CN114478949B - Preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber - Google Patents
Preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber Download PDFInfo
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- CN114478949B CN114478949B CN202011264517.3A CN202011264517A CN114478949B CN 114478949 B CN114478949 B CN 114478949B CN 202011264517 A CN202011264517 A CN 202011264517A CN 114478949 B CN114478949 B CN 114478949B
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- 238000009826 distribution Methods 0.000 title claims abstract description 94
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 133
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 132
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 93
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002667 nucleating agent Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 49
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 48
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000013329 compounding Methods 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 84
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 56
- 238000010438 heat treatment Methods 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 42
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 36
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 29
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
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- 239000002904 solvent Substances 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 14
- -1 methyl butyllithium Chemical compound 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
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- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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
- 229910052799 carbon Inorganic materials 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
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical group ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims description 3
- 229940050176 methyl chloride Drugs 0.000 claims description 3
- 239000012046 mixed solvent 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
- 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
- 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
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- FLFGMNFGOKXUQY-UHFFFAOYSA-L dichloro(propan-2-yl)alumane Chemical compound [Cl-].[Cl-].CC(C)[Al+2] FLFGMNFGOKXUQY-UHFFFAOYSA-L 0.000 claims description 2
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000011261 inert gas 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
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 claims description 2
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
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- 239000008096 xylene Substances 0.000 claims description 2
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims 1
- 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
- WXRBQHOKNRLOQI-UHFFFAOYSA-N dichloromethylaluminum Chemical compound [Al]C(Cl)Cl WXRBQHOKNRLOQI-UHFFFAOYSA-N 0.000 claims 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims 1
- UUXZFMKOCRKVDG-UHFFFAOYSA-N methane;hydrofluoride Chemical compound C.F UUXZFMKOCRKVDG-UHFFFAOYSA-N 0.000 claims 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 abstract description 41
- 230000008569 process Effects 0.000 abstract description 13
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
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- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention firstly adopts an anionic polymerization method, takes isoprene, styrene, butadiene and Divinylbenzene (DVB) as reaction monomers, utilizes variable temperature polymerization, is coupled by a trihalogenated benzene coupling agent, and then utilizes divinylbenzene and a catalyst to polymerize a quaternary three-arm star-shaped nucleating agent with wide distribution ([ -PS- (DVB) BR- (DVB) IR ]] n Ph), and finally, using isobutene and isoprene as reaction monomers and a wide-distribution quaternary three-arm star-shaped nucleating agent to prepare the wide-distribution three-arm comb-shaped star-shaped branched butyl rubber through cationic polymerization by a first-arm and then-core method under a catalytic system of Lewis acid and protonic acid compounding. The butyl rubber has the characteristics of quick stress relaxation and good viscoelasticity on the premise of ensuring strength and air tightness, realizes the balance between the processability and the physical properties of the butyl rubber, and ensures that the butyl rubberThe performance is more comprehensively improved. 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 wide-distribution three-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing wide-distribution three-arm comb-shaped star-branched butyl rubber by using an isoprene/butadiene/styrene/Divinylbenzene (DVB) quaternary three-arm nucleating agent.
Background
Butyl Rubber (IIR) is known to be copolymerized from isobutylene and a small amount of isoprene by cationic polymerization. Butyl rubber has been industrialized by Exxon corporation in the united states in the 40 th century for over seventy years, and has been widely used in the fields of inner tubes, inner liners, curing bladder, medical plugs, etc. for manufacturing tires for vehicles because of its excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance, etc.
However, the molecular chain of butyl rubber mainly consists of single bonds of carbon and carbon, the number of double bonds is small, substituent methyl groups are symmetrically arranged, and the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesion, poor compatibility with other general rubber and the like exist, so that the butyl rubber is easy to excessively flow and deform in the processing process. How to achieve a balance of physical and mechanical properties and processability of butyl rubber has become a bottleneck in the preparation of high performance butyl rubber materials.
In recent years, researchers have found that star-branched butyl rubber with a unique three-dimensional network structure, which consists of a high molecular weight grafted structure and a low molecular weight linear structure, has excellent viscoelastic properties, high green strength and fast stress relaxation rate, can keep low melt viscosity in the processing process, can obtain a high molecular weight polymer, and realizes uniform balance of physical and mechanical properties and processing properties. The star-branched structure has therefore become one of the hot spots in the future butyl rubber research field.
