CN114478953B - Preparation method of three-arm comb-shaped star-branched butyl rubber - Google Patents
Preparation method of three-arm comb-shaped star-branched butyl rubber Download PDFInfo
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- CN114478953B CN114478953B CN202011264546.XA CN202011264546A CN114478953B CN 114478953 B CN114478953 B CN 114478953B CN 202011264546 A CN202011264546 A CN 202011264546A CN 114478953 B CN114478953 B CN 114478953B
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- shaped
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- arm
- butyl rubber
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- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 239000002667 nucleating agent Substances 0.000 claims abstract description 51
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 49
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 43
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 120
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 64
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 36
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 34
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 28
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 20
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- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
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- 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
- 238000007599 discharging Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
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- 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
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical group ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims description 4
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
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- 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
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
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- 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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- 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
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- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 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
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 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
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- 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
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
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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
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- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of three-arm comb-shaped star-branched butyl rubber. The invention uses isoprene, styrene and butadiene as reaction monomers, and utilizes trihalogenated benzene to couple the star-shaped copolymer [ -SBR-IR [ -IR ]]nPh followed by [ -SBR-IR ]]nPh and Divinylbenzene (DVB) to prepare the three-arm comb-shaped star-shaped nucleating agent [ - (DVB) SBR- (DVB) IR ]] n And Ph, finally, preparing the three-arm comb-shaped star-shaped branched butyl rubber by carrying out cationic polymerization on the three-arm star-shaped nucleating agent, isobutene and isoprene by adopting a first-arm and then-core method under a catalytic system of Lewis acid and protonic acid compounding. The invention effectively solves the problem of strength and air tightness reduction caused by the widening of the molecular weight distribution of the butyl rubber, realizes the balance between the processability and the physical properties of the butyl rubber, and ensures that the properties of the butyl rubber are more comprehensively improved.
Description
Technical Field
The invention relates to a preparation method of three-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing 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. CN88108392.5 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, by which star-branched polymers are prepared. 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 alThe trimesic acid is used as raw material to synthesize the initiator tricumyl alcohol with three-arm structure, then the tricumyl alcohol/aluminum trichloride initiating system is used to initiate the copolymerization of isobutene and isoprene in the inert organic solvent at-120-50 deg.C, the star-branched butyl rubber with bimodal molecular weight distribution is synthesized (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-Comb 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 (preparation of a star-branched polyisobutylene with divinylbenzene as a core) is synthesized at-80 ℃ by adopting 2-chloro-2, 4-trimethylpentane/titanium tetrachloride as an initiator system and chloromethane/cyclohexane as a solvent and adopting active positive ion polymerization Preparation and characterization "," synthetic rubber industry ", synthetic rubber industry, 2008, 31 (5): 362-365.
Disclosure of Invention
The invention aims to provide a preparation method of three-arm comb-shaped star-branched butyl rubber. The invention firstly takes alkyl lithium as an initiator, takes hydrocarbon as a solvent, takes isoprene, styrene and butadiene as reaction monomers, adds the reaction monomers into a polymerization system for synthesizing [ -IR-SBR- ] n linear chain segments according to a fixed sequence for two times, then adds coupling agent trihalogenated benzene for coupling to prepare star copolymer [ -SBR-IR- ] nPh with ternary three-arm structure with unsaturated double bond, then sequentially adds solvent, divinylbenzene (DVB) and initiator for polymerizing to obtain three-arm star-shaped nucleating agent, and finally takes isobutene and isoprene as reaction monomers and the three-arm star-shaped nucleating agent for cationic polymerization under a catalytic system compounded by Lewis acid and protonic acid to prepare the three-arm comb-shaped star-shaped branched butyl rubber by adopting a first-arm and then-core method. The three-arm comb-shaped star-branched butyl rubber not only effectively solves the problem that the butyl rubber is easy to have low stress relaxation rate in the processing process, but also maintains sufficient raw rubber strength and good air tightness of the butyl rubber, and realizes balance of physical and mechanical properties and processing properties of the butyl rubber.
