CN114163585A - Preparation method of ultra-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber - Google Patents
Preparation method of ultra-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber Download PDFInfo
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- CN114163585A CN114163585A CN202010952094.8A CN202010952094A CN114163585A CN 114163585 A CN114163585 A CN 114163585A CN 202010952094 A CN202010952094 A CN 202010952094A CN 114163585 A CN114163585 A CN 114163585A
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- 238000009826 distribution Methods 0.000 title claims abstract description 98
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 237
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 188
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 143
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 98
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000005859 coupling reaction Methods 0.000 claims abstract description 69
- 239000002667 nucleating agent Substances 0.000 claims abstract description 58
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 43
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 6
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 138
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 78
- 238000010438 heat treatment Methods 0.000 claims description 75
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 69
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 239000003292 glue Substances 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000002140 halogenating effect Effects 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229940050176 methyl chloride Drugs 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- YFIIENAGGCUHIQ-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptachloropropane Chemical compound ClC(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl YFIIENAGGCUHIQ-UHFFFAOYSA-N 0.000 claims description 2
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 claims description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-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 compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-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
- 239000012046 mixed solvent Substances 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims 1
- 239000003607 modifier Substances 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
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 abstract description 63
- 238000012545 processing Methods 0.000 abstract description 8
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- 238000012360 testing method Methods 0.000 description 23
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 22
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-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
- 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
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical group Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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Abstract
The invention discloses a preparation method of super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber, which is used for preparing 3, 9-dioxo [5.5]]Performing halogenation reaction on spiro undecane to synthesize a novel coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane with a linear long-chain symmetrical structure; then isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) are taken as reaction monomers, alkyl lithium and organic peroxide are taken as initiators, four-kettle reaction is carried out, temperature-changing and speed-changing polymerization is adopted, and then 1, 5-dihalo-3, 3-di (2-haloethyl) pentane coupling agent is used for coupling to prepare the quaternary four-heteroarm star-shaped nucleating agent ([ PS- (DVB) BR-]n[PS‑(DVB)IR‑]n Y[‑S(DVB)B/(S→(DVB)B)‑PS]n[‑(DVB)SBR‑]n) (ii) a Under a catalysis system compounded by alkyl aluminum halide and protonic acid, the four-element four-hetero-arm star-shaped nucleating agent, isobutene and isoprene adopt a first-arm-second-core method to prepare the ultra-wide distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber through cationic polymerization. The preparation method has the characteristics of short process flow, controllable molecular weight, good product processing performance, suitability for industrial production and the like.
Description
Technical Field
The invention relates to a preparation method of super-wide distribution four-hetero-arm comb-shaped branched butyl rubber, in particular to a method for preparing the super-wide distribution four-hetero-arm comb-shaped branched butyl rubber by cationic polymerization of a quaternary four-hetero-arm nucleating agent synthesized by isoprene/butadiene/styrene/divinyl benzene (DVB), isobutene and isoprene.
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 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 ℃. CN88108392.5 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. CN101353403B 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 methane chloride to cyclohexane v: v 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 an unsaturated chain 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-tetramethyl-1-pentene, to a mixture of isoolefin monomers and diolefin monomers. CN107793535A provides a butyl rubber having a molecular weight of 90 to 260 ten thousand, log (mw) >6, and containing structural units derived from isobutylene, structural units derived from a conjugated diene, and optionally structural units derived from an aryl olefin. CN200710129810.7 provides a method of synthesizing linear butyl rubber by a first arm and then core method, and then coupling the linear butyl rubber by divinylbenzene to obtain star-shaped branched butyl rubber. Puskas and the like adopt pyromellitic acid as a raw material to synthesize initiator tetra-cumyl alcohol with a four-arm structure, and then adopt a tetra-cumyl alcohol/aluminum tetrachloride initiation system to initiate isobutylene and isoprene copolymerization in an inert organic solvent under the condition of-120 to-50 ℃ to synthesize star-shaped branched butyl rubber with bimodal molecular weight distribution (Catalysts for manufacturing efficiency of IIR with bi-modal molecular weight distribution: US, 5194538[ P ] 1993-3-16.). Wieland et al successfully prepared multi-armed star butyl rubber (Polymer Chemistry, 2002, 40: 3725 @. and cationic polymerization [ J. Polymer Science: Polymer Chemistry, 2002, 3725 @ -3733.) by synthesizing a macroinitiator P (MMA-b-St-co-CMS) containing a quaternary of 4-chloromethylstyrene, styrene, and methyl methacrylate in the presence of 1, 2-Diphenylethylene (DPE) and then initiating cationic polymerization of isobutylene and isoprene using the macroinitiator. Hadjichhritids et al synthesized PI-PS-PBd four-arm copolymers (Iatrou H, Hadjichrtitids N.Synthesisof a model 3-miktoarm star polymer [ J ]. Macromolecules,1992,25:4649) using CH3SiCl3 by strictly controlling the order of addition of the monomers and the overranging of the coupling agent in four steps. Hadjchrismists adopts high vacuum technology to obtain styrene polybutadiene macromonomer through the reaction of active polybutadiene lithium and silicon chloride group of p-chlorodimethylsilylstyrene, the macromonomer then copolymerizes with butadiene in the presence of a random regulator to obtain active Comb polybutadiene, and finally reacts with methyl silicon tetrachloride or silicon tetrachloride to obtain 3-arm or 4-arm Star-shaped Comb polybutadiene (KOUTALAS G, IATROU H, LOHSE D J, et al. well-Defined Comb, Star-Com b, and dComb-on-Comb polymers by Anionic Polymerization and the macromolecular monomer molecules [ J ]. Macromolecules,2005,38(12): 4996-5001). Gong Hui Qin et al synthesized a star-branched polymer (preparation and characterization of star-branched polyisobutylene with divinylbenzene as core; 2008, 31(5):362 and 365.) with divinylbenzene as core and polyisobutylene as arm at-80 deg.C by using 2-chloro-2, 4, 4-tetramethylpentane/titanium tetrachloride as initiator system and monochloromethane/cyclohexane as solvent and using active cationic polymerization.
