CN116355151A - Brominated grafting agent and preparation method and application thereof - Google Patents
Brominated grafting agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN116355151A CN116355151A CN202111631170.6A CN202111631170A CN116355151A CN 116355151 A CN116355151 A CN 116355151A CN 202111631170 A CN202111631170 A CN 202111631170A CN 116355151 A CN116355151 A CN 116355151A
- Authority
- CN
- China
- Prior art keywords
- brominated
- agent
- block
- grafting agent
- isoprene
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 188
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 137
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 73
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 26
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 24
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 24
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 238000005893 bromination reaction Methods 0.000 claims description 59
- 230000031709 bromination Effects 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 58
- 239000002994 raw material Substances 0.000 claims description 48
- 239000003505 polymerization initiator Substances 0.000 claims description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 38
- 239000003999 initiator Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- 239000003085 diluting agent Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 239000007822 coupling agent Substances 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 7
- 239000005060 rubber Substances 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229920005549 butyl rubber Polymers 0.000 abstract description 24
- 238000004073 vulcanization Methods 0.000 abstract description 18
- 239000003607 modifier Substances 0.000 abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 66
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- 238000006116 polymerization reaction Methods 0.000 description 42
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 33
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 32
- 229910001220 stainless steel Inorganic materials 0.000 description 27
- 239000010935 stainless steel Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 25
- 229910052786 argon Inorganic materials 0.000 description 21
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 17
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229920001400 block copolymer Polymers 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- FQEKAFQSVPLXON-UHFFFAOYSA-N butyl(trichloro)silane Chemical group CCCC[Si](Cl)(Cl)Cl FQEKAFQSVPLXON-UHFFFAOYSA-N 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- LMVTTXFQRCBOJU-UHFFFAOYSA-N 1,1-dibromo-3-methylbuta-1,3-diene Chemical compound CC(=C)C=C(Br)Br LMVTTXFQRCBOJU-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 125000001246 bromo group Chemical group Br* 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- -1 hydrocarbyl mono-lithium compounds Chemical class 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- GVTJVTFUVRQJKK-UHFFFAOYSA-N 2,3-dibromobuta-1,3-diene Chemical compound BrC(=C)C(Br)=C GVTJVTFUVRQJKK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 238000007342 radical addition reaction Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- MOOUPSHQAMJMSL-UHFFFAOYSA-N tert-butyl(trichloro)silane Chemical compound CC(C)(C)[Si](Cl)(Cl)Cl MOOUPSHQAMJMSL-UHFFFAOYSA-N 0.000 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 description 2
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical compound CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 description 1
- MARXMDRWROUXMD-UHFFFAOYSA-N 2-bromoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(Br)C(=O)C2=C1 MARXMDRWROUXMD-UHFFFAOYSA-N 0.000 description 1
- ZJCZFAAXZODMQT-UHFFFAOYSA-N 2-methylpentadecane-2-thiol Chemical group CCCCCCCCCCCCCC(C)(C)S ZJCZFAAXZODMQT-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- YXMVRBZGTJFMLH-UHFFFAOYSA-N butylsilane Chemical group CCCC[SiH3] YXMVRBZGTJFMLH-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002131 composite material Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- FLFGMNFGOKXUQY-UHFFFAOYSA-L dichloro(propan-2-yl)alumane Chemical compound [Cl-].[Cl-].CC(C)[Al+2] FLFGMNFGOKXUQY-UHFFFAOYSA-L 0.000 description 1
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 description 1
- UUXZFMKOCRKVDG-UHFFFAOYSA-N methane;hydrofluoride Chemical compound C.F UUXZFMKOCRKVDG-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- KNSVRQSOPKYFJN-UHFFFAOYSA-N tert-butylsilicon Chemical group CC(C)(C)[Si] KNSVRQSOPKYFJN-UHFFFAOYSA-N 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical group CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- QWBBTCQPNIEDSP-UHFFFAOYSA-N tribromo(tert-butyl)silane Chemical compound CC(C)(C)[Si](Br)(Br)Br QWBBTCQPNIEDSP-UHFFFAOYSA-N 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention provides a brominated grafting agent and a preparation method and application thereof, wherein the brominated grafting agent has a structure shown in a formula 1, in the formula 1, bu is tertiary butyl, ps is a homopolymerization block of styrene, E is a homopolymerization block of dibrominated 1, 3-butadiene, A is a homopolymerization block of dibrominated isoprene, D is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, l is not less than 1, m is not less than 1, and n is not less than 1; in the brominated grafting agent, the mass percentage of bromine element is 15-25%. The brominated grafting agent can be used as a modifier for the butyl rubber to modify the butyl rubber into brominated butyl rubber, and the properties of the brominated butyl rubber including dimensional stability, vulcanization processability and the like are obviously improved, so that the application range of the butyl rubber is widened.
Description
Technical Field
The invention relates to a grafting agent, in particular to a brominated grafting agent, a preparation method and application thereof, and belongs to the technical field of high polymer materials.
Background
As one of the most important synthetic Rubber varieties, butyl Rubber (IIR for short) produced by cationic polymerization and copolymerization of isobutylene and a small amount of isoprene as raw materials is widely used in the fields of inner tubes, inner liners, curing bladders, and the like for manufacturing tires for vehicles.
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, remarkable extrusion swelling effect, long vulcanization scorching time, low vulcanization speed and the like, and the processability of the butyl rubber cannot meet the processing requirements and application scenes of gradual diversification, thus becoming the bottleneck of expanding the application of the butyl rubber material.
Therefore, how to modify butyl rubber to have more excellent application performance is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
The invention provides a brominated grafting agent which is used as a modifier of p-butyl rubber, can modify butyl rubber into brominated butyl rubber, and can obviously improve properties of the brominated butyl rubber including dimensional stability, vulcanization processability and the like, thereby widening the application range of the butyl rubber.
The invention also provides a preparation method of the brominated grafting agent, which can modify butyl rubber and ensure that the modified brominated butyl rubber has excellent processability.
The invention also provides a brominated butyl rubber which comprises the brominated grafting agent, and therefore, has excellent processability, and is particularly characterized by lower unsaturation degree, air permeability and extrusion expansion ratio, shorter vulcanization scorch time and positive vulcanization time, longer static ozone property break time and higher branching degree.
The invention also provides a rubber product which is obtained by processing the brominated butyl rubber and has excellent performances in the aspects of ageing resistance, product dimensional stability and the like.
The invention provides a brominated grafting agent, which has a structure shown in a formula 1:
wherein Bu is tertiary butyl, ps is a styrene homopolymerization block, E is a dibrominated 1, 3-butadiene homopolymerization block, A is a dibrominated isoprene homopolymerization block, D is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, l is not less than 1, m is not less than 1, n is not less than 1;
in the brominated grafting agent, the mass percentage of bromine element is 15% -25%.
The brominated grafting agent as described above, wherein the number average molecular weight of the brominated grafting agent is 70000 to 90000 and the molecular weight distribution is 10.16 to 11.65.