The "%" of the invention refers to mass percent.
The preparation of the 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) Preparation of a three-arm star-shaped nucleating agent: based on the total mass parts of reaction monomers, firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200% of solvent, 20-40% of isoprene, 0.05-0.5% of structure regulator and initiator into the polymerization kettle, heating to 40-55 ℃, and reacting for 30-60 min until the isoprene monomer conversion rate reaches 100%; then adding 100% -200% solvent, 0.05% -0.5% structure regulator, heating to 60-75 deg.C, mixing 45% -60% styrene and 20% -35% 1, 3-butadiene for 10-20 min, adding togetherReacting for 50-70 min in a polymerization kettle to form an-IR-SBR-chain segment; then heating to 80-90 ℃, adding a coupling agent for coupling reaction for 60-80 min, sequentially adding 100-200% of solvent, 2-6% of Divinylbenzene (DVB) and 0.001-0.1% of catalyst into a polymerization kettle after the reaction is completed, heating to 70-80 ℃, reacting for 40-60 min, treating the coupled reaction mixture with water after the reaction is completed, condensing and drying the glue solution by a wet method to prepare the nucleating agent with a three-arm star structure ([ - (DVB) SBR- (DVB) IR ] ] n Ph)。
(2) Preparation of 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 ℃, 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, mixing and dissolving 30-60% of solvent and 0.5-1.5% of nucleating agent with a three-arm star-shaped structure obtained in the step (1) for 2.0-3.0 hr, aging the mixture at minus 95-minus 85 ℃ for 2.0-5.0 hr, adding a terminator for discharging and agglomerating, washing and drying to obtain the three-arm comb-shaped branched butyl rubber product.
The nucleating agent is a quaternary three-arm star polymer containing isoprene, butadiene, styrene and divinylbenzene, and the structural general formula of the nucleating agent is shown in formula I:
Wherein IR is an isoprene homopolymer block, the 1, 2-structure content of the block is 12-17%, and the 3, 4-structure content of the block is 5-10%; SBR is a styrene and 1, 3-butadiene random block copolymer, wherein the content of styrene is 40-60%, and the content of 1, 3-butadiene is 20-34%; the content of polyisoprene blocks in the quaternary three-arm star polymer is 20% -40%, and the content of polybutadiene and styrene blocks is 60% -74%; the quaternary three-arm star polymer has a number average molecular weight (Mn) of 20000-50000 and a molecular weight distribution (Mw/Mn) of 2.85-4.71.
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 HCl. 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 0.05:1-0.2:1.
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 firstly adopts alkyl lithium as an initiator, hydrocarbon as a solvent and organic matters with certain polarity as a structure regulator, a reaction monomer is composed of isoprene, styrene, butadiene and divinylbenzene, the initiator is added once, the reaction monomer is added into a polymerization system in a definite sequence in two times, and then a coupling agent trihalogenated benzene is used for coupling to prepare a copolymer [ -SBR-IR [ -room temperature butyl rubber-IR ] ]nPh and then adding divinylbenzene and catalyst again to obtain nucleating agent with reactive three-arm star structure [ - (DVB) SBR- (DVB) IR ]] n Ph. Finally, isobutene and isoprene are polymerized by cations under a catalytic system compounded by alkyl aluminum halide and protonic acid to obtain butyl rubber chain segments, and then a nucleating agent with a three-arm star-shaped structure is added to prepare the three-arm comb-shaped star-shaped branched butyl rubber. The butyl rubber prepared by the three-arm star-shaped nucleating agent designed by the invention contains three componentsThe arm comb star structure can effectively widen the molecular weight distribution of the whole butyl rubber macromolecule properly while not damaging the molecular chain regularity of the single isobutene and isoprene copolymer, the flexibility of the chain segment is improved, and a faster stress relaxation rate can be obtained; in addition, the-IR-and-SBR-chain segments in the nucleating agent contain a certain amount of vinyl and benzene ring, the vinyl can improve the flexibility of the chain segments, and the benzene ring can obtain high strength and barrier property. Therefore, the invention organically combines the three-arm comb star-shaped structural characteristic with the performances of various chain segments and cooperatively plays a role, and the synergistic 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 performances of the butyl rubber are more comprehensively improved. The preparation method of the three-arm comb-shaped star-branched butyl rubber provided by the invention has the characteristics of short process flow, controllable molecular weight, good product processability, suitability for industrial production and the like.
