CN113493549A - Preparation method of high-width distribution and high-branching butyl rubber - Google Patents
Preparation method of high-width distribution and high-branching butyl rubber Download PDFInfo
- Publication number
- CN113493549A CN113493549A CN202010271960.7A CN202010271960A CN113493549A CN 113493549 A CN113493549 A CN 113493549A CN 202010271960 A CN202010271960 A CN 202010271960A CN 113493549 A CN113493549 A CN 113493549A
- Authority
- CN
- China
- Prior art keywords
- polymerization
- reaction
- polymerization kettle
- butyl rubber
- kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 80
- 238000009826 distribution Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 164
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 94
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 88
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 49
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 76
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 70
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 70
- 238000005859 coupling reaction Methods 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 43
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 38
- 229910052786 argon Inorganic materials 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 13
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- UGFDIXXDKBKDSR-UHFFFAOYSA-N di(propan-2-yl)aluminum Chemical compound CC(C)[Al]C(C)C UGFDIXXDKBKDSR-UHFFFAOYSA-N 0.000 claims 1
- UKOVZLWSUZKTRL-UHFFFAOYSA-N naphthalid Chemical compound C1=CC(C(=O)OC2)=C3C2=CC=CC3=C1 UKOVZLWSUZKTRL-UHFFFAOYSA-N 0.000 claims 1
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 8
- 229920001971 elastomer Polymers 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 239000005060 rubber Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 46
- 229910001220 stainless steel Inorganic materials 0.000 description 45
- 239000010935 stainless steel Substances 0.000 description 45
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 38
- 238000012360 testing method Methods 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 230000032683 aging Effects 0.000 description 13
- 230000008859 change Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 238000007599 discharging Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000005345 coagulation Methods 0.000 description 12
- 230000015271 coagulation Effects 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000002902 bimodal effect Effects 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 229920002367 Polyisobutene Polymers 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical group [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 1
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- MJMQIMYDFATMEH-UHFFFAOYSA-N 2-chloro-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)Cl MJMQIMYDFATMEH-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- BQAZYKYBFAMHPG-UHFFFAOYSA-N 3,5-dimethylhex-2-ene Chemical compound CC=C(C)CC(C)C BQAZYKYBFAMHPG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910008046 SnC14 Inorganic materials 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 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
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- 238000010552 living cationic polymerization reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- ZYTJPPRBIGGXRO-UHFFFAOYSA-N propan-2-ylalumane Chemical compound C(C)(C)[AlH2] ZYTJPPRBIGGXRO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention adopts alkyl lithium as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers comprise isoprene, styrene and butadiene, the three-kettle reaction and the three-time addition of the initiator are carried out, the temperature-changing and speed-changing polymerization is adopted, and then the ternary star-arm copolymer ([ -SB/(S → B) -]nY[‑PS‑B‑]n[‑IR‑]n) Finally, the ternary star-shaped hybrid arm copolymer is used as a grafting agent to be polymerized with isobutene and isoprene under a catalyst system compounded by alkyl aluminum halide and protonic acid to prepare the high-branched butyl rubber with high broad molecular weight distribution through cationic polymerization. The butyl rubber realizesBalance between physical and mechanical properties and processability, and guarantee that the butyl rubber has good viscoelasticity, sufficient crude rubber strength and good air tightness.
Description
Technical Field
The invention relates to a preparation method of high-width distribution and high-branching butyl rubber, in particular to high-width molecular weight distribution and high-branching butyl rubber prepared by taking isoprene/styrene/butadiene ternary heteroarm star-shaped copolymer as a grafting agent and a preparation method thereof.
Background
It is known that Butyl Rubber (IIR) is produced by the cationic polymerization of isobutylene and a small amount of isoprene. Butyl rubber has been commercialized by Exxon corporation in the 40 th century for over seventy years since now, and has excellent properties such as airtightness, damping properties, thermal aging resistance, ozone resistance, and weather resistance, and thus it is widely used in the fields of manufacturing inner tubes, airtight layers, curing bladders, medical stoppers of tires for vehicles, and the like, and is one of the most important synthetic rubber products.
However, the molecular chain of the butyl rubber is mainly composed of carbon-carbon single bonds, the number of double bonds is small, and the substituent methyl groups are symmetrically arranged, so that the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesiveness, poor compatibility with other general rubbers and the like exist, and the butyl rubber is easy to excessively flow and deform in the processing process. Therefore, how to balance the physical and mechanical properties and the processability of the butyl rubber becomes a bottleneck for preparing high-performance butyl rubber materials.
In recent years, researchers find that star-shaped highly-branched butyl rubber which is composed of a high-molecular-weight graft structure and a low-molecular-weight linear structure and has a unique three-dimensional net structure has excellent viscoelastic property, high crude rubber strength and a fast stress relaxation rate, low melt viscosity can be kept in a processing process, a high-molecular-weight polymer can be obtained, and balance and unification of physical and mechanical properties and processing properties are realized. Therefore, the star-shaped highly-branched structure becomes one of the hot spots in the research field of future butyl rubber.