In the prior art, the synthesis of star-branched butyl rubber is mainly prepared by adopting a method of a first-nucleus and then-arm method, a first-arm and then-nucleus method and a nucleus-arm simultaneous method. Such as: US5395885 discloses a star-branched polymer, which is synthesized by a method of first-arm-then-core method at-90 to-100 ℃ by taking polyisobutylene as an arm, polydivinylbenzene (PDVB) as a core, a complex of alkyl aluminum chloride and water as an initiator, and chloromethane as a diluent. CN88108392.57 discloses a star-shaped graft butyl rubber with comb structure prepared by using a hydrochloride polystyrene-isoprene copolymer as a polyfunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN101353403B discloses a method for preparing star-branched polyisobutylene or butyl rubber, which uses a polystyrene/isoprene block copolymer with a silicon-chlorine group at the end or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the end as a grafting agent for initiating cationic polymerization, and takes part in the cationic polymerization directly in a cationic polymerization system of a mixed solvent with a chloromethane/cyclohexane v ratio of 20-80/80-20 at the temperature of 0-100 ℃ to initiate cationic polymerization by the silicon-chlorine group, and takes part in grafting reaction by an unsaturated chain to prepare the star-branched polyisobutylene or butyl rubber product. CN01817708.5 provides a method of adding a multiolefin crosslinking agent such as divinylbenzene and a chain transfer agent (such as 2,4, 1-trimethyl-1-pentene) to a mixture of isoolefin monomers and diolefins, preparing star-branched by the multiolefin crosslinking agent A polymer. CN107793535 a provides a butyl rubber having a molecular weight of 90 to 260 tens of thousands, log (MW)>6 and contains structural units derived from isobutylene, structural units derived from conjugated dienes, and optionally structural units derived from aryl olefins. CN200710129810.7 provides a first arm and then core method to synthesize linear butyl rubber, and then coupling with divinylbenzene to obtain star branched butyl rubber. Puskas et al synthesized an initiator triscumyl alcohol with a three-arm structure from trimesic acid, and then initiated isobutylene and isoprene copolymerization in an inert organic solvent at-120-50deg.C by a triscumyl alcohol/aluminum trichloride initiation system to synthesize a star-branched butyl rubber with bimodal molecular weight distribution (Catalysts for manufacture of IIR with bimodal molecular weight distribution:US,5194538[ P ]].1993-3-16.). Wieland et al synthesized a macroinitiator P (MMA-b-St-co-CMS) containing a ternary of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-stilbene (DPE) by free radical polymerization, and initiated cationic polymerization of isobutylene and isoprene with the macroinitiator to successfully prepare a multi-arm star butyl rubber (Synthesis of new graft copolymers containing polyisobutylene by acombination of the 1,1-diphenylethylene techniqueand cationic polymerization [ J) ]Polymer Science: polymer Chemistry,2002, 40: 3725-3733.). Hadjichristididis et al uses CH 3 SiCl 3 PI-PS-PBd three-arm copolymer (Iatrou H, hadjichristidis N.Synthesis of a model 3-miktoarm star terpolymer [ J ] was synthesized by three-step coupling with strict control of the order of addition of the monomers and the degree of excess of the coupling agent]Macromolecules,1992, 25:4649). Hadjchristids react with the silicon-chlorine group of p-chlorodimethylsilyl styrene by high vacuum technique to obtain styrene-based polybutadiene macromonomer, which is then copolymerized with butadiene in the presence of random regulator to obtain active Comb-shaped polybutadiene, and finally react with methyl silicon trichloride or silicon tetrachloride to obtain 3-arm or 4-arm Star-shaped Comb-shaped polybutadiene (KORTALAS G, IATROU H, LOHSE D J, et al well-Defined Comb, star-Comb, and Comb-on-Co)mb Polybutadienes by Anionic Polymerization and the MacromonomerStrategy[J]Macromolecules,2005,38 (12): 4996-5001). Huiqin A star-branched polymer with divinylbenzene as a core and polyisobutylene as an arm was synthesized by living cationic polymerization at-80℃using 2-chloro-2, 4-trimethylpentane/titanium tetrachloride as an initiator system and methane chloride/cyclohexane as a solvent ("preparation and characterization of star-branched polyisobutylene with divinylbenzene as a core", "synthetic rubber industry", synthetic rubber industry, 2008, 31 (5): 362-365 ").
Disclosure of Invention
The invention aims to provide a preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber. The invention firstly takes alkyl lithium as an initiator and hydrocarbon as a solvent, the reaction monomer is composed of isoprene, 1, 3-butadiene and styrene, and a temperature-variable polymerization method is adopted to synthesize the wide distribution [ -IR-BR-PS ]]n linear chain segment, and then adding coupling agent trihalogenated benzene to make coupling reaction so as to obtain the broad-distribution star-shaped copolymer [ -PS-BR-IR [ -BR-IR ]]n Ph, then sequentially adding solvent, divinylbenzene (DVB) and catalyst to polymerize wide-distribution quaternary three-arm star-shaped nucleating agent ([ -PS- (DVB) BR- (DVB) IR ]] n Ph), and finally, under a catalytic system compounded by Lewis acid and protonic acid, using isobutene and isoprene as reaction monomers and a wide-distribution three-arm star-shaped nucleating agent, and adopting a first-arm and then-core method to carry out cationic polymerization to prepare the wide-distribution three-arm comb-shaped star-shaped branched butyl rubber. The wide-distribution three-arm comb-shaped star-branched butyl rubber has the characteristics of high stress relaxation rate and small extrusion swelling effect, has enough green rubber strength and good air tightness, and realizes balance of physical and mechanical properties and processability of the butyl rubber.
The "%" of the invention refers to mass percent.
The preparation of the wide-distribution three-arm comb-shaped star-branched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) Wide distribution quaternary three-arm star-shaped nucleating agent: based on the total mass of the reaction monomers, firstly, the reaction mixture is arranged on a beltIn a jacketed 15L stainless steel reaction kettle, argon is introduced to replace for 2-4 times, 300-400 percent of solvent, 40-50 percent of 1, 3-butadiene, 0.05-0.5 percent of structure regulator and initiator are sequentially added into the polymerization kettle, the reaction is temperature-variable polymerization, the temperature is gradually increased from 40 ℃ to 65 ℃ within 40-60 min, and the temperature rising speed is increased<1.2 ℃/min to form a wide-distribution BR chain segment, wherein the conversion rate of the 1, 3-butadiene monomer reaches 100%; then adding 30-40% of isoprene and 0.05-0.5% of structure regulator into the polymerization kettle in turn, and reacting to obtain variable-temperature polymerization, in 30-50 min, gradually raising the temperature from 65 ℃ to 75 ℃ and raising the temperature speed<2.0 ℃/min to form a wide-distribution IR chain segment, wherein the conversion rate of isoprene monomer reaches 100%; sequentially adding 10% -20% of styrene and 0.05% -0.1% of structure regulator into a polymerization kettle, heating to 75-80 ℃ and reacting for 30-50 min to form widely distributed-IR-BR-PS-chain segments, wherein the conversion rate of styrene monomer reaches 100%; finally, heating to 80-90 ℃, adding a coupling agent for coupling reaction for 70-90 min, sequentially adding 100-200% of solvent, 3-7% of Divinylbenzene (DVB) and 0.001-0.1% of catalyst into a polymerization kettle after the reaction is completed, heating to 75-85 ℃, reacting for 30-50 min, and performing wet condensation and drying on the glue solution after the reaction is completed to obtain the nucleating agent ([ -PS- (DVB) BR- (DVB) IR) with a wide distribution and three-arm star-shaped structure ] n Ph)。
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3-5 times to replace the reaction monomer in total mass parts, and sequentially adding 200% -300% of diluent/solvent V into the polymerization kettle: mixing 94-98% of isobutene and 2-6% of isoprene in a V ratio of 60-40/40-60 mixed solvent, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, then mixing and aging 40-60% of diluent and 0.05-3.0% of co-initiator for 30-40 min at minus 95-minus 85 ℃, adding the mixture into the polymerization system together for stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 40-70% of solvent and 1.0-3.0% of nucleating agent with a three-arm star-shaped structure obtained in the step (1) for 3.0-5.0 hr, aging at minus 95-minus 85 ℃ for 3.0-5.0 hr, adding a terminator together for discharging and agglomerating, washing and drying to obtain the wide-distribution three-arm star-shaped branched butyl rubber product.