A brominated grafting agent as described above, wherein the brominated grafting agent is prepared by a process comprising:
the first raw material system is reacted for 20 to 30 minutes at the temperature of between 40 and 50 ℃, then a first monomer and a first structure regulator A are added into the system, and the reaction is carried out for 40 to 50 minutes at the temperature of between 50 and 60 ℃ to obtain a first block system; adding a first organic brominating agent and a first molecular weight regulator into the first block system, heating to 70-80 ℃, adding a first organic brominating initiator, and reacting for 3-4 hours to obtain a first brominating system;
the second raw material system reacts for 30 to 40 minutes at the temperature of between 40 and 50 ℃, then a second monomer is added into the system, and then the reaction is carried out for 50 to 60 minutes at the temperature of between 50 and 60 ℃ to obtain a second block system; adding a second organic brominating agent and a second molecular weight regulator into the second block system, heating to 70-80 ℃, adding a second organic brominating initiator, and reacting for 2-3 hours to obtain a second brominating system;
reacting the third raw material system at 60-70 ℃ for 20-30 min to obtain a third block system;
adding the second bromination system and the third block system into the first bromination system, adding a tertiary butyl trihalosilane coupling agent at 80-90 ℃ for reaction for 130-150 min, and then adding an activating end capping agent for reaction for 20-30 min to obtain the brominated grafting agent;
Wherein the first raw material system comprises isoprene, a first structure regulator B and a first polymerization initiator; the second raw material system comprises isoprene, a second structure regulator and a second polymerization initiator; the third raw material system comprises a third monomer, a third structure regulator and a third polymerization initiator;
the first monomer and the activated end-capping agent are 1, 3-butadiene, and the second monomer and the third monomer are styrene.
The brominated grafting agent as described above, wherein the mass ratio of the organic brominating agent to the mass ratio of isoprene, the first structure regulator B, the first monomer, the first structure regulator a, the first molecular weight regulator and the first organic brominating initiator in the first raw material system is 1: (0.2-0.3): (0.001-0.003): (0.4-0.5): (0.001-0.003): (0.002-0.005): (0.002-0.005); and/or the number of the groups of groups,
the mass ratio of the organic brominating agent to the mass ratio of the isoprene, the second structure regulator, the second monomer, the second molecular weight regulator and the second organic brominating initiator in the second raw material system is 1: (0.1-0.2): (0.001-0.003): (0.2-0.3): (0.001-0.003): (0.001-0.003); and/or the number of the groups of groups,
the mass ratio of the organic brominating agent to the third monomer and the third structure regulator is 1: (0.05-0.1): (0.001-0.003);
Wherein the mass of the organic brominating agent is the total mass of the first organic brominating agent and the second brominating agent, and the mass ratio of the first organic brominating agent to the second organic brominating agent is (0.7-0.8): (0.2-0.3).
The brominated grafting agent, wherein the molar ratio of the tertiary butyl trihalosilane coupling agent to the polymerization initiator is 2:1-5:1;
the polymerization initiator is composed of the first polymerization initiator, a second polymerization initiator, and a third polymerization initiator.
The invention also provides a preparation method of the brominated grafting agent, which comprises the following steps:
the first raw material system is reacted for 20 to 30 minutes at the temperature of between 40 and 50 ℃, then a first monomer and a first structure regulator A are added into the system, and the reaction is carried out for 40 to 50 minutes at the temperature of between 50 and 60 ℃ to obtain a first block system; adding a first organic brominating agent and a first molecular weight regulator into the first block system, heating to 70-80 ℃, adding a first organic brominating initiator, and reacting for 3-4 hours to obtain a first brominating system;
the second raw material system reacts for 30 to 40 minutes at the temperature of between 40 and 50 ℃, then a second monomer is added into the system, and then the reaction is carried out for 50 to 60 minutes at the temperature of between 50 and 60 ℃ to obtain a second block system; adding a second organic brominating agent and a second molecular weight regulator into the second block system, heating to 70-80 ℃, adding a second organic brominating initiator, and reacting for 2-3 hours to obtain a second brominating system;
Reacting the third raw material system at 60-70 ℃ for 20-30 min to obtain a third block system;
adding the second bromination system and the third block system into the first bromination system, adding a tertiary butyl trihalosilane coupling agent at 80-90 ℃ for reaction for 130-150 min, and then adding an activating end capping agent for reaction for 20-30 min to obtain the brominated grafting agent;
wherein the first raw material system comprises isoprene, a first structure regulator B and a first polymerization initiator; the second raw material system comprises isoprene, a second structure regulator and a second polymerization initiator; the third raw material system comprises a third monomer, a third structure regulator and a third polymerization initiator;
the first monomer and the activated end-capping agent are 1, 3-butadiene, and the second monomer and the third monomer are styrene;
wherein Bu is tertiary butyl, ps is a styrene homopolymerization block, E is a dibrominated 1, 3-butadiene homopolymerization block, A is a dibrominated isoprene homopolymerization block, D is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, l is not less than 1, m is not less than 1, n is not less than 1;
in the brominated grafting agent, the mass percentage of bromine element is 15% -25%.
The invention also provides a brominated butyl rubber, which is obtained by the polymerization reaction of the brominated graft described in any one of the above and a system comprising isobutene and isoprene;
The mass ratio of the brominated grafting agent to the isobutene to the isoprene is (9-12): (85-90): (1-3).
A brominated butyl rubber as described above, wherein the brominated butyl rubber is prepared by a process comprising:
adding a first diluent, isobutene and isoprene into a solution system of the brominated grafting agent at the temperature of-95 to-85 ℃ and then adjusting the temperature to be between-100 ℃ and-90 ℃ to obtain a first system;
mixing a second diluent and a co-initiator at a temperature of between-95 and-85 ℃ and aging for 40 to 50 minutes to obtain a second system;
and mixing the first system and the second system, reacting for 1-3h, and stopping the reaction to obtain the brominated butyl rubber.
The brominated butyl rubber as described above, wherein the mass ratio of the reaction main body, the first diluent, the second diluent and the co-initiator is 1: (1-2): (0.1-0.2): (0.002-0.005);
the mass of the reaction main body is the total mass of the brominated grafting agent, isobutene and isoprene.
The invention also provides a rubber product, which is processed by the brominated butyl rubber.
The brominated grafting agent is used for modifying butyl rubber, and the special structure and bromine content of the brominated butyl rubber can ensure that the modified brominated butyl rubber has the characteristics of stable bromine structure, high branching degree and high saturation, thereby being beneficial to improving the vulcanization processing characteristics (shorter vulcanization scorching time and positive vulcanization time), the processing dimensional stability (lower extrusion expansion ratio), the ageing resistance (longer static ozone property break time) and the airtight property (lower air permeability) of the brominated butyl rubber.
Therefore, the rubber product processed from the brominated butyl rubber has excellent performances in vulcanization processing characteristics, product dimensional stability, aging resistance, air tightness and the like.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The first aspect of the present invention provides a brominated grafting agent having a structure represented by the following formula 1:
wherein Bu is tertiary butyl, ps is a styrene homopolymerization block, E is a dibrominated 1, 3-butadiene homopolymerization block, A is a dibrominated isoprene homopolymerization block, D is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, l is not less than 1, m is not less than 1, n is not less than 1;
in the brominated grafting agent, the mass percentage of bromine element is 15% -25%.
The brominated grafting agent is used for carrying out bromination modification on butyl rubber to obtain brominated butyl rubber. The invention is not limited to the molecular weight of the brominated grafting agent, as long as the polymer satisfying the structure and the mass percentage of bromine element is the brominated grafting agent of the invention.
The brominated grafting agent is a ternary three-hetero-arm star-shaped brominated grafting agent, namely the grafting agent comprises different polymer substituent groups formed by polymerizing three monomers. Specifically, the brominated grafting agent can be considered to be t-butylsilane substituted with three polymer substituents, wherein one polymer substituent is a block copolymer of a dibromo 1, 3-butadiene homo-block E and a dibromo isoprene homo-block A, one polymer substituent is a block copolymer of a styrene homo-block Ps and a dibromo isoprene homo-block A, and one polymer substituent is a styrene homo-block Ps.
The structure of the styrene homo-block Ps is shown as 1-a, the structure of the dibromo 1, 3-butadiene homo-block E is shown as 1-b, and the structure of the dibromo isoprene homo-block A is shown as 1-c.
The molecular weights of the three homo-blocks, i.e., o, p, q, may be any number of 1 or more.
