CN113493546A - Preparation method of butyl rubber with wide molecular weight distribution - Google Patents
Preparation method of butyl rubber with wide molecular weight distribution Download PDFInfo
- Publication number
- CN113493546A CN113493546A CN202010271853.4A CN202010271853A CN113493546A CN 113493546 A CN113493546 A CN 113493546A CN 202010271853 A CN202010271853 A CN 202010271853A CN 113493546 A CN113493546 A CN 113493546A
- Authority
- CN
- China
- Prior art keywords
- butadiene
- polymerization
- butyl rubber
- styrene
- reaction
- 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 86
- 238000009826 distribution Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 129
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 126
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 48
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 16
- -1 alkyl aluminum halide Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 230000007704 transition Effects 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 84
- 239000003795 chemical substances by application Substances 0.000 claims description 80
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 28
- 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 16
- MOOUPSHQAMJMSL-UHFFFAOYSA-N tert-butyl(trichloro)silane Chemical compound CC(C)(C)[Si](Cl)(Cl)Cl MOOUPSHQAMJMSL-UHFFFAOYSA-N 0.000 claims description 16
- 238000005345 coagulation Methods 0.000 claims description 15
- 230000015271 coagulation Effects 0.000 claims description 15
- 238000005859 coupling reaction Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 13
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 10
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 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
- 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
- 238000013329 compounding Methods 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
- 229920001519 homopolymer Polymers 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
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- QWBBTCQPNIEDSP-UHFFFAOYSA-N tribromo(tert-butyl)silane Chemical compound CC(C)(C)[Si](Br)(Br)Br QWBBTCQPNIEDSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 2
- 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
- 229920001577 copolymer Polymers 0.000 abstract description 7
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 40
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 37
- 238000012360 testing method Methods 0.000 description 29
- 229910001220 stainless steel Inorganic materials 0.000 description 27
- 239000010935 stainless steel Substances 0.000 description 27
- 239000005062 Polybutadiene Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000005070 sampling Methods 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 7
- 230000035882 stress Effects 0.000 description 7
- 230000002902 bimodal effect Effects 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 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
- 239000003054 catalyst Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229940050176 methyl chloride Drugs 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
- 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
- 125000004432 carbon atom Chemical group C* 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
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 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
- 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
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 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
- 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
- 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
- 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
- 230000001112 coagulating effect Effects 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
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- 238000004090 dissolution Methods 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 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
- 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
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
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- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
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- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 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
- 229920002554 vinyl polymer Polymers 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
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- 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 firstly adopts lithium alkyl as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers comprise styrene and butadiene, the initiator is added twice, variable-speed polymerization is adopted, and then the star copolymer [ -BR-PS-SB/(S → B) -B-]nAnd Y, finally, preparing the butyl rubber with wide molecular weight distribution by cationic polymerization of the star-shaped copolymer with the three-arm structure, isobutene and isoprene in a catalytic system compounded by alkyl aluminum halide and protonic acid. The invention adopts a variable-speed polymerization mode to realize random gradual transition from styrene to butadiene, can obviously destroy the regularity of a molecular chain, obviously broaden the molecular weight distribution of butyl rubber and ensure butyl rubberThe base rubber has viscoelastic property, crude rubber strength and good air tightness, and realizes the balance of physical and mechanical properties and processability of the butyl rubber.
Description
Technical Field
The invention relates to a preparation method of butyl rubber with wide molecular weight distribution, in particular to a method for preparing butyl rubber with wide molecular weight distribution by grafting polyisobutylene with a styrene/butadiene star copolymer.
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 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 performance, 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-branched structure has become one of the hot spots in the research field of future butyl rubber.
In the prior art, the star-branched butyl rubber is mainly prepared by a method of a first-nucleus-second-arm method, a first-arm-second-nucleus method and a nuclear-arm simultaneous method. Such as: US5395885 discloses a star-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; and thirdly, contacting the butyl rubber slurry with broad/bimodal molecular weight distribution with water, removing unreacted monomers and a diluent to obtain colloidal particle water, and then dehydrating and drying the colloidal particle water to obtain the butyl rubber with broad/bimodal molecular weight distribution and molecular weight distribution (Mw/Mn) of at least 5.0. CN1427851A discloses a preparation method of butyl rubber with wide molecular weight distribution. The process uses a mixed catalyst system (comprising a large amount of internalized dialkylaluminumA small amount of monoalkylaluminum dihalide and a minor amount of aluminoxane) to give 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-branched polyisobutylene or butyl rubber, which adopts a polystyrene/isoprene block copolymer with a silicon-chlorine group at the terminal or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the terminal as a grafting initiating 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 methyl chloride to cyclohexane of 20-80/80-20 at the temperature of 0-100 ℃, and prepares a star-branched polyisobutylene or butyl rubber product by the participation of unsaturated chains in a grafting reaction through the initiated positive ion polymerization of the silicon-chlorine group. CN01817708.5 provides a method of making star-branched polymers by adding a multiolefin cross-linking 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 cationic polymerization of star-branched polyisobutylene or butyl rubber, 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 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 star-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 wide-distribution butyl rubber. The invention firstly takes alkyl lithium as an initiator, takes hydrocarbon as a solvent, and a reaction monomer consists of styrene and butadiene to synthesize a wide-distribution random-transition long chain segment [ -BR-PS-SB/(S → B) -B- ] n, and then prepares a star copolymer [ -BR-PS-SB/(S → B) -B- ] n Y with a three-arm structure as a grafting agent through a trihalosilane coupling agent, and prepares the wide-distribution butyl rubber by adopting cationic polymerization with isobutene and isoprene under a catalysis system compounded by Lewis acid and protonic acid. The widely distributed butyl rubber not only well solves the problems of slow stress relaxation rate and obvious extrusion swelling in the processing process of the butyl rubber, but also keeps the sufficient crude rubber strength and good air tightness of the butyl rubber and realizes the balance of the physical and mechanical properties and the processing performance of the butyl rubber.
