, preferably 40-50min. The third polymerization reaction time is too short, so that the content of polar group ester groups is too low, and the wide-temperature-range modification effect of the butyl rubber cannot be achieved when the butyl rubber is applied; the third polymerization reaction time is too long, and the applicable temperature range widening of the butyl rubber is not obvious during application.
According to a particularly preferred embodiment of the present invention, an organic solvent, p-bromomethylstyrene and a structure-controlling agent are sequentially added into a polymerization vessel under an inert atmosphere, and after the temperature is raised to 50-60 ℃, an initiator is added for reaction for 100-120min; then adding para-alkylstyrene and a structure regulator into a polymerization kettle, heating to 70-80 ℃ and reacting for 60-70min; then adding unsaturated acrylic ester and a structure regulator into a polymerization kettle, and reacting for 40-50min; finally, adding isoprene into a polymerization kettle for end capping, reacting for 20-30min until no free monomer exists, and performing wet condensation and drying on the glue solution to obtain the multipolymer;
wherein the mass ratio of the p-bromomethylstyrene to the p-alkylstyrene to the unsaturated acrylic ester to the isoprene is 100:30-40:15-20:2-3;
the mass ratio of the p-bromomethylstyrene to the structure regulator is 100:0.5-0.7;
the mass ratio of the para-alkylstyrene to the structure regulator is 30-40:0.3-0.5;
the mass ratio of the unsaturated acrylic ester to the structure regulator is 15-20:0.2-0.3.
In a third aspect, the present invention provides a multipolymer obtainable by the process described above.
In a fourth aspect, the present invention provides the use of the aforementioned multipolymer as grafting agent in the preparation of diene rubber.
In some embodiments of the invention, the diene rubber is butyl rubber.
In a fifth aspect, the present invention provides a halogenated branched butyl rubber, wherein the halogenated branched butyl rubber comprises: structural units I from isobutene, structural units II from isoprene and structural units III from halogenated grafting agents;
wherein the halogenated grafting agent is the multipolymer.
In some embodiments of the invention, the mass ratio of structural unit I, structural unit II, and structural unit III is from 100:4 to 6:7 to 10, such as 100:4:7, 100:5:6, 100:6:10, and any value in the range of any two values recited above, based on the total weight of the halogenated branched butyl rubber. In the invention, the mass ratio of the structural unit I, the structural unit II and the structural unit III is controlled within a specific range, and an effective damping temperature range (tan delta is more than or equal to 0.3) exceeding the range of minus 50 ℃ to 62 ℃ can be obtained; maximum damping factor tan delta max Not less than 1.9; butyl rubber having a tensile strength of 22MPa to 24 MPa.
The multipolymer provided by the invention combines p-alkylphenyl, p-haloalkylbenzene and ester group on a macromolecular chain to form an Interpenetrating Polymer Network (IPN), so that the p-alkylphenyl, halogen atom and ester group have the characteristics of high rigidity, high steric hindrance, high adsorption capacity and the like, when the multipolymer is used as a halogenated grafting agent for preparing halogenated branched butyl rubber, obvious synergistic effect can be generated in the aspect of widening the effective damping temperature range of the halogenated branched butyl rubber, the effective damping temperature range of the halogenated branched butyl rubber can be greatly widened, and the effective damping temperature range (tan delta is more than or equal to 0.3) exceeds the range of minus 50 ℃ to 62 ℃ can be prepared max Halogenated branched butyl rubber with wide temperature range and high damping of more than 1.9.
In a sixth aspect, the present invention provides a process for preparing the halogenated branched butyl rubber described above, wherein the process comprises:
contacting isobutylene, isoprene and the multipolymer in the presence of a diluent, an organic solvent and a co-initiator for cationic polymerization to obtain the halogenated branched butyl rubber.
The halogenated branched butyl rubber prepared by the invention is prepared by using the multipolymer as a grafting agent through addition polymerization instead of ion substitution, thus blocking the condition of isomerization of a halogen structure, improving the stability of effective damping temperature range and damping performance of the halogenated branched butyl rubber and widening the application range of the halogenated branched butyl rubber. The effective damping temperature range (tan delta) of the halogenated branched butyl rubber prepared by the invention max Not less than 0.3) exceeds the range of-50 ℃ to 62 ℃.
In addition, the preparation process has the characteristics of no emission of Volatile Organic Compounds (VOC) and byproducts (HBr), environment-friendly preparation method, short process flow, low production cost, suitability for industrial production and the like.
In some embodiments of the invention, the mass ratio of isobutylene, isoprene, and the aforementioned multipolymer is from 100:4 to 6:7 to 10, such as 100:4:7, 100:5:6, 100:6:10, and any value within the range of any two values recited above. In the invention, the mass ratio of the isobutene, the isoprene and the multipolymer is controlled within a specific range, so that the complete reaction of the multipolymer in the preparation reaction of the butyl rubber can be effectively ensured.