In addition, the brominated grafting agent also comprises an activated end sealing group B, wherein the activated end sealing group B is used for improving the reactivity of the brominated grafting agent and butyl rubber so as to improve the modification efficiency of the butyl rubber. Specifically, the end-capping group B is a copolymer of 1, 3-butadiene and has a number average molecular weight of not more than 1000.
The brominated grafting agent has higher mass percent of bromine element, so that the brominated grafting agent has excellent stability, particularly the stability of a secondary carbon atom bromine structure is excellent, the problem that the butyl rubber is hard to vulcanize due to less double bonds caused by high saturation is solved, and the vulcanization speed is improved.
In addition, from the structure, the ternary three-hetero-arm star-shaped structure of the brominated grafting agent can destroy the regular molecular structure of butyl rubber, and the modified brominated butyl rubber can obtain good viscoelastic performance by increasing the disorder of chain segments, so that the extrusion swelling effect is reduced, and the modified brominated butyl rubber is ensured to have excellent processing dimensional stability.
It is also notable that the content of unsaturated double bonds in the brominated grafting agent is obviously lower, so that the introduction of unsaturated double bonds into the butyl rubber can be avoided in the modification process, the saturation of the modified brominated butyl rubber is improved, and the modified brominated butyl rubber is excellent in ozone resistance and air tightness.
Therefore, the brominated grafting agent has the characteristics of stable bromine structure, high disorder degree and high saturation degree, and the brominated butyl rubber modified by the brominated grafting agent is favorable for improving the vulcanization processability, the extrusion swelling effect, the ozone aging resistance and the air tightness of the modified brominated butyl rubber, so that the modified brominated butyl rubber has excellent processability to meet various application requirements.
Further, the inventors have found that when the number average molecular weight of the above brominated grafting agent is 70000 to 90000 and the molecular weight distribution (Mw/Mn) is 10.16 to 11.65, the promotion effect on the processability of the brominated butyl rubber can be achieved with higher economic efficiency.
The present invention is not limited to the method of preparing the brominated grafting agent, and in one embodiment, the brominated grafting agent is prepared by a method comprising the following process.
The method comprises a preparation step of a first bromination system, a preparation step of a second bromination system, a preparation step of a third block system and a coupling activation step, wherein the coupling activation step is a process of coupling the first bromination system, the second bromination system and the third bromination system through a coupling agent and then blocking and activating. It will be appreciated that there is no relationship between the steps of preparing the first bromination system, the steps of preparing the second bromination system, and the steps of preparing the third block system, and thus the first bromination system, the second bromination system, and the third block system can be prepared separately and independently of each other.
These four steps are described below.
The first bromination system of the present invention refers to a system comprising a block copolymer of a dibromo 1, 3-butadiene homo-block and a dibromo isoprene homo-block. Specifically, a first raw material system is reacted for 20-30 min at 40-50 ℃, then a first monomer and a first structure regulator A are added into the system, and then the reaction is carried out for 40-50 min at 50-60 ℃ to obtain a first block system; and adding a first organic brominating agent and a first molecular weight regulator into the first block system, heating to 70-80 ℃, adding a first organic brominating initiator, and reacting for 3-4 hours to obtain a first brominating system. Wherein the first raw material system comprises isoprene, a first structure regulator B and a first polymerization initiator, and the first monomer is 1, 3-butadiene. In the process, isoprene monomers are homopolymerized to obtain isoprene homopolymerized blocks, then 1, 3-butadiene which is added as a first monomer is homopolymerized, and the generated 1, 3-butadiene homopolymerized blocks are segmented with isoprene homopolymerization to obtain a block copolymer of the 1, 3-butadiene homopolymerized blocks and the isoprene homopolymerized blocks. Then, the addition of the first organic brominating agent can generate free radical bromination addition reaction with the block copolymer of the 1, 3-butadiene homopolymerization block and the isoprene homopolymerization block to obtain the block copolymer of the dibrominated 1, 3-butadiene homopolymerization block and the dibrominated isoprene homopolymerization block.
The second brominated system of the present invention is a system comprising a block copolymer of a styrene homo-block and a dibromoisoprene homo-block. Specifically, the second raw material system is reacted for 30 to 40 minutes at the temperature of between 40 and 50 ℃, then a second monomer is added into the system, and the reaction is carried out for 50 to 60 minutes at the temperature of between 50 and 60 ℃ to obtain a second block system; and adding a second organic brominating agent and a second molecular weight regulator into the second block system, heating to 70-80 ℃, adding a second organic brominating initiator, and reacting for 2-3 h to obtain a second brominating system. Wherein the second raw material system comprises isoprene, a second structure regulator and a second polymerization initiator, and the second monomer is styrene. In the process, isoprene monomers are homopolymerized to obtain an isoprene homopolymerized block, then styrene which is a second monomer is added to homopolymerize, and the generated styrene homopolymerized block is segmented with isoprene homopolymerization to obtain a block copolymer of the styrene homopolymerized block and the isoprene homopolymerized block. Then, the addition of the second organic brominating agent can generate free radical bromination addition reaction with the block copolymer of the styrene homopolymerization block and the isoprene homopolymerization block to obtain the block copolymer of the styrene homopolymerization block and the dibrominated isoprene homopolymerization block.
The third block system of the present invention is a system comprising styrene homo-blocks. Specifically, the third block system is obtained after the third raw material system reacts for 20 to 30 minutes at the temperature of between 60 and 70 ℃. The third raw material system comprises a third monomer, a third structure regulator and a third polymerization initiator, wherein the third monomer is styrene. In this process, homopolymerization of the styrene monomer occurs to give a styrene homopolymerization block.
After the preparation of the first bromination system, the second bromination system and the third block system is finished, the second bromination system and the third block system are added into the first bromination system, tertiary butyl trihalogenosilane coupling agent is added at 80-90 ℃ and reacts for 130-150 min, and then activated end capping agent 1, 3-butadiene is added and reacts for 20-30 min, so that the brominated grafting agent is obtained. After the activated end capping reagent is added for reaction for 20-30 min, the reaction system is subjected to post-treatment including discharging coagulation, washing and drying to finally obtain the brominated grafting reagent.
As mentioned previously, in the preparation of the first and second bromination systems, both the brominating agent employed and the brominating initiator are organic compounds, and thus the bromination process is a free radical addition reaction. On the one hand, the free radical addition reaction is beneficial to avoiding the generation of byproduct hydrogen bromide (HBr) and avoiding the molecular rearrangement of a bromine structure, so that the high bromine content and the high bromine structure stability of the brominated grafting agent are realized, and meanwhile, the alkaline washing recovery flow of the byproduct HBr is omitted, thereby shortening the process flow and reducing the production cost. On the other hand, the content of unsaturated double bonds in the brominated grafting agent is obviously reduced by the bromination reaction of free radical addition, and the introduction of unsaturated double bonds in the modification process of the butyl rubber is avoided, so that the saturation of the modified brominated butyl rubber is improved.
In the preparation process, the preparation of the brominated grafting agent with the target molecular weight can be realized by further controlling the dosage of each raw material, the preparation time and other factors.
As a preferred embodiment, the mass ratio of the organic brominating agent to the mass ratio of isoprene, the first structure regulator B, the first monomer, the first structure regulator a, the first molecular weight regulator and the first organic brominating initiator in the first raw material system is 1: (0.2-0.3): (0.001-0.003): (0.4-0.5): (0.001-0.003): (0.002-0.005): (0.002-0.005); and/or the number of the groups of groups,
the mass ratio of the organic brominating agent to the isoprene, the second structure regulator, the second monomer, the second molecular weight regulator and the second organic brominating initiator in the second raw material system is 1: (0.1-0.2): (0.001-0.003): (0.2-0.3): (0.001-0.003): (0.001-0.003); and/or the number of the groups of groups,
the mass ratio of the organic brominating agent to the third monomer and the third structure regulator is 1: (0.05-0.1): when (0.001-0.003), not only the brominated grafting agent with proper molecular weight can be prepared, but also the economic benefit of the preparation method can be increased by improving the yield of the product.