Disclosure of Invention
The invention aims to provide a preparation method of super-wide distribution three-hybrid-arm comb-shaped star-branched butyl rubber. The preparation method takes alkyl lithium and organic peroxide as initiators, isoprene, 1, 3-butadiene, styrene and divinyl benzene (DVB) as reaction monomers, and prepares the ultra-wide distribution quaternary quadri-fust arm star nucleating agent by coupling with a novel long-chain tetrahalide coupling agent 1, 5-dihalo-3, 3 bis (2-haloethyl) pentane and adopting a temperature-variable and variable-speed polymerization method; finally, under a catalysis system compounded by Lewis acid and protonic acid, the ultra-wide distribution quaternary four-hetero-arm star-shaped nucleating agent, isobutene and isoprene are subjected to cationic polymerization by adopting a first-arm-second-core method to prepare the ultra-wide distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber. The method solves the problems of extrusion swelling and low stress relaxation rate of the butyl rubber in the processing process, so that the super-wide distribution four-hybrid-arm comb-shaped star-shaped branched butyl rubber has the characteristics of high stress relaxation rate and small extrusion swelling effect, and meanwhile, the sufficient crude rubber strength and good air tightness are maintained, and the balance of the physical and mechanical properties and the processing performance of the butyl rubber is realized.
All the percentages in the present invention are percentages by mass.
The preparation of the ultra-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
preparation of a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: according to one hundred percent of the total mass of reactants, firstly, introducing argon into a 4L stainless steel polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200 percent of deionized water, 3, 9-dioxo [5.5] spiro undecane, a halogenating agent and 1-5 percent of catalyst into the polymerization kettle, heating to 50-80 ℃, reacting for 1-3 hours, adding 20-40 percent of NaOH aqueous solution with the mass concentration of 10-20 percent to terminate the reaction, and finally adding 200-300 percent of monochloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane (the yield is 85-95 percent).
b, preparation of a quaternary four-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 2-3 times, sequentially adding 100-200% of solvent, 10-20% of 1, 3-butadiene and 0.01-0.5% of structure regulator into the polymerization kettle A, heating to 40 ℃, adding an initiator 1, reacting to obtain temperature-changing polymerization, gradually increasing the temperature from 40 ℃ to 60 ℃ within 40-60 min, and increasing the temperature at a speed of temperature increase<1.3 ℃/min to form a wide-distribution BR chain segment, then adding 5-10 percent of styrene and 0.01-0.5 percent of structure regulator into the polymerization kettle A in sequence, and reacting for 20-40 min to form the wide-distribution PS-BR-]nA chain segment, after the monomer is completely converted, heating to 70-90 ℃, and adding a coupling agent for coupling reaction for 40-60 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 2-3 times, sequentially adding 100-200% of solvent, 10-20% of isoprene and 0.01-0.5% of structure regulator, heating to 50 ℃, adding an initiator 1, reacting to obtain variable temperature polymerization, gradually heating from 50 ℃ to 70 ℃ within 30-50 min, and heating at a speed of 50 ℃ to 70 DEG<1.2 ℃/min to form a wide distribution IR chain segment, then adding 5 to 10 percent of styrene and 0.01 to 0.5 percent of structure regulator into the polymerization kettle B in sequence, and reacting for 20 to 40min to form the wide distribution PS-IR-]An n segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 40-60 min; meanwhile, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2-3 times, sequentially adding 100-200% of solvent and 0.01-0.5% of structure regulator, heating to 70-80 ℃, adding initiator 1, and mixing 10-20% of styrene and 1, 3-butadiene5 to 10 percent of the mixture is stirred and mixed for 20 to 30min, the mixture is added into a polymerization kettle in a mode of continuous injection for reaction of variable-speed polymerization and reacts within 50 to 60min at the initial feeding speed>5.0 percent of mixture/min, 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, then 5 to 10 percent of styrene and 0.05 to 0.1 percent of structure regulator are sequentially added into the polymerization kettle for reaction for 20 to 40min to form random and gradual change [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 50-70 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle D to replace the system for 2-3 times, sequentially adding 100-200% of solvent, 10-20% of styrene, 5-10% of 1, 3-butadiene and 0.01-0.5% of structure regulator, heating to 50-70 ℃, adding an initiator 1, and reacting for 30-40 min to form [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 40-60 min; after the coupling reaction is finished, sequentially adding 3-7% of Divinylbenzene (DVB) into a polymerization kettle A, heating to 70-80 ℃, adding 0.05-1.0% of initiator 2, reacting for 50-70 min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on a glue solution to obtain the quaternary quadri-arm star-shaped nucleating agent ([ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n)。
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: according to the total mass parts of reaction monomers, firstly introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 3-4 times, and sequentially adding 200-300% of diluent/solvent V into the polymerization kettle: mixing a solvent mixture with a V ratio of 60-40/40-60, isobutene 92-98% and isoprene 2-8%, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then adding 40-60% of a diluent and 0.05-3.0% of a co-initiator into the polymerization system for mixing and aging for 30-40 min under the condition of-95 to-85 ℃, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 50-70% of the solvent and 3.0-7.0% of the nucleating agent obtained in the step (1) for 5.0-7.0 hr, aging for 30-40 min under the condition of-95 to-85 ℃, adding the solvent and the nucleating agent into the polymerization system for stirring and reacting for 5.0-7.0 hr, finally adding a terminator, discharging, condensing, washing and drying to obtain the ultra-wide distribution four-hybrid arm comb-shaped branched butyl rubber product.
The nucleating agent is a quaternary quadri-armed star copolymer (PS- (DVB) BR-]n[PS-(DVB)IR-]n Y[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n) The structural general formula is shown as formula I:
wherein Y is 3, 3-diethylpentane; DVB is divinylbenzene; BR is a butadiene homopolymer section with widely distributed vinyl groups, and the 1, 2-structure content of the BR is 15-20 percent; IR is an isoprene homopolymer segment with widely distributed vinyl groups, and the 1, 2-structure content of the isoprene homopolymer segment is 5-10 percent; SBR is a styrene and 1, 3-butadiene random block copolymer; PS is a styrene homopolymer segment; SB is a random section of styrene and butadiene; (S → B) is a transition of styrene and butadiene; the content of styrene in the super-wide distribution quaternary four-hybrid arm star-shaped copolymer is 30-60%, the content of butadiene is 20-30%, and the content of isoprene is 10-20%; the quaternary four-hetero-arm star-shaped copolymer has the number average molecular weight (Mn) of 80000-100000 and the molecular weight distribution (Mw/Mn) of 14.23-16.72.
The halogenating agent is one of liquid chlorine and liquid bromine, preferably liquid bromine, the dosage of the halogenating agent is determined according to the dosage of the 3, 9-dioxo [5.5] spiroundecane, and the molar ratio of the dosage of the liquid bromine to the 3, 9-dioxo [5.5] spiroundecane is 4.5-6.5.
The catalyst of the invention is HCl-CH3A mixed aqueous solution of OH, wherein the molar concentration of HCl is: 0.1 to 0.7 mol/L.
The dosage of the coupling agent is determined according to the amount of the initiator, and the molar ratio of the dosage of the coupling agent to the organic lithium is 1.0-5.0.
The initiator 1 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 initiator 2 is an organic peroxide selected from dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, preferably dibenzoyl peroxide (BPO).