In the prior art, the synthesis of star-shaped highly branched butyl rubber is mainly prepared by a method of a first-arm-after-core method, a first-arm-after-core method and a core-arm simultaneous method. Such as: US5395885 discloses a star-shaped highly-branched polyisobutylene-polydivinylbenzene polymer, which is synthesized by taking polyisobutylene as an arm, Polydivinylbenzene (PDVB) as a core, a complex of aluminium chloride and water as an initiator, and methyl chloride as a diluent through a first-arm-second-core method at-90 ℃ to-100 ℃. CN 107344982 a discloses a method for producing a wide/bimodal molecular weight distribution butyl rubber, which comprises: mixing isobutene and isoprene at a molar ratio of 97:3 to 99:1, then mixing the mixture with a diluent (methane chloride) to obtain a monomer stream, mixing an initiator (an aluminum chloride system and an HCl/alkylaluminum chloride complex) with the diluent (methane chloride) to obtain an initiator stream, mixing the monomer stream and the initiator stream, conveying the mixture into a first loop reactor zone, and carrying out polymerization reaction for 5-10min at a temperature of-98 ℃ to-96 ℃ and a pressure of 0.3 to 0.4MPa to obtain a first part of butyl rubber slurry; secondly, sending the first part of butyl rubber slurry into a second loop reactor zone, and carrying out polymerization reaction for 5-10min at the temperature of-92 ℃ to-90 ℃ and the pressure of 0.1 to 0.2Mpa to finally obtain the butyl rubber slurry with broad/bimodal molecular weight distribution; third step of contacting the butyl rubber slurry having broad/bimodal molecular weight distribution with water to remove unreacted monomers and diluent to obtain water in the form of colloidal particles, and then dehydrating and drying the water in the form of colloidal particles to obtain a butyl rubber slurry having broad/bimodal molecular weight distribution with a molecular weight distribution (Mw/Mn) of at least 5.0Butyl rubber. CN1427851A discloses a preparation method of butyl rubber with wide molecular weight distribution. The process uses a mixed catalyst system comprising a mixture of a major amount of an internalized dialkylaluminum, a minor amount of a monoalkylaluminum dihalide, and a minor amount of an aluminoxane to provide a broad distribution butyl rubber having a molecular weight distribution of greater than 3.5 up to 7.6. CN 101353403B discloses a preparation method of star-shaped highly-branched polyisobutylene or butyl rubber, which adopts a polystyrene/isoprene block copolymer with a silicon-chlorine group at the tail end or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the tail end as an initiating grafting agent for positive ion polymerization, directly participates in the positive ion polymerization in a positive ion polymerization system of a mixed solvent with a ratio of v: v of monochloro methane to cyclohexane of 20-80/80-20 at the temperature of 0-100 ℃, and prepares a star-shaped highly-branched polyisobutylene or butyl rubber product by the initiation of the silicon-chlorine group and the participation of a grafting reaction of an unsaturated chain. CN01817708.5 provides a method for preparing star-shaped highly branched polymers by adding a multiolefin crosslinking agent such as divinylbenzene and a chain transfer agent such as 2,4, 1-trimethyl-1-pentene to a mixture of isoolefin monomers and diolefin monomers. CN88108392.57 discloses a star-shaped grafted butyl rubber with a comb-shaped structure, which is prepared by using a hydrochloric acid polystyrene-isoprene copolymer as a multifunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN 107793535A provides a butyl rubber having a molecular weight of 90 to 260 ten thousand, Log (MW)>And contains structural units derived from isobutylene, structural units derived from a conjugated diene, and optionally structural units derived from an aryl olefin. US3780002 teaches a composite initiator using a halide of a metal from group II or III of the periodic Table of the elements in combination with a tetrahalide of a metal from group IV of the periodic Table of the elements, e.g. AICl3And TiC14Combined use, or A1C13And SnC14The composite use enables each initiator to independently initiate cationic polymerization, and butyl rubber with molecular weight distribution index Mw/Mn of above 5.0 is synthesized under the conventional butadiene rubber polymerization condition.
CN 101353386A discloses an initiation system for starlike highly branched polyisobutylene or butyl rubber cationic polymerization, which is composed of an initiation-grafting agent, a coinitiator and a nucleophilic reagent, and is used for initiating vinyl monomers to perform homopolymerization, block copolymerization, star polymerization and graft copolymerization, wherein the obtained polymer presents obvious bimodal distribution. Puskas (Catalysts for manufacturing of IIR with bi-modal molecular weight distribution: US, 5194538[ P ] 1993-3-16.) adopts trimesic acid as raw material to synthesize initiator tri-cumyl alcohol with a three-arm structure, and then adopts a tri-cumyl alcohol/aluminum trichloride initiating system to initiate isobutylene and isoprene to copolymerize in an inert organic solvent under the condition of-120 to-50 ℃ to synthesize star-shaped highly branched butyl rubber with bi-modal molecular weight distribution. Wieland et al (Synthesis of new graft copolymer polymerization by polymerization of the 1,1-diphenylethylene technology and cationic polymerization [ J ]. Polymer Science: Polymer Chemistry, 2002, 40: 3725-co-3733.) synthesized a macroinitiator P (MMA-b-St-co-CMS) containing the three members of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-Diphenylethylene (DPE) by a radical polymerization method, and then initiated cationic polymerization of isobutylene and isoprene to successfully prepare the multi-arm star butyl rubber. Wubo et al (Davang S H, et al. Ski resistant coatings for air craft carrier decks [ J ]. Coat Technol, 1980, 52 (671): 65-69.) prepared a poly (isoprene-styrene) block copolymer as a grafting agent by living anionic polymerization, and prepared a star-shaped highly branched butyl rubber exhibiting significant bimodal properties by living cationic polymerization in an initiation system of 2-chloro-2, 4, 4-trimethylpentane/titanium tetrachloride/proton scavenger.
Disclosure of Invention
The invention aims to provide a preparation method of high-width distribution and high-branching butyl rubber. The invention firstly takes alkyl lithium as an initiator, takes hydrocarbons as a solvent, and a reaction monomer consists of isoprene, styrene and butadiene, and the ternary star-shaped hybrid-arm copolymer with wide vinyl distribution and random gradual change section is prepared by coupling a coupling agent of trihalogenated benzene. Under the catalysis system of compounding Lewis acid and protonic acid, the ternary star-shaped hybrid arm copolymer is used as a grafting agent to carry out cationic polymerization with isobutene and isoprene to prepare the high-branched butyl rubber with high and wide molecular weight distribution. The high-width-distribution high-branching butyl rubber not only has enough crude rubber strength and good air tightness, but also has high stress relaxation rate and small extrusion swelling effect in the processing process, and realizes the balance of the physical and mechanical properties and the processing properties of the butyl rubber.
All the percentages in the present invention are percentages by mass.