Drawings
FIG. 1 is 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 。
Determination of mooney viscosity and stress relaxation: GT-7080-S2 type Mooney produced by Taiwan high-speed rail company
And (5) measuring by a viscometer. The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.
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 three-arm star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 1010g of cyclohexane, 200g of isoprene and 0.5g THF,14.3mmo1 n-butyllithium into the polymerization kettle, heating to 40 ℃, and reacting for 30min to form an IR chain segment; then 1120g cyclohexane and 1.6g THF are added into a polymerization kettle in sequence, the temperature is raised to 60 ℃, 450g styrene and 200g1, 3-butadiene are stirred and mixed for 10min, and then added into the polymerization kettle together for reaction for 50min, so as to form an-IR-SBR-chain segment; then heating to 80 ℃, addingAdding 8.5 mmol of 11,3, 5-trichlorobenzene, reacting for 60min to form [ -SBR-IR ] ] n Ph; after the reaction is completed, 1010g of cyclohexane and 20g DVB,0.03g BPO are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃, after the reaction is carried out for 40min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph (Mn 22050, mw/Mn 2.85).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 3 times, 240g of methyl chloride, 360g of cyclohexane, 264g of isobutene and 6g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 90 ℃, then 120g of methyl chloride, 1.7g of aluminum sesquichloride and 0.05g of HCl are mixed at minus 85 ℃ and aged for 30 minutes, then added into the polymerization system together and stirred and reacted for 0.5 hour, then 90g of cyclohexane and 1.5g of [ - (DVB) SBR- (DVB) IR [ (ultraviolet radiation) are added into the mixture] 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 ℃, added into a polymerization system together and stirred for 2.0hr, then 100mL 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 2
(1) Preparation of a three-arm star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 1140g of cyclohexane, 230g of isoprene and 1.2g THF,15.2mmo1 n-butyllithium into the polymerization kettle, heating to 42 ℃, and reacting for 35min to form an IR chain segment; then 1250g cyclohexane, 1.9g THF are added into a polymerization kettle in turn, the temperature is raised to 63 ℃, 480g styrene and 220g1, 3-butadiene are stirred and mixed for 12min and then added into the polymerization kettle together for reaction for 54min, and an-IR-SBR-chain segment is formed; then heating to 82 ℃, adding 10.1 mmol of 11,3, 5-trichlorobenzene, reacting for 65min to form [ -SBR-IR ]] n Ph; after the reaction is completed, 1050g of cyclohexane and 27g DVB,0.09g BPO are sequentially added into a polymerization kettle, the temperature is raised to 72 ℃, after the reaction is carried out for 43min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- ] with a three-arm star-shaped structure is preparedDVB)IR-] n Ph (Mn 23050, mw/Mn 2.92).
(2) Preparation of 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 3 times, 280g of methyl chloride, 340g of cyclohexane, 270g of isobutene and 10g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 90 ℃, then 130g of methyl chloride, 2.3g 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 0.6 hour, and then 100g of cyclohexane and 2.2g of [ - (DVB) SBR- (DVB) IR [ ] are added ] n Ph is stirred and dissolved for 2.2 hours until the grafting agent is completely dissolved, then aged for 35 minutes at the temperature of minus 87 ℃, added into a polymerization system together and stirred for 2.5 hours, then added with 120mL of methanol to terminate 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 three-arm star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 1220g cyclohexane, 270g isoprene and 1.7g THF,17.9mmo1 n-butyllithium into the polymerization kettle, heating to 45 ℃, and reacting for 40min to form an IR chain segment; then 1310g of cyclohexane and 2.1g of THF are sequentially added into a polymerization kettle, the temperature is raised to 65 ℃, 500g of styrene and 260g of 1, 3-butadiene are stirred and mixed for 13min, and then added into the polymerization kettle together for 57min to react, so that an-IR-SBR-chain segment is formed; then heating to 83 ℃, adding 12.1 mmol of 11,3, 5-trichlorobenzene, reacting for 68min to form [ -SBR-IR ]] n Ph; after the reaction is completed, 1150g cyclohexane and 32g DVB,0.11g BPO are added into a polymerization kettle in turn, the temperature is raised to 75 ℃, after 49min of reaction, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) IR ] ] n Ph (Mn 26050, mw/Mn 3.26).