It should be noted that the mass of the organic brominating agent means the total mass of the first organic brominating agent and the second organic brominating agent, and the mass ratio of the first organic brominating agent to the second organic brominating agent is (0.7-0.8): (0.2-0.3).
In addition, the mass ratio of the organic brominating agent to the activated end capping agent is 1: (0.01-0.02).
It will be appreciated that the first, second and third feed systems comprise solvents in addition to the aforementioned compositions. Further, the mass of the solvent in each raw material system is 100% -200% of that of the organic brominating agent. The solvent is selected from linear alkane, arene and cycloalkane, and can be selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
In addition, the preparation process is carried out in an oxygen-free and water-free environment, so that the reaction environment needs to be protected by inert gas at the beginning of the preparation.
In the preparation process of the invention, the first organic brominating agent and the second organic brominating agent are independently selected from one of N-bromosuccinimide, N-bromophthalimide and N, N '-dibromo-5, 5' -dimethylhydantoin, and preferably N-bromosuccinimide.
The first polymerization initiator, the second polymerization initiator and the third polymerization initiator are all hydrocarbyl mono-lithium compounds, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or composite group of the above groups containing 1-20 carbon atoms. The first polymerization initiator, the second polymerization initiator and the third polymerization initiator are each independently selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthalenelithium, cyclohexyllithium and dodecyllithium, preferably n-butyllithium. The amount of each polymerization initiator added is determined by the molecular weight of the target brominated grafting agent, for example, the amount of material of butyllithium is calculated by the following formula.
Wherein, the total mass of the glue refers to the expected preparation mass of the target brominated grafting agent, and the molecular weight refers to the molecular weight of the target brominated grafting agent.
The first organic bromination initiator and the second organic bromination initiator are both organic peroxides and are each independently selected from one of di-tert-butyl hydroperoxide (TBHP), 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide (BPDH), di-tert-butyl peroxide (DTBP), dicumyl peroxide (DCP), preferably TBHP.
The first structure modifier a, the first structure modifier B, the second structure modifier and the third structure modifier are all polar organic compounds for generating a solvation effect in the polymerization reaction. The first structure regulator A, the first structure regulator B, the second structure regulator and the third structure regulator are each independently selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME) and triethylamine, preferably Tetrahydrofuran (THF).
The first molecular weight regulator and the second molecular weight regulator are each independently selected from one of tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan, tertiary hexadecyl mercaptan, preferably tertiary dodecyl mercaptan.
The trihalosilane coupling agent is selected from one of tert-butyltrichlorosilane and tert-butyltribromosilane, and preferably tert-butyltrichlorosilane. Further, the molar ratio of the trihalosilane coupling agent to the polymerization initiator is 2:1-5:1, wherein the polymerization initiator is a set of a first polymerization initiator, a second polymerization initiator and a third polymerization initiator.
The brominated grafting agent is an organic combination of a 1, 3-butadiene homopolymerization block, an isopentene homopolymerization block, a styrene homopolymerization block, trihalogenated tertiary butyl silane and a secondary bromine structure, and the parts are combined together and cooperatively played, so that the brominated grafting agent can be finally used for modifying butyl rubber, and the modified brominated butyl rubber has excellent vulcanization processability, ageing resistance, air tightness and dimensional stability.
The second aspect of the invention provides a preparation method of a brominated grafting agent, which comprises the steps of adding a first monomer and a first structure regulator A into a first raw material system after reacting for 20-30 min at 40-50 ℃, and then reacting for 40-50 min at 50-60 ℃ to obtain a first block system; adding a first organic brominating agent and a first molecular weight regulator into the first block system, heating to 70-80 ℃, adding a first organic brominating initiator, and reacting for 3-4 hours to obtain a first brominating system;
The second raw material system reacts for 30 to 40 minutes at the temperature of between 40 and 50 ℃, then a second monomer is added into the system, and then the reaction is carried out for 50 to 60 minutes at the temperature of between 50 and 60 ℃ to obtain a second block system; adding a second organic brominating agent and a second molecular weight regulator into the second block system, heating to 70-80 ℃, adding a second organic brominating initiator, and reacting for 2-3 hours to obtain a second brominating system;
reacting the third raw material system at 60-70 ℃ for 20-30 min to obtain a third block system;
adding the second bromination system and the third block system into the first bromination system, adding a tertiary butyl trihalosilane coupling agent at 80-90 ℃ for reaction for 130-150 min, and then adding an activating end capping agent for reaction for 20-30 min to obtain the brominated grafting agent;
wherein the first raw material system comprises isoprene, a first structure regulator B and a first polymerization initiator; the second raw material system comprises isoprene, a second structure regulator and a second polymerization initiator; the third raw material system comprises a third monomer, a third structure regulator and a third polymerization initiator;
the first monomer and the activated end-capping agent are 1, 3-butadiene, and the second monomer and the third monomer are styrene;
The brominated grafting agent has a structure shown in a formula 1,
wherein Bu is tertiary butyl, ps is a styrene homopolymerization block, E is a dibrominated 1, 3-butadiene homopolymerization block, A is a dibrominated isoprene homopolymerization block, D is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, l is not less than 1, m is not less than 1, n is not less than 1;
in the brominated grafting agent, the mass percentage of bromine element is 15% -25%.
The specific description of the preparation method is the same as that mentioned in the first aspect, and is not repeated here.
The preparation method takes isoprene, styrene and butadiene as reaction monomers to polymerize in different combinations or independently, and finally adopts tertiary butyl trihalogenosilane coupling agent to couple each polymer to prepare the ternary tri-hetero-arm star-shaped brominated grafting agent. On one hand, the brominated grafting agent prepared by the method has high mess. On the other hand, in the process, the free radical bromine addition reaction is realized by adopting an organic brominating agent and an organic brominating initiator, so that the brominated grafting agent with high bromine content and high stability is prepared by avoiding the generation of hydrogen bromide and avoiding bromine rearrangement, and the unsaturation degree of the brominated grafting agent is reduced.
In a third aspect, the present invention provides a brominated butyl rubber obtained by polymerizing the brominated grafting agent of the first or second aspect with a system comprising isobutylene and isoprene;
the mass ratio of the brominated grafting agent to the isobutene to the isoprene is (9-12): (85-90): (1-3).
The brominated butyl rubber obtained by modified grafting according to the proportion of the raw materials has excellent vulcanization processability, ageing resistance, air tightness and dimensional stability because the brominated grafting agent has the characteristics of high stability, high disorder degree and high saturation degree.
The present invention is not limited to a specific graft modification method.
In one embodiment, to better adapt the aforementioned brominated grafting agent, the brominated butyl rubber is prepared by a process comprising the following steps:
adding a first diluent, isobutene and isoprene into a solution system of the brominated grafting agent at the temperature of-95 to-85 ℃ and then adjusting the temperature to be between-100 ℃ and-90 ℃ to obtain a first system;
mixing a second diluent and a co-initiator at a temperature of between-95 and-85 ℃ and aging for 40 to 50 minutes to obtain a second system;
and mixing the first system and the second system, reacting for 1-3h, and stopping the reaction to obtain the brominated butyl rubber.
The order of preparation of the first system and the second system is not particularly limited.
The invention is not limited to the dissolution mode of the brominated grafting agent, for example, the brominated grafting agent is added into a mixed solvent of which the volume ratio of the diluent to the solvent is 7:3-3:7, and stirred for 90-100 min until the brominated grafting agent is dissolved. Wherein the solvent is selected from linear alkane, arene and cycloparaffin, and can be selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane. The diluent is selected from halogenated alkanes, wherein halogen atoms in the halogenated alkanes can be chlorine, bromine or fluorine, and the number of carbon atoms in the halogenated alkanes is C1-C4, for example, one selected from chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, and preferably chloromethane.