The preparation of the highly branched star-shaped butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) preparation of grafting agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 20-30% of isoprene, 0.01-0.1% of structure regulator and initiator into the polymerization kettle, wherein the reaction is temperature-changing polymerization, the temperature is gradually increased from 40 ℃ to 65 ℃ within 40-60 min to form a widely distributed IR chain segment, and the conversion rate of the isoprene monomer reaches 100%; heating to 70-90 ℃, adding a coupling agent to carry out coupling reaction for 60-90 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3-5 times, sequentially adding 100-200% of a solvent, 0.1-0.3% of a structure regulator, and an initiator, heating to 70-80 ℃, stirring and mixing 40-50% of styrene and 10-20% of 1, 3-butadiene for 10-30 min, wherein the reaction is variable-speed polymerization, adding the mixture into the polymerization kettle in a continuous injection manner, reacting within 60-80 min, wherein the initial feeding speed is more than 10.0% of the mixture/min, and the reduction range of the feeding speed is determined according to the reaction time to form a random and long gradual change section-SB/(S → B) -chain segment, when the conversion rate of the styrene and the 1, 3-butadiene monomer reaches 100%, then adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 50-70 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 10-20% of styrene, 0.05-0.1% of structure regulator and initiator, heating to 60-80 ℃, reacting for 50-70 min to form a-PS-chain segment, adding the materials in the polymerization kettle C into a polymerization kettle A when the conversion rate of styrene monomer reaches 100%, and performing coupling reaction for 60-90 min; and then adding 1-5% of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 20-30 min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped ternary hybrid-arm copolymer.
(2) Preparing high-width distribution high-branching butyl rubber: according to one hundred percent of the total mass of reaction monomers, firstly introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3-5 times, and adding 100-200 percent of diluent/solvent V: the V ratio is 70-30/30-70, the mixed solvent and the grafting agent are 2-10%, and the mixed solvent and the grafting agent are stirred and dissolved for 20-30 min until the grafting agent is completely dissolved; and then cooling to-75 to-85 ℃, sequentially adding 100 to 200 percent of diluent, 85 to 95 percent of isobutene and 1 to 5 percent of isoprene, stirring and mixing until the temperature of the polymerization system is reduced to-100 to-90 ℃, then adding 30 to 50 percent of diluent and 0.05 to 3.0 percent of co-initiator into the polymerization system for stirring and reacting for 1.0 to 3.0 hours after mixing and aging for 20 to 30 minutes at-85 to-95 ℃, discharging and condensing, washing and drying to obtain the high-wide distribution high-branching butyl rubber product.
The grafting agent is a ternary star-shaped hetero-arm copolymer of isoprene, styrene and butadiene ([ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n), and the structural general formula of the grafting agent is shown as a formula I:
wherein Y is a benzene ring; IR is a homopolymer segment with wide vinyl distribution of isoprene, and the 1, 2-structure content of the segment is 10-20%; PS is a styrene homopolymer segment; SB is a random section of styrene and butadiene; (S → B) is a transition of styrene and butadiene; b is terminated butadiene, and n is 1-4; the three-arm star polymer contains 20-30% of isoprene, 50-70% of styrene and 10-20% of butadiene; the number average molecular weight (Mn) of the three-arm star polymer is 110000-140000, and the molecular weight distribution (Mw/Mn) is 8.23-13.24.
The structure regulator of the invention is a polar organic compound which generates solvation effect in a polymerization system and can regulate the reactivity ratio of styrene and butadiene so as to ensure that the styrene and the butadiene are randomly copolymerized. Such polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), Tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, preferably Tetrahydrofuran (THF).
The initiator is an alkyl monolithium compound, namely RLi, wherein R is a saturated aliphatic alkyl, alicyclic alkyl, aromatic alkyl containing 1-20 carbon atoms or a composite group of the above groups. The alkyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the polymer being designed.
The coupling agent used in the invention is one of 1,3, 5-trichlorobenzene and 1,3, 5-tribromobenzene, and preferably 1,3, 5-trichlorobenzene. The dosage of the coupling agent is determined according to the amount of the initiator, the star polymer with the hybrid arm structure is finally formed through stepwise polymerization of excessive coupling agent, and the molar ratio of the dosage of the coupling agent to the total organic lithium is 3.0-5.0.
The diluent is halogenated alkane, wherein halogen atoms in the halogenated alkane can be chlorine, bromine or fluorine; the number of carbon atoms in the halogenated alkane is C1-C4. The alkyl halide is selected from one of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably methyl chloride.
The co-initiator is prepared by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from the group consisting of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, isopropylaluminum dichloroide, dimethylaluminum chloride and ethylaluminum chloride, preferably ethylaluminum sesquichloride. The protonic acid is selected from one of HCI, HF, HBr, H2SO4, H2CO3, H3PO4 and HNO3, preferably HCI. Wherein the total addition amount of the coinitiator is 0.1-3.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.
The polymerization reaction of the present invention is carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution are carried out in a hydrocarbon solvent, which is a hydrocarbon solvent including straight-chain alkanes, aromatic hydrocarbons and cycloalkanes, and is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention firstly adopts alkyl lithium as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers consist of isoprene, styrene and butadiene, three-kettle reaction and three-time addition of the initiator are carried out, temperature-changing and speed-changing polymerization is adopted, then a trihydric hetero-arm star copolymer ([ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n) is prepared by coupling with a trihydric benzene coupling agent, and finally the trihydric hetero-arm star copolymer is used as a grafting agent to prepare the high-breadth molecular weight distribution high-branching butyl rubber (shown in figure 1) by cationic polymerization with isobutene and isoprene in a catalytic system compounded by alkyl aluminum halide and protonic acid.
According to the invention, three chain segments with different microstructures are combined on a macromolecular chain to form a heteroarm star-shaped structure through a multi-kettle feeding method, a condition gradual change method and accurate control on the type and the dosage of a coupling agent, so that the performances of different chain segments are organically combined together and play a role in a synergistic manner, the randomness and the gradual change of a-SB/(S → B) -chain segment and the difference of reactivity ratio and steric hindrance effect of each chain segment in the heteroarm structure are utilized, the disorder of the molecular chain segment is increased in the grafting polymerization process of the butyl rubber, the regularity of the molecular chain is obviously damaged, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic performance, the stress relaxation rate is high, and the processing performance of the butyl rubber is improved; meanwhile, the-PS-and-SB/(S → B) -chain segments contain a large number of benzene rings, so that the reduction of strength and air tightness caused by the broadening of the molecular weight distribution of the butyl rubber is avoided, and the high strength and good air tightness of the butyl rubber are ensured.