The nucleating agent of the invention is a quaternary three-arm star polymer ([ -PS- (DVB) BR- (DVB) IR ] ] n Ph) with a structural general formula shown in formula I:
wherein IR is an isoprene homopolymer block, the 1, 2-structure content of the block is 13-18%, and the 3, 4-structure content of the block is 7-11%; BR is a 1, 3-butadiene homopolymer block, the 1, 2-structure content of which is 15-20% and the 3, 4-structure content of which is 5-10%; PS is a styrene homopolymer block; the content of polyisoprene block (IR) in the quaternary three-arm star polymer is 30-40%, the content of polybutadiene Block (BR) is 40-50%, and the content of polystyrene block (PS) is 10-20%; the quaternary three-arm star polymer has a number average molecular weight (Mn) of 30000-50000 and a molecular weight distribution (Mw/Mn) of 5.15-6.71.
The coupling agent is one of 1,3, 5-benzene trichloride and 1,3, 5-benzene tribromide, preferably 1,3, 5-benzene trichloride. The amount of the coupling agent is determined by the amount of the initiator, and the molar ratio of the coupling agent to the organic lithium is 1.0-3.0.
The initiator is a hydrocarbyl mono-lithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or composite group of the above groups containing 1-20 carbon atoms. The hydrocarbyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, dodecyllithium, preferably n-butyllithium.
The catalyst is an organic peroxide selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, preferably dibenzoyl peroxide (BPO).
The structure regulator is a polar organic compound which generates solvation effect in a polymerization system, and can regulate the reactivity ratio of styrene and butadiene to enable the styrene and the butadiene to be 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 co-initiator is formed by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from diethyl aluminum chloride, diisobutyl aluminum chloride, methyl aluminum dichloride, aluminum sesquioxide, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride, preferably aluminum sesquioxide. The protonic acid is selected from HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCI. Wherein the total addition amount of the co-initiator is 0.03-2.5%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01:1-0.2:1.
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 being C 1 ～C 4 . The haloalkane is selected from one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably chloromethane.
The terminator can be selected from one or more of methanol, ethanol and butanol.
The polymerization reactions of the present invention are all carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution processes are both carried out in a hydrocarbon solvent, which is a hydrocarbon solvent, including straight chain alkanes, aromatic hydrocarbons and cycloalkanes, selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention adopts an anionic polymerization method, takes isoprene, styrene, butadiene and Divinylbenzene (DVB) as reaction monomers, utilizes variable temperature polymerization, and couples a wide-distribution star-shaped copolymer [ -PS-BR-IR [ -BR-IR ] ]nPh; then polymerizing a wide distribution of quaternary three-arm star-shaped nucleating agent ([ -PS- (DVB) BR- (DVB) IR ]] n Ph), and finally preparing the wide-distribution three-arm comb-shaped star-shaped branched butyl rubber by adopting a first-arm and then-core method and taking isobutene and isoprene as reaction monomers and a wide-distribution quaternary three-arm star-shaped nucleating agent for cationic polymerization under a catalytic system of Lewis acid and protonic acid.
The nucleating agent designed by the invention is [ -PS- (DVB) BR- (DVB) IR ]] n The Ph contains a three-arm comb star-shaped structure, the structure can properly widen the molecular weight distribution of the whole butyl rubber macromolecule on the premise of not damaging the molecular chain regularity of the single isobutene and isoprene copolymer, meanwhile, the-IR-and-BR-chain segments in the nucleating agent adopt temperature-changing polymerization to lead to the distribution of a certain amount of wide vinyl groups, the two aspects can obviously improve the flexibility of the butyl rubber macromolecule chain segments, so that the butyl rubber can obtain good viscoelastic property, has a faster stress relaxation rate and small extrusion swelling effect, and improves the processing performance of the butyl rubber; in addition, the-PS-chain segment in the nucleating agent contains a large amount of benzene rings, so that the strength and air tightness are prevented from being reduced due to the improvement of the flexibility of the macromolecular chain segment of the butyl rubber, and the high strength and good air tightness of the butyl rubber are ensured. Therefore, the invention organically combines the characteristics of the three-arm comb-shaped star structure with the characteristics of wide distribution and rigidity of various chain segments and cooperatively plays roles, and the 'cooperative effect' solves the problems of slow stress relaxation and poor viscoelasticity of the butyl rubber in the processing process, solves the problems of strength and air tightness reduction caused by the widening of the molecular weight distribution of the butyl rubber, realizes the balance of the processability and the physical properties of the butyl rubber, and ensures that the performance of the butyl rubber is more comprehensively improved.
Drawings
FIG. 1 is 1 # Comparative examples 1 samples and 2 # Comparison of GPC spectra of the samples of example 1.
Detailed Description
The following examples and comparative examples are given to illustrate the inventive effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial polymer grade, and are used after purification without other special requirements.
Raw material sources:
styrene, butadiene, polymer grade China petrochemical Co
Isobutene, isoprene, polymeric grade Zhejiang Xinhui New Material Co., ltd
Divinylbenzene (DVB), analytically pure Albumin Co., ltd
N-butyllithium with purity of 98% Nanjing Tonglian chemical Co., ltd
Dibenzoyl peroxide (BPO), a lanzhou auxiliary plant
1,3, 5-Trichlorobenzene purity 99% of Yangzhou sea chemical Co., ltd
1,3, 5-tribrominated benzene purity 99% of the Chemicals Limited in sea Chemicals of Yangzhou
Sesquiethyl aluminum chloride with purity of 98% of carbofuran technology Co., ltd
Other reagents are commercial industrial products
The analysis and test method comprises the following steps:
determination of molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min -1 。
Measurement of stress relaxation: the measurement was carried out by using a GT-7080-S2 Mooney viscometer manufactured by Taiwan high-speed rail company.
The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.
Determination of die swell ratio: RH2000 capillary rheometer manufactured by British Markov company
The temperature is 100 ℃, the length-diameter ratio is 16:1, and the shear rate is 10-1000S -1 Is measured in the interval of (2).
Measurement of air tightness: an automatic air tightness tester is adopted to measure the air permeability number according to ISO 2782:1995,
the test gas is N 2 The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.
Tensile strength: the method in standard GB/T528-2009 is performed.