In some preferred embodiments of the invention, the diluent is a haloalkane, wherein the halogen atoms in the haloalkane are preferably F, cl or Br, and the number of carbon atoms in the haloalkane is preferably 1-4, such as 1, 2, 3, 4.
In some preferred embodiments of the present invention, the diluent is selected from at least one of methane chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
In some preferred embodiments of the invention, the mass ratio of the isobutylene to the diluent is from 100:180 to 320, such as 100:180, 100:220, 100:250, 100:300, 100:320, and any value within the range of any two values recited above. In the invention, the mass ratio of the isobutene to the diluent is controlled within a specific range, so that the butyl rubber with high molecular weight can be prepared.
In some preferred embodiments of the present invention, the organic solvent is a hydrocarbon solvent, preferably at least one of linear alkanes, aromatic hydrocarbons, and cycloalkanes, and more preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
The amount of the organic solvent is not particularly limited, and may be added in accordance with the conventional amounts in the art.
In some preferred embodiments of the invention, the co-initiator comprises an alkyl aluminum halide and a protic acid.
In some preferred embodiments of the invention, the molar ratio of the alkyl aluminum halide to the protic acid in the co-initiator is in the range of 10-100:1, for example 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, and any value in the range of any two values recited above.
In some preferred embodiments of the present invention, 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.
In some preferred embodiments of the invention, the protic acid is selected from HCI, HF, HBr, H 2 SO 4 、 H 2 CO 3 、H 3 PO 4 And HNO 3 At least one of them.
In some preferred embodiments of the invention, the mass ratio of the isobutylene to the co-initiator is in the range of 100:0.1 to 0.3, such as 100:0.1, 100:0.15, 100:0.2, 100:0.25, 100:0.3, and any value in the range of any two values recited above.
In some preferred embodiments of the invention, the cationic polymerization conditions include: the cationic polymerization temperature is from-100 ℃ to-75 ℃, such as-100 ℃, -95 ℃, -90 ℃, -85 ℃, -80 ℃, -75 ℃, and any value within the range of any two values recited above. Too low cationic polymerization temperature causes too long reaction time and difficult structure control; too high a cationic polymerization temperature causes chain transfer reaction, resulting in a decrease in molecular weight. The cationic polymerization time is 3 to 4 hours, for example 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, and any value within the range of any two values recited above. Too short a cationic polymerization time, resulting in a smaller molecular weight; the cationic polymerization time is too long, and structural instability occurs.
In the present invention, a terminator may be added to take out the halogenated branched butyl rubber. The terminator of the present invention may be selected from at least one of methanol, ethanol and butanol.
According to a particularly preferred embodiment of the invention, the mixed solvent (V (Diluent) :V (solvent) 70-30/30-70) and the multipolymer, stirring and dissolving for 60-70min until the multipolymer is completely dissolved; then cooling to-85 ℃ to-75 ℃, sequentially adding a diluent, isobutene and isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃ to-85 ℃, then mixing and ageing the diluent and a co-initiator for 50-60min at-100 ℃ to-90 ℃, adding the mixture into the polymerization system together for stirring and reacting for 3-4h, finally adding a terminator, discharging and condensing, washing and drying to obtain halogenated branched butyl rubber;
Wherein the mass ratio of the isobutene to the isoprene to the multipolymer is 100:4-6:7-10;
the mass ratio of the isobutene to the diluent is 100:180-320;
the mass ratio of the isobutene to the coinitiator is 100:0.1-0.3.
In a seventh aspect, the present invention provides a halogenated branched butyl rubber obtained by the aforementioned method of preparation.
In an eighth aspect the present invention provides the use of the halogenated branched butyl rubber described above in instrument and electrical shock absorbers.
The halogenated branched butyl rubber not only solves the problem that the effective damping temperature range of the halogenated branched butyl rubber is widened to lower the damping performance, but also improves the tensile strength and air tightness of the halogenated branched butyl rubber, and can be completely applied to electromechanical devices, such as the requirements of an instrument damper, an electric appliance damper and the like on the damping performance in a wide temperature range.
The present invention will be described in detail by examples.
The following examples and comparative examples were conducted under conventional conditions or conditions recommended by the manufacturer, where specific conditions were not noted. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge. The mass ratio relationship of each structural unit contained in the obtained multipolymer product and the halogenated branched butyl rubber is determined according to the feed amount of raw materials.