According to the invention, through the design of the miktoarm star-shaped structure, the problem of contradiction between the processability and the physical and mechanical properties of the butyl rubber is solved, and the optimal balance between the processability and the physical and mechanical properties of the butyl rubber is finally realized. The preparation method provided by the invention has the characteristics of controllable process bars, stable product performance, suitability for industrial production and the like.
Drawings
FIG. 1 is a comparison of GPC spectra of 1# -butyl rubber IIR301 samples with 2# -example 1 samples.
Detailed Description
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. All the raw materials used in the examples are of industrial polymerization grade, and are used after purification without other special requirements.
The raw material sources are as follows:
other reagents are all commercial products
The analysis and test method comprises the following steps:
determination of the molecular weights and their distribution: the measurement was carried out by using 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation, USA. Taking a polystyrene standard sample as a calibration curve, taking tetrahydrofuran as a mobile phase, controlling the column temperature to be 40 ℃, the sample concentration to be 1mg/ml, the sample injection amount to be 50 mu L, the elution time to be 40min and the flow rate to be 1 ml.min < -1 >.
Determination of Mooney viscosity and stress relaxation: adopting the model GT-7080-S2 Menni of high-speed rail company in Taiwan
And (5) measuring by a viscometer. The Mooney relaxation time, determined with a large rotor at 125 ℃ C (1+8) according to the method of GB/T1232.1-2000, is 120 s.
Measurement of airtightness: the air permeability was determined using an automated air tightness tester according to ISO 2782:1995,
the test gas is N2, the test temperature is 23 ℃, and the test sample is a circular sea piece with the diameter of 8cm and the thickness is 1 mm.
Tensile strength: the method in standard GB/T528-2009 is executed.
Example 1
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 1750g of cyclohexane, 305g of isoprene and 1.1g of THF into the polymerization kettle A, heating to 40 ℃, adding 15.2mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 40min to form an IR chain segment with wide distribution, heating to 70 ℃ again, adding 192mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 60 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2190g of cyclohexane, 2.1g of THF and 23.6mmo1 of n-butyllithium, heating to 70 ℃, then stirring and mixing 620g of styrene and 170g of 1, 3-butadiene for 10min, within 60min, reducing the mixture by 2g per minute at an initial feeding speed of 85 g/min to form a random and long gradual change section-SB/(S → B) -chain segment, after the monomer is completely converted, adding the material in the polymerization kettle B into the polymerization kettle A, and continuing the coupling reaction for 50 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1520g of cyclohexane, 157g of styrene, 0.6g of THF and 10.5mmo1 of n-butyllithium, heating to 60 ℃, reacting for 50min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 60 min; and finally, adding 21g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 20min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped copolymer with the ternary miktoarm [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n (Mn is 111350, and Mw/Mn is 8.51).
(2) Preparing high-width distribution high-branching butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 590g of methane chloride, 265g of cyclohexane, 21.5g of grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n into the polymerization kettle, stirring and dissolving for 20min until the grafting agent is completely dissolved; and then cooling to-75 ℃, sequentially adding 525g of methane chloride, 426g of isobutene and 6g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 160g of methane chloride, 3.18g of aluminum sesquiethylate chloride and 0.089g of HCl at-85 ℃, aging for 20min, then adding the materials into the polymerization system together, stirring and reacting for 1.0hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 1820g of cyclohexane, 335g of isoprene and 1.2g of THF into the polymerization kettle A, heating to 40 ℃, adding 16.2mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 45min to form a widely distributed IR chain segment, heating to 75 ℃ again, adding 205mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 65 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2250g of cyclohexane, 2.7g of THF and 24.6mmo1 of n-butyllithium, heating to 75 ℃, then stirring and mixing 650g of styrene and 190g of 1, 3-butadiene for 15min, within 65min, reducing the mixture by 2g per minute at an initial feeding speed of 95 g/min to form a random and long gradual change section-SB/(S → B) -chain segment, after the monomer is completely converted, adding the material in the polymerization kettle B into the polymerization kettle A, and continuing the coupling reaction for 55 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1560g of cyclohexane, 178g of styrene, 0.8g of THF and 12.1mmo1 n-butyl lithium, heating to 70 ℃, reacting for 55min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 65 min; and finally, adding 28g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 22min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped copolymer with the ternary miktoarm [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n (Mn is 118260 and Mw/Mn is 9.51).
(2) Preparing high-width distribution high-branching butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 600g of methane chloride, 283g of cyclohexane, 27.5g of grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-80 ℃, sequentially adding 541g of methane chloride, 435g of isobutene and 9g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 170g of methane chloride, 4.23g of aluminum sesquiethylate chloride and 0.109g of HCl at-90 ℃, aging for 25min, then adding the mixture into the polymerization system together, stirring and reacting for 1.8hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 1920g of cyclohexane, 362g of isoprene and 1.4g of THF into the polymerization kettle A, heating to 40 ℃, adding 17.8mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 50min to form an IR chain segment with wide distribution, heating to 80 ℃, adding 226mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 75 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2420g of cyclohexane, 3.2g of THF and 26.5mmo1 n-butyllithium, heating to 77 ℃, then stirring and mixing 670g of styrene and 210g of 1, 3-butadiene for 20min, within 70min, reducing the mixture by 3g per minute at an initial feeding speed of 10 g/min to form a random and long gradual change section-SB/(S → B) -chain segment, after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and continuing the coupling reaction for 60 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1660g of cyclohexane, 190g of styrene, 1.0g of THF and 14.1mmo1 n-butyllithium, heating to 75 ℃, reacting for 60min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 70 min; and finally, adding 39g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 25min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped copolymer with the ternary hetero-arm [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n (Mn is 122350 and Mw/Mn is 11.52).