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 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 solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene or ethylbenzene, and cyclohexane is preferred.
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. Selection of protonic acidFrom HCl, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3Of (1), preferably HCl. Wherein the total addition amount of the coinitiator is 0.1-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05: 1-0.5: 1.
The terminator provided by the invention can be selected from one or more of methanol, ethanol and butanol.
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 treats 3, 9-dioxo [5.5]]Performing halogenation reaction on spiro undecane to synthesize a novel coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane with a linear long-chain symmetrical structure; then isoprene, 1, 3-butadiene, styrene and divinyl benzene (DVB) are taken as reaction monomers, alkyl lithium and organic peroxide are taken as initiators, four-kettle reaction is carried out, temperature-changing and speed-changing polymerization is adopted, and then 1, 5-dihalo-3, 3 di (2-haloethyl) pentane coupling agent is used for coupling to prepare the quaternary quadri-armed star nucleating agent (PS- (DVB) BR-]n[PS-(DVB)IR-]n Y[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n) And finally, under a catalysis system compounded by alkyl aluminum halide and protonic acid, preparing the ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber by cationic polymerization by adopting a first-arm-second-core method for the four-hetero-arm star-shaped nucleating agent, isobutene and isoprene.
The invention designs a super-wide distribution quaternary four-hybrid-arm star-shaped nucleating agent ([ PS- (DVB) BR-]n[PS-(DVB)IR-]n Y[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n) Y, the nucleating agent contains a four-hybrid arm structure, and the structure is characterized in that structural units on each arm are different, and the lengths of chain segments are different; in addition, the-BR-, -IR-chain segments in the nucleating agent are all subjected to temperature-variable polymerization and contain a large number of widely distributed vinyl groups; also, the chain segment of-SB/(S → B) -adopts variable speed polymerization to ensure that the chain segment has certain randomness and degeneration; due to the three reasons, the disorder of the molecular chain segment is obviously increased in the polymerization process of the butyl rubber, the regularity of the molecular chain is obviously destroyed, the flexibility of the molecular chain segment is obviously improved, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic property, has high stress relaxation rate and small extrusion swelling effect, and the processing property of the butyl rubber is improved; meanwhile, the-PS-and-SBR-chain segments in the nucleating agent contain a large number of benzene rings, the problem of reduction of strength and air tightness caused by broadening of molecular weight distribution of butyl rubber is solved by using the characteristics of barrier property and rigidity of the benzene rings, and the high strength and good air tightness of the butyl rubber are ensured. Therefore, the temperature of the molten metal is controlled,
the invention organically combines the characteristics of the four-hybrid-arm star structure and the characteristics of wide distribution, randomness, gradient, barrier property and rigidity of various chain segments together and synergistically plays a role by synthesizing a novel linear long-chain symmetrical structure coupling agent and designing the four-hybrid-arm star structure, thereby solving the problem of contradiction relation between the processability and the physical and mechanical properties of butyl rubber and finally realizing the optimal balance between the processability and the physical and mechanical properties of the butyl rubber.
Drawings
FIG. 1: 1#Comparative example 1 sample and 2#Comparison of the GPC spectra of the samples of example 1.
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.
(1) The raw material sources are as follows:
other reagents are all commercial products
(2) 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 polystyrene standard sample as calibration curve, tetrahydrofuran as mobile phase, column temperature of 40 deg.C, sample concentration of 1mg/ml, sample amount of 50 μ L, elution time of 40min, and flow rate of 1 ml/min-1。
Measurement of stress relaxation: the measurement was carried out by using a Mooney viscometer model GT-7080-S2 manufactured by Taiwan high-speed railway.
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 the extrusion swell ratio: using a capillary rheometer of the RH2000 type manufactured by Marwin, UK
At a temperature of 100 ℃, an aspect ratio of 16:1 and a shear rate of 10-1000S-1Is measured within the interval of (1).
Measurement of airtightness: the air permeability was determined using an automated air tightness tester according to ISO 2782:1995,
test gas is N2The test temperature is 23 ℃, and the test sample is a circular sea piece with the diameter of 8cm and the thickness of 1 mm.
Tensile strength: the method in standard GB/T528-2009 is executed.
Example 1
(1) Preparation of a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, introducing argon for 3 times of replacement, and then adding 600g of deionized water and 58g of 3, 9-dioxygen [5.5] into the polymerization kettle in sequence]Spiroundecane, 320g of liquid bromine, 18g of HCl-CH3OH solution(HCl molar concentration: 0.7mol/L), heating to 70 ℃, reacting for 3.0hr, adding 300g of NaOH aqueous solution with mass concentration of 15% to terminate the reaction, and finally adding 800g of monochloromethane to extract, separate, wash and dry to obtain the coupling agent 1, 5-dibromo-3, 3 bis (2-bromoethyl) pentane (yield 93%).