The percentages stated in the invention are all percentages by mass.
The preparation of the butyl rubber with wide molecular weight distribution is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) preparation of grafting agent: according to the total mass percentage of reaction monomers, firstly, introducing argon into a 15L stainless steel polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200% of solvent, 10-20% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator into the polymerization kettle, heating to 45-60 ℃, and reacting for 40-70 min to form a BR chain segment, wherein the conversion rate of the 1, 3-butadiene monomer reaches 100%; then sequentially adding 20-30% of styrene and 0.05-0.1% of structure regulator into a polymerization kettle, heating to 60-70 ℃, and reacting for 40-60 min to form a-BR-PS-chain segment, wherein the conversion rate of a styrene monomer reaches 100%; secondly, sequentially adding 100-200% of solvent, 0.05-0.2% of structure regulator and initiator into a polymerization kettle, heating to 70-80 ℃, stirring and mixing 30-50% of styrene and 10-20% of 1, 3-butadiene for 10-20 min, wherein the reaction is variable-speed polymerization, adding the mixture into the polymerization kettle in a continuous injection manner, reacting within 50-80 min, and determining the reduction range of the initial feeding speed to be more than 10.0% of mixture/min, and forming a random and long gradual change section-SB/(S → B) -chain segment; then adding 1-4% of 1, 3-butadiene into the polymerization kettle for end capping, and reacting for 10-30 min until no free monomer exists to form a-BR-PS-SB/(S → B) -B-chain segment; and finally, heating to 80-90 ℃, adding a coupling agent for coupling reaction for 50-80 min, 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 grafting agent with the three-arm structure.
(2) Preparation of wide distribution butyl rubber: according to the total mass percentage of reaction monomers, firstly introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3-5 times, and adding 200-300% of diluent/solvent V: the V ratio is 70-30/30-70, the mixed solvent and the grafting agent are 2-7%, and the mixed solvent and the grafting agent are stirred and dissolved for 10-30 min until the grafting agent is completely dissolved; and then cooling to-65 to-85 ℃, sequentially adding 100 to 200 percent of diluent, 87 to 95 percent of isobutene and 3 to 5 percent of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then adding 30 to 50 percent of diluent and 0.05 to 2.0 percent of co-initiator into the polymerization system for stirring and reacting for 0.5 to 2.5 hours after mixing and aging for 20 to 30 minutes at-95 to-85 ℃, discharging and coagulating, washing and drying to obtain the wide distribution butyl rubber product.
The grafting agent is a three-arm star polymer (E-BR-PS-SB/(S → B) -B- ] nY) containing styrene and butadiene block copolymer, and the structural general formula is shown as formula I:
wherein Y is Si and Bu is tert-butyl; BR is a butadiene homopolymer section, and the 1, 2-structure content of the BR is 15-25%; 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 2-3; the three-arm star polymer contains 60-80% of styrene and 20-40% of butadiene; the number average molecular weight (Mn) of the three-arm star polymer is 70000-110000, and the molecular weight distribution (Mw/Mn) is 4.23-8.16.
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 halosilane coupling agents selected from tert-butyltrichlorosilane and tert-butyltribromosilane, and tert-butyltrichlorosilane is preferred. The amount of the coupling agent is determined according to the amount of the initiator, and the molar ratio of the amount of the coupling agent to the organic lithium is 0.2-2.0.
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 HCI, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3Preferably HCI. Wherein the total addition amount of the coinitiator is 0.05-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.
The polymerization 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 lithium alkyl as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers comprise styrene and butadiene, the initiator is added twice, variable-speed polymerization is adopted, and then the star copolymer [ -BR-PS-SB/(S → B) -B-]nAnd Y, finally, preparing the high-broad molecular weight distribution butyl rubber by cationic polymerization of the star-shaped copolymer with the three-arm structure, isobutene and isoprene in a catalyst system compounded by alkyl aluminum halide and protonic acid (see attached figure 1). The invention adopts variable-speed polymerization to lead the polymerization reaction speed to be continuously changed, thereby obtaining the chain segment-SB/(S → B) -with certain length, high randomness and gradual change. Such a segment can significantly destroy the regularity of the molecular chain, resulting in a significant broadening of the molecular weight distribution.