(2) Preparation of 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, sequentially adding 300g of chloromethane, 330g of cyclohexane and 275g of isobutyl into the polymerization kettleMixing 15g of alkene and 15g of isoprene under stirring until the temperature of the polymerization system is reduced to-92 ℃, then mixing 140g of chloromethane, 2.8g of sesquiethylaluminum chloride and 0.12g of HCl at-87 ℃ and aging for 35min, adding 110g of cyclohexane and 2.7g of [ - (DVB) SBR- (DVB) IR-fluvium into the polymerization system together for stirring reaction for 0.7hr] n Ph is stirred and dissolved for 2.4 hours until the grafting agent is completely dissolved, then aged for 38 minutes at the temperature of minus 89 ℃, added into a polymerization system together and stirred for 3.0 hours, then added with 130mL of methanol to terminate 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 three-arm star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 1350g cyclohexane, 300g isoprene and 2.1g THF,18.7mmo1 n-butyllithium into the polymerization kettle, heating to 47 ℃, and reacting for 45min to form an IR chain segment; then sequentially adding 1390g of cyclohexane, 2.7g of THF into a polymerization kettle, heating to 69 ℃, stirring and mixing 530g of styrene and 290g of 1, 3-butadiene for 15min, adding the mixture into the polymerization kettle together, and reacting for 61min to form an-IR-SBR-chain segment; then heating to 85 ℃, adding 14.2 mmol of 11,3, 5-trichlorobenzene, reacting for 72min to form [ -SBR-IR ] ] n Ph; after the reaction is completed, 1260g of cyclohexane and 40g DVB,0.23g BPO are sequentially added into a polymerization kettle, the temperature is raised to 76 ℃, after the reaction is carried out for 51min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph (Mn 29100, mw/Mn 3.86).
(2) Preparation of 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 methyl chloride, 310g of cyclohexane, 280g of isobutene and 20g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to-93 ℃, then 150g of methyl chloride, 3.1g of aluminum sesquichloride and 0.23g of HCl are mixed at-88 ℃ and aged for 37 minutes, then added into the polymerization system together and stirred and reacted for 0.8hr, and then 130g of cyclohexane and 3.0g of [ - (DVB) SBR- (DVB) IR are added-] n Ph is stirred and dissolved for 2.6 hours until the grafting agent is completely dissolved, then aged for 40 minutes at the temperature of minus 90 ℃, added into a polymerization system together and stirred for 4.0 hours, then 140mL 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 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 1410g of cyclohexane, 330g of isoprene and 2.5g THF,19.6mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, and reacting for 50min to form an IR chain segment; then adding 1420g cyclohexane, 3.1g THF into a polymerization kettle in turn, heating to 71 ℃, mixing 550g styrene and 310g1, 3-butadiene for 17min, adding the mixture into the polymerization kettle together, and reacting for 67min to form an-IR-SBR-chain segment; then heating to 87 ℃, adding 16.5 mmol of 11,3, 5-trichlorobenzene, reacting for 75min to form [ -SBR-IR ]] n Ph; after the reaction is completed, 1310g of cyclohexane and 45g DVB,0.42g BPO are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, after the reaction is carried out for 54min, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph (Mn 34000, mw/Mn 4.06).
