CN116355156A - Brominated grafting agent and preparation method and application thereof - Google Patents
Brominated grafting agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN116355156A CN116355156A CN202111633777.8A CN202111633777A CN116355156A CN 116355156 A CN116355156 A CN 116355156A CN 202111633777 A CN202111633777 A CN 202111633777A CN 116355156 A CN116355156 A CN 116355156A
- Authority
- CN
- China
- Prior art keywords
- brominated
- agent
- block
- raw material
- grafting agent
- 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 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 198
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 172
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 128
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 67
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 claims abstract description 31
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 25
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 21
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 230000008859 change Effects 0.000 claims abstract description 13
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 118
- 239000002994 raw material Substances 0.000 claims description 109
- 239000000178 monomer Substances 0.000 claims description 44
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 40
- 230000031709 bromination Effects 0.000 claims description 33
- 238000005893 bromination reaction Methods 0.000 claims description 33
- 230000008878 coupling Effects 0.000 claims description 30
- 238000010168 coupling process Methods 0.000 claims description 30
- 238000005859 coupling reaction Methods 0.000 claims description 30
- 239000007822 coupling agent Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 26
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000003505 polymerization initiator Substances 0.000 claims description 12
- 230000002140 halogenating effect Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 230000003213 activating effect Effects 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 239000005060 rubber Substances 0.000 claims description 9
- 125000003003 spiro group Chemical group 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920005549 butyl rubber Polymers 0.000 abstract description 23
- 238000004073 vulcanization Methods 0.000 abstract description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 76
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 66
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 40
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 25
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 18
- 229910001220 stainless steel Inorganic materials 0.000 description 18
- 239000010935 stainless steel Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 9
- 229920001400 block copolymer Polymers 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- -1 hydrocarbyl monolithium compounds Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 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
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000002522 swelling effect Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WPUBUMYDZKJTBD-UHFFFAOYSA-N 1,5-dibromo-3,3-bis(2-bromoethyl)pentane Chemical compound BrCCC(CCBr)(CCBr)CCBr WPUBUMYDZKJTBD-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
- 230000004913 activation Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 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
- 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
- 238000010539 anionic addition polymerization reaction Methods 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
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical group C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-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
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000006227 byproduct Substances 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
- NEHMKBQYUWJMIP-OUBTZVSYSA-N chloromethane Chemical group Cl[13CH3] NEHMKBQYUWJMIP-OUBTZVSYSA-N 0.000 description 1
- 239000002131 composite material Chemical group 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 230000000694 effects Effects 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
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-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
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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, IR is an isoprene homo-block, BR is a 1, 3-butadiene homo-block, SB/(S→B) is a random gradual change block of styrene and butadiene, D is a p-bromomethylstyrene homo-block, B is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, and n is more than or equal to 1; in the brominated grafting agent, the mass percentage of bromine element is 17-23%. 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 lower unsaturation degree and the substituent methyl groups are symmetrically arranged, and the molecular structure determines the unavoidable problems of obvious extrusion swelling effect, long vulcanization scorching time, low vulcanization speed, poor green strength, poor air tightness and the like, so that the processability of the butyl rubber cannot meet the processing requirements and application scenes of gradual diversification, and the molecular structure becomes a bottleneck for 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 present invention also provides a brominated butyl rubber comprising the aforementioned brominated grafting agent, and therefore having excellent processability, as embodied by lower extrusion swell ratio and air permeability, shorter vulcanization scorch time and time to orthovulcanization, higher tensile strength and broader molecular weight distribution.
The invention also provides a rubber product which is obtained by processing the brominated butyl rubber and has excellent performances in the aspects of mechanical properties, product dimensional stability and the like.
The invention provides a brominated grafting agent, which has a structure shown in a formula 1:
wherein IR is an isoprene homo-block, BR is a 1, 3-butadiene homo-block, SB/(S.fwdarw.B) is a random gradual change block of styrene and butadiene, D is a p-bromomethylstyrene homo-block, B is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, and n is not less than 1;
in the brominated grafting agent, the mass percentage of bromine element is 17-23%.
The brominated grafting agent as described above, wherein the brominated grafting agent has a number average molecular weight of 100000 ～ 110000 and a molecular weight distribution of 15.65 to 16.73.
A brominated grafting agent as described above, wherein the brominated grafting agent is prepared by a process comprising:
The coupling raw material system is reacted for 60 to 180 minutes at the temperature of between 60 and 80 ℃ to terminate the reaction, and then the coupling agent is obtained by extraction;
reacting the first raw material system at 40-50 ℃ for 40-60min to obtain a first block system;
adding a second raw material system into the first block system, and reacting at 50-60 ℃ for 30-40min to obtain a second block system;
continuously decelerating and adding a third raw material system into the second block system at 60-70 ℃ to obtain a third block system after 70-90min of time for adding the third raw material system;
adding a brominating agent and a brominating structure regulator into the third block system, heating to 70-80 ℃, then adding a brominating initiator, and reacting for 90-110min to obtain a brominating system;
adding the coupling agent into the bromination system at 80-90 ℃ and reacting for 100-120min, and then adding the activating end capping agent and reacting for 30-40min to obtain the bromination grafting agent;
wherein the coupling raw material system comprises 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and a catalyst; the first raw material system comprises isoprene, a first structure regulator and a polymerization initiator; the second feed system comprises a second monomer and a second structure modifier; the third raw material system comprises styrene, a third monomer and a third structure regulator; the second monomer, the third monomer and the activating end capping agent are 1, 3-butadiene; the brominating agent is p-bromomethylstyrene;
In the continuous deceleration, V 0 ＞5％*M 3 ，V 0 G/min for the initial rate of addition of the third feed system; m is M 3 Is the total weight of the third feed system.
The brominated grafting agent comprises a coupling main raw material and a catalyst, wherein the coupling main raw material comprises 10-30% of 3, 9-dioxy [5.5] spiro undecane and 70-90% of halogenating agent according to mass percentage, and the mass ratio of the coupling main raw material to the catalyst is 1: (1-5); and/or the number of the groups of groups,
the mass ratio of the brominating agent to the isoprene in the first raw material system and the first structure regulator is 1: (0.3-0.4): (0.001-0.004);
the mass ratio of the brominating agent to the second monomer in the second raw material system to the second structure regulator is 1: (0.2-0.3): (0.001-0.003);
the mass ratio of the brominating agent to the third monomer, the styrene and the third structure regulator in the third raw material system is 1: (0.3-0.4): (0.5-0.7): (0.004-0.008);
the mass ratio of the brominating agent to the brominating structure regulator is 1: (0.004-0.006).
A brominated grafting agent as described above, wherein the molar ratio of coupling agent to initiator is (1:1) - (4:1);
the initiator is composed of the bromination initiator and the polymerization initiator.