b, preparation of a quaternary four-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 100g of 1, 3-butadiene and 0.5g of THF into the polymerization kettle A, heating to 40 ℃, adding 33.5mmo1 n-butyllithium to start reaction, reacting within 40min, gradually increasing the temperature from 40 ℃ to 60 ℃, wherein the heating rate is 0.6 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 50g of styrene and 0.6g of THF into the polymerization kettle A, and reacting for 20min to form a wide-distribution PS-BR-shell-type copolymer]nHeating to 70 ℃, adding 260mmo11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and performing coupling reaction for 40 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 100g of isoprene and 0.6g of THF, heating to 50 ℃, adding 13.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.8 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 50g of styrene and 0.6g of THF into the polymerization kettle B to react for 20min to form PS-IR-doped silicon with wide distribution]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 40 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane and 1.9g of THF, heating to 70 ℃, adding 16.5mmo1 n-butyllithium to start reaction, stirring and mixing 100g of styrene and 50g of 1, 3-butadiene for 20min, and within 50min, reducing the mixture by 2g 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; then, 50g of styrene and 0.6g of THF are sequentially added into the polymerization kettle C for reaction for 20min to form a wide distribution of random and gradual [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 50 min; meanwhile, in a 15L stainless steel polymerization kettle D, argon is introduced to place the systemChanging for 2 times, sequentially adding 1000g of cyclohexane, 100g of styrene, 50g of 1, 3-butadiene and 1.2g of THF, heating to 50 ℃, adding 17.5mmo1 n-butyllithium, and reacting for 30min to form [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 40 min; after the coupling reaction is finished, sequentially adding 30g of DVB into a polymerization kettle A, heating to 70 ℃, adding 0.11g of BPO, reacting for 50min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n(Mn 82000, Mw/Mn 14.23).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 310g of methane chloride, 370g of cyclohexane, 276g of isobutene and 6g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then adding 120g of methane chloride, 2.8g of aluminum sesquiethylate chloride and 0.09g of HCl into the polymerization system after mixing at-85 ℃, aging for 30min, stirring and reacting for 0.5hr, then adding 160g of cyclohexane and 9.0g of [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nStirring and dissolving for 5.0hr until the solution is completely dissolved, then aging for 30min at-85 ℃, adding the solution into a polymerization system, stirring and reacting for 5.0hr, adding 300mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the ultra-wide distribution four-hybrid-arm comb-shaped star-branched 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 a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b, preparation of a quaternary four-hybrid-arm star nucleating agent: in a 15L stainless steel polymerizer A equipped with a jacket, the system was replaced with argon gas 2 times, 1300g of cyclohexane, 130g of 1, 3-butadiene and 0.7g of THF were sequentially added to the polymerizer A, and the temperature was raised to 40 ℃ to add34.6mmo1 n-butyllithium is added to start reaction, the reaction is carried out within 40min, the temperature is gradually increased from 40 ℃ to 60 ℃, the temperature rising speed is 0.6 ℃/min, a BR chain segment with wide distribution is formed, then 60g of styrene and 0.9g of THF are sequentially added into a polymerization kettle A, and after the reaction is carried out for 25min, the PS-BR-ion-exchanger with wide distribution is formed]nCutting the chain, heating to 75 ℃, adding 280mmo11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and performing coupling reaction for 45 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 120g of isoprene and 0.8g of THF, heating to 50 ℃, adding 14.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.8 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 70g of styrene and 0.9g of THF into the polymerization kettle B to react for 26min to form PS-IR-doped silicon with wide distribution]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 45 min; meanwhile, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1300g of cyclohexane and 2.3g of THF, heating to 70 ℃, adding 18.5mmo1 n-butyllithium to start reaction, stirring and mixing 130g of styrene and 60g of 1, 3-butadiene for 20min, and within 50min, reducing the mixture by 3g per minute at an initial feeding speed of 11 g/min to form a random and long gradual change section-SB/(S → B) -chain segment; then 60g of styrene and 0.8g of THF are sequentially added into the polymerization kettle C for reaction for 25min to form a wide distribution of random and gradual [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 55 min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 2 times, 1200g of cyclohexane, 130g of styrene, 60g of 1, 3-butadiene and 1.5g of THF are sequentially added, the temperature is raised to 55 ℃, 18.5mmo1 n-butyllithium is added for reaction for 32min, and [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 45 min; after the coupling reaction is finished, sequentially adding 40g of DVB into a polymerization kettle A, heating to 72 ℃, adding 0.14g of BPO, reacting for 55min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS ]-(DVB)BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n(Mn 85000, Mw/Mn 14.89).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 330g of methane chloride, 350g of cyclohexane, 280g of isobutene and 10g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 140g of methane chloride, 3.1g of aluminum sesquiethylate chloride and 0.11g of HCl at-87 ℃, aging for 32min, adding into the polymerization system together, stirring and reacting for 0.6hr, then adding 170g of cyclohexane and 12.0g of [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nStirring and dissolving for 5.5hr until the solution is completely dissolved, then aging for 33min at-87 ℃, adding the solution into a polymerization system, stirring and reacting for 5.5hr, adding 320mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the ultra-wide distribution four-hybrid-arm comb-shaped star-branched 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 a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b, preparation of a quaternary four-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1500g of cyclohexane, 150g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 36.6mmo1 n-butyllithium to start reaction, reacting within 50min, gradually increasing the temperature from 40 ℃ to 60 ℃, wherein the heating rate is 0.4 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 70g of styrene and 1.2g of THF into the polymerization kettle A, and reacting for 30min to form a wide-distribution [ PS-BR-]nHeating to 80 ℃ after chain segmentation, adding 300mmo11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 50 min; meanwhile, in a 15L stainless steel polymerizer B, argon gas was introduced to replace the system for 3 times, 1400g of cyclohexane, 140g of isoprene and 0.9g of THF were sequentially added, and the temperature was raised to 5Adding 16.5mmo1 n-butyllithium at 0 ℃ to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at the temperature rise speed of 0.5 ℃/min to form a wide distribution IR chain segment, then sequentially adding 80g of styrene and 1.3g of THF into a polymerization kettle B to react for 31min to form a wide distribution PS-IR-]n chain segment, adding the material in the polymerization kettle B into the polymerization kettle A after the monomer is completely converted, and performing coupling reaction for 50 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1500g of cyclohexane and 2.5g of THF, heating to 75 ℃, adding 20.5mmo1 n-butyllithium to start reaction, stirring and mixing 150g of styrene and 80g of 1, 3-butadiene for 25min, and within 55min, reducing the mixture by 2g per minute at an initial feeding speed of 13 g/min to form a random and long gradual change section-SB/(S → B) -chain segment; then 70g of styrene and 1.1g of THF are sequentially added into the polymerization kettle C for reaction for 30min to form a wide distribution of random and gradual [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60 min; meanwhile, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1400g of cyclohexane, 150g of styrene, 80g of 1, 3-butadiene and 1.9g of THF are sequentially added, the temperature is raised to 60 ℃, 20.5mmo1 n-butyllithium is added for reaction for 35min, and [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 50 min; after the coupling reaction is finished, sequentially adding 50g of DVB into a polymerization kettle A, heating to 75 ℃, adding 0.21g of BPO, reacting for 60min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n(Mn 89000, Mw/Mn 15.39).