(2) Preparation of 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, 310g of methyl chloride, 330g of cyclohexane, 284 g of isobutene and 25g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to-93 ℃, then 160g of methyl chloride, 3.8g of aluminum sesquichloride and 0.29g of HCl are mixed at-88 ℃ and aged for 38 minutes, then added into the polymerization system together and stirred and reacted for 0.8hr, and then 140g of cyclohexane and 3.5g of [ - (DVB) SBR- (DVB) IR [ (ultraviolet radiation) are added into the polymerization system ] n Ph is stirred and dissolved for 2.8 hours until the grafting agent is completely dissolved, then aged for 43 minutes at the temperature of minus 92 ℃, added into a polymerization system together and stirred for 4.2 hours, then added with 150mL of methanol to terminate the reaction, finally discharged and coagulated, washed and dried to obtain the three-arm comb-shaped star-branched butyl rubber product. SamplingAnalysis: standard samples were prepared and the test performance is shown in table 1.
Example 6
(1) Preparation of a 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 1520g cyclohexane, 370g isoprene and 3.4g THF,21.5mmo1 n-butyllithium into the polymerization kettle, heating to 52 ℃, and reacting for 55min to form an IR chain segment; then 1510g of cyclohexane, 3.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 73 ℃, 570g of styrene and 330g of 1, 3-butadiene are stirred and mixed for 19min, and then added into the polymerization kettle together for 68min to react, so that an-IR-SBR-chain segment is formed; then heating to 88 ℃, adding 17.9mmo11,3, 5-trichlorobenzene, reacting for 78min to form [ -SBR-IR ]] n Ph; sequentially adding 1430g cyclohexane and 51g DVB,0.51g BPO into a polymerization kettle after the reaction is completed, heating to 79 ℃, reacting for 58min, and performing wet condensation and drying on the glue solution to obtain the nucleating agent [ - (DVB) SBR- (DVB) IR ] ] n Ph (Mn 39000, mw/Mn 4.35).
(2) Preparation of 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, 300g of methyl chloride, 350g of cyclohexane, 290g 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 95 ℃, then 170g of methyl chloride, 4.2g of aluminum sesquichloride and 0.35g of HCl are mixed at minus 89 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred and reacted for 0.9hr, then 145g of cyclohexane and 4.1g of [ - (DVB) SBR- (DVB) IR [ (infrared radiation) are added into the mixture] n Ph is stirred and dissolved for 2.9 hours until the grafting agent is completely dissolved, then aged for 47 minutes at the temperature of minus 95 ℃, added into a polymerization system together and stirred for 4.6 hours, then 160mL 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 three-arm star-shaped nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, argon is introduced for replacement for 4 times, 1650g of cyclohexane is sequentially added into the polymerization kettle400g of isoprene, 3.9g THF,23.5mmo1 n-butyllithium, heating to 55 ℃, and reacting for 60min to form an IR chain segment; then adding 1610g cyclohexane and 4.3g THF into a polymerization kettle in turn, heating to 75 ℃, mixing 600g styrene and 350g1, 3-butadiene for 20min, adding the mixture into the polymerization kettle together, and reacting for 70min to form an-IR-SBR-chain segment; then heating to 90 ℃, adding 20.5 mmol of 11,3, 5-tribrominated benzene, reacting for 80min to form [ -SBR-IR ] ] n Ph; after the reaction is completed, sequentially adding 1500g of cyclohexane and 60g DVB,0.65g BPO into a polymerization kettle, heating to 80 ℃, reacting for 60min, and then performing wet condensation and drying on the glue solution to obtain the nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph (Mn 45000, mw/Mn 4.71).