The invention also provides a preparation method of the brominated grafting agent, which comprises the following steps:
the coupling raw material system is reacted for 60 to 180 minutes at the temperature of between 60 and 80 ℃ to terminate the reaction, and then the coupling agent is obtained by extraction;
reacting the first raw material system at 40-50 ℃ for 40-60min to obtain a first block system;
adding a second raw material system into the first block system, and reacting at 50-60 ℃ for 30-40min to obtain a second block system;
continuously decelerating and adding a third raw material system into the second block system at 60-70 ℃ to obtain a third block system after 70-90min of time for adding the third raw material system;
adding a brominating agent and a brominating structure regulator into the third block system, heating to 70-80 ℃, then adding a brominating initiator, and reacting for 90-110min to obtain a brominating system;
adding the coupling agent into the bromination system at 80-90 ℃ and reacting for 100-120min, and then adding the activating end capping agent and reacting for 30-40min to obtain the bromination grafting agent;
wherein the coupling raw material system comprises 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and a catalyst; the first raw material system comprises isoprene, a first structure regulator and a polymerization initiator; the second feed system comprises a second monomer and a second structure modifier; the third raw material system comprises styrene, a third monomer and a third structure regulator; the second monomer, the third monomer and the activating end capping agent are 1, 3-butadiene; the brominating agent is p-bromomethylstyrene;
In the continuous deceleration, V 0 ＞5％*M 3 ，V 0 G/min for the initial rate of addition of the third feed system; m is M 3 Is the total weight of the third feed system;
the brominated grafting agent has a structure shown in a formula 1,
wherein IR is an isoprene homo-block, BR is a 1, 3-butadiene homo-block, SB/(S.fwdarw.B) is a random gradual change block of styrene and butadiene, D is a p-bromomethylstyrene homo-block, B is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, and n is not less than 1;
in the brominated grafting agent, the mass percentage of bromine element is 17-23%.
The invention also provides a brominated butyl rubber, wherein the brominated butyl rubber is obtained by polymerizing the brominated grafting agent or the brominated grafting agent prepared by the preparation method of the brominated grafting agent and a system comprising isobutene and isoprene;
the mass ratio of the brominated grafting agent to the isobutene to the isoprene is (4-8): (85-90): (6-7).
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-90 to-80 ℃ and controlling the temperature to be-100 to-90 ℃ to obtain a first system;
Mixing a second diluent and a co-initiator at the temperature of minus 95 ℃ to minus 85 ℃ and aging for 20 min to 30min, adding an aging system into the first system, and stopping the reaction after reacting for 5 h to 7h 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): (0.003-0.008);
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, wherein the rubber product 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 wide molecular weight distribution and stable bromine structure, thereby being beneficial to improving the vulcanization processing characteristics (shorter vulcanization scorch time and positive vulcanization time), the processing dimensional stability (lower extrusion expansion ratio), the mechanical property (higher tensile strength) 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, mechanical properties, 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 IR is an isoprene homo-block, BR is a 1, 3-butadiene homo-block, SB/(S.fwdarw.B) is a random gradual change block of styrene and butadiene, D is a p-bromomethylstyrene homo-block, B is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, and n is not less than 1;
in the bromination grafting agent, the mass percentage of bromine element is 17-23%.
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 quaternary four-arm star-shaped block brominated grafting agent, namely the grafting agent is formed by cross connection of four structural units, each structural unit is formed by sequentially connecting four different blocks, namely each structural unit is formed by sequentially connecting an isoprene homo-polymer block (IR), a 1, 3-butadiene homo-polymer Block (BR), a random gradient block (SB/(S- & gtB)) of styrene and butadiene and a p-bromomethylstyrene homo-polymer block (D). Specifically, the random tapered block of styrene and butadiene includes a random block of Styrene and Butadiene (SB) and a tapered block of styrene and butadiene (S.fwdarw.B).
The structure of the isoprene homopolymerization block IR is shown as 1-a, the structure of the 1, 3-butadiene homopolymerization block BR is shown as 1-b, and the structure of the p-bromomethylstyrene homopolymerization block D 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 the present invention, in the random block SB of styrene and butadiene, the styrene molecular chains and the butadiene molecular chains are randomly distributed. In the gradual change block S-B of styrene and butadiene, one end of the block is taken as a starting end, the other end is taken as a tail end, and the content of styrene molecular chains is gradually reduced from the starting end to the tail end, and the content of butadiene molecular chains is gradually increased. The random gradual change block SB/(S-B) of the styrene and the butadiene can effectively destroy the regularity of the copolymer molecular chains of the butadiene and the isoprene, increase the disorder of the segments of the brominated grafting agent, further increase the disorder of the segments of the modified brominated butyl rubber and improve the processability of the modified brominated butyl rubber.
In addition, the brominated grafting agent also comprises a blocking group B, wherein the blocking 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 Quan Ba carbon atom bromine structure is excellent, and the brominated grafting agent is favorable for solving the problem that butyl rubber is hard to vulcanize due to less double bonds caused by high saturation and improving the vulcanization speed.
In addition, from the structure, the quaternary four-arm star 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 unsaturated vinyl groups contained in the brominated grafting agent can increase the internal rotation of the molecular chain segments and also can enable the brominated butyl rubber to obtain good viscoelastic properties, thereby reducing the extrusion swelling effect and ensuring that the modified brominated butyl rubber has excellent processing dimensional stability. In addition, the brominated grafting agent also contains a large amount of benzene rings, so that the mechanical strength and the air tightness of the brominated butyl rubber can be improved.
Therefore, the brominated grafting agent has the characteristics of stable bromine structure, large rotation in a molecular chain segment and high disorder degree, and the brominated grafting agent is used for improving the vulcanization processability, the extrusion swelling effect, the mechanical property 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 brominated grafting agent is 100000 ～ 110000 and the molecular weight distribution is 15.65 to 16.73, further promotion of the processability of 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 coupling agent, a preparation step of a first block system, a preparation step of a second block system, a preparation step of a third block system, a preparation step of a bromination system and a coupling activation step, wherein the coupling activation step is a process of coupling the bromination system by using the coupling agent and then performing end capping activation by using an end capping agent. It will be appreciated that there is no relationship between the preparation steps of the coupling agent and the bromination system described above, and therefore, the coupling agent and the bromination system can be prepared separately and independently of each other.
These three steps are described below.
The coupling agent of the invention is 1, 5-dihalo-3, 3-di (2-haloethyl) pentane, and the preparation steps comprise: the coupling raw material system is reacted for 60 to 180 minutes at the temperature of between 60 and 80 ℃ to terminate the reaction, and then the coupling agent is obtained by extraction; wherein the first feed system comprises 3, 9-dioxo [5.5] spirocyclic undecane, a halogenating agent and a catalyst.