In addition, the invention combines the chain segments of three different microstructures on a macromolecular chain to form a three-arm star structure, so that the properties of different chain segments and the characteristics of the three-arm structure are organically combined together and act synergistically, the molecular weight distribution of the butyl rubber can be obviously widened by utilizing the vinyl group in the BR chain segment, -SB/(S → B) -random degeneration and the three-arm structure in the BR chain segment, the butyl rubber can obtain good viscoelastic property, the stress relaxation rate is high, and the processing property 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.
Therefore, the butyl rubber with wide molecular weight distribution has high stress relaxation rate, excellent viscoelasticity and high crude rubber strength and air tightness, solves the problem of contradiction between poor processability and good physical and mechanical properties of the butyl rubber, improves the performance of the butyl rubber more comprehensively, and realizes the balance of the physical and mechanical properties and the processability. The preparation method of the wide-distribution butyl rubber provided by the invention has the characteristics of short process flow, controllable molecular weight, good product processability, 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 of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
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:
styrene, butadiene, Polymer grade, Petroleum Lanzhou petrochemical Co Ltd
Isobutene, isoprene, Polymer grade Zhejiang Credit New materials Co Ltd
N-butyl lithium, 98% purity Nanjing Tongtiang chemical Co., Ltd
New Shanghai Gillede Material Co., Ltd. with a purity of 99% of t-butyltrichlorosilane
Aluminum sesquiethylate chloride, 98% pure Profenor technologies Ltd
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: adopts GT-7080-S2 model Menni produced by Taiwan high-speed railway company of China
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 with a jacket for replacement for 2 times, sequentially adding 1550g of cyclohexane, 156g of 1, 3-butadiene, 1.5g of THF and 20.9mm of 1 n-butyllithium into a polymerization kettle, heating to 45 ℃, and reacting for 40min to form a BR chain segment; then, 310g of styrene and 0.5g of THF are sequentially added into a polymerization kettle, the temperature is raised to 60 ℃, the reaction is carried out for 40min, a-BR-PS-chain segment is formed, next, 1620g of cyclohexane, 1.2g of THF and 15.6mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, then 470g of styrene and 170g of 1, 3-butadiene are stirred and mixed for 10min, and within 50min, the initial feeding speed is 65g of mixture/min, the feeding speed is reduced by 2g of mixture per minute, and a random and long gradual change segment-SB/(S → B) -chain segment is formed; then adding 25g of butadiene into the polymerization kettle, and carrying out end capping reaction for 10min to form a-BR-PS-SB/(S → B) -B-chain segment; and finally, heating to 80 ℃, adding 9.5mmo1 tert-butyl trichlorosilane, reacting for 50min, 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 grafting agent with the [ -BR-PS-SB/(S → B) -B- ] nY three-arm structure (Mn is 71350 and Mw/Mn is 4.59).
(2) Preparation of wide distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 790g of methane chloride, 285g of cyclohexane and 12.5g of [ -BR-PS-SB/(S → B) -B- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 10min until the grafting agent is completely dissolved; and then cooling to-65 ℃, sequentially adding 506g of methane chloride, 471g of isobutene and 35g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 120g of methane chloride, 1.98g of aluminum sesquiethylate chloride and 0.092g of HCl at-85 ℃, aging for 20min, then adding the materials into the polymerization system together, stirring and reacting for 0.5hr, discharging, condensing, washing and drying to obtain the wide-distribution 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 with a jacket for replacement for 2 times, sequentially adding 1870g of cyclohexane, 183g of 1, 3-butadiene, 2.1g of THF and 21.5mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, and reacting for 50min to form a BR chain segment; then, sequentially adding 330g of styrene and 0.7g of THF into a polymerization kettle, heating to 62 ℃, reacting for 45min to form a-BR-PS-chain segment, sequentially adding 1730g of cyclohexane, 1.7g of THF and 16.5mmo1 n-butyllithium into the polymerization kettle, heating to 70 ℃, then stirring and mixing 520g of styrene and 190g of 1, 3-butadiene for 15min, and within 50min, reducing the initial feeding speed of 70g of mixture/min to 3g of mixture per minute to form a random and long gradual-change segment-SB/(S → B) -chain segment; then adding 31g of butadiene into the polymerization kettle, and carrying out end capping reaction for 15min to form a-BR-PS-SB/(S → B) -B-chain segment; and finally, heating to 80 ℃, adding 19.5mmo1 tert-butyl trichlorosilane, reacting for 55min, 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 grafting agent with the [ -BR-PS-SB/(S → B) -B- ] nY three-arm structure (Mn is 82620, and Mw/Mn is 6.12).