(2) Preparing high-width distribution high-branching butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 610g of methane chloride, 323 g of cyclohexane, 35.5g of grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 561g of methane chloride, 455g of isobutene and 13g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 180g of methane chloride, 5.63g of sesquiethylaluminum chloride and 0.229g of HCl at-95 ℃, aging for 25min, then adding the mixture into the polymerization system together, stirring and reacting for 2.0hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 2020g of cyclohexane, 385g of isoprene and 1.6g of THF into the polymerization kettle A, heating to 40 ℃, adding 19.8mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 55min to form a widely distributed IR chain segment, heating to 80 ℃ again, adding 235mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 80 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2500g of cyclohexane, 3.7g of THF and 28.1mmo1 n-butyllithium, heating to 77 ℃, then stirring and mixing 690g of styrene and 230g of 1, 3-butadiene for 25min, within 75min, reducing the mixture by 4g per minute at an initial feeding speed of 14 g/min to form a random and long gradual change section-SB/(S → B) -chain segment, after the monomer is completely converted, adding the material in the polymerization kettle B into the polymerization kettle A, and continuing the coupling reaction for 65 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1750g of cyclohexane, 210g of styrene, 1.2g of THF and 16.1mmo1 of n-butyl lithium, heating to 75 ℃, reacting for 65min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 75 min; and finally, adding 35g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 24min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped copolymer with the ternary hetero-arm [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n (Mn is 128950 and Mw/Mn is 12.12).
(2) Preparing high-width distribution high-branching butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 590g of methane chloride, 423g of cyclohexane, 40.2g of grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 582g of methane chloride, 465g of isobutene and 17g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 200g of methane chloride, 6.12g of aluminum sesquiethylate chloride and 0.256g of HCl at-95 ℃, aging for 25min, then adding the materials into the polymerization system together, stirring and reacting for 2.5hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 2230g of cyclohexane, 405g of isoprene and 1.8g of THF into the polymerization kettle A, heating to 40 ℃, adding 21.8mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 60min to form a widely distributed IR chain segment, heating to 80 ℃ again, adding 245mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 85 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2610g of cyclohexane, 3.9g of THF and 29.5mmo1 of n-butyllithium, heating to 80 ℃, then stirring and mixing 710g of styrene and 250g of 1, 3-butadiene for 25min, within 80min, reducing the mixture by 4g per minute at an initial feeding speed of 16 g/min to form a random and long gradual change section-SB/(S → B) -chain segment, after the monomer is completely converted, adding the material in the polymerization kettle B into the polymerization kettle A, and continuing the coupling reaction for 70 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1850g of cyclohexane, 240g of styrene, 1.5g of THF and 18.1mmo1 n-butyl lithium, heating to 80 ℃, reacting for 70min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 80 min; and finally, adding 40g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 27min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped copolymer with the ternary miktoarm [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n (Mn is 131950, and Mw/Mn is 12.85).
(2) Preparing high-width distribution high-branching butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 500g of methane chloride, 473g of cyclohexane, 45.2g of grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n into the polymerization kettle, and stirring and dissolving for 27min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 590g of methane chloride, 470g of isobutene and 20g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 210g of methane chloride, 6.89g of sesquiethylaluminum chloride and 0.276g of HCl at-95 ℃, aging for 27min, then adding the mixture into the polymerization system together, stirring and reacting for 2.7hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 5 times, sequentially adding 2510g of cyclohexane, 432g of isoprene and 2.3g of THF into the polymerization kettle A, heating to 40 ℃, adding 23.8mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 60min to form a widely distributed IR chain segment, heating to 90 ℃ again, adding 256mmo11,3, 5-tribromobenzene, and carrying out coupling reaction for 90 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 5 times, sequentially adding 2720g of cyclohexane, 4.2g of THF and 31.5mmo1 of n-butyllithium, heating to 80 ℃, then stirring and mixing 730g of styrene and 280g of 1, 3-butadiene for 30min, within 80min, forming a random and long gradual change section-SB/(S → B) -chain segment by reducing the initial feeding speed by 5g of mixture per minute at 18g of mixture/min and reducing the feeding speed by 5g of mixture per minute, adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 70 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 5 times, sequentially adding 1900g of cyclohexane, 260g of styrene, 1.8g of THF and 19.1mmo1 n-butyl lithium, heating to 80 ℃, reacting for 70min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 90 min; and finally, adding 50g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 30min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped copolymer with the ternary hetero-arm [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n (Mn is 138550, and Mw/Mn is 13.15).
(2) Preparing high-width distribution high-branching butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 490g of methane chloride, 513g of cyclohexane, 49.2g of [ SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n grafting agent into the polymerization kettle, stirring and dissolving for 30min until the grafting agent is completely dissolved; and then cooling to-85 ℃, sequentially adding 620g of methane chloride, 475g of isobutene and 25g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-97 ℃, then mixing 230g of methane chloride, 7.29g of aluminum sesquiethylate chloride and 0.316g of HCl at-95 ℃, aging for 30min, then adding the mixture into the polymerization system together, stirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 1
(1) Preparation of grafting agent: the other conditions were the same as in example 1 except that: in polymerizer A, no-SB/(S → B) -segment was added, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 1750g of cyclohexane, 305g of isoprene and 1.1g of THF into the polymerization kettle A, heating to 40 ℃, adding 15.2mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 40min to form an IR chain segment with wide distribution, heating to 70 ℃ again, adding 192mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 60 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1520g of cyclohexane, 157g of styrene, 0.6g of THF and 10.5mmo1 of n-butyllithium, heating to 60 ℃, reacting for 50min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 60 min; and finally, adding 21g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 20min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped ternary hetero-arm copolymer Y < - > (PS-B < - >) n < - > (IR < - >) n (Mn is 70350, and Mw/Mn is 3.52).