In some embodiments of the invention, after 60-180min of reaction of the coupling raw materials, a terminator may be added to the system to terminate the reaction, followed by extraction, separation, washing and drying by adding an extractant to obtain a coupling agent; wherein, the terminator can be sodium hydroxide aqueous solution, and the mass percentage of the sodium hydroxide aqueous solution can be 20-40%; the extractant is chloromethane.
The first block system of the present invention is an isoprene homo-block. Specifically, the first raw material system is reacted at 40-50 ℃ for 40-60min to obtain a first block system, wherein the first raw material system comprises isoprene, a first structure regulator and a polymerization initiator. In the process, isoprene monomer is homopolymerized under the action of a first structure regulator and a polymerization initiator to obtain isoprene homopolymerized block.
The second block system of the present invention is a block copolymer system of isoprene homo-blocks and 1, 3-butadiene homo-blocks. Specifically, a second raw material system is added into the first block system, and the reaction is carried out for 30-40min at 50-60 ℃ to obtain a second block system, wherein the second raw material system comprises a second monomer and a second structure regulator, and the second monomer is 1, 3-butadiene. In the process, a 1, 3-butadiene homo-block formed by homo-polymerizing a 1, 3-butadiene monomer is subjected to block copolymerization with isoprene homo-polymerization to obtain a block copolymer system of the isoprene homo-block and the 1, 3-butadiene homo-block.
The second block system of the present invention is a block copolymer system of isoprene homo-blocks, 1, 3-butadiene homo-blocks, random tapered blocks of styrene and butadiene. Specifically, at 60-70 ℃, continuously decelerating and adding a third raw material system into the second block system, and obtaining the third block system after 70-90min of adding the third raw material system, wherein the third raw material system comprises styrene, a third monomer and a third structure regulator, and the third monomer is 1, 3-butadiene.
In some embodiments of the invention, styrene, a third monomer, and a third structure modifier may be mixed for 20-30 minutes to form a third feed system. In the present invention, continuous deceleration means that the third raw material system is continuously added, and the feeding speed of the third raw material system is gradually reduced in the continuous adding process. The continuous deceleration is started from the time when the third raw material is just added, and the third block system is obtained after 70-90min, the feeding time is generally controlled to be 20-30min, and the rest time is only used for reaction and no feeding is performed.
In continuous deceleration, V 0 ＞5％*M 3 ，V 0 The initial adding speed of the third raw material system is g/min; m is M 3 Is the total weight of the third feed system. It is understood that the total weight of the third feed system is the sum of the mass of styrene, the third monomer and the third structure modifier. In the process, 1, 3-butadiene monomer and styrene monomer are copolymerized to form random gradual change blocks of styrene and butadiene, and the random gradual change blocks of styrene and butadiene are copolymerized with block copolymers of isoprene homopolymerization blocks and 1, 3-butadiene homopolymerization blocks to form isoprene homopolymerization blocks and 1, 3-butadieneBlock copolymer systems of olefin homo-blocks, random tapered blocks of styrene and butadiene.
The bromination system of the present invention is a block copolymer system of isoprene homo-block, 1, 3-butadiene homo-block, random gradual change block of styrene and butadiene, p-bromomethylstyrene homo-block. Specifically, adding a brominating agent and a brominating structure regulator into the third block system, heating to 70-80 ℃, then adding a brominating initiator and reacting for 90-110min to obtain a brominating system, wherein the brominating agent can be p-bromomethylstyrene.
In this process, p-bromomethylstyrene will polymerize to form a p-bromomethylstyrene block, which will polymerize with the block copolymer of isoprene homopolymer block, 1, 3-butadiene homopolymer block and the random tapered block of 1, 3-butadiene and styrene to form a block copolymer of isoprene homopolymer block, 1, 3-butadiene homopolymer block, the random tapered block of 1, 3-butadiene and styrene, and the p-bromomethylstyrene homopolymer block.
After the preparation of the bromination system and the coupling agent is completed, the coupling agent is added into the bromination system and reacts for 100-120min, and then the end capping agent is added for reacting for 30-40min, so that the bromination grafting agent is obtained. After the end capping reagent is added for reaction for 30-40min, the reaction system is subjected to post-treatment including discharging coagulation, washing and drying to finally obtain the brominated grafting reagent; wherein the end capping agent is 1, 3-butadiene.
In the preparation process of the brominating system, the adopted brominating agent is a reactive brominating agent containing unsaturated double bonds, and can directly participate in anionic polymerization reaction, on one hand, the generation of hydrogen bromide (HBr) can be avoided, the harm to human and environment is reduced, and the alkaline washing recovery process of a byproduct HBr can be omitted, so that the process flow is shortened, and the production cost is reduced; on the other hand, the brominating agent participates in the anionic polymerization reaction, so that the brominated grafting agent with a full primary carbon atom bromine structure can be obtained, 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 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.
In the present invention, the coupling raw material system includes a coupling main raw material and a catalyst. As a preferred embodiment, when the coupling main body raw material comprises 10-30% of 3, 9-dioxy [5.5] spiro undecane and 70-90% of halogenating agent according to the mass percentage, the mass ratio of the coupling main body raw material to the catalyst is 1: (1-5); and/or the number of the groups of groups,
the mass ratio of the brominating agent to the isoprene in the first raw material system and the first structure regulator is 1: (0.3-0.4): (0.001-0.004);
the mass ratio of the brominating agent to the second monomer in the second raw material system and the second structure regulator is 1: (0.2-0.3): (0.001-0.003);
the mass ratio of the brominating agent to the third monomer, the styrene and the third structure regulator in the third raw material system is 1: (0.3-0.4): (0.5-0.7): (0.004-0.008);
the mass ratio of the brominating agent to the brominating structure regulator is 1: (0.004-0.006), the economic benefit of the preparation method can be increased by improving the yield of the product.
It will be appreciated that the coupling feed system comprises deionized water in addition to the aforementioned composition; further, the mass ratio of the coupling main raw material to deionized water is 1: (1-2). And the mass ratio of the coupling main body raw material to the sodium hydroxide aqueous solution to the extractant is 1: (0.1-0.2): (2-3).
The first raw material system is used for treating the composition and comprises a solvent; further, the mass of the solvent in the first raw material system is 300-400% of the mass of the brominating agent. Adding a solvent in addition to the brominating agent and the brominating structure regulator to the third block system; further, the mass of the solvent is 100-200% of the mass of the brominating agent.
The solvent is selected from linear alkane, arene and cycloparaffin, and can be specifically selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably octane.
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 above preparation process, the halogenating agent is liquid chlorine or liquid bromine, preferably liquid bromine.
The catalyst is HCl and CH 3 Mixed aqueous solution of OH, wherein the molar concentration of HCl is 0.4-0.9 mol/L, CH 3 The molar concentration of OH is 0.3-0.7mol/L.