(2) Preparation of wide distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 950g of methane chloride, 375g of cyclohexane and 22.5g of [ -BR-PS-SB/(S → B) -B- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 17min until the grafting agent is completely dissolved; then when the temperature is reduced to-70 ℃, 576g of methyl chloride, 482g of isobutene and 40g of isoprene are sequentially added and mixed until the temperature of a polymerization system is reduced to-92 ℃, then 150g of methyl chloride, 2.38g of sesquiethylaluminum chloride and 0.102g of HCl are mixed and aged for 25min at the temperature of-87 ℃, then the mixture is added into the polymerization system together and stirred for reaction for 1.0hr, and then the discharged material is coagulated, washed and dried to obtain a wide-distribution 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 with a jacket for replacement for 2 times, sequentially adding 1920g of cyclohexane, 203g of 1, 3-butadiene, 2.7g of THF and 22.7 g of 22.7mmo1 n-butyllithium into a polymerization kettle, heating to 55 ℃, and reacting for 55min to form a BR chain segment; then, 350g of styrene and 1.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 65 ℃, the reaction is carried out for 55min, a-BR-PS-chain segment is formed, 1850g of cyclohexane, 2.1g of THF and 18.5mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 75 ℃, 570g of styrene and 205g of 1, 3-butadiene are stirred and mixed for 15min, the initial feeding speed is 75g of mixture/min within 60min, the feeding speed reducing amplitude is 3g of mixture per minute, and a random and long gradual change segment-SB/(S → B) -chain segment is formed; then adding 39g of butadiene into the polymerization kettle, and carrying out end capping reaction for 20min to form a-BR-PS-SB/(S → B) -B-chain segment; and finally, heating to 85 ℃, adding 23.5mmo1 tert-butyl trichlorosilane, reacting for 65min, 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 grafting agent with the [ -BR-PS-SB/(S → B) -B- ] nY three-arm structure (Mn is 89130, and Mw/Mn is 7.34).
(2) Preparation of wide distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 970g of methane chloride, 405g of cyclohexane and 25.5g of [ -BR-PS-SB/(S → B) -B- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 587g of methane chloride, 492g of isobutene and 41g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then mixing 160g of methane chloride, 2.57g of sesquiethylaluminum chloride and 0.187g of HCl at-89 ℃, aging for 25min, then adding the mixture into the polymerization system together, stirring and reacting for 1.5hr, discharging, condensing, washing and drying to obtain the wide-distribution 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 with a jacket for replacement for 2 times, sequentially adding 2020g of cyclohexane, 223g of 1, 3-butadiene, 3.1g of THF and 25.6mmo1 n-butyllithium into a polymerization kettle, heating to 57 ℃, and reacting for 55min to form a BR chain segment; then 365g of styrene and 1.7g of THF are sequentially added into the polymerization kettle, the temperature is raised to 65 ℃ and the reaction is carried out for 55min to form a-BR-PS-chain segment, 1920g of cyclohexane, 2.7g of THF and 19.5mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 77 ℃, 590g of styrene and 215g of 1, 3-butadiene are stirred and mixed for 17min, and the initial feeding speed of 80g of mixture/min is reduced by 3g of mixture per minute within 70min to form a random and long gradual change segment-SB/(S → B) -chain segment; then adding 41g of butadiene into the polymerization kettle, and carrying out end capping reaction for 22min to form a-BR-PS-SB/(S → B) -B-chain segment; and finally, heating to 87 ℃, adding 25.6 mmols 1 tert-butyl trichlorosilane, reacting for 65min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet coagulation and drying on the glue solution to obtain the grafting agent with the [ -BR-PS-SB/(S → B) -B- ] nY three-arm structure (Mn is 92150, and Mw/Mn is 7.84).
(2) Preparation of wide distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 4 times, adding 980g of methane chloride, 420g of cyclohexane and 27.1g of [ -BR-PS-SB/(S → B) -B- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 25min until the grafting agent is completely dissolved; and then cooling to-80 ℃, sequentially adding 592g of methane chloride, 502g of isobutene and 39g of isoprene, mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 170g of methane chloride, 3.57g of sesquiethylaluminum chloride and 0.217g of HCl at-90 ℃, aging for 25min, then adding the mixture into the polymerization system together, stirring and reacting for 1.7hr, discharging, condensing, washing and drying to obtain the wide-distribution 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 with a jacket for replacement for 2 times, sequentially adding 2210g of cyclohexane, 241g of 1, 3-butadiene, 4.5g of THF and 27.6mmo1 n-butyllithium into the polymerization kettle, heating to 60 ℃, and reacting for 60min to form a BR chain segment; then 376g of styrene and 2.7g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, the reaction is carried out for 60min, a-BR-PS-chain segment is formed, 2120g of cyclohexane, 3.9g of THF and 22.5mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 80 ℃, 610g of styrene and 235g of 1, 3-butadiene are stirred and mixed for 20min, the initial feeding speed is 85g of mixture/min within 75min, the feeding speed reducing amplitude is 4g of mixture per minute, and a random and long gradual change segment-SB/(S → B) -chain segment is formed; then adding 45g of butadiene into the polymerization kettle, and carrying out end capping reaction for 25min to form a-BR-PS-SB/(S → B) -B-chain segment; and finally, heating to 89 ℃, adding 30.6mmo1 tert-butyl trichlorosilane, reacting for 70min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet coagulation and drying on the glue solution to obtain the grafting agent with the [ -BR-PS-SB/(S → B) -B- ] nY three-arm structure (Mn is 100150 and Mw/Mn is 7.95).