(1) The raw material sources are as follows:
isobutene, isoprene: polymerization grade from Zhejiang Xinhui New Material Co., ltd
P-methylstyrene: polymerization grade from Jiande City wave Peak chemistry Co., ltd
P-n-butylstyrene: aggregation level from Luoyang Yi energy technology Co., ltd
P-bromomethylstyrene: polymerization grade from Hubei double inflammatory chemical Co., ltd
Methyl Methacrylate (MMA): from Tianjin chemical reagent II plant
N-butyllithium: purity is 98%, from Nanjing Tonglian chemical Co., ltd
Sesquiethyl aluminum chloride: purity of 98%, from the technical Co.Ltd
The other reagents are all commercial products.
(2) The analytical test method comprises the following steps:
determination of number average molecular weight and Mn distribution index (Mw/Mn): measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. Using polystyrene standard sample as correction curve, mobile phase asTetrahydrofuran, column temperature of 40 ℃, sample concentration of 1mg/mL, sample injection amount of 50 mu L, elution time of 40min and flow rate of 1 mL.min -1 。
Bromine content measurement: 10mg of the sample is weighed, and the sample is thermally degraded in a nitrogen atmosphere with the flow rate of 50mL/min by adopting a Q600 type TG/DTG thermogravimetric analyzer and the heating rate of 10 ℃/min. The first stage of thermal degradation is to remove bromine from a bromine-containing unit of a sample to form HBr, and then reversely calculate the bromine content (X) in the sample by the percentage of the removed HBr, wherein the calculation formula is as follows:
Wherein: y-percent of sample at 220 ℃; 79.904-relative atomic mass of bromine; 1.008-elemental hydrogen relative to atomic mass.
Determination of apparent viscosity: the measurement was carried out by using an Ubbelohde viscometer according to GB/T10247-2008.
Measurement of air tightness: the number of ventilation was determined using an automated air tightness tester according to ISO 2782:1995. The test gas is N 2 The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.
Dynamic Mechanical Analysis (DMA): the measurement was carried out on a dynamic mechanical analyzer 242C from Netzsch, germany, using a tensile mode. The sample size is 10mm long, 6mm wide and 2mm thick, the temperature range is-90 ℃ to 90 ℃, the heating speed is 3 ℃/min, and data at the frequency of 10Hz are selected for analysis.
Tensile strength: the method in standard GB/T528-2009 is performed.
Example 1
This example illustrates the preparation of a multipolymer.
Firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 3000g of hexane, 1000g of p-bromomethylstyrene, 5.0g of THF into the polymerization kettle, heating to 50 ℃, and adding 18.5 mmol 1 of n-butyllithium to start reaction for 100min; then adding 300g of p-methylstyrene, 3.0g of THF into the polymerization kettle, heating to 70 ℃ and reacting for 60min; then 150g MMA,2.0g THF is added into the polymerization kettle to react for 40min; finally, adding 20g of isoprene into a polymerization kettle, carrying out end-capping reaction for 20min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the multipolymer S-1. Wherein the mass ratio of the p-bromomethylstyrene to the p-methylstyrene to the MMA to the isoprene is 100:30:15:2.
As tested, the multipolymer S-1 had Mn of 40100, mw/Mn of 1.45, bromine content of 4.05% and apparent viscosity at 25℃of 8cps.
Example 2
This example illustrates the preparation of a multipolymer.
Firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 3100g of hexane, 1000g of p-bromomethylstyrene, 5.4g of THF into the polymerization kettle, heating to 52 ℃, and adding 19.3mmo1 of n-butyllithium to start reaction for 105min; then adding 310g of p-methylstyrene, 3.5g of THF into the polymerization kettle, heating to 72 ℃ and reacting for 62min; then 160g MMA,2.2g THF is added into the polymerization kettle to react for 42min; finally, adding 22g of isoprene into a polymerization kettle, carrying out end-capping reaction for 21min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the multipolymer S-2. Wherein the mass ratio of the p-bromomethylstyrene, the p-methylstyrene, the MMA and the isoprene is 100:31:16:2.2.
The multipolymer S-2 was tested to have Mn of 42300, mw/Mn of 1.51, bromine content of 4.21%, apparent viscosity at 25℃of 11.2cps.
Example 3
This example illustrates the preparation of a multipolymer.
Firstly, in a 15L stainless steel reaction kettle with a jacket, argon is introduced for replacement for 4 times, 3300g of hexane, 1000g of p-bromomethylstyrene and 5.7g of THF are sequentially added into the polymerization kettle, the temperature is raised to 55 ℃, and 21.5mm 1 of n-butyllithium is added for starting the reaction for 110min; then 330g of p-methylstyrene, 4.0g of THF are added into the polymerization kettle, the temperature is raised to 74 ℃ and the reaction is carried out for 64min; then 170g MMA,2.4g THF is added into the polymerization kettle to react for 44min; finally, adding 24g of isoprene into a polymerization kettle, carrying out end-capping reaction for 23min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the multipolymer S-3. Wherein the mass ratio of the p-bromomethylstyrene, the p-methylstyrene, the MMA and the isoprene is 100:33:17:2.4.