(2) Preparation of 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, 280g of chloromethane, 370g of cyclohexane, 256 g of isobutene and 36g 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 chloromethane, 4.8g of sesquiethylaluminum chloride and 0.41g of HCl are mixed at minus 90 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred for 1.0hr, and then 150g of cyclohexane and 4.5g of [ - (DVB) SBR- (DVB) IR [ (ultraviolet radiation) are added into the mixture] n Ph is stirred and dissolved for 3.0hr until the grafting agent is completely dissolved, then aged for 50min at the temperature of minus 95 ℃, added into a polymerization system together and stirred for 5.0hr, then 170mL 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 1
Preparation of three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 1 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, sequentially adding 240g of methane chloride, 360g of cyclohexane, 264g of isobutene and 6g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to minus 90 ℃, and then adding 120g of methane chloride and 120g of silsesquioxaneMixing 1.7g of aluminum chloride and 0.05g of HCL at the temperature of minus 85 ℃ and aging for 30min, adding the mixture into a polymerization system together and stirring the mixture for 0.5hr, adding 100mL of methanol to terminate the reaction, discharging and condensing the mixture, washing the mixture, and drying the mixture to obtain the branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
(1) Preparation of a 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, introducing argon for replacement for 2 times, sequentially adding 1140g of cyclohexane, 230g of isoprene and 1.2g THF,15.2mmo1 n-butyllithium into the polymerization kettle, heating to 42 ℃, and reacting for 35min to form an IR chain segment; then 1250g cyclohexane, 1.9g THF are added into a polymerization kettle in turn, the temperature is raised to 63 ℃, 480g styrene and 220g1, 3-butadiene are stirred and mixed for 12min and then added into the polymerization kettle together for reaction for 54min, and an-IR-SBR-chain segment is formed; then 1050g cyclohexane and 27g DVB,0.09g BPO are added into a polymerization kettle in turn, the temperature is raised to 72 ℃, after 43min of reaction, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) IR-room-temperature-heating agent with a linear structure is prepared ] n (Mn 18000, mw/Mn 1.92).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 2 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph, but with the addition of nucleating agents [ - (DVB) SBR- (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 for 3 times, 280g of methyl chloride, 340g of cyclohexane, 270g of isobutene and 10g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to minus 90 ℃, then 130g of methyl chloride, 2.3g 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 0.6 hour, and then 100g of cyclohexane and 2.2g of [ - (DVB) SBR- (DVB) IR [ ] are added] n Stirring and dissolving for 2.2hr until grafting agent is completely dissolved, aging at-87 deg.C for 35min, adding into polymerization system, stirring and reacting for 2.5hr, adding 120mL of methanolStopping the reaction, finally discharging, condensing, washing and drying to obtain the linear branched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
(1) Preparation of a three-arm star-shaped nucleating agent: other conditions were the same as in example 3 except that: during the synthesis, not 1,3, 5-trichlorobenzene but methyl silicon trichloride (CH 3 SiCl 3 ) The method comprises the following steps: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 1220g cyclohexane, 270g isoprene and 1.7g THF,17.9mmo1 n-butyllithium into the polymerization kettle, heating to 45 ℃, and reacting for 40min to form an IR chain segment; then 1310g of cyclohexane and 2.1g of THF are sequentially added into a polymerization kettle, the temperature is raised to 65 ℃, 500g of styrene and 260g of 1, 3-butadiene are stirred and mixed for 13min, and then added into the polymerization kettle together for 57min to react, so that an-IR-SBR-chain segment is formed; then the temperature was raised to 83℃and 12.1 mmol of 1 CH was added 3 SiCl 3 Reacting for 68min to form [ -SBR-IR ]] n Si CH 3 The method comprises the steps of carrying out a first treatment on the surface of the After the reaction is completed, 1150g cyclohexane and 32g DVB,0.11g BPO are added into a polymerization kettle in turn, the temperature is raised to 75 ℃, after 49min of reaction, the glue solution is subjected to wet condensation and drying, and the nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Si CH 3 (Mn 24000 and Mw/Mn 2.81).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 3 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph, but with the addition of nucleating agents [ - (DVB) SBR- (DVB) IR ]] n Si CH 3 The method comprises the following steps: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 3 times, 300g of methyl chloride, 330g of cyclohexane, 275g of isobutene and 15g 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 140g of methyl chloride, 2.8g of sesqui-ethylaluminum chloride and 0.12g of HCl are mixed at minus 87 ℃ and aged for 35min, then added into the polymerization system together and stirred and reacted for 0.7hr, then 110g of cyclohexane and 2.7g of [ - (DVB) SBR- (DVB) IR [ ] ] n Si CH 3 Stirring and dissolving for 2.4hrAnd (3) completely dissolving the grafting agent, aging for 38min at the temperature of minus 89 ℃, adding the grafting agent into a polymerization system together, stirring and reacting for 3.0hr, adding 130mL of methanol to terminate the reaction, discharging and condensing, washing, and drying 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 4