Further, the mass ratio of the reaction main body, the first diluent, the second diluent and the co-initiator is 1: (1-2): (0.1-0.2): (0.002-0.005); the mass of the reaction body is the total mass of the brominated grafting agent, isobutene and isoprene. It should be noted that isobutylene and isoprene herein refer to raw materials for polymerization to prepare butyl rubber.
In addition, termination of the reaction may be achieved by addition of a terminator. The terminator is one or more selected from methanol, ethanol and butanol, and the mass ratio of the terminator to the reaction main body is (0.05-0.1): 1. after the reaction is terminated, the reaction system is coagulated, washed and dried to obtain the brominated butyl rubber of the present invention.
In the above preparation process, the first diluent and the second diluent are each independently selected from one of methane chloride, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane, preferably methane chloride.
The co-initiator is a combination of an alkyl aluminum halide and a protic acid. The alkyl aluminum halide is at least one selected from diethyl aluminum chloride, diisobutyl aluminum chloride, methyl aluminum dichloride, aluminum sesquioxide, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride, preferably aluminum sesquioxide. The protonic acid is selected from HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCl. Wherein the total addition amount of the co-initiator is 0.2-0.7% of the mass of the main reaction body, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1-0.1:1.
In a fourth aspect, the present invention provides a rubber article processed from the brominated butyl rubber of the third aspect.
The rubber product has the characteristics of excellent dimensional stability, air tightness and ageing resistance.
The brominated grafting agent and the brominated butyl rubber of the present invention are described in detail below by way of specific examples.
The specific sources of part of raw materials in the following preparation process are as follows:
other reagents are commercial industrial products
Example 1
The preparation method of the brominated grafting agent comprises the following steps:
1) Introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 2 times, sequentially adding 1000g of cyclohexane and 200g,THF 1.0g,12.8mmo1 n-butyllithium isoprene into the polymerization kettle, heating to 40 ℃ for reaction for 20min, sequentially adding 400g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle A, heating to 50 ℃ for reaction for 40min, and obtaining a first block system;
then 700g of N-bromosuccinimide and 2.0g of tertiary dodecyl mercaptan are sequentially added into the first block system, the temperature is raised to 70 ℃, 2.0g of TBHP is added for reaction for 3.0h, and a first bromination system is obtained;
2) In a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1000g of cyclohexane and 100g,THF 1.0g,10.8mmo1 n-butyllithium isoprene, heating to 40 ℃ and then reacting for 30min, then adding 200g of styrene into the polymerization kettle B, heating to 50 ℃ and reacting for 50min to obtain a second block system;
Sequentially adding 300g of N-bromosuccinimide and 1.0g of tertiary dodecyl mercaptan into a second block system, heating to 70 ℃, adding 1.0g of TBHP for reacting for 2.0h to obtain a second bromination system;
3) In a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane and 50g,THF 1.0g,6.8mmo1 n-butyllithium styrene, heating to 60 ℃ and reacting for 20min to obtain a third block system;
4) Adding the second bromination system and the third block system into the first bromination system, heating to 80 ℃, adding 60.5 mmol 1 of tertiary butyl trichlorosilane for coupling reaction, adding 10g of 1, 3-butadiene for end-capping activation after 130min of reaction, reacting for 20min until no free monomer exists, and carrying out wet condensation and drying on the reaction solution to obtain the brominated grafting agent A of the embodiment.
The brominated butyl rubber of this example is prepared according to the following preparation method:
1) In a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 300g of methyl chloride, 700g of cyclohexane and 60g of brominated grafting agent A into the reaction kettle, stirring and dissolving for 90min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 500g of chloromethane, 425g of isobutene and 15g of isoprene, and stirring and mixing until the system temperature is reduced to-90 ℃ to obtain a first system;
2) 50g of methyl chloride, 1.125g of aluminum sesquichloride and 0.009g of HCl are mixed and aged for 40min at the temperature of minus 85 ℃ to obtain a second system;
3) The second system was added to the first system, stirred and reacted for 1.0 hour, then 25g of butanol was added, and finally, the mixture was discharged and coagulated, washed and dried to obtain brominated butyl rubber A of this example.
Example 2
The preparation method of the brominated grafting agent comprises the following steps:
1) In a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 2 times, sequentially adding 1200g of cyclohexane and 220g,THF 1.5g,14.2mmo1 n-butyllithium isoprene into the polymerization kettle, heating to 42 ℃, reacting for 22min, sequentially adding 420g of 1, 3-butadiene and 1.7g of THF into the polymerization kettle A, heating to 52 ℃, and reacting for 42min to form a first block system;
sequentially adding 720g of N-bromosuccinimide and 2.6g of tertiary dodecyl mercaptan into the first block system, heating to 72 ℃, adding 2.7g of TBHP for reaction for 3.2 hours, and obtaining a first bromination system;
2) In a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1200g of cyclohexane and 120g,THF 1.5g,11.8mmo1 n-butyllithium isoprene, heating to 42 ℃ and then reacting for 32min, then adding 220g of styrene into the polymerization kettle B, heating to 53 ℃ and reacting for 52min to obtain a second block system;
Then 280g of N-bromosuccinimide and 1.6g of tertiary dodecyl mercaptan are sequentially added into the second block system, the temperature is raised to 72 ℃, 1.4g of TBHP is added for reaction for 2.2 hours, and a first bromination system is obtained;
3) In a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1200g of cyclohexane and 60g,THF 1.3g,8.2mmo1 n-butyllithium styrene, heating to 62 ℃, and then starting to react for 22min to form a third block system;
4) Adding the second bromination system and the third block system into the first bromination system, heating to 82 ℃, adding 80.5 mmol 1 of tertiary butyl trichlorosilane for coupling reaction, adding 12g of 1, 3-butadiene for end-capping activation after 135min of reaction, reacting for 22min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent B of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Adding 400g of methyl chloride, 600g of cyclohexane and 57g of brominated grafting agent B into a polymerization kettle, stirring and dissolving for 92min until the grafting agent is completely dissolved, then cooling to the temperature of minus 87 ℃, sequentially adding 600g of methyl chloride, 430g of isobutene and 13g of isoprene when the grafting agent is cooled to the temperature of minus 87 ℃, and stirring and mixing until the system temperature is reduced to the temperature of minus 92 ℃ to obtain a first system;
2) 60g of methyl chloride, 1.312g of aluminum sesquichloride and 0.013g of HCl are mixed and aged for 42min at the temperature of minus 87 ℃ to obtain a second system;
3) Adding the second system into the first system, stirring and reacting for 1.5 hours, finally adding 30g of butanol, discharging and condensing, washing and drying to obtain the brominated butyl rubber B of the embodiment.