Both the bromination initiator and the polymerization initiator are hydrocarbyl monolithium 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 bromination initiator and the polymerization initiator are each independently selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, dodecyllithium, preferably n-butyllithium. The amount of each initiator added is determined by the molecular weight of the target brominated grafting agent, for example, the amount of material of n-butyllithium is calculated by the following formula.
The first structure modifier, the second structure modifier, the third structure modifier, and the brominated structure modifier are all polar organic compounds for producing a solvation effect in the polymerization reaction. The first structure modifier, the second structure modifier, the third structure modifier and the brominated structure modifier 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), triethylamine, preferably Tetrahydrofuran (THF).
Further, the molar ratio of coupling agent to initiator is (1:1) - (4:1); wherein the initiator consists of a bromination initiator and a polymerization initiator.
The brominated grafting agent is an organic combination of an isoprene homopolymerization block, a 1, 3-butadiene homopolymerization block, a random gradual change block of 1, 3-butadiene and styrene and a p-bromomethyl styrene homopolymerization block, and the parts are combined together and cooperatively exerted, so that the brominated grafting agent can be finally used for modifying butyl rubber, and the modified brominated butyl rubber has excellent vulcanization processability, mechanical property, air tightness and dimensional stability.
The second aspect of the present invention provides a method for preparing a brominated grafting agent, comprising the steps of:
The coupling raw material system is reacted for 60 to 180 minutes at the temperature of between 60 and 80 ℃ to terminate the reaction, and then the coupling agent is obtained by extraction;
reacting the first raw material system at 40-50 ℃ for 40-60min to obtain a first block system;
adding a second raw material system into the first block system, and reacting at 50-60 ℃ for 30-40min to obtain a second block system;
continuously decelerating and adding a third raw material system into the second block system at 60-70 ℃ to obtain a third block system after the third raw material system is added for 70-90 min;
adding a brominating agent and a brominating structure regulator into the third block system, heating to 70-80 ℃, then adding a brominating initiator, and reacting for 90-110min to obtain a brominating system;
adding the coupling agent into a bromination system at 80-90 ℃ and reacting for 100-120min, and then adding an activated end capping agent and reacting for 30-40min to obtain a bromination grafting agent;
wherein the coupling raw material system comprises 3, 9-dioxy [5.5] spiro undecane, halogenating agent and catalyst; the first raw material system comprises isoprene, a first structure regulator and a polymerization initiator; the second feed system comprises a second monomer and a second structure modifier; the third raw material system comprises styrene, a third monomer and a third structure regulator; the second monomer, the third monomer and the activating end capping agent are 1, 3-butadiene; the brominating agent is p-bromomethylstyrene;
In continuous deceleration, V 0 ＞5％*M 3 ，V 0 The initial adding speed of the third raw material system is g/min; m is M 3 Is the total weight of the third feed system;
the brominated grafting agent has a structure shown in a formula 1,
wherein IR is an isoprene homo-block, BR is a 1, 3-butadiene homo-block, SB/(S.fwdarw.B) is a random gradual change block of styrene and butadiene, D is a p-bromomethylstyrene homo-block, B is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, and n is not less than 1;
in the bromination grafting agent, the mass percentage of bromine element is 17-23%.
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 comprises the steps of reacting 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and a catalyst to obtain a coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane, then polymerizing isoprene, styrene, 1, 3-butadiene and p-bromomethylstyrene serving as reaction monomers in different combinations or independently to obtain a block copolymer, and finally coupling the obtained block copolymer by adopting the 1, 5-dihalo-3, 3-di (2-haloethyl) pentane coupling agent to prepare the quaternary four-arm star-shaped brominated grafting agent. The brominated grafting agent with high disorder degree and Quan Ba carbon atom bromine structure can be prepared by the method, and the vulcanization processing characteristic, the processing dimensional stability, the mechanical property and the airtight property of the styrene-butadiene rubber can be improved.
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 (4-8): (85-90): (6-7).
The brominated butyl rubber obtained by modified grafting according to the proportion of the raw materials has excellent vulcanization processability, mechanical properties, air tightness and dimensional stability because the brominated grafting agent has the characteristics of high stability, high disorder degree and high bromine content.
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 a brominated grafting agent at the temperature of-90 to-80 ℃ and controlling the temperature to be-100 to-90 ℃ to obtain a first system;
mixing a second diluent and a co-initiator at the temperature of minus 95 ℃ to minus 85 ℃ and aging for 20 min to 30min, adding an aging system into the first system, and stopping the reaction after reacting for 5 h to 7h 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 of the brominated grafting agent, for example, the ratio of the volume of the brominated grafting agent added to the diluent to the volume of the solvent is 7-3:3-7, and stirring for 60-80 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 octane. 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 dichloromethane is preferred.
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): (0.003-0.008); 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 (0.03-0.7): 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 dichloromethane.
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 0.1-3.0% of the mass of the main reaction body, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1-0.2:1.
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 mechanical property.
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:
example 1
The preparation method of the brominated grafting agent comprises the following steps:
1) In a 4L stainless steel polymerizer with a jacket, argon is introduced for 2 times, 600g of deionized water, 70g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerizer]Spirocyclic undecane, 350g liquid bromine, 10g HCl and CH 3 OH aqueous mixtures (molar HCl 0.5mol/L; CH) 3 OH molar concentration is 0.4 mol/L), heating to 65 ℃ for reaction for 1.5h, adding 60g of 10wt% NaOH aqueous solution for stopping reaction, finally adding 1200g of chloromethane for extraction, and then separating, washing and drying to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane A (yield 91%).
2) A, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 3000g of octane, 300g of isoprene and 1.0g THF,37.5mmo1 n-butyllithium into the reaction kettle, heating to 40 ℃ and then reacting for 40min to form a first block system (IR block);
B. Then 200g of 1, 3-butadiene and 1.0g of THF are sequentially added into the reaction kettle, and the temperature is raised to 50 ℃ for reaction for 30min to form a second block system (BR-IR block);
C. then 500g of styrene, 300g of 1, 3-butadiene and 4.0g of THF are stirred and mixed for 20min to form a third raw material system, the third raw material system is continuously added into a second block system at 60 ℃ in a decelerating way, the reaction is completed in 70min when the raw material addition is just started, the initial feeding speed is 60g/min, and the feeding speed is reduced by 2g per minute, so that a third block system (SB/(S-B) -BR-IR block) is obtained;
D. then 1000g of octane, 1000g of p-bromomethylstyrene and 4.0g of THF are sequentially added into the reaction kettle, the temperature is raised to 70 ℃, 41.4mmo1 of n-butyllithium is added for reaction for 90min, and a bromination system (D-SB/(S.fwdarw.B) -BR-IR block) is obtained.