Example 1
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3000g of cyclohexane, 400g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle, heating to 40 ℃, adding 19.1 mmol of n-butyllithium, starting to react, gradually heating from 40 ℃ to 65 ℃ within 40min, and heating at a speed of 0.7 ℃/min to form a wide-distribution BR chain segment; then 300g of isoprene and 0.6g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 30min, the temperature is gradually increased from 65 ℃ to 75 ℃, the heating speed is 0.4 ℃/min, and a wide-distribution IR chain segment is formed; then adding 100g of styrene and 0.4g of THF into the polymerization kettle in sequence, heating to 75 ℃, and reacting for 30min to form a wide-distribution-IR-BR-PS-chain segment; then, when the temperature is raised to 80 ℃, 10.1 mmol of 11,3, 5-trichlorobenzene is added to react for 70min to form [ -PS-BR-IR ] ] n Ph; after the reaction is completed, 1000g cyclohexane, 30g DVB and 0.05g BPO are sequentially added into a polymerization kettle, when the temperature is raised to 75 ℃, the reaction is started, after the reaction is carried out for 30min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ -PS- (DVB) BR- (DVB) IR [ -A ] with wide distribution and three-arm star-shaped structure is prepared] n Ph (Mn 31000, mw/Mn 5.15).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times, and sequentially adding chloromethane 2 into the polymerization kettle50g of cyclohexane 370g,265g of isobutene and 8g of isoprene are stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 120g of methyl chloride, 2.0g of aluminum sesquichloride and 0.06g of HCl are mixed at minus 85 ℃ and then aged for 30min, and then added into the polymerization system together and stirred and reacted for 0.5hr, then 120g of cyclohexane and 3.5g of [ -PS- (DVB) BR- (DVB) IR [ -17 ]] n Ph is stirred and dissolved for 2.0hr until the grafting agent is completely dissolved, then aged for 30min at the temperature of minus 85 ℃, then added into a polymerization system for stirring and reacting for 3.0hr, then 130mL of methanol is added for terminating the reaction, finally discharging is carried out for coagulation, washing and drying are carried out, and the three-arm comb-shaped star-branched butyl rubber product is obtained. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 2
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, argon is introduced for replacement for 3 times, 3200g of cyclohexane, 410g of 1, 3-butadiene and 1.2g of THF are sequentially added into the polymerization kettle, the temperature is raised to 40 ℃, 20.5 mmol 1 of n-butyllithium is added for starting the reaction, the reaction is carried out within 45min, the temperature is gradually raised to 65 ℃ from 40 ℃, the temperature raising speed is 0.6 ℃/min, and a BR chain segment with wide distribution is formed; then 320g of isoprene and 0.9g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 35min, the temperature is gradually increased from 65 ℃ to 75 ℃, the heating speed is 0.3 ℃/min, and a wide-distribution IR chain segment is formed; then sequentially adding 110g of styrene and 0.6g of THF into a polymerization kettle, heating to 76 ℃, and reacting for 34min to form a wide-distribution-IR-BR-PS-chain segment; then when the temperature is raised to 82 ℃, 12.5 mmol of 11,3, 5-trichlorobenzene is added to react for 73min to form [ -PS-BR-IR ]] n Ph; after the reaction is completed, sequentially adding 1100g cyclohexane, 35g DVB and 0.19g BPO to the polymerization kettle when the temperature is raised to 77 ℃ to start the reaction, after the reaction is carried out for 35min, the glue solution is subjected to wet condensation and drying to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR [ -A ] with wide distribution and three-arm star-shaped structure ] n Ph (Mn 38000, mw/Mn 5.48).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 280g of chloromethane, 320g of cyclohexane and 268g of iso-methyl chloride into the polymerization kettle in sequenceButene, 12g of isoprene, stirring and mixing until the temperature of the polymerization system is reduced to-92 ℃, then mixing 130g of chloromethane, 2.9g of sesquiethylaluminum chloride and 0.09g of HCl at-85 ℃ and aging for 32min, adding the mixture into the polymerization system together and stirring and reacting for 0.6hr, then adding 140g of cyclohexane and 4.2g of [ -PS- (DVB) BR- (DVB) IR [ -A [ -B) R ]] n Ph is stirred and dissolved for 2.5 hours until the grafting agent is completely dissolved, then aged for 35 minutes at the temperature of minus 85 ℃, then added into a polymerization system for stirring and reacting for 3.3 hours, then 150mL of methanol is added for terminating the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 3
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3300g of cyclohexane, 430g of 1, 3-butadiene and 1.4g of THF into the polymerization kettle, heating to 40 ℃, adding 21.6mmo1 of n-butyllithium, starting to react, and gradually heating from 40 ℃ to 65 ℃ within 50min at a heating rate of 0.5 ℃/min to form a wide-distribution BR chain segment; then 340g of isoprene and 1.1g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 40min, the temperature is gradually increased from 65 ℃ to 75 ℃, the heating speed is 0.3 ℃/min, and a wide-distribution IR chain segment is formed; then sequentially adding 130g of styrene and 0.9g of THF into a polymerization kettle, heating to 77 ℃, and reacting for 38min to form a wide-distribution-IR-BR-PS-chain segment; then, when the temperature is raised to 84 ℃, 14.1 mmol of 11,3, 5-trichlorobenzene is added to react for 78min to form [ -PS-BR-IR ] ] n Ph; after the reaction is completed, 1300g cyclohexane and 39g DVB are sequentially added into a polymerization kettle, 0.21g BPO is added when the temperature is raised to 78 ℃ to start the reaction, after 39min of the reaction, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ -PS- (DVB) BR- (DVB) IR [ -A ] with wide distribution and three-arm star-shaped structure is prepared] n Ph (Mn 41000, mw/Mn 5.93).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 330g of chloromethane, 310g of cyclohexane, 273g of isobutene and 17g of isoprene are added into the polymerization kettle in sequence,stirring and mixing until the temperature of the polymerization system is reduced to-93 ℃, then mixing 140g of methyl chloride, 3.7g of aluminum sesquichloride and 0.11g of HCl at-87 ℃ and aging for 33min, adding 160g of cyclohexane and 5.3g of [ -PS- (DVB) BR- (DVB) IR [ -7 ] to the polymerization system together and stirring for reaction for 0.7hr] n Ph is stirred and dissolved for 2.8 hours until the grafting agent is completely dissolved, then aged for 40 minutes at the temperature of minus 87 ℃, then added into a polymerization system for stirring and reacting for 3.7 hours, then 180mL of methanol is added for terminating the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 4