Example 3
The preparation method of the brominated grafting agent comprises the following steps:
1) In a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 3 times, sequentially adding 1400g of cyclohexane and 240g,THF 1.8g,17.1mmo1 n-butyllithium isoprene into the polymerization kettle, heating to 45 ℃, starting to react for 25min, sequentially adding 450g of 1, 3-butadiene, 2.0g of THF into the polymerization kettle A, heating to 55 ℃, and reacting for 44min to obtain a first block system;
then 740g of N-bromosuccinimide and 3.0g of tertiary dodecyl mercaptan are sequentially added into the first block system, the temperature is raised to 75 ℃, 3.5g of TBHP is added for reaction for 3.5 hours, and a first bromination system is obtained;
2) Introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1500g of cyclohexane and 140g,THF 2.0g,13.1mmo1 n-butyllithium isoprene, heating to 44 ℃, starting to react for 35min, then adding 240g of styrene into the polymerization kettle B, heating to 55 ℃, and reacting for 54min to obtain a second block system;
Sequentially adding 260g of N-bromosuccinimide and 2.0g of tertiary dodecyl mercaptan into the second block system, heating to 75 ℃, adding 1.9g of TBHP for reacting for 2.5 hours to obtain a second bromination system;
3) Introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1500g of cyclohexane and 70g,THF 1.7g,9.5mmo1 n-butyllithium styrene, heating to 64 ℃, and then starting to react for 25min to obtain a third block system;
4) Adding a second bromination system and a third block system into the first block system, heating to 85 ℃, adding 100.5 mmol 1 of tertiary butyl trichlorosilane for coupling reaction, reacting for 140min, then adding 15g of 1, 3-butadiene for end-capping activation, reacting for 25min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent C.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Adding 500g of methyl chloride, 500g of cyclohexane and 52g of brominated grafting agent C into a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times, stirring and dissolving for 95min until the grafting agent is completely dissolved, then sequentially adding 700g of methyl chloride, 438g of isobutene and 10g of isoprene when the grafting agent is cooled to-90 ℃, and stirring and mixing until the system temperature is reduced to-95 ℃ to obtain a first system;
2) 70g of methyl chloride, 1.552g of aluminum sesquichloride and 0.028g of HCl are mixed and aged for 45min at the temperature of minus 90 ℃ to obtain a second system;
3) Adding the second system into the first system, stirring and reacting for 2.0h, finally adding 35g of butanol, discharging and condensing, washing and drying to obtain the brominated butyl rubber C of the embodiment.
Example 4
The preparation method of the brominated grafting agent comprises the following steps:
1) Introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 1500g of cyclohexane and 260g,THF 2.2g,19.5mmo1 n-butyllithium isoprene into the polymerization kettle, heating to 47 ℃, starting to react for 27min, sequentially adding 470g of 1, 3-butadiene, 2.5g of THF into the polymerization kettle A, heating to 57 ℃, and reacting for 46min to obtain a first block system;
sequentially adding 760g of N-bromosuccinimide and 3.5g of tertiary dodecyl mercaptan into the first block system, heating to 77 ℃, adding 4.0g of TBHP, and reacting for 3.6h to obtain a first bromination system;
2) In a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1600g of cyclohexane and 160g,THF 2.2g,15.2mmo1 n-butyllithium isoprene, heating to 46 ℃, starting to react for 37 minutes, then adding 260g of styrene into the polymerization kettle B, heating to 57 ℃, and reacting for 56 minutes to obtain a second block system;
Sequentially adding 240g of N-bromosuccinimide and 2.2g of tertiary dodecyl mercaptan into the second block system, heating to 76 ℃, adding 2.2g of TBHP for reacting for 2.6 hours to obtain a second bromination system;
3) In a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1600g of cyclohexane and 80g,THF 1.9g,10.2mmo1 n-butyllithium styrene, heating to 65 ℃, and starting to react for 27min to obtain a third block system;
4) Adding the second bromination system and the third block system into the first bromination system, heating to 87 ℃, adding 150.5 mmol 1 of tertiary butyl trichlorosilane for coupling reaction, adding 17g of 1, 3-butadiene for end-capping activation after 143min of reaction, reacting for 27min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent D of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Adding 600g of methyl chloride, 400g of cyclohexane and 50g of brominated grafting agent D into a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times, stirring and dissolving for 97min until the grafting agent is completely dissolved, then sequentially adding 800g of methyl chloride, 442g of isobutene and 8g of isoprene when the grafting agent is cooled to-91 ℃, and stirring and mixing until the system temperature is reduced to-97 ℃ to obtain a first system;
2) Mixing and aging 80g of methyl chloride, 1.642g of aluminum sesquichloride and 0.035g of HCl at the temperature of-92 ℃ for 47min to obtain a second system;
3) Adding the second system into the first system, stirring and reacting for 2.3 hours, finally adding 40g of butanol, discharging and condensing, washing and drying to obtain the brominated butyl rubber D of the embodiment.
Example 5
The preparation method of the brominated grafting agent comprises the following steps:
1) In a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 1800g of cyclohexane and 280g,THF 2.5g,20.6mmo1 n-butyllithium isoprene into the polymerization kettle, heating to 48 ℃, starting to react for 29min, sequentially adding 480g of 1, 3-butadiene, 2.7g of THF into the polymerization kettle A, heating to 58 ℃, and reacting for 48min to obtain a first block system;
sequentially adding 780g of N-bromosuccinimide and 4.0g of tertiary dodecyl mercaptan into the first block system, heating to 79 ℃, adding 4.5g of TBHP for reacting for 3.8 hours to obtain a first bromination system;
2) Introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 4 times, sequentially adding 1800g of cyclohexane and 180g,THF 2.6g,16.8mmo1 n-butyllithium of isoprene, heating to 48 ℃, starting to react for 39min, then adding 280g of styrene into the polymerization kettle B, heating to 58 ℃, and reacting for 58min to obtain a second block system;
220g of N-bromosuccinimide and 2.6g of tertiary dodecyl mercaptan are sequentially added into the second block system, the temperature is raised to 78 ℃, 2.5g of TBHP is added for reaction for 2.8 hours, and a second bromination system is obtained;
3) In a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 4 times, sequentially adding 1800g of cyclohexane, 90g of styrene, 2.1g of THF and 12.1 mmol of n-butyllithium, heating to 68 ℃, and then starting to react for 29min to obtain a third block system;
4) Adding the second bromination system and the third block system into the first bromination system, heating to 89 ℃, adding 200.5 mmol 1 of tertiary butyl trichlorosilane for coupling reaction, reacting for 147min, then adding 19g of 1, 3-butadiene for end-capping activation, reacting for 28min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent E of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 4 times, adding 650g of methyl chloride, 350g of cyclohexane, 48g of brominated grafting agent E into the polymerization kettle, stirring and dissolving for 97min until the grafting agent is completely dissolved, then cooling to-93 ℃, sequentially adding 800g of methyl chloride, 446g of isobutene and 6g of isoprene, stirring and mixing until the system temperature is reduced to-97 ℃ to obtain a first system;
2) Mixing and aging 90g of methyl chloride, 1.722g of aluminum sesquichloride and 0.048g of HCl at the temperature of minus 94 ℃ for 49min to obtain a second system;
3) Adding the second system into the first system, stirring and reacting for 2.7h, finally adding 45g of butanol, discharging and condensing, washing and drying to obtain the brominated butyl rubber E of the embodiment.
Example 6
The preparation method of the brominated grafting agent comprises the following steps:
1) Introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 4 times, sequentially adding 2000g of cyclohexane and 300g,THF 3.0g,21.5mmo1 n-butyllithium isoprene into the polymerization kettle, heating to 50 ℃, starting to react for 30min, sequentially adding 500g of 1, 3-butadiene and 3.0g of THF into the polymerization kettle A, heating to 60 ℃, and reacting for 50min to obtain a first block system;
sequentially adding 800g of N-bromosuccinimide and 5.0g of tertiary dodecyl mercaptan into a first block system, heating to 80 ℃, adding 5.0g of TBHP for reacting for 4.0h to obtain a first bromination system;
2) In a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 2000g of cyclohexane and 200g,THF 3.0g,17.5mmo1 n-butyllithium isoprene, heating to 50 ℃, starting to react for 40min, then adding 300g of styrene into the polymerization kettle B, heating to 60 ℃, and reacting for 60min to obtain a second block system;
Sequentially adding 200g of N-bromosuccinimide and 2.8g of tertiary dodecyl mercaptan into the second block system, heating to 80 ℃, adding 3.0g of TBHP for reacting for 3.0h to obtain a second bromination system;
3) In a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 4 times, sequentially adding 2000g of cyclohexane and 100g,THF 3.0g,13.5mmo1 n-butyllithium styrene, heating to 70 ℃, and then starting to react for 30min to obtain a third block system;
4) Adding the second bromination system and the third block system into the first bromination system, heating to 90 ℃, adding 260.5 mmol 1 of tertiary butyl trichlorosilane for coupling reaction, reacting for 150min, adding 20g of 1, 3-butadiene for end-capping activation, reacting for 30min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent F of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 700g of methyl chloride, 300g of cyclohexane and 45g of brominated grafting agent F into the polymerization kettle, stirring and dissolving for 100min until the grafting agent is completely dissolved, then cooling to-95 ℃, sequentially adding 1000g of methyl chloride, 450g of isobutene and 5g of isoprene, stirring and mixing until the system temperature is reduced to-100 ℃ to obtain a first system;
2) Mixing and aging 100g of methyl chloride, 1.852g of aluminum sesquichloride and 0.059g of HCl at the temperature of-95 ℃ for 50min to obtain a second system;
3) Adding the second system into the first system, stirring and reacting for 3.0h, finally adding 50g of butanol, discharging and condensing, washing and drying to obtain the brominated butyl rubber F of the embodiment.