Preparation of Star-branched butyl rubber: other conditions were the same as in example 4 except that: no nucleating agent [ - (DVB) SBR- (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, 280g of isobutene and 20g of isoprene are sequentially added into the polymerization kettle, the mixture is stirred and mixed until the temperature of the polymerization system is reduced to minus 93 ℃, then 150g of methyl chloride, 3.1g of aluminum sesquichloride and 0.23g of HCl are mixed and aged for 37 minutes at minus 88 ℃, then the mixture is added into the polymerization system together for stirring and reacting for 0.8 hours, then 130g of cyclohexane and 3.0g of DVB are stirred and dissolved for 2.6 hours until the grafting agent is completely dissolved, then aged for 40 minutes at minus 90 ℃, then added into the polymerization system together for stirring and reacting for 4.0 hours, 140mL of methanol is added for terminating the reaction, finally the mixture is discharged and condensed, washed and dried, and the three-arm star-shaped branched butyl rubber product is obtained. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 5
(1) Preparation of a three-arm star-shaped nucleating agent: other conditions were the same as in example 5 except that: isoprene 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 1410g of cyclohexane and 2.5g THF,19.6mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, sequentially adding 1420g of cyclohexane and 3.1g of THF into the polymerization kettle, heating to 71 ℃, mixing 550g of styrene and 310g of 1, 3-butadiene for 17min, adding the mixture into the polymerization kettle together, and reacting for 67min to form a-SBR-chain segment; then heating to 87 ℃, adding 16.5 mmol of 11,3, 5-trichlorobenzene, reacting for 75min to form [ -SBR ]] n Ph; after the reaction is completed, sequentially adding into a polymerization kettleAdding 1310g cyclohexane, 45g DVB,0.42g BPO, heating to 77 ℃, reacting for 54min, wet condensing and drying the glue solution to obtain the nucleating agent [ - (DVB) SBR [ (sic) with three-arm star-shaped structure ]] n Ph (Mn 22000, mw/Mn 3.36).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 5 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph, but with addition of nucleating agent [ - (DVB) SBR ] ] n Ph, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 310g of methyl chloride, 330g of cyclohexane, 284 g of isobutene and 25g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of the polymerization system is reduced to-93 ℃, then 160g of methyl chloride, 3.8g of aluminum sesquichloride and 0.29g of HCl are mixed at-88 ℃ and aged for 38min, then added into the polymerization system together and stirred and reacted for 0.8hr, and then 140g of cyclohexane and 3.5g [ - (DVB) SBR [ (styrene-butadiene) are added into the polymerization kettle] n Ph is stirred and dissolved for 2.8 hours until the grafting agent is completely dissolved, then aged for 43 minutes at the temperature of minus 92 ℃, added into a polymerization system together and stirred for 4.2 hours, then added with 150mL of methanol to terminate 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 three-arm star-shaped nucleating agent: other conditions were the same as in example 6 except that: styrene and 1, 3-butadiene are 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 1520g cyclohexane, 370g isoprene and 3.4g THF,21.5mmo1 n-butyllithium into the polymerization kettle, heating to 52 ℃, and reacting for 55min to form an IR chain segment; then heating to 88 ℃, adding 17.9mmo of 11,3, 5-trichlorobenzene, reacting for 78min to form [ -IR ] ] n Ph; sequentially adding 1430g cyclohexane and 51g DVB,0.51g BPO into a polymerization kettle after the reaction is completed, heating to 79 ℃, reacting for 58min, and performing wet condensation and drying on the glue solution to obtain the nucleating agent [ - (DVB) IR [ ] with a three-arm star-shaped structure] n Ph (Mn 23000, mw/Mn 3.32).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 6 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR ]] n Ph, but with the addition of nucleating agents [ - (DVB) IR ]] n Ph, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 4 times, 300g of methyl chloride, 350g of cyclohexane, 290g of isobutene and 30g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 95 ℃, then 170g of methyl chloride, 4.2g of aluminum sesquichloride and 0.35g of HCl are mixed at minus 89 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred and reacted for 0.9hr, and then 145g of cyclohexane and 4.1g of [ - (DVB) IR [ (IR ]] n Ph is stirred and dissolved for 2.9 hours until the grafting agent is completely dissolved, then aged for 47 minutes at the temperature of minus 95 ℃, added into a polymerization system together and stirred for 4.6 hours, then 160mL 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 three-arm star-shaped nucleating agent: same as in example 7.