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3600g of cyclohexane, 450g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle, heating to 40 ℃, adding 23.1 mmol of n-butyllithium, starting the reaction, and gradually heating from 40 ℃ to 65 ℃ within 50min at a heating rate of 0.5 ℃/min to form a wide-distribution BR chain segment; then sequentially adding 360g of isoprene and 1.3g of THF into a polymerization kettle, gradually increasing the temperature from 65 ℃ to 75 ℃ within 40min, and forming a wide-distribution IR chain segment at a heating rate of 0.3 ℃/min; then sequentially adding 150g of styrene and 1.0g of THF into a polymerization kettle, heating to 78 ℃, and reacting for 41min to form a wide-distribution-IR-BR-PS-chain segment; then when the temperature is raised to 85 ℃, 16.2 mmol of 11,3, 5-trichlorobenzene is added for reaction for 82min to form [ -PS-BR-IR ]] n Ph; after the reaction is completed, 1400g cyclohexane and 43g DVB are sequentially added into a polymerization kettle, 0.32g BPO is added when the temperature is raised to 80 ℃ to start the reaction, after 41min of the reaction, the glue solution is subjected to wet condensation and drying to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR [ -PS- (DVB) IR [ -IR ] ] n Ph (Mn 43000, mw/Mn 6.13).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced for replacement for 4 times, 340g of chloromethane, 300g of cyclohexane, 278g of isobutene and 21g of isoprene are added into the polymerization kettle in sequence, and stirred and mixed to a polymerization systemWhen the temperature is reduced to-95 ℃, 150g of methyl chloride, 4.1g of aluminum sesquichloride and 0.15g of HCl are mixed at-90 ℃ and then aged for 35min, and then added into a polymerization system together to be stirred and reacted for 0.8hr, and then 180g of cyclohexane and 6.2g of [ -PS- (DVB) BR- (DVB) IR [ -A ]] n Ph is stirred and dissolved for 3.2 hours until the grafting agent is completely dissolved, then aged for 42 minutes at the temperature of minus 90 ℃, then added into a polymerization system for stirring and reacting for 4.0 hours, then 200mL of methanol is added for terminating the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 5
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 3800g of cyclohexane, 470g of 1, 3-butadiene and 2.6g of THF into the polymerization kettle, heating to 40 ℃, adding 25.1 mmol of n-butyllithium, starting to react, and gradually heating from 40 ℃ to 65 ℃ within 55min at a heating rate of 0.45 ℃/min to form a wide-distribution BR chain segment; then adding 380g of isoprene and 1.7g of THF into the polymerization kettle in sequence, gradually increasing the temperature from 65 ℃ to 75 ℃ within 40min, and forming a wide-distribution IR chain segment at a heating rate of 0.3 ℃/min; then 170g of styrene and 1.2g of THF are sequentially added into the polymerization kettle, the temperature is raised to 78 ℃, and after the reaction is carried out for 45min, a wide-distribution-IR-BR-PS-chain segment is formed; then when the temperature is raised to 87 ℃, 18.1 mmol of 11,3, 5-trichlorobenzene is added to react for 85min to form [ -PS-BR-IR ] ] n Ph; after the reaction is completed, 1600g cyclohexane and 50g DVB are sequentially added into a polymerization kettle, 0.56g BPO is added when the temperature is raised to 82 ℃ to start the reaction, after 45min of the reaction, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ -PS- (DVB) BR- (DVB) IR [ -A ] with wide distribution and three-arm star-shaped structure is prepared] n Ph (Mn 45000, mw/Mn 6.35).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of chloromethane, 290g of cyclohexane, 282g of isobutene and 27g of isoprene are added into the polymerization kettle in sequence, and stirred and mixed until the temperature of a polymerization system is reduced to minus 96 DEG C160g of methyl chloride, 4.9g of sesquiethyl aluminum chloride and 0.21g of HCl are mixed at the temperature of minus 90 ℃ and then aged for 37 minutes, and then added into a polymerization system together to be stirred and reacted for 0.9 hour, and then 190g of cyclohexane and 7.5g of [ -PS- (DVB) BR- (DVB) IR [ -] n Ph is stirred and dissolved for 3.5 hours until the grafting agent is completely dissolved, then aged for 45 minutes at the temperature of minus 91 ℃, then added into a polymerization system for stirring and reacting for 4.3 hours, then 220mL of methanol is added for stopping the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 6
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 3900g of cyclohexane, 480g of 1, 3-butadiene and 3.1g of THF into the polymerization kettle, heating to 40 ℃, adding 27.1 mmol of n-butyllithium, starting to react, and gradually heating from 40 ℃ to 65 ℃ within 60 minutes at a heating rate of 0.42 ℃/min to form a wide-distribution BR chain segment; then 390g of isoprene and 2.1g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 50min, the temperature is gradually increased from 65 ℃ to 75 ℃, the heating speed is 0.2 ℃/min, and a wide-distribution IR chain segment is formed; then adding 190g of styrene and 1.8g of THF into a polymerization kettle in turn, heating to 80 ℃, and reacting for 47min to form a wide-distribution-IR-BR-PS-chain segment; then, when the temperature is raised to 89 ℃, 19.5 mmol of 11,3, 5-tribromide benzene is added for reaction for 88min to form [ -PS-BR-IR ]] n Ph; after the reaction is completed, 1800g of cyclohexane, 60g of DVB and 0.63g of BPO are sequentially added into a polymerization kettle to start the reaction when the temperature is raised to 85 ℃, after 47min of the reaction, the glue solution is subjected to wet condensation and drying to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR [ -A ] with wide distribution and three-arm star-shaped structure ] n Ph (Mn 47000, mw/Mn 6.52).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 5 times for replacement, sequentially adding 360g of methyl chloride, 280g of cyclohexane, 284 g of isobutene and 30g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to minus 98 ℃, then 170g of methyl chloride,5.3g of aluminum sesquichloride and 0.35g of HCl are mixed at-93 ℃ and aged for 39min, and then added into a polymerization system together to be stirred and reacted for 0.9hr, 200g of cyclohexane and 8.4g of [ -PS- (DVB) BR- (DVB) IR [ -A [ -P- (B) R- ] are added into the polymerization system together] n Ph is stirred and dissolved for 3.8 hours until the grafting agent is completely dissolved, then aged for 47 minutes at the temperature of minus 95 ℃, then added into a polymerization system for stirring and reacting for 4.7 hours, then 260mL of methanol is added for terminating the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 7