Example 7
The preparation method of the brominated grafting agent comprises the following steps:
1) Introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 4 times, sequentially adding 2000g of cyclohexane and 320g,THF 3.3g,24.3mmo1 n-butyllithium isoprene into the polymerization kettle, heating to 50 ℃, starting to react for 30min, sequentially adding 500g of 1, 3-butadiene and 3.0g of THF into the polymerization kettle A, heating to 60 ℃, and reacting for 50min to obtain a first block system;
sequentially adding 800g of N-bromosuccinimide and 5.0g of tertiary dodecyl mercaptan into a first block system, heating to 80 ℃, adding 5.0g of TBHP for reacting for 4.0h to obtain a first bromination system;
2) In a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 2000g of cyclohexane and 210g,THF 3.2g,20.5mmo1 n-butyllithium isoprene, heating to 50 ℃, starting to react for 40min, then adding 300g of styrene into the polymerization kettle B, heating to 60 ℃, and reacting for 60min to obtain a second block system;
Sequentially adding 200g of N-bromosuccinimide and 2.8g of tertiary dodecyl mercaptan into the second block system, heating to 80 ℃, adding 3.0g of TBHP for reacting for 3.0h to obtain a second bromination system;
3) In a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 4 times, sequentially adding 2000g of cyclohexane and 100g,THF 3.0g,15.6mmo1 n-butyllithium styrene, heating to 70 ℃, and then starting to react for 30min to obtain a third block system;
4) Adding the second bromination system and the third block system into the first bromination system, heating to 90 ℃, adding 260.5 mmol 1 t-butyl trichlorosilane for coupling reaction, reacting for 150min, adding 20G of 1, 3-butadiene for end-capping activation, reacting for 30min until no free monomer exists, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent G of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 700G of methyl chloride, 300G of cyclohexane and 45G of brominated grafting agent into the polymerization kettle, stirring and dissolving for 100min until the grafting agent is completely dissolved, then cooling to the temperature of minus 95 ℃, sequentially adding 1000G of methyl chloride, 450G of isobutene and 5G of isoprene, stirring and mixing until the system temperature is reduced to minus 100 ℃ to obtain a first system;
2) Mixing and aging 100g of methyl chloride, 1.852g of aluminum sesquichloride and 0.059g of HCl at the temperature of-95 ℃ for 50min to obtain a second system;
3) Adding the second system into the first system, stirring and reacting for 3.0h, finally adding 50g of butanol, discharging and condensing, washing and drying to obtain the brominated butyl rubber F of the embodiment.
Comparative example 1
The preparation of brominated grafting agent a of this comparative example was essentially identical to that of example 1, except that HBr was used in place of N-bromosuccinimide of example 1.
The preparation method of the brominated butyl rubber a of this comparative example is substantially the same as that of example 1, except that the brominated butyl rubber a of example 1 is replaced with the brominated butyl rubber a.
Comparative example 2
The preparation of the brominated grafting agent b of this comparative example is essentially identical to that of example 2, except that H is used 2 O 2 The TBHP of example 2 was replaced.
The preparation method of the brominated butyl rubber B of this comparative example is substantially the same as that of example 2, except that the brominated butyl rubber B of example 2 is replaced with the brominated butyl rubber B.
Comparative example 3
The preparation of the brominated grafting agent c of this comparative example was essentially identical to that of example 3, except that 300g of N-bromosuccinimide was used in step 1).
The preparation method of the brominated butyl rubber C of this comparative example is substantially the same as that of example 3, except that the brominated butyl rubber C of example 3 is replaced with the brominated butyl rubber C.
Comparative example 4
The preparation of the brominated butyl rubber D of this comparative example was substantially identical to that of example 4, except that the mass of the brominated grafting agent D added was 20g.
Comparative example 5
The preparation of the brominated grafting agent e of this comparative example was essentially identical to that of example 5, except that the tertiary butyl trichlorosilane of example 5 was replaced by methyltrichlorosilane.
The preparation method of the brominated butyl rubber E of this comparative example is substantially the same as that of example 5, except that the brominated butyl rubber E of example 5 is replaced with brominated butyl rubber E.
Comparative example 6
The preparation of the brominated grafting agent f of this comparative example is essentially identical to example 6, except that the preparation of the third block system in step 3) is not included.
The preparation method of the brominated butyl rubber F of this comparative example is substantially the same as that of example 6, except that the brominated butyl rubber F in example 6 is replaced with the brominated butyl rubber F.
Test examples
1. The following parameters were examined in the brominated grafting agent in the above examples and comparative examples, and the specific results are shown in Table 1.
The mass percent of bromine is as follows: the detection method comprises the following steps: 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: the percentage of the sample at 220 ℃;79.904: bromine element relative atomic mass; 1.008: hydrogen element relative to atomic mass.
Molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min -1 。
TABLE 1
| Bromine mass percent% | Number average molecular weight/molecular weight distribution | |
| Example 1 | 15.3％ | 72000/10.16 |
| Example 2 | 16.9％ | 76000/10.48 |
| Example 3 | 19.7％ | 81000/10.75 |
| Example 4 | 21.4％ | 84000/11.05 |
| Example 5 | 22.7％ | 87000/11.35 |
| Example 6 | 24.1％ | 89000/11.65 |
| Example 7 | 24.7％ | 96000/11.78 |
| Comparative example 1 | 8.6％ | 69000/9.85 |
| Comparative example 2 | 7.5％ | 67000/7.26 |
| Comparative example 3 | 9.3％ | 79000/10.12 |
| Comparative example 4 | 21.4％ | 84000/11.05 |
| Comparative example 5 | 22.7％ | 85000/7.15 |
| Comparative example 6 | 23.9％ | 72000/6.25 |
As can be seen from Table 1, the preparation method provided by the invention can prepare the brominated grafting agent with the bromine content not less than 15 wt%.
2. The brominated butyl rubber in the above examples and comparative examples was sampled and tested after preparing standard samples according to the test requirements of the following relevant parameters, and the results are shown in table 2.
The mass percent of bromine is as follows: the method is the same as above.
Unsaturation degree: the magnetic field strength of AVANCE300 nuclear magnetic resonance apparatus of Bruker company is 9.20 Tesla, CDC1 is adopted 3 TMS was used as an internal standard as solvent and measured at room temperature (25 ℃).
Degree of branching: degree of branching = polymer molecular weight after branching/polymer molecular weight before branching.
Static ozone performance: the TD-401A type thermal aging tester is adopted, and the testing method comprises the following steps: stretching 25%, ozone mass fraction 50×10 -8 The temperature is 40 ℃ and the time is 1000 hours.
Vulcanization characteristics: according to GB/T16584-1996. Wherein T is 10 To reflect the scorch safety window size, T 90 The positive vulcanization time reflects the vulcanization speed.
Air tightness: an automatic air tightness tester is adopted to test the air tightness,the number of ventilation was determined according to ISO 2782:1995, test gas N 2 The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.
Die swell ratio: RH2000 capillary rheometer manufactured by Markov company in England was used at a temperature of 100℃and an aspect ratio of 16:1 and a shear rate of 10-1000S -1 Is measured in the interval of (2).
TABLE 2
As can be seen from Table 2, the bromine grafting agent of the present invention contributes to achieving efficient modification of butyl rubber, and the modified brominated butyl rubber exhibits excellent vulcanization processing characteristics, aging resistance, dimensional stability and air tightness.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A brominated grafting agent, characterized in that the brominated grafting agent has a structure represented by formula 1:
wherein Bu is tertiary butyl, ps is a styrene homopolymerization block, E is a dibrominated 1, 3-butadiene homopolymerization block, A is a dibrominated isoprene homopolymerization block, D is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, l is not less than 1, m is not less than 1, n is not less than 1;
In the brominated grafting agent, the mass percentage of bromine element is 15% -25%.
2. The brominated grafting agent of claim 1, wherein the brominated grafting agent has a number average molecular weight of 70000 to 90000 and a molecular weight distribution of 10.16 to 11.65.
3. The brominated grafting agent of claim 1 or 2, wherein the brominated grafting agent is prepared by a process comprising:
the first raw material system is reacted for 20 to 30 minutes at the temperature of between 40 and 50 ℃, then a first monomer and a first structure regulator A are added into the system, and the reaction is carried out for 40 to 50 minutes at the temperature of between 50 and 60 ℃ to obtain a first block system; adding a first organic brominating agent and a first molecular weight regulator into the first block system, heating to 70-80 ℃, adding a first organic brominating initiator, and reacting for 3-4 hours to obtain a first brominating system;
the second raw material system reacts for 30 to 40 minutes at the temperature of between 40 and 50 ℃, then a second monomer is added into the system, and then the reaction is carried out for 50 to 60 minutes at the temperature of between 50 and 60 ℃ to obtain a second block system; adding a second organic brominating agent and a second molecular weight regulator into the second block system, heating to 70-80 ℃, adding a second organic brominating initiator, and reacting for 2-3 hours to obtain a second brominating system;
Reacting the third raw material system at 60-70 ℃ for 20-30 min to obtain a third block system;
adding the second bromination system and the third block system into the first bromination system, adding a tertiary butyl trihalosilane coupling agent at 80-90 ℃ for reaction for 130-150 min, and then adding an activating end capping agent for reaction for 20-30 min to obtain the brominated grafting agent;
wherein the first raw material system comprises isoprene, a first structure regulator B and a first polymerization initiator; the second raw material system comprises isoprene, a second structure regulator and a second polymerization initiator; the third raw material system comprises a third monomer, a third structure regulator and a third polymerization initiator; the first monomer and the activated end-capping agent are 1, 3-butadiene, and the second monomer and the third monomer are styrene.
4. A brominated grafting agent as claimed in claim 3, characterized in that,
the mass ratio of the organic brominating agent to the isoprene, the first structure regulator B, the first monomer, the first structure regulator A, the first molecular weight regulator and the first organic brominating initiator in the first raw material system is 1: (0.2-0.3): (0.001-0.003): (0.4-0.5): (0.001-0.003): (0.002-0.005): (0.002-0.005); and/or the number of the groups of groups,
The mass ratio of the organic brominating agent to the mass ratio of the isoprene, the second structure regulator, the second monomer, the second molecular weight regulator and the second organic brominating initiator in the second raw material system is 1: (0.1-0.2): (0.001-0.003): (0.2-0.3): (0.001-0.003): (0.001-0.003); and/or the number of the groups of groups,
the mass ratio of the organic brominating agent to the third monomer and the third structure regulator is 1: (0.05-0.1): (0.001-0.003);
wherein the mass of the organic brominating agent is the total mass of the first organic brominating agent and the second brominating agent, and the mass ratio of the first organic brominating agent to the second organic brominating agent is (0.7-0.8): (0.2-0.3).
5. The brominated grafting agent of claim 3 or 4, wherein the molar ratio of t-butyl trihalosilane coupling agent to polymerization initiator is from 2:1 to 5:1;
the polymerization initiator is composed of the first polymerization initiator, a second polymerization initiator, and a third polymerization initiator.
6. The preparation method of the brominated grafting agent is characterized by comprising the following steps:
the first raw material system is reacted for 20 to 30 minutes at the temperature of between 40 and 50 ℃, then a first monomer and a first structure regulator A are added into the system, and the reaction is carried out for 40 to 50 minutes at the temperature of between 50 and 60 ℃ to obtain a first block system; adding a first organic brominating agent and a first molecular weight regulator into the first block system, heating to 70-80 ℃, adding a first organic brominating initiator, and reacting for 3-4 hours to obtain a first brominating system;
The second raw material system reacts for 30 to 40 minutes at the temperature of between 40 and 50 ℃, then a second monomer is added into the system, and then the reaction is carried out for 50 to 60 minutes at the temperature of between 50 and 60 ℃ to obtain a second block system; adding a second organic brominating agent and a second molecular weight regulator into the second block system, heating to 70-80 ℃, adding a second organic brominating initiator, and reacting for 2-3 hours to obtain a second brominating system;
reacting the third raw material system at 60-70 ℃ for 20-30 min to obtain a third block system;
adding the second bromination system and the third block system into the first bromination system, adding a tertiary butyl trihalosilane coupling agent at 80-90 ℃ for reaction for 130-150 min, and then adding an activating end capping agent for reaction for 20-30 min to obtain the brominated grafting agent;
wherein the first raw material system comprises isoprene, a first structure regulator B and a first polymerization initiator; the second raw material system comprises isoprene, a second structure regulator and a second polymerization initiator; the third raw material system comprises a third monomer, a third structure regulator and a third polymerization initiator;
the first monomer and the activated end-capping agent are 1, 3-butadiene, and the second monomer and the third monomer are styrene;
The brominated grafting agent has a structure shown in a formula 1,
wherein Bu is tertiary butyl, ps is a styrene homopolymerization block, E is a dibrominated 1, 3-butadiene homopolymerization block, A is a dibrominated isoprene homopolymerization block, D is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, l is not less than 1, m is not less than 1, n is not less than 1;
in the brominated grafting agent, the mass percentage of bromine element is 15% -25%.
7. A brominated butyl rubber obtained by polymerizing a brominated grafting agent as defined in any one of claims 1 to 5 or a brominated graft prepared by the method of claim 6 with a system comprising isobutylene and isoprene;
the mass ratio of the brominated grafting agent to the isobutene to the isoprene is (9-12): (85-90): (1-3).
8. The brominated butyl rubber of claim 7, wherein the brominated butyl rubber is prepared by a process comprising:
adding a first diluent, isobutene and isoprene into a solution system of the brominated grafting agent at the temperature of-95 to-85 ℃ and then adjusting the temperature to be between-100 ℃ and-90 ℃ to obtain a first system;
mixing a second diluent and a co-initiator at a temperature of between-95 and-85 ℃ and aging for 40 to 50 minutes to obtain a second system;
And mixing the first system and the second system, reacting for 1-3h, and stopping the reaction to obtain the brominated butyl rubber.
9. The brominated butyl rubber of claim 8 wherein the mass ratio of the reaction mass, the first diluent, the second diluent, and the co-initiator is 1: (1-2): (0.1-0.2): (0.002-0.005);
the mass of the reaction main body is the total mass of the brominated grafting agent, isobutene and isoprene.
10. A rubber article, wherein said rubber article is processed from the brominated butyl rubber of any one of claims 7-9.
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