(2) Preparing high-width distribution high-branching butyl rubber: the other conditions were the same as in example 1 except that: during the synthesis process, no grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n is added, but a grafting agent of Y [ -PS-B- ] n [ -IR- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 590g of methane chloride, 265g of cyclohexane and 21.5g of Y [ -PS-B- ] n [ -IR- ] n grafting agent into a polymerization kettle, stirring and dissolving for 20min until the grafting agent is completely dissolved; and then cooling to-75 ℃, sequentially adding 525g of methane chloride, 426g of isobutene and 6g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 160g of methane chloride, 3.18g of aluminum sesquiethylate chloride and 0.089g of HCl at-85 ℃, aging for 20min, then adding the materials into the polymerization system together, stirring and reacting for 1.0hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of grafting agent: the other conditions were the same as in example 2 except that: adopting single kettle polymerization, namely monomer materials are not reacted in a polymerization kettle B and a polymerization kettle C, but the monomer materials in the polymerization kettle B and the polymerization kettle C are added into a polymerization kettle A for reaction by two times, namely: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 1820g of cyclohexane, 335g of isoprene and 1.2g of THF into the polymerization kettle A, heating to 40 ℃, adding 16.2mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 45min to form a widely distributed IR chain segment, heating to 75 ℃ again, adding 205mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 65 min; then adding 2250g of cyclohexane, 2.7g of THF and 24.6 mmol of 1 n-butyllithium in sequence, heating to 75 ℃, then stirring and mixing 650g of styrene and 190g of 1, 3-butadiene for 15min, within 65min, reducing the initial feeding speed by 2g of mixture per minute at 95g of mixture/min and the feeding speed reduction amplitude to form a random and long gradual change section-SB/(S → B) -chain segment, and continuing the coupling reaction for 55 min; then adding 1560g of cyclohexane, 178g of styrene, 0.8g of THF and 12.1mmo1 n-butyllithium in sequence, heating to 70 ℃, reacting for 55min to form a-PS-chain segment, and continuing the coupling reaction for 65 min; and finally, adding 28g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 22min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the copolymer Y [ -SB/(S → B) - ] n [ -PS-B- ] n [ -IR- ] n (Mn is 98260, and Mw/Mn is 5.52) with a ternary random structure.
(2) Preparing high-width distribution high-branching butyl rubber: the other conditions were the same as in example 2 except that: during the synthesis process, no grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n is added, and instead, grafting agent of Y [ -SB/(S → B) - ] n [ -PS-B- ] n [ -IR- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 600g of methane chloride, 283g of cyclohexane, and 27.5g of grafting agent of Y [ -SB/(S → B) - ] n [ -PS-B- ] n [ -IR- ] n into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-80 ℃, sequentially adding 541g of methane chloride, 435g of isobutene and 9g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 170g of methane chloride, 4.23g of aluminum sesquiethylate chloride and 0.109g of HCl at-90 ℃, aging for 25min, then adding the mixture into the polymerization system together, stirring and reacting for 1.8hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparation of grafting agent: the other conditions were the same as in example 3 except that: instead of using a variable speed polymerization in polymerizer B, the styrene and 1, 3-butadiene mixture was not continuously fed into the polymerizer, but was fed in one portion, namely: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 1920g of cyclohexane, 362g of isoprene and 1.4g of THF into the polymerization kettle A, heating to 40 ℃, adding 17.8mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 50min to form an IR chain segment with wide distribution, heating to 80 ℃, adding 226mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 75 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2420g of cyclohexane, 3.2g of THF and 26.5mmo1 n-butyllithium, heating to 77 ℃, then stirring and mixing 670g of styrene and 210g of 1, 3-butadiene for 20min, injecting into the polymerization kettle B for one time, reacting for 70min to form a random segment-SBR-chain segment, adding the materials into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 60 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1660g of cyclohexane, 190g of styrene, 1.0g of THF and 14.1mmo1 n-butyllithium, heating to 75 ℃, reacting for 60min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 70 min; and finally, adding 39g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 25min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped copolymer with ternary hetero arms, wherein the star-shaped copolymer has the characteristics of < -SBR < - > nY < -PS-B < - > n < -IR < - > (the Mn is 102350, and the Mw/Mn is 6.52).
(2) Preparing high-width distribution high-branching butyl rubber: the other conditions were the same as in example 3 except that: during the synthesis process, no grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n is added, but the grafting agent of [ -SBR- ] nY [ -PS-B- ] n [ -IR- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 610g of methane chloride, 323 g of cyclohexane, 35.5g of [ -SBR- ] nY [ -PS-B- ] n [ -IR- ] n grafting agent into the polymerization kettle, and stirring for dissolving for 25min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 561g of methane chloride, 455g of isobutene and 13g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 180g of methane chloride, 5.63g of sesquiethylaluminum chloride and 0.229g of HCl at-95 ℃, aging for 25min, then adding the mixture into the polymerization system together, stirring and reacting for 2.0hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
(1) Preparation of grafting agent: the other conditions were the same as in example 4 except that: 1,3, 5-trichlorobenzene is not added in the synthesis process, namely: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 2020g of cyclohexane, 385g of isoprene and 1.6g of THF into the polymerization kettle A, heating to 40 ℃, adding 19.8mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 55min to form a widely distributed IR chain segment, heating to 80 ℃ again, and reacting for 80 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2500g of cyclohexane, 3.7g of THF and 28.1mmo1 n-butyllithium, heating to 77 ℃, then stirring and mixing 690g of styrene and 230g of 1, 3-butadiene for 25min, within 75min, reducing the mixture by 4g per minute at an initial feeding speed of 14 g/min to form a random and long gradual change section-SB/(S → B) -chain segment, after the monomer is completely converted, adding the material in the polymerization kettle B into the polymerization kettle A, and continuing the coupling reaction for 65 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1750g of cyclohexane, 210g of styrene, 1.2g of THF and 16.1mmo1 of n-butyl lithium, heating to 75 ℃, reacting for 65min to form a-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and continuing the coupling reaction for 75 min; and finally, adding 35g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 24min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the terpolymer of [ -SB/(S → B) - ] n [ -PS-B- ] n [ -IR- ] n (Mn is 108950, and Mw/Mn is 3.12).