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 4 times, adding 340g of methane chloride, 330g of cyclohexane, 284g of isobutene and 14g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, and then adding 150g of methane chloride and 3.5g of aluminum sesquiethylate chlorideMixing with HCl 0.15g at-90 deg.C, aging for 35min, adding into polymerization system, stirring, reacting for 0.7hr, adding cyclohexane 180g, and mixing with PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)S BR-]nStirring and dissolving for 6.0hr until the solution is completely dissolved, then aging for 35min at-90 ℃, adding the solution into a polymerization system together, stirring and reacting for 6.0hr, adding 350mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the ultra-wide distribution four-hybrid-arm comb-shaped star-branched 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 a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b, preparation of a quaternary four-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 170g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle A, heating to 40 ℃, adding 38.6mmo1 n-butyllithium to start reaction, reacting within 50min, gradually increasing the temperature from 40 ℃ to 60 ℃, wherein the heating rate is 0.4 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 90g of styrene and 1.6g of THF into the polymerization kettle A, and reacting for 35min to form a wide-distribution [ PS-BR-]nCutting the chain, heating to 85 ℃, adding 320mmo11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and performing coupling reaction for 55 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1600g of cyclohexane, 180g of isoprene and 1.3g of THF, heating to 50 ℃, adding 18.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at the heating speed of 0.5 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 90g of styrene and 1.7g of THF into the polymerization kettle B to react for 36min to form PS-IR-doped silicon with wide distribution]n chain segment, adding the material in the polymerization kettle B into the polymerization kettle A after the monomer is completely converted, and performing coupling reaction for 55 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1700g of cyclohexane and 2.7g of THF, heating to 75 ℃, adding 23.5mmo1 n-butyllithium to start reaction, and reacting170g of styrene and 90g of 1, 3-butadiene were mixed with stirring for 27min, at an initial feed rate of 13g of mixture/min and a feed rate reduction of 2g of mixture per minute over 55min, to form a random, long transition-SB/(S → B) -segment; then 90g of styrene and 1.4g of THF are sequentially added into the polymerization kettle C for reaction for 35min to form a wide distribution of random and gradual [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 65 min; meanwhile, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1600g of cyclohexane, 170g of styrene, 90g of 1, 3-butadiene and 2.2g of THF are sequentially added, the temperature is raised to 65 ℃, 23.5mmo1 n-butyllithium is added for reaction for 38min, and [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 55 min; after the coupling reaction is finished, sequentially adding 60g of DVB into a polymerization kettle A, heating to 77 ℃, adding 0.32g of BPO, reacting for 65min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n(Mn 93000, Mw/Mn 16.12).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 4 times, sequentially adding 360g of methane chloride, 310g of cyclohexane, 290g of isobutene and 20g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-97 ℃, then mixing 170g of methane chloride, 4.1g of aluminum sesquiethylate chloride and 0.26g of HCl at-95 ℃, aging for 37min, adding into the polymerization system together, stirring and reacting for 0.8hr, then adding 200g of cyclohexane and 19.0g of [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nStirring and dissolving for 6.5hr until completely dissolving, aging at-95 deg.C for 38min, adding into polymerization system, stirring and reacting for 6.5hr, adding 400mL methanol to terminate reaction, discharging, coagulating, washing, and drying to obtain ultra-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber productAnd (5) preparing the product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Preparation of a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, introducing argon for 4 times of replacement, and sequentially adding 600g of deionized water and 60g of 3, 9-dioxygen [5.5]]Spiroundecane, 280g of liquid chlorine, 14g of HCl-CH3OH solution (HCl molar concentration: 0.7mol/L), heating to 85 deg.C, reacting for 4.0hr, adding 300g NaOH aqueous solution with mass concentration of 20% to terminate the reaction, and finally adding 920g methane chloride to extract, separate, wash and dry to obtain the coupling agent 1, 5-dichloro-3, 3 bis (2-chloroethyl) pentane (yield 91%).
b, preparation of a quaternary four-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 2000g of cyclohexane, 200g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle A, heating to 40 ℃, adding 40.6mmo1 n-butyllithium to start reaction, reacting within 60min, gradually increasing the temperature from 40 ℃ to 60 ℃, wherein the heating rate is 0.5 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 100g of styrene and 1.8g of THF into the polymerization kettle A, and reacting for 40min to form a wide-distribution [ PS-BR-]nCutting the chain, heating to 90 ℃, adding 340mmo11, 5-dichloro-3, 3 di (2-chloroethyl) pentane, and performing 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 1800g of cyclohexane, 200g of isoprene and 1.5g of THF, heating to 50 ℃, adding 19.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 50min at the heating speed of 0.4 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 100g of styrene and 1.9g of THF into the polymerization kettle B to react for 40min to form PS-IR-doped silicon with wide distribution]n chain segment, adding the material in the polymerization kettle B into the polymerization kettle A after the monomer is completely converted, and performing coupling reaction for 60 min; simultaneously, in a 15L stainless steel polymerizer C, argon gas was introduced to displace the system 3 times, 1900g of cyclohexane and 3.1g of THF were sequentially added, the temperature was raised to 80 ℃ and 25.5mmo1 of n-butyllithium was added to start the reaction, 200g of styrene and 100g of 1, 3-butadiene were mixed by stirring for 30min, and the initial charge was started within 60minThe feeding speed is 14g of mixture/min, the reduction amplitude of the feeding speed is 3g of mixture per minute, and a random and long gradual section-SB/(S → B) -chain segment is formed; then 100g of styrene and 1.8g of THF are sequentially added into the polymerization kettle C for reaction for 40min to form a wide distribution of random and gradual [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 70 min; meanwhile, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1600g of cyclohexane, 170g of styrene, 90g of 1, 3-butadiene and 2.2g of THF are sequentially added, the temperature is raised to 65 ℃, 24.5mmo1 n-butyllithium is added for reaction for 40min, and [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60 min; after the coupling reaction is finished, sequentially adding 70g of DVB into a polymerization kettle A, heating to 80 ℃, adding 0.45g of BPO, reacting for 70min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n(Mn of 100000 and Mw/Mn of 16.72).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 380g of methane chloride, 300g of cyclohexane, 294g of isobutene and 24g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then mixing 180g of methane chloride, 5.2g of sesquiethylaluminum chloride and 0.37g of HCl at-95 ℃, aging for 40min, adding into the polymerization system together, stirring and reacting for 1.0hr, then adding 220g of cyclohexane and 21.0g of [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nStirring and dissolving for 7.0hr until the solution is completely dissolved, then aging for 40min at-95 ℃, adding the solution into a polymerization system, stirring and reacting for 7.0hr, adding 450mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the ultra-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 1
Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 1 except that: no nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY
[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nNamely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 310g of methane chloride, 370g of cyclohexane, 276g of isobutene and 6g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 120g of methane chloride, 2.8g of aluminum sesquiethylate chloride and 0.09g of HCl at-85 ℃, aging for 30min, adding the mixture into the polymerization system together, stirring and reacting for 0.5hr, adding 300mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the ultra-wide distribution four-hybrid arm comb-shaped branched 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 a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: the same as in example 2.