(2) Preparation of wide distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 4 times, adding 990g of methane chloride, 510g of cyclohexane and 30.1g of [ -BR-PS-SB/(S → B) -B- ] nY 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 602g of methane chloride, 512g of isobutene and 49g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methane chloride, 4.27g of sesquiethylaluminum chloride and 0.312g of HCl at-90 ℃, aging for 25min, then adding the materials into the polymerization system together, stirring and reacting for 2.0hr, discharging, condensing, washing and drying to obtain the wide-distribution 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 with a jacket for replacement for 3 times, sequentially adding 2510g of cyclohexane, 271g of 1, 3-butadiene, 5.6g of THF and 29.6mmo1 n-butyllithium into the polymerization kettle, heating to 60 ℃, and reacting for 70min to form a BR chain segment; then 386g of styrene and 3.5g of THF are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃, the reaction is carried out for 60min, a-BR-PS-chain segment is formed, then 2420g of cyclohexane, 4.9g of THF and 25.5mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 80 ℃, 670g of styrene and 255g of 1, 3-butadiene are stirred and mixed for 20min, and within 80min, the initial feeding speed is 95g of mixture/min, the feeding speed is reduced by 6g of mixture per minute, and a random and long gradual-change segment-SB/(S → B) -chain segment is formed; then adding 50g of butadiene into the polymerization kettle, and carrying out end capping reaction for 30min to form a-BR-PS-SB/(S → B) -B-chain segment; and finally, heating to 90 ℃, adding 30.6 mmols 1 tert-butyl silicon trichloride bromide, reacting for 80min, 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 grafting agent with the [ -BR-PS-SB/(S → B) -B- ] nY three-arm structure (Mn is 109150 and Mw/Mn is 8.05).
(2) Preparation of wide distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 1020g of methane chloride, 590g of cyclohexane and 33.1g of [ -BR-PS-SB/(S → B) -B- ] nY grafting agent into the polymerization kettle, stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 622g of methane chloride, 522g of isobutene and 51g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-97 ℃, then mixing 200g of methane chloride, 5.12g of sesquiethylaluminum chloride and 0.452g of HCl at-95 ℃, aging for 30min, then adding the materials into the polymerization system together, stirring and reacting for 2.5hr, discharging, condensing, washing and drying to obtain the wide-distribution 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: the styrene and 1, 3-butadiene mixture was not injected continuously into the polymerization vessel, but was added in one portion, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 1550g of cyclohexane, 156g of 1, 3-butadiene, 1.5g of THF and 20.9mm of 1 n-butyllithium into a polymerization kettle, heating to 45 ℃, and reacting for 40min to form a BR chain segment; then, adding 310g of styrene and 0.5g of THF into a polymerization kettle in sequence, heating to 60 ℃, reacting for 40min to form a-BR-PS-chain segment, then adding 1620g of cyclohexane, 1.2g of THF and 15.6mmo1 n-butyllithium into the polymerization kettle in sequence, heating to 70 ℃, then stirring and mixing 470g of styrene and 170g of 1, 3-butadiene for 10min, adding into the polymerization kettle, and reacting for 50min to form a-SBR-chain segment; then adding 25g of butadiene into the polymerization kettle, and carrying out end capping reaction for 10min to form a-BR-PS-SBR-B-chain segment; and finally, heating to 80 ℃, adding 9.5mmo1 tert-butyl trichlorosilane, reacting for 50min, 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 grafting agent with the [ -BR-PS-SBR-B- ] nY three-arm structure (Mn is 69350 and Mw/Mn is 3.02).
(2) Preparation of wide distribution butyl rubber: the other conditions were the same as in example 1 except that: during the synthesis process, no [ -BR-PS-SB/(S → B) -B- ] nY grafting agent is added, but the [ -BR-PS-SBR-B- ] nY grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 790g of methane chloride, 285g of cyclohexane and 12.5g of [ -BR-PS-SBR-B- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 10min until the grafting agent is completely dissolved; and then cooling to-65 ℃, sequentially adding 506g of methane chloride, 471g of isobutene and 35g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 120g of methane chloride, 1.98g of aluminum sesquiethylate chloride and 0.092g of HCl at-85 ℃, aging for 20min, then adding the materials into the polymerization system together, stirring and reacting for 0.5hr, discharging, condensing, washing and drying to obtain the wide-distribution 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: initial feed rate of styrene and 1, 3-butadiene mixture 15g mixture/min, feed rate less than polymerization rate, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 1870g of cyclohexane, 183g of 1, 3-butadiene, 2.1g of THF and 21.5mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, and reacting for 50min to form a BR chain segment; then, 330g of styrene and 0.7g of THF are sequentially added into a polymerization kettle, the temperature is raised to 62 ℃ and the reaction is carried out for 45min to form a-BR-PS-chain segment, 1730g of cyclohexane, 1.7g of THF and 16.5mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, then 520g of styrene and 190g of 1, 3-butadiene are stirred and mixed for 15min, and within 50min, the initial feeding speed is 15g of mixture/min, the feeding speed reducing amplitude is reduced by 3g of mixture per minute, and a random and long gradual change segment-SB/(S → B) -chain segment is formed; then adding 31g of butadiene into the polymerization kettle, and carrying out end capping reaction for 15min to form a-BR-PS-SB/(S → B) -B-chain segment; and finally, heating to 80 ℃, adding 19.5mmo1 tert-butyl trichlorosilane, reacting for 55min, 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 grafting agent with the [ BR-PS-SB1/(S → B)1-B- ] nY three-arm structure (Mn is 81620, and Mw/Mn is 3.23).
(2) Preparation of wide distribution butyl rubber: the other conditions were the same as in example 2 except that: during the synthesis process, no [ -BR-PS-SB/(S → B) -B- ] nY grafting agent is added, but [ -BR-PS-SB1/(S → B)1-B- ] nY grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 950g of methane chloride, 375g of cyclohexane and 22.5g of [ -BR-PS-SB1/(S → B)1-B- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 17min until the grafting agent is completely dissolved; then when the temperature is reduced to-70 ℃, 576g of methyl chloride, 482g of isobutene and 40g of isoprene are sequentially added and mixed until the temperature of a polymerization system is reduced to-92 ℃, then 150g of methyl chloride, 2.38g of sesquiethylaluminum chloride and 0.102g of HCl are mixed and aged for 25min at the temperature of-87 ℃, then the mixture is added into the polymerization system together and stirred for reaction for 1.0hr, and then the discharged material is coagulated, washed and dried to obtain a wide-distribution 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: a mixture of styrene and 1, 3-butadiene was fed at an initial feed rate of 75g of mixture/min at a constant rate into the polymerization vessel, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 1920g of cyclohexane, 203g of 1, 3-butadiene, 2.7g of THF and 22.7 g of 22.7mmo1 n-butyllithium into a polymerization kettle, heating to 55 ℃, and reacting for 55min to form a BR chain segment; then, 350g of styrene and 1.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 65 ℃, the reaction is carried out for 55min, a-BR-PS-chain segment is formed, 1850g of cyclohexane, 2.1g of THF and 18.5mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 75 ℃, 570g of styrene and 205g of 1 and 3-butadiene are stirred and mixed for 15min, and the mixture is added into the polymerization kettle at a feeding speed of 75 g/min within 60min, so that a random gradient-SB 2/(S → B) 2-chain segment is formed; then adding 39g of butadiene into the polymerization kettle, and carrying out end capping reaction for 20min to form a-BR-PS-SB 2/(S → B) 2-B-chain segment; and finally, heating to 85 ℃, adding 23.5mmo1 tert-butyl trichlorosilane, reacting for 65min, 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 grafting agent with the [ -BR-PS-SB2/(S → B)2-B- ] nY three-arm structure (Mn is 85210, and Mw/Mn is 3.42).
(2) Preparation of wide distribution butyl rubber: the other conditions were the same as in example 3 except that: during the synthesis process, no [ -BR-PS-SB/(S → B) -B- ] nY grafting agent is added, but [ -BR-PS-SB2/(S → B)2-B- ] nY grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 970g of methane chloride, 405g of cyclohexane and 25.5g of [ -BR-PS-SB/(S → B) -B- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 587g of methane chloride, 492g of isobutene and 41g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then mixing 160g of methane chloride, 2.57g of sesquiethylaluminum chloride and 0.187g of HCl at-89 ℃, aging for 25min, then adding the mixture into the polymerization system together, stirring and reacting for 1.5hr, discharging, condensing, washing and drying to obtain the wide-distribution 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: styrene monomer was not added for the first time, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2020g of cyclohexane, 223g of 1, 3-butadiene, 3.1g of THF and 25.6mmo1 n-butyllithium into a polymerization kettle, heating to 57 ℃, and reacting for 55min to form a BR chain segment; then adding 1920g of cyclohexane, 2.7g of THF and 19.5mmo1 of n-butyllithium into the polymerization kettle in sequence, heating to 77 ℃, stirring and mixing 590g of styrene and 215g of 1, 3-butadiene for 17min, and within 70min, reducing the initial feeding speed by 3g of mixture per minute at 80g of mixture/min, wherein the reduction range of the feeding speed is 3g of mixture per minute, so as to form a random and long gradual change section-SB/(S → B) -chain segment; then adding 41g of butadiene into the polymerization kettle, and carrying out end capping reaction for 22min to form a-BR-SB/(S → B) -B-chain segment; and finally, heating to 87 ℃, adding 25.6mmo1 tert-butyl trichlorosilane, reacting for 65min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet coagulation and drying on the glue solution to obtain the grafting agent with the [ -BR-SB/(S → B) -B- ] nY three-arm structure (Mn is 90150, and Mw/Mn is 6.84).
(2) Preparation of wide distribution butyl rubber: the other conditions were the same as in example 4 except that: during the synthesis process, no [ -BR-PS-SB/(S → B) -B- ] nY grafting agent is added, but the [ -BR-SB/(S → B) -B- ] nY grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 4 times, adding 980g of methane chloride, 420g of cyclohexane and 27.1g of [ -BR-SB/(S → B) -B- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 25min until the grafting agent is completely dissolved; and then cooling to-80 ℃, sequentially adding 592g of methane chloride, 502g of isobutene and 39g of isoprene, mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 170g of methane chloride, 3.57g of sesquiethylaluminum chloride and 0.217g of HCl at-90 ℃, aging for 25min, then adding the mixture into the polymerization system together, stirring and reacting for 1.7hr, discharging, condensing, washing and drying to obtain the wide-distribution 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: 1, 3-butadiene was not added for the first time, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2210g of cyclohexane, 4.5g of THF and 27.6mmo1 n-butyllithium into the polymerization kettle, and heating to 60 ℃; then 376g of styrene and 2.7g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, the reaction is carried out for 60min, a-PS-chain segment is formed, then 2120g of cyclohexane, 3.9g of THF and 22.5mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 80 ℃, 610g of styrene and 235g of 1, 3-butadiene are stirred and mixed for 20min, and the initial feeding speed of 85g of mixture/min is reduced by 4g of mixture per minute within 75min, so that a random and long gradual change segment-SB/(S → B) -chain segment is formed; then adding 45g of butadiene into the polymerization kettle, and carrying out end capping reaction for 25min to form a-PS-SB/(S → B) -B-chain segment; and finally, heating to 89 ℃, adding 30.6mmo1 tert-butyl trichlorosilane, reacting for 70min, 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 grafting agent with the [ -PS-SB/(S → B) -B- ] nY three-arm structure (Mn is 90150, and Mw/Mn is 5.95).
(2) Preparation of wide distribution butyl rubber: the other conditions were the same as in example 5 except that: during the synthesis process, no [ -BR-PS-SB/(S → B) -B- ] nY grafting agent is added, but the [ -PS-SB/(S → B) -B- ] nY grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 4 times, adding 990g of methane chloride, 510g of cyclohexane and 30.1g of [ -PS-SB/(S → B) -B- ] nY 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 602g of methane chloride, 512g of isobutene and 49g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methane chloride, 4.27g of sesquiethylaluminum chloride and 0.312g of HCl at-90 ℃, aging for 25min, then adding the materials into the polymerization system together, stirring and reacting for 2.0hr, discharging, condensing, washing and drying to obtain the wide-distribution 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) Preparation of wide distribution butyl rubber: the other conditions were the same as in example 6 except that the amount of the [ -BR-PS-SB/(S → B) -B- ] nY grafting agent added during the synthesis was 5.2g, that is: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 1020g of methane chloride, 590g of cyclohexane and 5.2g of [ -BR-PS-SB/(S → B) -B- ] nY grafting agent into the polymerization kettle, stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 622g of methane chloride, 522g of isobutene and 51g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-97 ℃, then mixing 200g of methane chloride, 5.12g of sesquiethylaluminum chloride and 0.452g of HCl at-95 ℃, aging for 30min, then adding the materials into the polymerization system together, stirring and reacting for 2.5hr, discharging, condensing, washing and drying to obtain the wide-distribution butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 7
(1) Preparation of grafting agent: the other conditions were the same as in example 6 except that: during the synthesis, tert-butyl trichloro silicon bromide is not added, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 2510g of cyclohexane, 271g of 1, 3-butadiene, 5.6g of THF and 29.6mmo1 n-butyllithium into the polymerization kettle, heating to 60 ℃, and reacting for 70min to form a BR chain segment; then 386g of styrene and 3.5g of THF are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃, the reaction is carried out for 60min, a-BR-PS-chain segment is formed, then 2420g of cyclohexane, 4.9g of THF and 25.5mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 80 ℃, 670g of styrene and 255g of 1, 3-butadiene are stirred and mixed for 20min, and within 80min, the initial feeding speed is 95g of mixture/min, the feeding speed is reduced by 6g of mixture per minute, and a random and long gradual-change segment-SB/(S → B) -chain segment is formed; then adding 50g of butadiene into a polymerization kettle, carrying out end-capping reaction for 30min to form a-BR-PS-SB/(S → B) -B-chain segment, and carrying out wet coagulation and drying on the glue solution to obtain the grafting agent of [ -BR-PS-SB/(S → B) -B- ] n (Mn is 79150, and Mw/Mn is 2.05).