As tested, the multipolymer S-3 had Mn of 45100, mw/Mn of 1.63, bromine content of 4.48%, and apparent viscosity at 25℃of 14.5cps.
Example 4
This example illustrates the preparation of a multipolymer.
Firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 3500g of hexane, 1000g of p-bromomethylstyrene, 6.0g of THF into the polymerization kettle, heating to 57 ℃, and adding 22.6mmo1 of n-butyllithium to start reaction for 113min; then 360g of p-methylstyrene, 4.4g of THF are added into the polymerization kettle, the temperature is raised to 76 ℃ and the reaction is carried out for 66min; then 180g MMA,2.6g THF is added into the polymerization kettle to react for 46min; finally, adding 25g of isoprene into a polymerization kettle, carrying out end-capping reaction for 25min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the multipolymer S-4. Wherein the mass ratio of the p-bromomethylstyrene, the p-methylstyrene, the MMA and the isoprene is 100:36:18:2.5.
The multipolymer S-4 was tested to have a Mn of 46500, mw/Mn of 1.76, bromine content of 4.62%, apparent viscosity at 25℃of 20.5cps.
Example 5
This example illustrates the preparation of a multipolymer.
Firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 5 times, sequentially adding 3700g of hexane, 1000g of p-bromomethylstyrene and 6.5g of THF into the polymerization kettle, heating to 59 ℃, and adding 23.4mmo1 of n-butyllithium to start reaction for 115min; then 380g of p-methylstyrene, 4.8g of THF are added into the polymerization kettle, the temperature is raised to 78 ℃ and the reaction is carried out for 68min; then 190g MMA,2.8g THF is added into the polymerization kettle to react for 48min; finally, 27g of isoprene is added into the polymerization kettle to carry out end-capping reaction for 27min until no free monomer exists, and the glue solution is subjected to wet condensation and drying to obtain the multipolymer S-5. Wherein the mass ratio of the p-bromomethylstyrene, the p-methylstyrene, the MMA and the isoprene is 100:38:19:2.7.
As tested, the multipolymer S-5 had Mn of 48900, mw/Mn of 1.87, bromine content of 4.85%, and apparent viscosity at 25℃of 24.1cps.
Example 6
This example illustrates the preparation of a multipolymer.
Firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 5 times, sequentially adding 4000g of hexane, 1000g of p-bromomethylstyrene and 7.0g of THF into the polymerization kettle, heating to 60 ℃, and adding 24.8mmo1 of n-butyllithium to start reaction for 120min; then 400g of p-butyl styrene and 5.0g of THF are added into the polymerization kettle, the temperature is raised to 80 ℃ and the reaction is carried out for 70min; then 200g MMA,3.0g THF is added into the polymerization kettle to react for 50min; and finally, adding 30g of isoprene into a polymerization kettle, carrying out end-capping reaction for 30min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the multipolymer S-6. Wherein the mass ratio of the p-bromomethylstyrene to the p-methylstyrene to the MMA to the isoprene is 100:40:20:30.
The multipolymer S-6 was tested to have Mn of 49700, mw/Mn of 1.95, bromine content of 4.98%, and apparent viscosity at 25℃of 29.1cps.
Example 7
This example illustrates the preparation of a multipolymer.
Firstly, in a 15L stainless steel reaction kettle with a jacket, introducing nitrogen for replacement for 5 times, sequentially adding 4000g of hexane, 1000g of p-bromomethylstyrene and 7.0g of THF into the polymerization kettle, heating to 40 ℃, and adding 16mmo1 of n-butyllithium to start reaction for 80min; then 200g of p-butyl styrene and 5.0g of THF are added into the polymerization kettle, the temperature is raised to 60 ℃ and the reaction is carried out for 50min; then 100g MMA,3.0g THF is added into the polymerization kettle to react for 30min; finally, adding 10g of isoprene into a polymerization kettle, carrying out end-capping reaction for 10min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the multipolymer S-7. Wherein the mass ratio of the p-bromomethylstyrene to the p-methylstyrene to the MMA to the isoprene is 100:20:20:1.
The multipolymer S-7 was tested to have a Mn of 25000, mw/Mn of 1.2, bromine content of 2.5% and apparent viscosity at 25℃of 35.4cps.
Example 8
This example illustrates the preparation of a multipolymer.
Firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 5 times, sequentially adding 4000g of hexane, 1000g of p-bromomethylstyrene and 7.0g of THF into the polymerization kettle, heating to 80 ℃, and adding 30mmo1 of n-butyllithium to start reaction for 150min; then adding 500g of p-butyl styrene and 5.0g of THF into a polymerization kettle, heating to 90 ℃ and reacting for 80min; then 250g MMA,3.0g THF is added into the polymerization kettle to react for 60min; finally, 50g of isoprene is added into the polymerization kettle to carry out end-capping reaction for 45min until no free monomer exists, and the glue solution is subjected to wet condensation and drying to obtain the multipolymer S-8. Wherein the mass ratio of the p-bromomethylstyrene to the p-methylstyrene to the MMA to the isoprene is 100:50:25:5.