b, preparation of a quaternary four-hybrid-arm star nucleating agent: the other conditions were the same as in example 2 except that: 1, 3-butadiene in the polymerizer A does not adopt temperature-variable polymerization, and reacts at a constant temperature of 40 ℃, namely: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 2 times, sequentially adding 1300g of cyclohexane, 130g of 1, 3-butadiene and 0.7g of THF into the polymerization kettle A, heating to 40 ℃, adding 34.6mmo1 n-butyllithium to start reaction for 40min to form a BR1 chain segment, then sequentially adding 60g of styrene and 0.9g of THF into the polymerization kettle A, and reacting for 25min to form a wide distribution of [ PS-BR1-]Heating the n chain segment to 75 ℃, adding 280mmo11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and performing coupling reaction for 45 min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 120g of isoprene and 0.8g of THF, heating to 50 ℃, adding 14.5mmo1 n-butyllithium to start reaction, and gradually increasing the temperature from 50 ℃ to 30min70 ℃, the heating rate is 0.8 ℃/min, an IR chain segment with wide distribution is formed, then 70g of styrene and 0.9g of THF are sequentially added into a polymerization kettle B, and the reaction is carried out for 26min, so as to form [ PS-IR-]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 45 min; meanwhile, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1300g of cyclohexane and 2.3g of THF, heating to 70 ℃, adding 18.5mmo1 n-butyllithium to start reaction, stirring and mixing 130g of styrene and 60g of 1, 3-butadiene for 20min, and within 50min, reducing the mixture by 3g per minute at an initial feeding speed of 11 g/min to form a random and long gradual change section-SB/(S → B) -chain segment; then 60g of styrene and 0.8g of THF are sequentially added into the polymerization kettle C for reaction for 25min to form a wide distribution of random and gradual [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 55 min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 2 times, 1200g of cyclohexane, 130g of styrene, 60g of 1, 3-butadiene and 1.5g of THF are sequentially added, the temperature is raised to 55 ℃, 18.5mmo1 n-butyllithium is added for reaction for 32min, and [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 45 min; after the coupling reaction is finished, sequentially adding 40g of DVB into a polymerization kettle A, heating to 72 ℃, adding 0.14g of BPO, reacting for 55min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS- (DVB) BR1-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n(Mn 83000, Mw/Mn 13.23).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 2 except that: no nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nInstead, a nucleating agent [ PS- (DVB) BR1-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nNamely: firstly, firstlyIntroducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 330g of methane chloride, 350g of cyclohexane, 280g of isobutene and 10g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 140g of methane chloride, 3.1g of aluminum sesquiethylate chloride and 0.11g of HCl at-87 ℃, aging for 32min, adding into the polymerization system together, stirring and reacting for 0.6hr, then adding 170g of cyclohexane, 12.0g of [ PS- (DVB) BR1-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nStirring and dissolving for 5.5hr until the solution is completely dissolved, then aging for 33min at-87 ℃, adding the solution into a polymerization system, stirring and reacting for 5.5hr, adding 320mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the ultra-wide distribution four-hybrid-arm comb-shaped star-branched 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 a quaternary four-hybrid-arm star nucleating agent: the other conditions were the same as in example 3 except that: in the synthesis process, 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added, but a conventional coupling agent of silicon tetrachloride (SiCl) is added4) Namely: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1500g of cyclohexane, 150g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 36.6mmo1 n-butyllithium to start reaction, reacting within 50min, gradually increasing the temperature from 40 ℃ to 60 ℃, wherein the heating rate is 0.4 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 70g of styrene and 1.2g of THF into the polymerization kettle A, and reacting for 30min to form a wide-distribution [ PS-BR-]nSegment, then heating to 80 ℃, adding 300mmo1 SiCl4Coupling reaction for 50 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1400g of cyclohexane, 140g of isoprene and 0.9g of THF, heating to 50 ℃, adding 16.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at the heating speed of 0.5 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 80g of styrene and 1.3g of THF into the polymerization kettle B to react for 31min to form the IR chain segment with wide distribution(PS-IR-)]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 50 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1500g of cyclohexane and 2.5g of THF, heating to 75 ℃, adding 20.5mmo1 n-butyllithium to start reaction, stirring and mixing 150g of styrene and 80g of 1, 3-butadiene for 25min, and within 55min, reducing the mixture by 2g per minute at an initial feeding speed of 13 g/min to form a random and long gradual change section-SB/(S → B) -chain segment; then 70g of styrene and 1.1g of THF are sequentially added into the polymerization kettle C for reaction for 30min to form a wide distribution of random and gradual [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60 min; meanwhile, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1400g of cyclohexane, 150g of styrene, 80g of 1, 3-butadiene and 1.9g of THF are sequentially added, the temperature is raised to 60 ℃, 20.5mmo1 n-butyllithium is added for reaction for 35min, and [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 50 min; after the coupling reaction is finished, sequentially adding 50g of DVB into a polymerization kettle A, heating to 75 ℃, adding 0.21g of BPO, reacting for 60min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nSi[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n(Mn 85000, Mw/Mn 10.12).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 2 except that: no nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nInstead, nucleation [ PS- (DVB) BR1-]n[PS-(DVB)IR-]nSi[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]n, namely: firstly, nitrogen gas is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 4 times, 340g of methane chloride, 330g of cyclohexane, 284g of isobutene and 14g of isoprene are sequentially added into a polymerization kettle, and the mixture is stirred and mixed until the mixture is polymerizedWhen the temperature of the system is reduced to-95 ℃, 150g of methane chloride, 3.5g of aluminum sesquiethyl chloride and 0.15g of HCl are mixed at-90 ℃, then aged for 35min, added into the polymerization system together and stirred for reaction for 0.7hr, and then 180g of cyclohexane, 16.0g of [ PS- (DVB) BR-]n[PS-(DVB)IR-]nSi[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nStirring and dissolving for 6.0hr until the solution is completely dissolved, then aging for 35min at-90 ℃, adding the solution into a polymerization system together, stirring and reacting for 6.0hr, adding 350mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the ultra-wide distribution four-hybrid-arm comb-shaped star-branched 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 a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: the same as in example 4.