(2) Preparing high-width distribution high-branching butyl rubber: the other conditions were the same as in example 4 except that: during the synthesis process, no grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n is added, and instead, the grafting agent of [ -SB/(S → B) - ] n [ -PS-B- ] n [ -IR- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 590g of methane chloride, 423g of cyclohexane, 40.2g of grafting agent of [ -SB/(S → B) - ] n [ -PS-B- ] n [ -IR- ] n into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 582g of methane chloride, 465g of isobutene and 17g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 200g of methane chloride, 6.12g of aluminum sesquiethylate chloride and 0.256g of HCl at-95 ℃, aging for 25min, then adding the materials into the polymerization system together, stirring and reacting for 2.5hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 5
(1) Preparation of grafting agent: the other conditions were the same as in example 5 except that: no-PS-segment was added to polymerizer a, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle A with a jacket for replacement for 3 times, sequentially adding 2230g of cyclohexane, 405g of isoprene and 1.8g of THF into the polymerization kettle A, heating to 40 ℃, adding 21.8mmo1 n-butyllithium to start reaction, gradually increasing the reaction temperature from 40 ℃ to 65 ℃ within 60min to form a widely distributed IR chain segment, heating to 80 ℃ again, adding 245mmo11,3, 5-trichlorobenzene, and carrying out coupling reaction for 85 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2610g of cyclohexane, 3.9g of THF and 29.5mmo1 of n-butyllithium, heating to 80 ℃, then stirring and mixing 710g of styrene and 250g of 1, 3-butadiene for 25min, within 80min, reducing the mixture by 4g per minute at an initial feeding speed of 16 g/min to form a random and long gradual change section-SB/(S → B) -chain segment, after the monomer is completely converted, adding the material in the polymerization kettle B into the polymerization kettle A, and continuing the coupling reaction for 70 min; and finally, adding 40g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 27min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star copolymer with the binary arms [ -SB/(S → B) - ] nY [ -IR- ] n (Mn is 92630, and Mw/Mn is 5.75).
(2) Preparing high-width distribution high-branching butyl rubber: the other conditions were the same as in example 5 except that: during the synthesis process, no grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n is added, and instead, the grafting agent of [ -SB/(S → B) - ] nY [ -IR- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 500g of methane chloride, 473g of cyclohexane and 45.2g of [ -SB/(S → B) - ] nY [ -IR- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 27min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 590g of methane chloride, 470g of isobutene and 20g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 210g of methane chloride, 6.89g of sesquiethylaluminum chloride and 0.276g of HCl at-95 ℃, aging for 27min, then adding the mixture into the polymerization system together, stirring and reacting for 2.7hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 6
(1) Preparation of grafting agent: the same as in example 6.
(2) Preparing high-width distribution high-branching butyl rubber: the other conditions were the same as in example 6 except that the amount of the grafting agent added during the synthesis of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n was 4.7g, that is: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 490g of methane chloride, 513g of cyclohexane, 4.7g of grafting agent of [ -SB/(S → B) - ] nY [ -PS-B- ] n [ -IR- ] n into the polymerization kettle, stirring and dissolving for 30min until the grafting agent is completely dissolved; and then cooling to-85 ℃, sequentially adding 620g of methane chloride, 475g of isobutene and 25g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-97 ℃, then mixing 230g of methane chloride, 7.29g of aluminum sesquiethylate chloride and 0.316g of HCl at-95 ℃, aging for 30min, then adding the mixture into the polymerization system together, stirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain the high-width distribution high-branching butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of highly branched butyl rubber with high and broad distributions
As can be seen from Table 1: the highly-broadly-distributed and highly-branched butyl rubber has a wider molecular weight distribution and a lower Mooney relaxation area, shows good processability (the smaller the area under a stress relaxation curve is, the lower the energy consumption of mixing processing is), and simultaneously has good air tightness and high tensile strength.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. A preparation method of high-width distribution and high-branching butyl rubber is characterized by comprising the following steps:
(1) preparation of grafting agent: according to the total mass percentage of reaction monomers, introducing argon to a polymerization kettle A with a jacket to replace a system for 3-5 times, sequentially adding 100-200% of a solvent, 20-30% of isoprene, 0.01-0.1% of a structure regulator and an initiator into the polymerization kettle, reacting at a variable temperature, heating to 55-65 ℃ within 40-60 min, and waiting until the conversion rate of the isoprene monomer reaches 100%; heating to 70-90 ℃, and adding a coupling agent to perform coupling reaction for 60-90 min; meanwhile, introducing argon into a polymerization kettle B to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 0.1-0.3% of structure regulator and initiator, heating to 70-80 ℃, stirring and mixing 40-50% of styrene and 10-20% of 1, 3-butadiene for 10-30 min, wherein the reaction is variable-speed polymerization, adding the mixture into the polymerization kettle in a continuous injection manner, reacting within 60-80 min, and adding the mixture with the initial feeding speed of more than 10.0% per min until the conversion rate of the styrene and the 1, 3-butadiene monomer reaches 100%, then adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 50-70 min; meanwhile, introducing argon into a polymerization kettle C to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 10-20% of styrene, 0.05-0.1% of structure regulator and initiator, heating to 60-80 ℃, reacting for 50-70 min, then adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 60-90 min; then adding 1-5% of 1, 3-butadiene into a polymerization kettle for end capping, reacting for 20-30 min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on glue solution to prepare a grafting agent;
(2) preparing high-width distribution high-branching butyl rubber: according to the total mass percentage of reaction monomers, firstly introducing nitrogen into a reaction kettle with a jacket for replacement for 3-5 times, adding 100-200% of a mixed solvent with a diluent/solvent volume ratio of 70-30/30-70 into a polymerization kettle, and stirring 2-10% of a grafting agent until the grafting agent is completely dissolved; then when the temperature is reduced to-75 to-85 ℃, 100 to 200 percent of diluent, 85 to 95 percent of isobutene and 1 to 5 percent of isoprene are sequentially added, stirred and mixed until the temperature of a polymerization system is reduced to-100 to-90 ℃; then 30-50% of diluent and 0.05-3.0% of co-initiator are mixed and aged for 20-30 min at-85 to-95 ℃, then the mixture is added into a polymerization system together to be stirred and reacted for 1.0-3.0 hr, and then the discharged material is coagulated, washed and dried to obtain a high-width distribution high-branching butyl rubber product;
the grafting agent is a ternary star-shaped hybrid-arm copolymer of isoprene, styrene and butadiene, and the structural general formula of the grafting agent is shown as a formula I:
wherein, IR is a homopolymer segment with wide vinyl distribution of isoprene, and the 1, 2-structure content of the segment is 10 to 20 percent; PS is a styrene homopolymer segment; SB is a random section of styrene and butadiene; (S → B) is a transition of styrene and butadiene; b is terminated butadiene, and n is 1-4.
2. The method of claim 1, wherein the three-arm star polymer comprises 20% to 30% isoprene, 50% to 70% styrene, and 10% to 20% butadiene.