The multipolymer S-8 was tested to have a Mn of 60000, mw/Mn of 2, bromine content of 5.5%, apparent viscosity at 25℃of 40.0cps.
Example 9
This example illustrates the preparation of a multipolymer.
A multipolymer was produced in the same manner as in example 1 except that 5g of isoprene was added during the production to obtain multipolymer S-9. Wherein the mass ratio of the p-bromomethylstyrene, the p-methylstyrene, the MMA and the isoprene is 100:30:15:0.5.
The multipolymer S-9 was tested to have Mn of 39900, mw/Mn of 1.43, bromine content of 4.09%, apparent viscosity at 25℃of 8.5cps.
Example 10
This example illustrates the preparation of a multipolymer.
A multipolymer was produced in the same manner as in example 1 except that 60g of isoprene was added during the production to give multipolymer S-10. Wherein the mass ratio of the p-bromomethylstyrene to the p-methylstyrene to the MMA to the isoprene is 100:30:15:6.
As tested, the multipolymer S-10 had Mn of 41000, mw/Mn of 1.51, bromine content of 4.01% and apparent viscosity at 25℃of 8.9cps.
Example 11
This example illustrates the preparation of halogenated branched butyl rubber.
Firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 350g of methylene dichloride and 150g of hexane into the polymerization kettle, stirring and dissolving 35g of the multipolymer S-1 for 60 minutes until the multipolymer S-1 is completely dissolved; then cooling to-75 ℃, sequentially adding 500g of methyl chloride, 500g of isobutene and 20g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-85 ℃, then mixing and ageing 50g of methyl chloride, 1.05g of aluminum sesquichloride and 0.012g of HCl at-90 ℃ for 50min, adding the mixture into the polymerization system together, stirring and reacting for 3.0h, finally adding 15g of methanol, discharging and condensing, washing, and drying to obtain the brominated and branched butyl rubber product. Wherein the mass ratio of the isobutene, the isoprene and the multipolymer S-1 in the preparation raw materials is 100:4:7.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 12
This example illustrates the preparation of halogenated branched butyl rubber.
Firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 300g of methylene dichloride and 200g of hexane into the polymerization kettle, stirring and dissolving 37g of the multipolymer S-2 for 62 minutes until the multipolymer S-2 is completely dissolved; then cooling to-77 ℃, sequentially adding 600g of methyl chloride, 500g of isobutene and 22g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-86 ℃, then mixing and aging 60g of methyl chloride, 1.13g of aluminum sesquichloride and 0.015g of HCl at-92 ℃ for 52min, adding the mixture into the polymerization system together, stirring and reacting for 3.2h, finally adding 17g of methanol, discharging and condensing, washing, and drying to obtain the brominated and branched butyl rubber product. Wherein the mass ratio of the isobutene, the isoprene and the multipolymer S-2 in the preparation raw materials is 100:4.4:7.4.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 13
This example illustrates the preparation of halogenated branched butyl rubber.
Firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for replacement for 4 times, adding 200g of methylene dichloride and 300g of hexane into the polymerization kettle, stirring and dissolving 40g of the multipolymer S-3, and dissolving for 64min until the multipolymer S-3 is completely dissolved; then cooling to-80 ℃, sequentially adding 700g of methyl chloride, 500g of isobutene and 24g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-87 ℃, then mixing and ageing 70g of methyl chloride, 1.24g of aluminum sesquichloride and 0.021g of HCl at-94 ℃ for 54min, adding the mixture into the polymerization system together for stirring and reacting for 3.4h, finally adding 19g of methanol, discharging and condensing, washing and drying to obtain the brominated and branched butyl rubber product. Wherein the mass ratio of the isobutene, the isoprene and the multipolymer S-3 in the preparation raw materials is 100:4.8:8.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 14
This example illustrates the preparation of halogenated branched butyl rubber.
Firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for replacement for 4 times, adding 700g of methylene dichloride and 300g of hexane into the polymerization kettle, stirring and dissolving 43g of multipolymer S-4, and dissolving for 65 minutes until the multipolymer S-4 is completely dissolved; then cooling to-81 ℃, sequentially adding 800g of methyl chloride, 500g of isobutene and 26g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-88 ℃, then mixing and ageing 80g of methyl chloride, 1.36g of aluminum sesquichloride and 0.035g of HCl at-96 ℃ for 56min, adding the mixture into the polymerization system together for stirring and reacting for 3.6h, finally adding 20g of methanol, discharging and condensing, washing and drying to obtain the brominated and branched butyl rubber product. Wherein the mass ratio of the isobutene, the isoprene and the multipolymer S-4 in the preparation raw materials is 100:5.5:8.6.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 15
This example illustrates the preparation of halogenated branched butyl rubber.
Firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 5 times for replacement, adding 500g of methylene dichloride and 500g of hexane into the polymerization kettle, stirring and dissolving for 67min, and completely dissolving the multipolymer S-5 48 g; then cooling to-83 ℃, sequentially adding 900g of methyl chloride, 500g of isobutene and 28g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-89 ℃, then mixing and ageing 90g of methyl chloride, 1.41g of aluminum sesquichloride and 0.042g of HCl at-98 ℃ for 58min, adding the mixture into the polymerization system together, stirring and reacting for 3.9h, finally adding 23g of methanol, discharging and condensing, washing and drying to obtain the brominated and branched butyl rubber product. Wherein the mass ratio of the isobutene, the isoprene and the multipolymer S-5 in the preparation raw materials is 100:5.6:9.6.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 16
This example illustrates the preparation of halogenated branched butyl rubber.
Firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 5 times for replacement, adding 300g of methylene dichloride and 700g of hexane into the polymerization kettle, stirring and dissolving 50g of multipolymer S-6 until the multipolymer S-6 is completely dissolved; then cooling to-85 ℃, sequentially adding 1000g of methyl chloride, 500g of isobutene and 30g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing and aging 100g of methyl chloride, 1.50g of aluminum sesquichloride and 0.065g of HCl at-100 ℃ for 60min, adding the mixture into the polymerization system together, stirring and reacting for 4.0h, finally adding 25g of methanol, discharging and condensing, washing and drying to obtain the brominated and branched butyl rubber product. Wherein the mass ratio of the isobutene, the isoprene and the multipolymer S-6 in the preparation raw materials is 100:6:10.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 17
Halogenated branched butyl rubber was prepared as in example 11, except that the multipolymer S-1 was replaced with multipolymer S-7 to give a brominated branched butyl rubber product.
Example 18
Halogenated branched butyl rubber was prepared as in example 11, except that the multipolymer S-1 was replaced with multipolymer S-8 to give a brominated branched butyl rubber product.
Example 19
Halogenated branched butyl rubber was prepared as in example 11, except that the multipolymer S-1 was replaced with multipolymer S-9 to give a brominated branched butyl rubber product.
Example 20
Halogenated branched butyl rubber was prepared as in example 11, except that the multipolymer S-1 was replaced with multipolymer S-10 to give a brominated branched butyl rubber product.
Comparative example 1
A multipolymer was prepared as in example 1, except that p-bromomethylstyrene was replaced with methallyl bromide to give multipolymer D-1.
Halogenated branched butyl rubber was prepared as in example 11, except that the multipolymer S-1 was replaced with multipolymer D-1 to give a brominated branched butyl rubber product.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
A multipolymer was prepared as in example 3, except that p-bromomethylstyrene was not added during the preparation to give multipolymer D-2.
Halogenated branched butyl rubber was prepared as in example 13, except that the multipolymer S-3 was replaced with multipolymer D-2 to give a brominated branched butyl rubber product.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
A multipolymer was prepared as in example 4, except that MMA was not added during the preparation to give multipolymer D-3.
Halogenated branched butyl rubber was prepared as described in example 14, except that the multipolymer S-4 was replaced with multipolymer D-3 to give a brominated branched butyl rubber product.
Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1
As can be seen from the results of Table 1, the monomers for preparing the multipolymers in comparative examples 1 to 3 are different from the present invention, and thus, they are inferior in effective damping temperature range, damping properties, air tightness and mechanical properties. Compared with comparative examples 1-3, the brominated and branched butyl rubber products prepared in examples 11-20 have wider effective damping temperature range, better damping performance, better air tightness and better mechanical property.
FIG. 1 is a dynamic mechanical spectrum of the brominated branched butyl rubber product (curve # 1) prepared in example 11 of the present invention versus the existing brominated butyl rubber (BIIR) 2302 (curve # 2).
As can be seen in FIG. 1, the brominated branched butyl rubber product prepared in example 11 of the present invention has a greater damping factor over a wide effective damping temperature range than the existing brominated butyl rubber (BIIR) 2302.
The halogenated branched butyl rubber prepared by the invention is prepared by using the multipolymer as a grafting agent through addition polymerization instead of ion substitution, thus blocking the condition of isomerization of a halogen structure, improving the stability of effective damping temperature range and damping performance of the halogenated branched butyl rubber and widening the application range of the halogenated branched butyl rubber.
In the preparation process of the halogenated branched butyl rubber, the invention has the characteristics of no emission of Volatile Organic Compounds (VOC) and byproducts (HBr), environment-friendly preparation method, short process flow, low production cost, suitability for industrial production and the like.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (18)
1. A multipolymer, characterized in that said multipolymer comprises: a structural unit a, a structural unit B, and a structural unit C; wherein the structural unit A has a structure represented by formula (1), the structural unit B has a structure represented by formula (2), the structural unit C has a structure represented by formula (3),
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 10 Straight or branched alkyl of (a); x is halogen, n is any integer from 1 to 10;
the terminal end of the multipolymer contains structural units derived from conjugated dienes.
2. The multipolymer of claim 1, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 6 Straight-chain or branched alkyl of (2), preferably hydrogen or C 1 -C 4 More preferably hydrogen, methyl or ethyl;
preferably, R 6 Is methyl;
preferably, X is selected from Cl and/or Br;
preferably, n is any integer from 1 to 5, preferably any integer from 1 to 3;
preferably, the conjugated diene is butadiene and/or isoprene;
preferably, the mass ratio of building blocks A, B, C and from conjugated diene is from 100:20 to 50:10 to 25:1 to 5, preferably from 100:30 to 40:15 to 20:2 to 3;
preferably, the mass percentage of halogen in the multipolymer is 2.5-5.5%, preferably 4-5%.
3. Multipolymer according to claim 1 or 2, wherein the multipolymer has a number average molecular weight of 2.5-6 g/mol, preferably 4-5 g/mol;
preferably, the multipolymer has a molecular weight distribution index of 1.2 to 2, preferably 1.45 to 1.95;
preferably, the apparent viscosity of the multipolymer at 25 ℃ is 8-40cps.
4. A method of preparing a multipolymer, the method comprising: under the polymerization reaction condition, in the presence of an initiator, an optional structure regulator and an organic solvent, polymerizing a monomer shown in a formula (I), a monomer shown in a formula (II) and a monomer shown in a formula (III) to obtain a polymer solution;
adding conjugated diene monomer into the polymer solution to carry out end-capping reaction to obtain the multipolymer;
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 10 Straight or branched alkyl of (a); x is halogen, and n is any integer from 1 to 10.
5. The process according to claim 4, wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Each independently is hydrogen or C 1 -C 6 Straight-chain or branched alkyl of (2), preferably hydrogen or C 1 -C 4 More preferably hydrogen, methyl or ethyl;
preferably, R 6 Is methyl;
Preferably, X is selected from Cl and/or Br;
preferably, n is any integer from 1 to 5, preferably any integer from 1 to 3.
6. The production process according to claim 4 or 5, wherein the conjugated diene is butadiene and/or isoprene;
preferably, the mass ratio of the monomer shown in the formula (I), the monomer shown in the formula (II), the monomer shown in the formula (III) and the conjugated diene is 100:20-50:10-25:1-5, preferably 100:30-40:15-20:2-3;
preferably, the polymerization is carried out under a protective atmosphere, preferably an inert atmosphere;
preferably, the initiator is a hydrocarbyl monolithium compound, preferably RLi, wherein R is selected from C 1 -C 20 Saturated aliphatic hydrocarbon radicals, C 3 -C 20 Alicyclic hydrocarbon group and C 6 -C 20 At least one of the aromatic hydrocarbon groups of (a);
preferably, the initiator is selected from at least one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and dodecyllithium;
preferably, the initiator is used in an amount of 16 to 30mmo1, preferably 18 to 25mmo1, relative to 1000g of the monomer of formula (I);
preferably, the structure modifier is a polar organic compound;
preferably, the structure regulator is selected from at least one of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether and triethylamine;
Preferably, the organic solvent is a hydrocarbon solvent, preferably at least one of linear alkane, aromatic hydrocarbon and cycloalkane, further preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
7. The production method according to any one of claims 4 to 6, wherein the conditions of the polymerization reaction include: the polymerization reaction temperature is 50-80 ℃, and the polymerization reaction time is 220-270min;
preferably, the end-capping reaction temperature is 60-90 ℃, preferably 70-80 ℃; the end capping reaction time is 10-45min, preferably 20-30min.
8. The preparation method according to any one of claims 4 to 7, wherein the method comprises the steps of:
(1) Mixing a monomer shown in a formula (I), a structure regulator, an organic solvent and an initiator to perform a first polymerization reaction to obtain a first polymerization product;
(2) Adding a monomer shown in a formula (II) and a structure regulator into the first polymerization product to be mixed for a second polymerization reaction, so as to obtain a second polymerization product;
(3) Adding a monomer shown in a formula (III) and a structure regulator into the second polymerization product to carry out mixing to generate a third polymerization reaction, so as to obtain a third polymerization product;
(4) And adding conjugated diene into the third polymerization product to carry out end-capping reaction, so as to obtain the multipolymer.