(2) Preparation of wide distribution butyl rubber: the other conditions were the same as in example 6 except that: during the synthesis process, no [ -BR-PS-SB/(S → B) -B- ] nY grafting agent is added, but the [ -BR-PS-SB/(S → B) -B- ] n grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 1020g of methane chloride, 590g of cyclohexane and 33.1g of [ -BR-PS-SB/(S → B) -B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 622g of methane chloride, 522g of isobutene and 51g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-97 ℃, then mixing 200g of methane chloride, 5.12g of sesquiethylaluminum chloride and 0.452g of HCl at-95 ℃, aging for 30min, then adding the materials into the polymerization system together, stirring and reacting for 2.5hr, discharging, condensing, washing and drying to obtain the wide-distribution butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of the Wide distribution butyl rubber
As can be seen from Table 1: the wide-distribution butyl rubber has wide molecular weight distribution and low 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 (14)
1. A preparation method of butyl rubber with wide molecular weight distribution is characterized in that the preparation process comprises the following steps:
(1) preparation of grafting agent: according to the total mass percentage of reaction monomers, firstly introducing argon into a polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200% of solvent, 10-20% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator into the polymerization kettle, heating to 45-60 ℃, and reacting for 40-70 min; then sequentially adding 20-30% of styrene and 0.05-0.1% of structure regulator into the polymerization kettle, heating to 60-70 ℃, and reacting for 40-60 min; secondly, sequentially adding 100-200% of solvent, 0.05-0.2% of structure regulator and initiator into a polymerization kettle, heating to 70-80 ℃, stirring and mixing 30-50% of styrene and 10-20% of 1, 3-butadiene for 10-20 min, wherein the reaction is variable-speed polymerization, adding the mixture into the polymerization kettle in a continuous injection manner, and reacting within 50-80 min, wherein the initial feeding speed is more than 10.0% of mixture/min; then adding 1-4% of 1, 3-butadiene into the polymerization kettle for end capping, and reacting for 10-30 min until no free monomer exists; finally, heating to 80-90 ℃, adding a coupling agent for coupling reaction for 50-80 min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on glue solution to obtain a grafting agent;
(2) preparation of wide distribution 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 200-300% of a diluent/solvent mixed solvent with the volume ratio of 70-30/30-70 and 2-7% of a grafting agent into a polymerization kettle, stirring and dissolving for 10-30 min until the grafting agent is completely dissolved, then cooling to-65-85 ℃, then sequentially adding 100-200% of the diluent, 87-95% of isobutene and 3-5% of isoprene, and stirring and mixing until the temperature of a polymerization system is reduced to-100-90 ℃; and then 30-50% of diluent and 0.05-2.0% of co-initiator are mixed and aged for 20-30 min at the temperature of-95 to-85 ℃, then the mixture is added into a polymerization system together to be stirred and react for 0.5-2.5 hr, and then the product of the wide-distribution butyl rubber is obtained after discharging, coagulation, washing and drying.
2. The method of claim 1, wherein the grafting agent is a three-armed star polymer comprising a styrene and butadiene block copolymer having the general structural formula shown in formula I:
wherein Bu is tert-butyl; BR is a butadiene homopolymer section, and the 1, 2-structure content of the BR is 15-25%; 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 2-3.
3. The method of claim 2, wherein the three-arm star polymer has a styrene content of 60 to 80% and a butadiene content of 20 to 40%.
4. The method of claim 2, wherein the three-arm star polymer has a number average molecular weight of from 70000 to 110000 and a ratio of weight average molecular weight to number average molecular weight of from 4.23 to 8.16.
5. 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.
6. The method of claim 5, wherein the structure modifier is tetrahydrofuran.
7. 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.
8. The method of claim 7 wherein said initiator is n-butyllithium.
9. The method according to claim 1, wherein the coupling agent is a halosilane coupling agent selected from the group consisting of t-butyltrichlorosilane and t-butyltribromosilane, and the molar ratio of the amount of the coupling agent to the amount of the initiator is 0.2 to 2.0.
10. The method according to claim 1, wherein the co-initiator is prepared by compounding an alkyl aluminum halide and a protonic acid according to different proportions, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.
11. The method of claim 10 wherein the alkyl aluminum halide is selected from at least one of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, diisopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride.
12. The method of claim 11 wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.
13. The method of claim 10, wherein the protic acid is selected from the group consisting of HCI, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3One kind of (1).
14. The method of claim 13, wherein the protic acid is HCI.
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