3) Heating the reaction kettle to 80 ℃, and adding 150mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane A for reacting for 100min; then adding 20g of 1, 3-butadiene into a reaction kettle for end capping, reacting for 30min until no free monomer exists, and performing wet condensation and drying on the glue solution to prepare 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 420g of methyl chloride, 180g of cyclohexane and 20g of brominated grafting agent A into the reaction kettle, and stirring and dissolving for 60min until the grafting agent is completely dissolved; then cooling to-80 ℃, sequentially adding 500g of dichloromethane, 450g of isobutene and 30g of isoprene, stirring and mixing until the system temperature is reduced to-90 ℃ to obtain a first system;
2) 50g of methylene dichloride, 1.56g of aluminum sesquichloride and 0.021g of HCl are mixed and aged for 20min at the temperature of minus 85 ℃, an aging system is added into a first system, after stirring and reacting for 5.0h, 15g of butanol is finally added, and then the bromobutyl rubber A of the embodiment is obtained after discharging, condensing, washing and drying.
Example 2
The preparation method of the brominated grafting agent comprises the following steps:
1) A, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 3200g of octane, 310g of isoprene and 1.5g THF,39.5mmo1 n-butyllithium into the reaction kettle, heating to 42 ℃ and then reacting for 45min to form a first block system (IR block);
B. then 220g of 1, 3-butadiene and 1.5g of THF are sequentially added into the reaction kettle, and the temperature is raised to 52 ℃ for reaction for 32min to form a second block system (BR-IR block);
C. Then 550g of styrene, 320g of 1, 3-butadiene and 4.5g of THF are stirred and mixed for 22min to form a third raw material system, the third raw material system is continuously added into the second block system at 62 ℃ in a decelerating way, the reaction is completed in 70min when the raw material addition is just started, the initial feeding speed is 60g/min, and the feeding speed is reduced by 2g per minute, so that a third block system (SB/(S.fwdarw.B) -BR-IR block) is obtained;
D. then 1200g of octane, 1000g of p-bromomethylstyrene and 4.5g of THF are sequentially added into the reaction kettle, the temperature is raised to 72 ℃, 44.5 mmol of n-butyllithium is added for a second time to react for 95min, and a bromination system (D-SB/(S.fwdarw.B) -BR-IR block) is obtained.
2) Heating the reaction kettle to 82 ℃, and adding 180mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane A to react for 105min; then adding 30g of 1, 3-butadiene into a reaction kettle for end capping, reacting for 32min until no free monomer exists, and performing wet condensation and drying on the glue solution to prepare the brominated grafting agent B 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 3 times, adding 400g of methylene dichloride, 200g of cyclohexane, 25g of brominated grafting agent B into the reaction kettle, stirring and dissolving for 65min until the grafting agent is completely dissolved, then cooling to the temperature of minus 82 ℃, sequentially adding 600g of methylene dichloride, 444g of isobutene and 31g of isoprene, stirring and mixing until the system temperature is reduced to minus 92 ℃ to obtain a first system;
2) 60g of methylene dichloride, 1.89g of aluminum sesquichloride and 0.035g of HCl are mixed and aged for 22min at the temperature of minus 87 ℃, an aging system is added into a first system to be stirred and reacted for 5.5h, and finally 20g of butanol is added, and then the brominated butyl rubber B of the embodiment is obtained after discharging, condensing, washing and drying.
Example 3
The preparation method of the brominated grafting agent comprises the following steps:
1) A, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 3400g of octane, 330g of isoprene and 2.0g THF,41.5mmo1 n-butyllithium into the reaction kettle, heating to 44 ℃ and then reacting for 48min to form a first block system (IR block);
B. then adding 230g of 1, 3-butadiene and 2.0g of THF into the reaction kettle in sequence, and heating to 54 ℃ to react for 34min to form a second block system (BR-IR block);
C. then 600g of styrene, 340g of 1, 3-butadiene and 5.0g of THF are stirred and mixed for 24min to form a third raw material system, the third raw material system is continuously added into a second block system at 64 ℃ in a decelerating way, the reaction is completed in 80min when the raw material addition is just started, the initial feeding speed is 70g/min, the feeding speed is reduced by 2.5g per minute, and a third block system (SB/(S-B) -BR-IR block) is obtained;
D. Then 1400g of octane, 1000g of p-bromomethylstyrene and 5.0g of THF are sequentially added into the reaction kettle, the temperature is raised to 74 ℃, 46.5 mmol 1 of n-butyllithium is added for reacting for 100min, and a bromination system (D-SB/(S.fwdarw.B) -BR-IR block) is obtained.
2) Heating the reaction kettle to 84 ℃, and adding 200mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane A for reacting for 110min; then adding 35g of 1, 3-butadiene into a reaction kettle for end capping, reacting for 34min until no free monomer exists, and performing wet condensation and drying on the glue solution to prepare the brominated grafting agent C 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 300g of dichloromethane, 300g of cyclohexane, 30g of brominated grafting agent C into the reaction kettle, stirring and dissolving for 70min until the grafting agent is completely dissolved, then cooling to-84 ℃, sequentially adding 700g of dichloromethane, 438g of isobutene and 32g of isoprene, stirring and mixing until the system temperature is reduced to-94 ℃ to obtain a first system;
2) 70g of methylene dichloride, 2.13g of aluminum sesquichloride and 0.051g of HCl are mixed and aged for 25min at the temperature of minus 90 ℃, an aging system is added into a first system to be stirred and reacted for 6.0h, and finally 25g of butanol is added, and then the brominated butyl rubber C of the embodiment is obtained after discharging, condensing, washing and drying.
Example 4
The preparation method of the brominated grafting agent comprises the following steps:
1) In a 4L stainless steel polymerizer with a jacket, argon is introduced for 3 times, 1000g of deionized water, 150g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerizer]Spirocyclic undecane, 450g liquid bromine, 25g HCl and CH 3 OH aqueous mixture (molar concentration of HCl 0.9mol/L; CH) 3 OH molar concentration is 0.6 mol/L), heating to 80 ℃ for reaction for 3 hours, adding 100g of 10wt% NaOH aqueous solution to terminate the reaction, finally adding 1500g of chloromethane for extraction, and then separating, washing and drying to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane D (yield 95%).
2) A, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 3600g of octane, 350g of isoprene and 3.0g THF,44.5mmo1 n-butyllithium into the reaction kettle, heating to 46 ℃ and then reacting for 52min to form a first block system (IR block);
B. then 250g of 1, 3-butadiene and 2.3g of THF are sequentially added into the reaction kettle, and the temperature is raised to 56 ℃ for reaction for 36min to form a second block system (BR-IR block);
C. then 630g of styrene, 360g of 1, 3-butadiene and 6.0g of THF are stirred and mixed for 26min to form a third raw material system, the third raw material system is continuously added into the second raw material system at 66 ℃ in a decelerating way, the reaction is completed in 80min when the raw material addition is just started, the initial feeding speed is 70g/min, the feeding speed is reduced by 2.5g per minute, and a third block system (SB/(S-B) -BR-IR block) is obtained;
D. Then 1600g of octane, 1000g of p-bromomethylstyrene and 5.3g of THF are sequentially added into the reaction kettle, the temperature is raised to 76 ℃, 48.5 mmol 1 of n-butyllithium is added for reacting for 103min, and a third block system (D-SB/(S.fwdarw.B) -BR-IR block) is obtained.