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 4000g of cyclohexane, 500g of 1, 3-butadiene and 3.8g of THF into the polymerization kettle, heating to 40 ℃, adding 28.5mm & lt 1 & gt n-butyllithium for starting reaction, gradually heating from 40 ℃ to 65 ℃ within 60 minutes, and heating at a speed of 0.42 ℃/min to form a wide-distribution BR chain segment; then sequentially adding 400g of isoprene and 2.9g of THF into a polymerization kettle, gradually increasing the temperature from 65 ℃ to 75 ℃ within 50min, and forming a wide-distribution IR chain segment at a heating rate of 0.2 ℃/min; then adding 200g of styrene and 2.1g of THF into the polymerization kettle in turn, heating to 80 ℃, and reacting for 50min to form a wide-distribution-IR-BR-PS-chain segment; then 22.5 mmol of 11,3, 5-tribrominated benzene is added when the temperature is raised to 90 ℃, and the reaction is carried out for 90min, thus forming [ -PS-BR-IR ] ] n Ph; after the reaction is completed, 2000g cyclohexane, 70g DVB and 0.65g BPO are sequentially added into a polymerization kettle, when the temperature is raised to 85 ℃, the reaction is started, after 50min of the reaction, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ -PS- (DVB) BR- (DVB) IR [ -PS- (DVB) IR ]] n Ph (Mn 49000, mw/Mn 6.71).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 360g of methyl chloride, 260g of cyclohexane, 288g of isobutene and 35g of isoprene are sequentially added into the polymerization kettle, and then 180g of methyl chloride and 6.5 g of sesquiethyl aluminum chloride are stirred and mixed until the temperature of a polymerization system is reduced to minus 100 DEG CMixing with HCl 0.41g at-95deg.C, aging for 40min, adding into polymerization system together, stirring for 1.0hr, adding cyclohexane 200g, and mixing with [ -PS- (DVB) BR- (DVB) IR [ -PS- (DVB) IR ]] n Ph is stirred and dissolved for 4.0hr until the grafting agent is completely dissolved, then aged for 50min at the temperature of minus 95 ℃, then added into a polymerization system for stirring and reacting for 5.0hr, then 300mL of methanol is added for terminating the reaction, finally discharging is carried out for coagulation, washing and drying are carried out, and the three-arm comb-shaped star-branched butyl rubber product is obtained. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 1
Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 1 except that: during the synthesis process, no nucleating agent [ -PS- (DVB) BR- (DVB) IR ]] n Ph, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 250g of methyl chloride, 370g of cyclohexane, 265g of isobutene and 8g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 120g of methyl chloride, 2.0g of aluminum sesquichloride and 0.06g of HCl are mixed at minus 85 ℃ and aged for 30 minutes, then added into the polymerization system together to be stirred and reacted for 0.5 hour, 130mL of methanol is added to terminate the reaction, finally, the mixture is discharged and condensed, washed and dried, and the three-arm comb-shaped star-branched butyl rubber product is obtained. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: other conditions were the same as in example 2 except that: 1,3, 5-trichlorobenzene is not added as a coupling agent, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, argon is introduced for replacement for 3 times, 3200g of cyclohexane, 410g of 1, 3-butadiene and 1.2g of THF are sequentially added into the polymerization kettle, the temperature is raised to 40 ℃, 20.5 mmol 1 of n-butyllithium is added for starting the reaction, the reaction is carried out within 45min, the temperature is gradually raised to 65 ℃ from 40 ℃, the temperature raising speed is 0.6 ℃/min, and a BR chain segment with wide distribution is formed; then 320g of isoprene and 0.9g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 35min, the temperature is gradually increased from 65 ℃ to 75 ℃, the heating speed is 0.3 ℃/min, and a wide-distribution IR chain segment is formed; subsequently Then 110g of styrene and 0.6g of THF are sequentially added into the polymerization kettle, the temperature is raised to 76 ℃, and after the reaction is carried out for 34min, a wide-distribution-IR-BR-PS-chain segment is formed; after the reaction is completed, sequentially adding 1100g cyclohexane, 35g DVB and 0.19g BPO to the polymerization kettle when the temperature is raised to 77 ℃ to start the reaction, after the reaction is carried out for 35min, the glue solution is subjected to wet condensation and drying to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR [ -A ] with wide distribution and three-arm star-shaped structure] n (Mn 33000, mw/Mn 3.36).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 2 except that: during the synthesis process, no nucleating agent [ -PS- (DVB) BR- (DVB) IR ]] n Ph, but with the addition of nucleating agents [ -PS- (DVB) BR- (DVB) IR ]] n The method comprises the following steps: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 3 times, 280g of methyl chloride, 320g of cyclohexane, 268g of isobutene and 12g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 92 ℃, then 130g of methyl chloride, 2.9g of aluminum sesquichloride and 0.09g of HCl are mixed at minus 85 ℃ and aged for 32 minutes, then added into the polymerization system together and stirred and reacted for 0.6hr, and then 140g of cyclohexane and 4.2g of [ -PS- (DVB) BR- (DVB) IR [ -17 ] are added into the polymerization system ] n Stirring and dissolving for 2.5hr until the grafting agent is completely dissolved, aging at-85deg.C for 35min, adding into polymerization system, stirring and reacting for 3.3hr, adding 150mL methanol to terminate the reaction, discharging and coagulating, washing, and drying to obtain the final product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 3 except that: during the synthesis process, no nucleating agent [ -PS- (DVB) BR- (DVB) IR ]] n Ph, but rather the nucleating agent DVB, i.e.: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 330g of methyl chloride, 310g of cyclohexane, 273g of isobutene and 17g of isoprene are added into the polymerization kettle in sequence, and stirred and mixed until the temperature of a polymerization system is reduced to-93 ℃, then 140g of methyl chloride, 3.7g of aluminum sesquichloride and HCl are addedMixing 0.11g at-87 ℃ and aging for 33min, adding the mixture into a polymerization system together, stirring and reacting for 0.7hr, then dissolving 160g of cyclohexane and 5.3g of DVB with stirring for 2.8hr until the grafting agent is completely dissolved, aging for 40min at-87 ℃, adding the mixture into the polymerization system, stirring and reacting for 3.7hr, adding 180mL of methanol to terminate the reaction, discharging and condensing, washing, and drying to obtain the three-arm comb-star branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 4
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: other conditions were the same as in example 4 except that: 1, 3-butadiene does not adopt variable temperature polymerization, and reacts at the constant temperature of 40 ℃, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, argon is introduced for replacement for 4 times, 3600g of cyclohexane, 450g of 1, 3-butadiene and 1.9g of THF are sequentially added into the polymerization kettle, the temperature is raised to 40 ℃, 23.1 mmol 1 of n-butyllithium is added for starting the reaction, and after 50 minutes of reaction, BR is formed 1 A segment; then sequentially adding 360g of isoprene and 1.3g of THF into a polymerization kettle, gradually increasing the temperature from 65 ℃ to 75 ℃ within 40min, and forming a wide-distribution IR chain segment at a heating rate of 0.3 ℃/min; then sequentially adding 150g of styrene and 1.0g of THF into a polymerization kettle, heating to 78 ℃, and reacting for 41min to form a wide-distribution-IR-BR-PS-chain segment; then when the temperature is raised to 85 ℃, 16.2 mmol of 11,3, 5-trichlorobenzene is added for reaction for 82min to form [ -PS-BR 1 -IR-] n Ph; after the reaction is completed, 1400g cyclohexane, 43g DVB and 0.32g BPO are sequentially added into a polymerization kettle, when the temperature is raised to 80 ℃, the reaction is started, after 41min of the reaction, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ -PS- (DVB) BR with a wide distribution and three-arm star-shaped structure is prepared 1 -(DVB)IR-] n Ph (Mn 40000, mw/Mn 4.22).