b, preparation of a quaternary four-hybrid-arm star nucleating agent: the other conditions were the same as in example 4 except that: only A, B and C three-pot polymerization were used, polymerizer D did not participate in the reaction, and-SBR-chain segment was not formed, i.e.: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 170g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle A, heating to 40 ℃, adding 38.6mmo1 n-butyllithium to start reaction, reacting within 50min, gradually increasing the temperature from 40 ℃ to 60 ℃, wherein the heating rate is 0.4 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 90g of styrene and 1.6g of THF into the polymerization kettle A, and reacting for 35min to form a wide-distribution [ PS-BR-]nCutting the chain, heating to 85 ℃, adding 320mmo11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and performing coupling reaction for 55 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1600g of cyclohexane, 180g of isoprene and 1.3g of THF, heating to 50 ℃, adding 18.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at the heating speed of 0.5 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 90g of styrene and 1.7g of THF into the polymerization kettle B to react for 36min to form PS-IR-doped silicon with wide distribution]nSegment, to be monomericAfter conversion, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 55 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1700g of cyclohexane and 2.7g of THF, heating to 75 ℃, adding 23.5mmo1 n-butyllithium to start reaction, stirring and mixing 170g of styrene and 90g of 1, 3-butadiene for 27min, and within 55min, reducing the mixture by 2g per minute at an initial feeding speed of 13g of mixture/min to form a random and long gradual change section-SB/(S → B) -chain segment; then 90g of styrene and 1.4g of THF are sequentially added into the polymerization kettle C for reaction for 35min to form a wide distribution of random and gradual [ PS-SB/(S → B) -]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 65 min; after the coupling reaction is finished, sequentially adding 60g of DVB into a polymerization kettle A, heating to 77 ℃, adding 0.32g of BPO, reacting for 65min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n(Mn 82000, Mw/Mn 8.63).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 4 except that: no nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nInstead, nucleation [ PS- (DVB) BR-]n[PS-(DVB)IR-]n Y[-S(DVB)B/(S→(DVB)B)-PS]nNamely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 4 times, sequentially adding 360g of methane chloride, 310g of cyclohexane, 290g of isobutene and 20g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-97 ℃, then mixing 170g of methane chloride, 4.1g of aluminum sesquiethylate chloride and 0.26g of HCl at-95 ℃, aging for 37min, adding into the polymerization system together, stirring and reacting for 0.8hr, then adding 200g of cyclohexane and 19.0g of [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]nStirring for dissolving for 6.5hr until completely dissolving, aging at-95 deg.C for 38min,adding the materials into a polymerization system, stirring and reacting for 6.5hr, adding 400mL of methanol to terminate the reaction, discharging and condensing, washing and drying to obtain the ultra-wide distribution four-hybrid-arm comb-shaped star-branched 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 a quaternary four-hybrid-arm star nucleating agent:
a preparation of a coupling agent: the same as in example 5.
b, preparation of a quaternary four-hybrid-arm star nucleating agent: the other conditions were the same as in example 5 except that: instead of using a variable speed polymerization, polymerizer C is fed at one time, i.e.: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 2000g of cyclohexane, 200g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle A, heating to 40 ℃, adding 40.6mmo1 n-butyllithium to start reaction, reacting within 60min, gradually increasing the temperature from 40 ℃ to 60 ℃, wherein the heating rate is 0.5 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 100g of styrene and 1.8g of THF into the polymerization kettle A, and reacting for 40min to form a wide-distribution [ PS-BR-]nCutting the chain, heating to 90 ℃, adding 340mmo11, 5-dichloro-3, 3 di (2-chloroethyl) pentane, and performing 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 1800g of cyclohexane, 200g of isoprene and 1.5g of THF, heating to 50 ℃, adding 19.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 50min at the heating speed of 0.4 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 100g of styrene and 1.9g of THF into the polymerization kettle B to react for 40min to form PS-IR-doped silicon with wide distribution]n chain segment, adding the material in the polymerization kettle B into the polymerization kettle A after the monomer is completely converted, and performing coupling reaction for 60 min; meanwhile, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1900g of cyclohexane and 3.1g of THF, heating to 80 ℃, adding 25.5mmo1 n-butyllithium to start reaction, stirring and mixing 200g of styrene and 100g of 1, 3-butadiene for 30min, then adding the mixture into the polymerization kettle C for reaction for 60min, and forming a-SBR 1-chain segment; then sequentially adding the mixture into a polymerization kettle C100g of styrene and 1.8g of THF were reacted for 40min to form [ PS-SBR1-]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 70 min; meanwhile, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1600g of cyclohexane, 170g of styrene, 90g of 1, 3-butadiene and 2.2g of THF are sequentially added, the temperature is raised to 65 ℃, 24.5mmo1 n-butyllithium is added for reaction for 40min, and [ -SBR-]nA chain segment, namely adding the materials in the polymerization kettle D into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60 min; after the coupling reaction is finished, sequentially adding 70g of DVB into a polymerization kettle A, heating to 80 ℃, adding 0.45g of BPO, reacting for 70min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary four-hybrid-arm star-shaped nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-(DVB)SBR1-PS]n[-(DVB)SBR-]n(Mn of 91000 and Mw/Mn of 10.56).
(2) Preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 5 except that: no nucleating agent [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-S(DVB)B/(S→(DVB)B)-PS]n[-(DVB)SBR-]nInstead, nucleation [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-(DVB)SBR1-PS]n[-(DVB)SBR-]nNamely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 380g of methane chloride, 300g of cyclohexane, 294g of isobutene and 24g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then mixing 180g of methane chloride, 5.2g of sesquiethylaluminum chloride and 0.37g of HCl at-95 ℃, aging for 40min, adding into the polymerization system together, stirring and reacting for 1.0hr, then adding 220g of cyclohexane and 21.0g of [ PS- (DVB) BR-]n[PS-(DVB)IR-]nY[-(DVB)SBR1-PS]n[-(DVB)SBR-]nStirring for dissolving for 7.0hr until completely dissolving, aging at-95 deg.C for 40min, adding into polymerization system, stirring for reaction for 7.0hr, adding 450mL methanol to terminate reaction, discharging, coagulating, washing, and drying to obtain ultra-wide distribution four-hybrid-arm comb-like star-branched butylA rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Performance of ultra-wide distribution four-hybrid-arm comb-like star-branched butyl rubber
As can be seen from Table 1: the ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber has high tensile strength, good air tightness, smaller Mooney relaxation area and low extrusion swell ratio, and shows good processability (the smaller the area under a stress relaxation curve is, the lower the mixing processing energy consumption is).
Claims (24)
1. A preparation method of super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber comprises the following steps:
(1) styrene, 1, 3-butadiene, isoprene and divinylbenzene are taken as reaction monomers, 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane is taken as a coupling agent, and the quaternary quadri-heteroarm star-shaped nucleating agent is prepared by utilizing a method of combining temperature-variable and speed-variable polymerization, anion polymerization and free radical polymerization;
(2) isobutene and isoprene are taken as reaction monomers, and cationic polymerization is carried out under the condition of-95 to-85 ℃ in the presence of a quaternary four-hetero-arm star nucleating agent to prepare the ultra-wide distribution four-hetero-arm comb-shaped star-branched butyl rubber; the structural general formula of the quaternary four-hybrid-arm star nucleating agent is shown as the formula I:
wherein BR is a butadiene homopolymer section with wide distribution of vinyl, IR is an isoprene homopolymer section with wide distribution of vinyl, SBR is a random block copolymer of styrene and 1, 3-butadiene, PS is a styrene homopolymer section, and SB is a random polymerization section of styrene and butadiene; (S → B) is a transition of styrene and butadiene;
the number average molecular weight of the quaternary four-hetero-arm star-shaped nucleating agent is 80000-100000, and the ratio of the weight average molecular weight to the number average molecular weight is 14.23-16.72.