3) Heating the reaction kettle to 86 ℃, and adding 230mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane D for reacting for 113min; then adding 40g of 1, 3-butadiene into a reaction kettle for end capping, reacting for 36min until no free monomer exists, and performing wet condensation and drying on the glue solution to prepare the brominated grafting agent D of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Adding 300g of dichloromethane, 700g of cyclohexane and 34g of brominated grafting agent D into a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for replacement for 4 times, stirring and dissolving for 73min until the grafting agent is completely dissolved, then cooling to the temperature of-86 ℃, sequentially adding 800g of dichloromethane, 433g of isobutene and 33g of isoprene, stirring and mixing until the system temperature is reduced to the temperature of-96 ℃ to obtain a first system;
2) 80g of methylene dichloride, 2.83g of aluminum sesquichloride and 0.065g of HCl are mixed and aged for 27min at the temperature of minus 92 ℃, an aging system is added into a first system to be stirred and reacted for 6.3h, 30g of butanol is finally added, and then the brominated butyl rubber D of the embodiment is obtained after discharging, condensing, washing and drying.
Example 5
The preparation method of the brominated grafting agent comprises the following steps:
1) A, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 3800g of octane, 370g of isoprene and 3.5g THF,48.5mmo1 n-butyllithium into the reaction kettle, heating to 48 ℃ and then reacting for 55min to form a first block system (IR block);
B. then adding 280g of 1, 3-butadiene and 2.7g of THF into the reaction kettle in sequence, and heating to 58 ℃ to react for 38min to form a second block system (BR-IR block);
C. then 670g of styrene, 380g of 1, 3-butadiene and 6.5g of THF are stirred and mixed for 28min to form a third raw material system, the third raw material system is continuously added into a second block system at 68 ℃ in a decelerating way, the reaction is completed in 90min when the raw material addition is just started, the initial feeding speed is 80g/min, and the feeding speed is reduced by 3g per minute, so that a second block system (SB/(S-B) -BR-IR block) is obtained;
D. then 1800g of octane, 1000g of p-bromomethylstyrene and 5.7g of THF are added into the reaction kettle in turn, the temperature is raised to 78 ℃, 50.5 mmol 1 of n-butyllithium is added for reaction for 107min, and a bromination system (D-SB/(S.fwdarw.B) -BR-IR block) is obtained.
2) Heating the reaction kettle to 88 ℃, and adding 280mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane D for reacting for 118min; then adding 45g of 1, 3-butadiene into a reaction kettle for end capping, reacting for 38min until no free monomer exists, and performing wet condensation and drying on the glue solution to prepare the brominated grafting agent E of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Adding 400g of methylene dichloride, 600g of cyclohexane and 37g of brominated grafting agent E into a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for replacement for 5 times, stirring and dissolving for 76min until the grafting agent is completely dissolved, then cooling to-88 ℃, sequentially adding 900g of methylene dichloride, 429g of isobutene and 34g of isoprene, stirring and mixing until the system temperature is reduced to-98 ℃ to obtain a first system;
2) 90g of methylene dichloride, 3.15g of aluminum sesquichloride and 0.078g of HCl are mixed and aged for 29min at the temperature of minus 94 ℃, an aging system is added into a first system to be stirred and reacted for 6.7h, and finally 33g of butanol is added, and then the brominated butyl rubber E of the embodiment is obtained after discharging, condensing, washing and drying.
Example 6
The preparation method of the brominated grafting agent comprises the following steps:
1) A, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 4000g of octane, 400g of isoprene and 4.0g THF,50.5mmo1 n-butyllithium into the reaction kettle, heating to 50 ℃ and then reacting for 60 minutes to form a first block system (IR block);
B. then 300g of 1, 3-butadiene and 3.0g of THF are sequentially added into the reaction kettle, and the temperature is raised to 60 ℃ for reaction for 40min to form a second block system (BR-IR block);
C. Then 700g of styrene, 400g of 1, 3-butadiene and 7.0g of THF are stirred and mixed for 30min to form a third raw material system, the third raw material system is continuously added into the second block system at 70 ℃ in a decelerating way, the reaction is completed in 90min when the raw material is just added, the initial feeding speed is 80g/min, the feeding speed is reduced by 3g per minute, and the third block system (SB/(S-B) -BR-IR block) is obtained;
D. then 2000g of octane, 1000g of p-bromomethylstyrene and 6.0g of THF are added into the reaction kettle in sequence, the temperature is raised to 80 ℃, 52.5 mmol 1 of n-butyllithium is added for reaction for 110min, and a bromination system (D-SB/(S.fwdarw.B) -BR-IR block) is obtained.
2) Heating the reaction kettle to 88 ℃, and adding 300mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane D for reaction for 120min; then 50g of 1, 3-butadiene is added into a reaction kettle for end capping, the reaction is carried out for 40min until no free monomer exists, and the glue solution is subjected to wet condensation and drying to prepare the brominated grafting agent F of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Adding 500g of dichloromethane, 500g of cyclohexane, 40g of brominated grafting agent F into a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for replacement for 5 times, stirring and dissolving for 80min until the grafting agent is completely dissolved, then cooling to-90 ℃, sequentially adding 1000g of dichloromethane, 425g of isobutene and 35g of isoprene, stirring and mixing until the system temperature is reduced to-100 ℃ to obtain a first system;
2) 100g of methylene dichloride, 3.56g of aluminum sesquichloride and 0.085g of HCl are mixed and aged for 30min at the temperature of minus 95 ℃, an aging system is added into a first system to be stirred and reacted for 7.0h, and finally 35g of butanol is added, and then the brominated butyl rubber F of the embodiment is obtained after discharging, condensing, washing and drying. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 7
The preparation method of the brominated grafting agent comprises the following steps:
1) A, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 4000g of octane, 410g of isoprene and 4.0g THF,55.4mmo1 n-butyllithium into the reaction kettle, heating to 50 ℃ and then reacting for 60 minutes to form a first block system (IR block);
B. then 320g of 1, 3-butadiene and 3.0g of THF are sequentially added into the reaction kettle, and the temperature is raised to 60 ℃ for reaction for 40min to form a second block system (BR-IR block);
C. then, 710g of styrene, 400g of 1, 3-butadiene and 7.0g of THF are stirred and mixed for 30min to form a third raw material system, the third raw material system is continuously added into a second block system at 70 ℃ in a decelerating way, the reaction is completed in 90min when the raw material is just added, the initial feeding speed is 80g/min, and the feeding speed is reduced by 2g per minute, so that a third block system (SB/(S-B) -BR-IR block) is obtained;
D. Then 2000g of octane, 1000g of p-bromomethylstyrene and 6.0g of THF are added into the reaction kettle in sequence, the temperature is raised to 80 ℃, 55.5 mmol 1 of n-butyllithium is added for reaction for 110min, and a bromination system (D-SB/(S.fwdarw.B) -BR-IR block) is obtained.