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 4 except that: during the synthesis process, no nucleating agent [ -PS- (DVB) BR- (DVB) IR ]] n Ph, but with the addition of nucleating agents [ -PS- (DVB) BR 1 -(DVB)IR-] n Ph, namely: first, the reaction was carried out in jacketed 4L stainless steelIntroducing nitrogen gas into a reactor for replacement for 4 times, sequentially adding 340g of chloromethane, 300g of cyclohexane, 278g of isobutene and 21g of isoprene into the polymerization reactor, stirring and mixing until the temperature of the polymerization system is reduced to minus 95 ℃, then mixing 150g of chloromethane, 4.1g of sesquiethylaluminum chloride and 0.15g of HCl at minus 90 ℃ and aging for 35min, adding the mixture into the polymerization system together for stirring and reacting for 0.8hr, and then adding 180g of cyclohexane and 6.2g of [ -PS- (DVB) BR 1 -(DVB)IR-] n Ph is stirred and dissolved for 3.2 hours until the grafting agent is completely dissolved, then aged for 42 minutes at the temperature of minus 90 ℃, then added into a polymerization system for stirring and reacting for 4.0 hours, then 200mL of methanol is added for terminating the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 5
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: other conditions were the same as in example 5 except that: isoprene does not adopt variable temperature polymerization, and reacts at a constant temperature of 65 ℃, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 3800g of cyclohexane, 470g of 1, 3-butadiene and 2.6g of THF into the polymerization kettle, heating to 40 ℃, adding 25.1 mmol of n-butyllithium, starting to react, and gradually heating from 40 ℃ to 65 ℃ within 55min at a heating rate of 0.45 ℃/min to form a wide-distribution BR chain segment; then 380g of isoprene, 1.7g of THF are added into the polymerization kettle in turn, the temperature is raised to 65 ℃, and after 40min of reaction, IR is formed 1 A segment; then 170g of styrene and 1.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 78 ℃, and the reaction is carried out for 45min, thus forming wide-distribution-IR 1 -BR-PS-segments; then heating to 87 ℃, adding 18.1 mmol of 11,3, 5-trichlorobenzene, reacting for 85min to form [ -PS-BR-IR 1 -] n Ph; after the reaction is completed, 1600g cyclohexane and 50g DVB are sequentially added into a polymerization kettle, 0.56g BPO is added when the temperature is raised to 82 ℃ to start the reaction, after 45min of the reaction, the glue solution is subjected to wet condensation and drying to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR with wide distribution and three-arm star-shaped structure 1 -] n Ph (Mn 43000, mw/Mn 4.87).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 5 except that: during the synthesis process, no nucleating agent [ -PS- (DVB) BR- (DVB) IR ]] n Ph, but with the addition of nucleating agents [ -PS- (DVB) BR- (DVB) IR 1 -] n Ph, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 350g of chloromethane, 290g of cyclohexane, 282g of isobutene and 27g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 96 ℃, then 160g of chloromethane, 4.9g of sesquiethylaluminum chloride and 0.21g of HCl are mixed at minus 90 ℃ and aged for 37 minutes, then added into the polymerization system together and stirred for reaction for 0.9hr, and then 190g of cyclohexane and 7.5g of [ -PS- (DVB) BR- (DVB) IR are added 1 -] n Ph is stirred and dissolved for 3.5 hours until the grafting agent is completely dissolved, then aged for 45 minutes at the temperature of minus 91 ℃, then added into a polymerization system for stirring and reacting for 4.3 hours, then 220mL of methanol is added for stopping the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 6
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: other conditions were the same as in example 6 except that: styrene is not added in the synthesis process, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 3900g of cyclohexane, 480g of 1, 3-butadiene and 3.1g of THF into the polymerization kettle, heating to 40 ℃, adding 27.1 mmol of n-butyllithium, starting to react, and gradually heating from 40 ℃ to 65 ℃ within 60 minutes at a heating rate of 0.42 ℃/min to form a wide-distribution BR chain segment; then 390g of isoprene and 2.1g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 50min, the temperature is gradually increased from 65 ℃ to 75 ℃, the heating speed is 0.2 ℃/min, and a wide-distribution-IR-BR-chain segment is formed; then, when the temperature is raised to 89 ℃, 19.5 mmol of 11,3, 5-tribrominated benzene is added for reaction for 88min to form [ -BR-IR ] ] n Ph; after the reaction is completed, 1800g of cyclohexane, 60g of DVB and 0.63g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 85 ℃ and 0.63g of BPO is added for starting the reaction, after the reaction is carried out for 47min, the glue solution is subjected to wet condensation and dryingDrying to obtain nucleating agent [ - (DVB) BR- (DVB) IR ]] n Ph (Mn 39000, mw/Mn 5.06).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 6 except that: during the synthesis process, no nucleating agent [ -PS- (DVB) BR- (DVB) IR ]] n Ph, but with the addition of nucleating agents [ - (DVB) BR- (DVB) IR 1 -] n Ph, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 360g of methyl chloride, 280g of cyclohexane, 284 g of isobutene and 30g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 98 ℃, then 170g of methyl chloride, 5.3g of aluminum sesquichloride and 0.35g of HCl are mixed at minus 93 ℃ and aged for 39 minutes, then added into the polymerization system together and stirred and reacted for 0.9hr, then 200g of cyclohexane and 8.4g of [ - (DVB) BR- (DVB) IR-form] n Ph is stirred and dissolved for 3.8 hours until the grafting agent is completely dissolved, then aged for 47 minutes at the temperature of minus 95 ℃, then added into a polymerization system for stirring and reacting for 4.7 hours, then 260mL of methanol is added for terminating the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 7