2. The method of claim 1, wherein the BR section 1, 2-structure content is between 15% and 20%.
3. The method of claim 1, wherein the IR segment 1, 2-structure content is 5% to 10%.
4. The method according to claim 1, wherein the quaternary four-hetero-arm star-shaped nucleating agent has a styrene content of 30% to 60%, a 1, 3-butadiene content of 20% to 30%, and an isoprene content of 10% to 20%.
5. The method according to any one of claims 1 to 4, wherein the specific process comprises the steps of:
(1) preparation of a quaternary four-hybrid-arm star nucleating agent: based on the total mass of reaction monomers, firstly, sequentially adding a solvent, 10-20% of 1, 3-butadiene and 0.01-0.5% of a structure regulator into a polymerization kettle A, heating to 40 ℃, adding an initiator 1, wherein the reaction is variable temperature polymerization, gradually raising the temperature from 40 ℃ to 60 ℃ within 40-60 min, then sequentially adding 5-10% of styrene and 0.01-0.5% of the structure regulator into the polymerization kettle A, heating to 70-90 ℃ after the monomers are completely converted, adding a coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane, and carrying out coupling reaction for 40-60 min; simultaneously, sequentially adding a solvent, 10-20% of isoprene and 0.01-0.5% of a structure regulator into a polymerization kettle B, heating to 50 ℃, adding an initiator 1, reacting to obtain temperature-variable polymerization, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30-50 min, then sequentially adding 5-10% of styrene and 0.01-0.5% of the structure regulator into the polymerization kettle B, adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 40-60 min; simultaneously, sequentially adding a solvent and 0.01-0.5% of a structure regulator into a polymerization kettle C, heating to 70-80 ℃, adding an initiator 1, stirring and mixing 10-20% of styrene and 5-10% of 1, 3-butadiene for 20-30 min, then adding the mixture into the polymerization kettle C in a continuous injection mode, wherein the initial feeding speed is more than 5.0% of the mixture/min, the feeding speed is gradually reduced, the reduction amplitude is determined according to the reaction time, and the reaction is completed within 50-60 min; then, sequentially adding 5-10% of styrene and 0.05-0.1% of structure regulator into the polymerization kettle C, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 50-70 min; simultaneously, sequentially adding a solvent, 10-20% of styrene, 5-10% of 1, 3-butadiene and 0.01-0.5% of a structure regulator into a polymerization kettle D, heating to 50-70 ℃, adding an initiator 1, and adding materials in the polymerization kettle D into a polymerization kettle A for coupling reaction after the monomers are completely converted; after the coupling reaction is finished, sequentially adding 3-7% of divinylbenzene into a polymerization kettle A, heating to 70-80 ℃, adding 0.05-1.0% of initiator 2, after the reaction is finished, treating the coupled reaction mixture with water, and performing wet condensation and drying on a glue solution to prepare the quaternary four-hybrid-arm star-shaped nucleating agent;
(2) preparing super-wide distribution four-hybrid-arm comb-shaped star-branched butyl rubber: firstly, sequentially adding a diluent/solvent mixed solvent with the volume ratio of 60-40/40-60, isobutene of 92-98% and isoprene of 2-8% into a polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then adding 0.05-3.0% of the diluent and a co-initiator into the polymerization kettle for reaction after mixing and aging at-95 to-85 ℃, then adding the solvent and 3.0-7.0% of the quaternary four-hybrid-arm star-shaped nucleating agent into the polymerization kettle for mixing and dissolving for 5.0-7.0 hours, aging for 30-40 min at-95 to-85 ℃, adding the solvent and the quaternary four-hybrid-arm star-shaped nucleating agent into the polymerization kettle for reaction, adding a terminator after the reaction is finished, discharging and condensing, washing, and drying to obtain the ultra-wide distribution four-hybrid-arm comb-shaped branched butyl rubber.
Wherein, the polymerization reactions in the step (1) and the step (2) are carried out in an oxygen-free and water-free environment.
6. The preparation method according to claim 5, wherein the halogenating agent is one of liquid chlorine and liquid bromine, and the molar ratio of the halogenating agent to the 3, 9-dioxo [5.5] spiroundecane is 4.5-6.5.
7. The method of claim 6, wherein the halogenating agent is liquid bromine.
8. The method of claim 5, wherein the initiator 1 is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, lithium cyclohexylate, and lithium dodecylate.
9. The method of claim 8, wherein the initiator is n-butyllithium.
10. The method according to claim 5, wherein the initiator 2 is an organic peroxide selected from the group consisting of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-t-butyl peroxide.
11. The method of claim 10, wherein the initiator 2 is dibenzoyl peroxide.
12. The method according to claim 5, wherein the structure-regulating agent is one selected from the group consisting of diglyme, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether and triethylamine.
13. The method of claim 12, wherein the structure modifier is tetrahydrofuran.
14. The preparation method of claim 5, wherein the co-initiator is a combination of an alkyl aluminum halide and a protonic acid, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05: 1-0.5: 1.
15. The method according to claim 14, wherein the alkylaluminum halide is at least one member selected from the group consisting of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, diisopropylaluminum dichloroide, dimethylaluminum chloride and ethylaluminum chloride.
16. The method of claim 15, wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.
17. The method of claim 14, wherein the protic acid is selected from the group consisting of HCl, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3One kind of (1).
18. The method of claim 17, wherein the protic acid is HCl.
19. The method of claim 5, wherein the diluent is selected from one of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
20. The method of claim 19, wherein the diluent is methyl chloride.
21. The method of claim 5, wherein the solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
22. The method of claim 21, wherein the solvent is cyclohexane.
23. The method according to claim 5, wherein the terminator is at least one selected from methanol, ethanol and butanol.
24. The method according to claim 5, wherein the steps (1) and (2) are carried out in an inert gas atmosphere.
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| CN102786621A (en) * | 2012-07-19 | 2012-11-21 | 大连理工大学 | Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method |
| CN109134765A (en) * | 2017-06-28 | 2019-01-04 | 北京化工大学 | A kind of polyisobutene and the graft copolymer of polyisoprene and preparation method thereof |
| US20190292290A1 (en) * | 2016-03-18 | 2019-09-26 | Zhejiang Zhongli Synthetic Material Technology Co., Ltd. | Functional Polymer of Styrene Derivative and Anionic Polymerization Preparation Method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102786621A (en) * | 2012-07-19 | 2012-11-21 | 大连理工大学 | Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method |
| US20190292290A1 (en) * | 2016-03-18 | 2019-09-26 | Zhejiang Zhongli Synthetic Material Technology Co., Ltd. | Functional Polymer of Styrene Derivative and Anionic Polymerization Preparation Method thereof |
| CN109134765A (en) * | 2017-06-28 | 2019-01-04 | 北京化工大学 | A kind of polyisobutene and the graft copolymer of polyisoprene and preparation method thereof |
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