9. The preparation method according to claim 8, wherein the mass ratio of the monomer shown in the formula (I) in the step (1) to the structure regulator is 100:0.5-0.7;
preferably, the mass ratio of the monomer shown in the formula (II) in the step (2) to the structure regulator is 30-40:0.3-0.5;
preferably, the mass ratio of the monomer shown in the formula (III) in the step (3) to the structure regulator is 15-20:0.2-0.3;
preferably, the first polymerization temperature is from 40 to 80 ℃, preferably from 50 to 60 ℃; the first polymerization time is 80-150min, preferably 100-120min;
preferably, the second polymerization temperature is 60-90 ℃, preferably 70-80 ℃; the second polymerization time is 50-80min, preferably 60-70min;
preferably, the third polymerization temperature is 60-90 ℃, preferably 70-80 ℃; the third polymerization time is 30-60min, preferably 40-50min.
10. A multipolymer obtainable by the process of any of claims 4 to 9.
11. Use of a multipolymer according to any of claims 1 to 3 and 10 as grafting agent in the preparation of diene rubbers.
12. Use according to claim 11, wherein the diene rubber is butyl rubber.
13. A halogenated branched butyl rubber, wherein the halogenated branched butyl rubber comprises: structural units I from isobutene, structural units II from isoprene and structural units III from halogenated grafting agents;
wherein the halogenated grafting agent is the multipolymer of any of claims 1-3 or 10.
14. The halogenated branched butyl rubber according to claim 13, wherein the mass ratio of structural unit I, structural unit II and structural unit III is 100:4-6:7-10, based on the total weight of the halogenated branched butyl rubber.
15. A process for the preparation of halogenated branched butyl rubber according to claim 13 or 14, characterized in that it comprises:
contacting isobutylene, isoprene and the multipolymer of any of claims 1-3 and 10 in the presence of a diluent, an organic solvent and a co-initiator to effect cationic polymerization to obtain the halogenated branched butyl rubber.
16. The production method according to claim 15, wherein the mass ratio of the isobutylene, isoprene and the multipolymer is 100:4 to 6:7 to 10;
preferably, the diluent is halogenated alkane, wherein halogen atoms in the halogenated alkane are preferably F, cl or Br, and preferably, the halogenated alkane is halogenated alkane with 1-4 carbon atoms;
Preferably, the diluent is selected from at least one of methane chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane;
preferably, the mass ratio of the isobutene to the diluent is 100:180-320;
preferably, the organic solvent is a hydrocarbon solvent, preferably at least one of linear alkanes, aromatic hydrocarbons, and cycloalkanes, further preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene;
preferably, the co-initiator comprises an alkyl aluminum halide and a protic acid;
preferably, the molar ratio of the alkyl aluminum halide to the protic acid in the co-initiator is from 10 to 100:1;
preferably, the alkyl aluminum halide is selected from at least one of diethyl aluminum chloride, diisobutyl aluminum chloride, dichloromethyl aluminum, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride;
preferably, the protic acid is selected from HCI, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 At least one of (a) and (b);
preferably, the mass ratio of the isobutene to the coinitiator is 100:0.1-0.3;
Preferably, the conditions of cationic polymerization include: the cationic polymerization temperature is-100 ℃ to-75 ℃; the cationic polymerization time is 3-4h.
17. A halogenated branched butyl rubber obtained according to the process of claim 15 or 16.
18. Use of the halogenated branched butyl rubber of any one of claims 13, 14 and 17 in instrument and electrical shock absorbers.
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| CN202211173637.1A CN117801191A (en) | 2022-09-26 | 2022-09-26 | Multi-copolymer, preparation method and application thereof, halogenated branched butyl rubber, and preparation method and application thereof |
| PCT/CN2023/117573 WO2024067013A1 (en) | 2022-09-26 | 2023-09-07 | Multi-component copolymer, preparation method therefor, and use thereof, and halogenated branched butyl rubber, preparation method therefor, and use thereof |
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| CN202211173637.1A CN117801191A (en) | 2022-09-26 | 2022-09-26 | Multi-copolymer, preparation method and application thereof, halogenated branched butyl rubber, and preparation method and application thereof |
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| GB8922677D0 (en) * | 1989-10-09 | 1989-11-22 | Dow Benelux | Rubber-reinforced polymer composition incorporating grafting agent |
| CN101353386A (en) * | 2007-07-27 | 2009-01-28 | 北京石油化工学院 | Initiation system for polymerization of star-branched polyisobutene or isobutene-diene rubber positive ion |
| CN101353403B (en) * | 2007-07-27 | 2012-02-08 | 中国石油化工股份有限公司 | Preparation of star-branched polyisobutene or isobutene-diene rubber |
| CN113493548B (en) * | 2020-04-08 | 2023-09-26 | 中国石油天然气股份有限公司 | Preparation method of branched butyl rubber |
| CN113831476B (en) * | 2020-06-24 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of low-saturation butyl rubber |
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