2) Heating the reaction kettle to 88 ℃, and adding 300mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane D for reaction for 120min; then 50G of 1, 3-butadiene is added into a reaction kettle for end capping, the reaction is carried out for 40min until no free monomer exists, and the glue solution is subjected to wet condensation and drying to prepare the brominated grafting agent G of the embodiment.
The preparation method of the brominated butyl rubber comprises the following steps:
1) Adding 500G of dichloromethane, 500G of cyclohexane, 40G of brominated grafting agent G into a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for replacement for 5 times, stirring and dissolving for 80min until the grafting agent is completely dissolved, then cooling to-90 ℃, sequentially adding 1000G of dichloromethane, 425G of isobutene and 35G of isoprene, stirring and mixing until the system temperature is reduced to-100 ℃ to obtain a first system;
2) 100G of methylene dichloride, 3.56G of aluminum sesquichloride and 0.085G of HCl are mixed and aged for 30min at the temperature of minus 95 ℃, an aging system is added into a first system to be stirred and reacted for 7.0h, and finally 35G of butanol is added, and then the brominated butyl rubber G of the embodiment is obtained after discharging, condensing, washing and drying.
Example 8
The preparation method of the brominated grafting agent comprises the following steps:
1) A, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 3000g of octane, 290g of isoprene and 1.0g THF,35.5mmo1 n-butyllithium into the reaction kettle, heating to 40 ℃ and then reacting for 40min to form a first block system (IR block);
B. then 200g of 1, 3-butadiene and 1.0g of THF are sequentially added into the reaction kettle, and the temperature is raised to 50 ℃ for reaction for 30min to form a second block system (BR-IR block);
C. then 490g of styrene, 300g of 1, 3-butadiene and 4.0g of THF are stirred and mixed for 20min to form a third raw material system, the third raw material system is continuously added into the second block system at 60 ℃ in a decelerating way, the reaction is completed in 70min when the raw material addition is just started, the initial feeding speed is 60g/min, and the feeding speed is reduced by 2g per minute, so that a third block system (SB/(S-B) -BR-IR block) is obtained;
D. then 1000g of octane, 1000g of p-bromomethylstyrene and 4.0g of THF are sequentially added into the reaction kettle, the temperature is raised to 70 ℃, 39.5 mmol 1 of n-butyllithium is added for reaction for 90min, and a bromination system (D-SB/(S.fwdarw.B) -BR-IR block) is obtained.
2) Heating the reaction kettle to 80 ℃, and adding 150mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane D for reacting for 100min; then adding 20g of 1, 3-butadiene into a reaction kettle for end capping, reacting for 30min until no free monomer exists, and performing wet condensation and drying on the glue solution to prepare the brominated grafting agent H 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 420g of methyl chloride, 180g of cyclohexane and 20g of brominated grafting agent H into the reaction kettle, and stirring and dissolving for 60min until the grafting agent is completely dissolved; then cooling to-80 ℃, sequentially adding 500g of dichloromethane, 450g of isobutene and 30g of isoprene, stirring and mixing until the system temperature is reduced to-90 ℃ to obtain a first system;
2) 50g of methylene dichloride, 1.56g of aluminum sesquichloride and 0.021g of HCl are mixed and aged for 20min at the temperature of minus 85 ℃, an aging system is added into a first system, after stirring and reacting for 5.0H, 15g of butanol is finally added, discharging is performed, coagulation is performed, washing and drying are performed, and the brominated butyl rubber H of the embodiment is obtained.
Comparative example 1
The preparation of the brominated grafting agent a of this comparative example was essentially identical to that of example 1, except that 200g of p-bromomethylstyrene was added in step 2).
The preparation of the brominated butyl rubber a of this comparative example was substantially identical to that of example 1, except that the brominated grafting agent a of example 1 was replaced with a brominated grafting agent a.
Comparative example 2
The preparation of brominated grafting agent b of this comparative example was essentially identical to that of example 2, except that allyl bromide was used in place of the p-bromomethylstyrene of example 2.
The preparation of the brominated butyl rubber B of this comparative example was substantially identical to that of example 2, except that the brominated grafting agent B of example 2 was replaced with a brominated grafting agent B.
Comparative example 3
The preparation of brominated butyl rubber C of this comparative example was substantially identical to that of example 3, except that brominated grafting agent C was added in an amount of 10g.
Comparative example 4
The preparation of brominated grafting agent d of this comparative example was essentially identical to that of example 4, except that the 1, 5-dibromo-3, 3-bis (2-bromoethyl) pentane coupling agent of example 4 was replaced with a silicon tetrachloride coupling agent.
The preparation of the brominated butyl rubber D of this comparative example was substantially identical to that of example 4, except that the brominated grafting agent D added was substituted for the brominated grafting agent D of example 4.
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 in step 1) C, a third raw material system was added once to the second block system at 68℃and reacted for 90 minutes to form a third block system which was an SBR-BR-IR block.
The preparation of brominated butyl rubber E of this comparative example is substantially identical to that of example 5, except that brominated grafting agent E of example 5 is replaced with brominated grafting agent E.
Comparative example 6
The preparation of the brominated grafting agent f of this comparative example was essentially identical to that of example 6, except that in step 1) A no IR block was formed, i.e., 4000g of octane was added to the reaction vessel during the operation and the addition of isoprene, THF and n-butyllithium was omitted by heating to 50 ℃.
The preparation of the brominated butyl rubber F of this comparative example was substantially identical to that of example 6, except that the brominated grafting agent F of example 6 was replaced with a brominated grafting agent 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 | 17.3％ | 101000/15.65 |
| Example 2 | 18.5％ | 103000/15.85 |
| Example 3 | 19.3％ | 105000/16.02 |
| Example 4 | 20.5％ | 107000/16.28 |
| Example 5 | 21.2％ | 109000/16.56 |
| Example 6 | 22.6％ | 110000/16.73 |
| Example 7 | 22.8％ | 121000/17.05 |
| Example 8 | 17.1％ | 97000/14.13 |
| Comparative example 1 | 14.5％ | 92000/12.58 |
| Comparative example 2 | 12.7％ | 83000/12.15 |
| Comparative example 3 | 19.3％ | 105000/16.02 |
| Comparative example 4 | 20.1％ | 99000/12.18 |
| Comparative example 5 | 20.3％ | 108000/10.27 |
| Comparative example 6 | 21.3％ | 98000/13.95 |
As can be seen from Table 1, the preparation method provided by the invention can prepare the brominated grafting agent shown in the formula 1 with the bromine content not less than 17 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.
Molecular weight and distribution thereof: the method is the same as above.
Vulcanization characteristics: the test is carried out according to GB/T16584-1996 by using a GT-M2000A rotor-free vulcanizing instrument manufactured by high-speed rail company in Taiwan area. 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 measure the air permeability number according to ISO 2782:1995, and the test gas is N 2 The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.
Die swell ratio: RH2000 capillary rheometer at temperature using Markov company, UK 100 ℃, length-diameter ratio of 16:1 and shear rate of 10-1000S -1 Is measured in the interval of (2).
Determination of tensile Strength: tested according to GB/T528-2009.
TABLE 2
As is clear 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, mechanical strength, 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 IR is an isoprene homo-block, BR is a 1, 3-butadiene homo-block, SB/(S.fwdarw.B) is a random gradual change block of styrene and butadiene, D is a p-bromomethylstyrene homo-block, B is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, and n is not less than 1;
In the brominated grafting agent, the mass percentage of bromine element is 17-23%.
2. The brominated grafting agent of claim 1, wherein the brominated grafting agent has a number average molecular weight of 100000 ～ 110000 and a molecular weight distribution of 15.65 to 16.73.
3. The brominated grafting agent of claim 1 or 2, wherein the brominated grafting agent is prepared by a process comprising:
the coupling raw material system is reacted for 60 to 180 minutes at the temperature of between 60 and 80 ℃ to terminate the reaction, and then the coupling agent is obtained by extraction;
reacting the first raw material system at 40-50 ℃ for 40-60min to obtain a first block system;
adding a second raw material system into the first block system, and reacting at 50-60 ℃ for 30-40min to obtain a second block system;
continuously decelerating and adding a third raw material system into the second block system at 60-70 ℃ to obtain a third block system after 70-90min of time for adding the third raw material system;
adding a brominating agent and a brominating structure regulator into the third block system, heating to 70-80 ℃, then adding a brominating initiator, and reacting for 90-110min to obtain a brominating system;
adding the coupling agent into the bromination system at 80-90 ℃ and reacting for 100-120min, and then adding the activating end capping agent and reacting for 30-40min to obtain the bromination grafting agent;
Wherein the coupling raw material system comprises 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and a catalyst; the first raw material system comprises isoprene, a first structure regulator and a polymerization initiator; the second feed system comprises a second monomer and a second structure modifier; the third raw material system comprises styrene, a third monomer and a third structure regulator; the second monomer, the third monomer and the activating end capping agent are 1, 3-butadiene; the brominating agent is p-bromomethylstyrene;
in the continuous deceleration, V 0 ＞5％*M 3 ，V 0 G/min for the initial rate of addition of the third feed system; m is M 3 Is the total weight of the third feed system.
4. A brominated grafting agent as claimed in claim 3, characterized in that,
the coupling raw material system comprises a coupling main body raw material and a catalyst, wherein the coupling main body raw material comprises 10-30% of 3, 9-dioxy [5.5] spiro undecane and 70-90% of halogenating agent according to the mass percentage, and the mass ratio of the coupling main body raw material to the catalyst is 1: (1-5); and/or the number of the groups of groups,
the mass ratio of the brominating agent to the isoprene in the first raw material system and the first structure regulator is 1: (0.3-0.4): (0.001-0.004);
The mass ratio of the brominating agent to the second monomer in the second raw material system to the second structure regulator is 1: (0.2-0.3): (0.001-0.003);
the mass ratio of the brominating agent to the third monomer, the styrene and the third structure regulator in the third raw material system is 1: (0.3-0.4): (0.5-0.7): (0.004-0.008);
the mass ratio of the brominating agent to the brominating structure regulator is 1: (0.004-0.006).
5. The brominated grafting agent of claim 3 or 4, wherein the molar ratio of coupling agent to initiator is (1:1) - (4:1);
the initiator is composed of the bromination initiator and the polymerization initiator.
6. The preparation method of the brominated grafting agent is characterized by comprising the following steps:
the coupling raw material system is reacted for 60 to 180 minutes at the temperature of between 60 and 80 ℃ to terminate the reaction, and then the coupling agent is obtained by extraction;
reacting the first raw material system at 40-50 ℃ for 40-60min to obtain a first block system;
adding a second raw material system into the first block system, and reacting at 50-60 ℃ for 30-40min to obtain a second block system;
continuously decelerating and adding a third raw material system into the second block system at 60-70 ℃ to obtain a third block system after 70-90min of time for adding the third raw material system;
Adding a brominating agent and a brominating structure regulator into the third block system, heating to 70-80 ℃, then adding a brominating initiator, and reacting for 90-110min to obtain a brominating system;
adding the coupling agent into the bromination system at 80-90 ℃ and reacting for 100-120min, and then adding the activating end capping agent and reacting for 30-40min to obtain the bromination grafting agent;
wherein the coupling raw material system comprises 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and a catalyst; the first raw material system comprises isoprene, a first structure regulator and a polymerization initiator; the second feed system comprises a second monomer and a second structure modifier; the third raw material system comprises styrene, a third monomer and a third structure regulator; the second monomer, the third monomer and the activating end capping agent are 1, 3-butadiene; the brominating agent is p-bromomethylstyrene;
in the continuous deceleration, V 0 ＞5％*M 3 ，V 0 G/min for the initial rate of addition of the third feed system; m is M 3 Is the total weight of the third feed system;
the brominated grafting agent has a structure shown in a formula 1,
wherein IR is an isoprene homo-block, BR is a 1, 3-butadiene homo-block, SB/(S.fwdarw.B) is a random gradual change block of styrene and butadiene, D is a p-bromomethylstyrene homo-block, B is a 1, 3-butadiene homopolymer with a number average molecular weight not higher than 1000, and n is not less than 1;
In the brominated grafting agent, the mass percentage of bromine element is 17-23%.
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 grafting agent prepared as defined in claim 6 with a system comprising isobutylene and isoprene;
the mass ratio of the brominated grafting agent to the isobutene to the isoprene is (4-8): (85-90): (6-7).
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-90 to-80 ℃ and controlling the temperature to be-100 to-90 ℃ to obtain a first system;
mixing a second diluent and a co-initiator at the temperature of minus 95 ℃ to minus 85 ℃ and aging for 20 min to 30min, adding an aging system into the first system, and stopping the reaction after reacting for 5 h to 7h 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): (0.003-0.008);
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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