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: other conditions were the same as in example 7 except that [ - (DVB) SBR- (DVB) IR ]] n The addition amount of Ph is 0.5g, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 5 times, 280g of chloromethane, 370g of cyclohexane, 256 g of isobutene and 36g 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 chloromethane, 4.8g of sesquiethylaluminum chloride and 0.41g of HCl are mixed at minus 90 ℃ and aged for 40 minutes, then added into the polymerization system together and stirred for 1.0hr, then 150g of cyclohexane and 0.5g of [ - (DVB) SBR- (DVB) IR [ ] are added] n Ph, stirring and dissolving for 3.0hr until grafting agent is completely dissolved, aging at-95deg.C for 50min, adding into polymerization system together, stirring and reacting for 5.0hr, adding 170mL methanol to terminate reaction, discharging and coagulating, washing, and drying to obtain three-arm comb star-shaped branchButyl rubber products. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 Properties of three-arm comb-like Star branched butyl rubber
As can be seen from table 1: the three-arm comb-shaped star-branched butyl rubber provided by the invention 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 (17)
1. A preparation method of 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, 20-40% of isoprene, 0.05-0.5% of structure regulator, an initiator and a temperature rise to 40-55 ℃ into a polymerization kettle according to the total mass parts of the reaction monomers, and reacting until the conversion rate of the isoprene monomers reaches 100%; then adding 100% -200% of solvent and 0.05% -0.5% of structure regulator into a polymerization kettle in sequence, heating to 60-75 ℃, stirring and mixing 45% -60% of styrene and 20% -35% of 1, 3-butadiene for 10-20 min, and then adding the mixture into the polymerization kettle together for reacting for 50-70 min to form an-IR-SBR-chain segment; then heating to 80-90 ℃, adding a coupling agent for coupling reaction for 60-80 min, sequentially adding 100-200% of solvent, 2-6% of divinylbenzene and 0.001-0.1% of catalyst into a polymerization kettle after the reaction is completed, heating to 70-80 ℃, reacting for 40-60 min, treating the coupled reaction mixture with water after the reaction is completed, and carrying out wet condensation and drying on the glue solution to obtain the three-arm star-shaped nucleating agent;
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, adding a diluent/solvent mixed solvent with the volume ratio of 60-40/40-60 into a polymerization kettle in sequence, 94-98% of isobutene and 2-6% of isoprene into the polymerization kettle, stirring and mixing until the temperature of the polymerization system is reduced to minus 100-minus 90 ℃, then adding 0.05-3.0% of diluent and co-initiator into the polymerization system for stirring and reacting for 0.5-1.0 hr under the condition of minus 95-minus 85 ℃, then adding 30-60% of solvent and 0.5-1.5% of the three-arm star-shaped nucleating agent obtained in the step (1) for dissolving for 2.0-3.0 hr, aging under the condition of minus 95-minus 85 ℃, adding into the polymerization system for stirring and reacting for 2.0-5.0 hr, finally adding a terminator for discharging and condensing, washing and drying to obtain the three-arm comb-shaped star-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 2, 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.
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