(1) Preparation of a wide-distribution three-arm star-shaped nucleating agent: other conditions were the same as in example 7 except that: in the variable temperature polymerization of 1, 3-butadiene, the temperature rising speed is 1.4 ℃/min, namely: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 4000g of cyclohexane, 500g of 1, 3-butadiene and 3.8g of THF into the polymerization kettle, heating to 40 ℃, adding 28.5mm of n-butyllithium, starting to react, gradually heating from 40 ℃ to 65 ℃ within 60 minutes, and heating at a speed of 1.4 ℃/min to form BR with wide distribution 2 A segment; then sequentially adding 400g of isoprene and 2.9g of THF into a polymerization kettle, gradually increasing the temperature from 65 ℃ to 75 ℃ within 50min, and forming a wide-distribution IR chain segment at a heating rate of 0.2 ℃/min; then 200g of styrene and 2.1g of THF are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, and the reaction is carried out for 50min, thus forming a wide rangedistributed-IR-BR-PS-segments; then 22.5 mmol of 11,3, 5-tribrominated benzene is added when the temperature is raised to 90 ℃, and the reaction is carried out for 90min to form [ -PS-BR 2 -IR-] n Ph; after the reaction is completed, 2000g cyclohexane, 70g DVB and 0.65g BPO are sequentially added into a polymerization kettle, when the temperature is raised to 85 ℃, the reaction is started, after 50min of the reaction, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ -PS- (DVB) BR with a wide distribution and three-arm star-shaped structure is prepared 2 -(DVB)IR-] n Ph (Mn 48000, mw/Mn 4.54).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 7 except that: during the synthesis process, no nucleating agent [ -PS- (DVB) BR- (DVB) IR ]] n Ph, but with the addition of nucleating agents [ - (DVB) BR 2 -(DVB)IR-] n Ph, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 360g of methyl chloride, 260g of cyclohexane, 288g of isobutene and 35g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 100 ℃, then 180g of methyl chloride, 6.5g of aluminum sesquichloride and 0.41g of HCl are mixed at minus 95 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred and reacted for 1.0hr, then 200g of cyclohexane and 9.0g of [ -PS- (DVB) BR are added 2 -(DVB)IR-] n Ph is stirred and dissolved for 4.0hr until the grafting agent is completely dissolved, then aged for 50min at the temperature of minus 95 ℃, then added into a polymerization system for stirring and reacting for 5.0hr, then 300mL of methanol is added for terminating the reaction, finally discharging is carried out for coagulation, washing and drying are carried out, and the three-arm comb-shaped star-branched butyl rubber product is obtained. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 Performance of widely distributed three-arm comb-like Star branched butyl rubber
As can be seen from table 1: the wide-distribution three-arm comb-shaped star-branched butyl rubber has high tensile strength, good air tightness, low Mooney relaxation area and good processability (the smaller the area under a stress relaxation curve is, the lower the energy consumption for mixing processing is).
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (18)
1. A preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber is characterized by comprising the following specific preparation steps:
(1) Preparation of a three-arm star-shaped nucleating agent: sequentially adding a solvent, 40-50% of 1, 3-butadiene, 0.05-0.5% of a structure regulator and an initiator into a polymerization kettle according to the total mass parts of reaction monomers, wherein the reaction is temperature-variable polymerization, the temperature is gradually increased from 40 ℃ to 65 ℃, and the heating speed is less than 1.2 ℃/min until the conversion rate of the 1, 3-butadiene monomers reaches 100%; then adding 30% -40% of isoprene and 0.05% -0.5% of structure regulator into a polymerization kettle in sequence, wherein the reaction is temperature-changing polymerization, the temperature is gradually increased from 65 ℃ to 75 ℃, and the heating speed is less than 2.0 ℃/min until the isoprene monomer conversion rate reaches 100%; sequentially adding 10-20% of styrene and 0.05-0.1% of structure regulator into a polymerization kettle, and heating to 75-80 ℃ until the conversion rate of the styrene monomer reaches 100%; finally, heating to 80-90 ℃, adding a coupling agent to react for 70-90 min, sequentially adding a solvent and 3-7% of divinylbenzene into a polymerization kettle after the reaction is completed, heating to 75-85 ℃ with 0.001-0.1% of catalyst, and performing wet condensation and drying on the glue solution after the reaction is completed to obtain the wide-distribution three-arm star-shaped nucleating agent;
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, adding a diluent/solvent volume ratio of 60-40/40-60 mixed solvent, 94-98% of isobutene and 2-6% of isoprene into a polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to minus 100-minus 90 ℃, mixing and aging for 30-40 min at minus 95-minus 85 ℃, adding the diluent and 0.05-3.0% of co-initiator into the polymerization kettle together, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving the solvent and 1.0-3.0% of the three-arm star-shaped nucleating agent obtained in the step (1) for 3.0-5.0 hr, aging at minus 95-minus 85 ℃, adding the three-arm star-shaped branched butyl rubber product into the polymerization kettle together, stirring and reacting for 3.0-5.0 hr, finally adding a terminator for discharging and agglomerating, washing and drying to obtain the wide-distribution three-arm comb-shaped branched butyl rubber product;
wherein, the steps (1) and (2) are carried out in an anaerobic and anhydrous environment;
the initiator is selected from one of n-butyllithium, sec-butyllithium, methyl butyllithium, phenyl butyllithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium;
the catalyst is an organic peroxide, and is selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide or di-tert-butyl peroxide;
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid, and the coupling agent is one of 1,3, 5-benzene trichloride and 1,3, 5-benzene tribromide.
2. The method of claim 1, wherein the molar ratio of the coupling agent to the initiator is from 1.0 to 3.0.
3. The method of claim 1, wherein the coupling agent is 1,3, 5-trichlorobenzene.
4. The method of claim 1, wherein the initiator is n-butyllithium.
5. The method of claim 1, wherein the catalyst is dibenzoyl peroxide.
6. The method of claim 1, wherein the structure modifier is selected from the group consisting of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
7. The method of claim 6, wherein the structure modifier is tetrahydrofuran.
8. The method of claim 1, wherein the molar ratio of the protic acid to the alkyl aluminum halide is between 0.05:1 and 0.2:1.
9. The method of claim 1, wherein the alkyl aluminum halide is selected from at least one of diethyl aluminum monochloride, diisobutyl aluminum monochloride, dichloromethyl aluminum, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride, and ethyl aluminum chloride.
10. The method of claim 9, wherein the alkyl aluminum halide is aluminum sesquichloride.
11. The method of claim 1, wherein said protonic acid is selected from the group consisting of HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 Or HNO (HNO) 3 One of them.
12. The method of claim 11, wherein the protic acid is HCl.
13. The method of claim 1, wherein the diluent is selected from the group consisting of methane chloride, methylene chloride, carbon tetrachloride, ethylene dichloride, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
14. The method of claim 13, wherein the diluent is methyl chloride.
15. The method of claim 1, wherein the solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
16. The method of claim 15, wherein the solvent is cyclohexane.
17. The method of claim 1, wherein the terminator is selected from one or more of methanol, ethanol, butanol.
18. The method of claim 1, wherein steps (1) and (2) are both performed in an inert gas atmosphere.
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