3. The method of claim 1, wherein the three-arm star polymer has a number average molecular weight of 110000 to 140000 and a ratio of weight average molecular weight to number average molecular weight of 8.23 to 13.24.
4. The method of claim 1, wherein the structure modifier is selected from the group consisting of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
5. The method of claim 4, wherein the structure modifier is tetrahydrofuran.
6. The method of claim 1, wherein the initiator is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, cyclohexyllithium, and dodecyllithium.
7. The method of claim 6 wherein said initiator is n-butyllithium.
8. The method according to claim 1, wherein the coinitiator is prepared by compounding an alkyl aluminum halide and a protonic acid in different proportions, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.
9. The method of claim 8 wherein the alkyl aluminum halide is selected from the group consisting of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, diisopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride.
10. The method of claim 9 wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.
11. The method of claim 8, wherein the protic acid is selected from the group consisting of HCI, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3One kind of (1).
12. The method of claim 11, wherein the protic acid is HCI.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010271960.7A CN113493549B (en) | 2020-04-08 | 2020-04-08 | Preparation method of high-width distribution and high-branching butyl rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010271960.7A CN113493549B (en) | 2020-04-08 | 2020-04-08 | Preparation method of high-width distribution and high-branching butyl rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113493549A true CN113493549A (en) | 2021-10-12 |
| CN113493549B CN113493549B (en) | 2023-10-31 |
Family
ID=77995699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010271960.7A Active CN113493549B (en) | 2020-04-08 | 2020-04-08 | Preparation method of high-width distribution and high-branching butyl rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113493549B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024066778A1 (en) * | 2022-09-26 | 2024-04-04 | 中国石油天然气集团有限公司 | Multicomponent copolymer, preparation method therefor, and use thereof, and halogenated branched butyl rubber, preparation method therefor, and use thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395885A (en) * | 1993-12-17 | 1995-03-07 | The University Of Akron | Multi-arm cationic star-polymers |
| US5458796A (en) * | 1994-03-31 | 1995-10-17 | Shell Oil Company | Synthesis of polyisobutylene star-branched polymers via living carbocationic polymerization |
| US6156859A (en) * | 1996-07-15 | 2000-12-05 | Bayer Ag | Process for producing highly branched polyisoolefins |
| CN101353386A (en) * | 2007-07-27 | 2009-01-28 | 北京石油化工学院 | Initiation system for polymerization of star-branched polyisobutene or isobutene-diene rubber positive ion |
| CN101353403A (en) * | 2007-07-27 | 2009-01-28 | 中国石油化工股份有限公司 | Preparation of star-branched polyisobutene or isobutene-diene rubber |
| CN110845650A (en) * | 2019-11-22 | 2020-02-28 | 北京石油化工学院 | Slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using terminal imino functionalized macromolecular branching agent |
-
2020
- 2020-04-08 CN CN202010271960.7A patent/CN113493549B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395885A (en) * | 1993-12-17 | 1995-03-07 | The University Of Akron | Multi-arm cationic star-polymers |
| US5458796A (en) * | 1994-03-31 | 1995-10-17 | Shell Oil Company | Synthesis of polyisobutylene star-branched polymers via living carbocationic polymerization |
| US6156859A (en) * | 1996-07-15 | 2000-12-05 | Bayer Ag | Process for producing highly branched polyisoolefins |
| CN101353386A (en) * | 2007-07-27 | 2009-01-28 | 北京石油化工学院 | Initiation system for polymerization of star-branched polyisobutene or isobutene-diene rubber positive ion |
| CN101353403A (en) * | 2007-07-27 | 2009-01-28 | 中国石油化工股份有限公司 | Preparation of star-branched polyisobutene or isobutene-diene rubber |
| CN110845650A (en) * | 2019-11-22 | 2020-02-28 | 北京石油化工学院 | Slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using terminal imino functionalized macromolecular branching agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024066778A1 (en) * | 2022-09-26 | 2024-04-04 | 中国石油天然气集团有限公司 | Multicomponent copolymer, preparation method therefor, and use thereof, and halogenated branched butyl rubber, preparation method therefor, and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113493549B (en) | 2023-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113493548B (en) | Preparation method of branched butyl rubber | |
| CN113493549B (en) | Preparation method of high-width distribution and high-branching butyl rubber | |
| CN113831470B (en) | Preparation method of middle-Mooney viscosity and low-saturation butyl rubber | |
| CN113831474B (en) | Preparation method of hyperbranched wide-distribution butyl rubber | |
| CN114478954B (en) | Preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber | |
| CN113831458A (en) | Preparation method of butyl rubber with medium Mooney viscosity and low saturation | |
| CN113831476A (en) | Preparation method of low-saturation butyl rubber | |
| CN113831469B (en) | Preparation method of hyperbranched butyl rubber | |
| CN113831466B (en) | Preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber | |
| CN113493552B (en) | Preparation method of wide-distribution butyl rubber | |
| CN113493550B (en) | Preparation method of high-width distribution high-branching butyl rubber | |
| CN113831473B (en) | Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber | |
| CN113831472B (en) | Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber | |
| CN113831467B (en) | Preparation method of hyperbranched wide-distribution butyl rubber | |
| CN113493547B (en) | Preparation method of hyperbranched butyl rubber | |
| CN113831475B (en) | Preparation method of low-saturation butyl rubber | |
| CN113493551B (en) | Preparation method of branched butyl rubber | |
| CN113831477B (en) | Preparation method of low-Mooney-viscosity low-saturation butyl rubber | |
| CN113493553B (en) | Preparation method of hyperbranched butyl rubber | |
| CN113493546B (en) | Preparation method of butyl rubber with wide molecular weight distribution | |
| CN113831468B (en) | Preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber | |
| CN114478950B (en) | Three-arm comb-shaped star-shaped branched butyl rubber and preparation method thereof, and preparation method of three-arm star-shaped nucleating agent | |
| CN113493556B (en) | Preparation method of hyperbranched butyl rubber | |
| CN114163586B (en) | Preparation method of four-arm comb-shaped star-branched butyl rubber | |
| CN113831471B (en) | Preparation method of low-Mooney-viscosity low-saturation butyl rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |