CN116217773A - Butyl rubber with wide molecular weight distribution and synthetic method thereof - Google Patents
Butyl rubber with wide molecular weight distribution and synthetic method thereof Download PDFInfo
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- CN116217773A CN116217773A CN202310321397.3A CN202310321397A CN116217773A CN 116217773 A CN116217773 A CN 116217773A CN 202310321397 A CN202310321397 A CN 202310321397A CN 116217773 A CN116217773 A CN 116217773A
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- Prior art keywords
- butyl rubber
- molecular weight
- polymerization
- initiator
- chain transfer
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- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 68
- 238000009826 distribution Methods 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 41
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 35
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 22
- 239000012046 mixed solvent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 10
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 6
- 229940050176 methyl chloride Drugs 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 6
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 6
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical group FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- VJGCZWVJDRIHNC-NSCUHMNNSA-N (e)-1-fluoroprop-1-ene Chemical compound C\C=C\F VJGCZWVJDRIHNC-NSCUHMNNSA-N 0.000 claims description 5
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical group F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- SZFRZEBLZFTODC-UHFFFAOYSA-N 2,3,4-trimethylpent-2-ene Chemical compound CC(C)C(C)=C(C)C SZFRZEBLZFTODC-UHFFFAOYSA-N 0.000 claims description 3
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 claims description 3
- AHQZRFBZJSCKAV-UHFFFAOYSA-N 2-methylcyclopenta-1,3-diene Chemical compound CC1=CCC=C1 AHQZRFBZJSCKAV-UHFFFAOYSA-N 0.000 claims description 3
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 3
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- HRLHOWWCFUKTIY-UHFFFAOYSA-L dichloroalumanylium Chemical compound Cl[Al+]Cl HRLHOWWCFUKTIY-UHFFFAOYSA-L 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 16
- 230000035882 stress Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- ASGWJZGDJGOLJJ-UHFFFAOYSA-L ethylaluminum(2+);hexane;dichloride Chemical compound [Cl-].[Cl-].CC[Al+2].CCCCCC ASGWJZGDJGOLJJ-UHFFFAOYSA-L 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- -1 aluminum alkoxide Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- TWRQCVNFACGORI-UHFFFAOYSA-N hexane;dihydrochloride Chemical compound Cl.Cl.CCCCCC TWRQCVNFACGORI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- TXHNVFGQJAAUNB-UHFFFAOYSA-N 1,2,3-trifluoroprop-1-ene Chemical compound FCC(F)=CF TXHNVFGQJAAUNB-UHFFFAOYSA-N 0.000 description 1
- DFWCPLGXFMSUCW-UHFFFAOYSA-N 3-(dimethylamino)propyl carbamimidothioate;hydron;dichloride Chemical compound Cl.Cl.CN(C)CCCSC(N)=N DFWCPLGXFMSUCW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides butyl rubber with wide molecular weight distribution and a synthesis method thereof, wherein the method comprises the following steps: polymerizing a polymerization monomer in a mixed solvent, and carrying out slurry polymerization reaction in the presence of an initiator and a chain transfer agent to obtain the butyl rubber; the polymerization monomer comprises isobutene and isoprene, the mixed solvent comprises a polarity regulator, a polymerization solvent of methyl chloride is optionally adopted, and the chain transfer agent is selected from C4-10 linear olefins, C4-10 branched olefins or cycloolefins; the polarity modifier is selected from fluorocarbon C x H y F z . The invention can realize the simultaneous regulation and control of the high molecular weight part and the low molecular weight part in the polymerization process of the butyl rubber to obtain the molecular weightThe butyl rubber with wider distribution ensures that the obtained butyl rubber has high green rubber strength, high stress relaxation rate and the like, and is beneficial to application.
Description
Technical Field
The invention belongs to the technical field of butyl rubber synthesis, in particular to butyl rubber with wide molecular weight distribution and a synthesis method thereof, and more particularly relates to a technology for regulating and controlling the molecular weight distribution of butyl rubber, and the butyl rubber with the molecular weight distribution Mw/Mn of more than 5 can be obtained, namely the aim of improving the processability of the butyl rubber is achieved by controlling the molecular weight distribution of the butyl rubber.
Background
Butyl rubber is a linear polymer prepared by taking Isobutene (IB) and a small amount of Isoprene (IP) as monomers and combining the monomers end to end and is prepared by cationic reaction at a low temperature of-90 ℃ to-100 ℃. The initiation system comprises an initiator and a co-initiator to form an ion pair with initiation activity, and the degree of tightness of the ion pair determines the activity of the initiator and the initiation rate of polymerization reaction. Typically, a cation donor is used as an initiator, typically comprising a carbocation donor and a proton donor; the Lewis acid is a co-initiator, and boron trifluoride, titanium tetrachloride, aluminum trichloride and ethyl aluminum dichloride are commonly used. Depending on the state of the polymer at the time of polymerization, it can be classified into solution polymerization and slurry polymerization, but mainly depends on the solubility of the polymer in the diluent; industrially, the typical solution polymerization diluent is hexane and the slurry polymerization diluent is methyl chloride. The slurry polymerization monomer has high concentration, low system viscosity, easy heat removal, difficult glue hanging and pipeline blockage, and is the polymerization method which is most popular in the industry at present.
The isoprene content of the commercial butyl rubber is only 0.6 to 2.5 percent of that of the main chain, and the butyl rubber has good chemical stability and thermal stability and particularly outstanding air tightness due to low unsaturation degree and a large number of side methyl groups of a molecular chain. To date, butyl rubber has been an irreplaceable material for the manufacture of tire innertubes and curing bladders.
When rubber products are processed, it is desirable that the green rubber have sufficient green strength to prevent excessive flow and deformation during various processing operations. It is considered that the green strength is related to the molecular weight, and as the molecular weight increases, the green strength increases. However, it is also desirable that the rubber have a fast stress relaxation rate so that the stress applied during the molding process is quickly released so that the rubber does not slowly deform or crack due to these unreleased stresses. However, the stress relaxation rate is also a function of the molecular weight, and decreases with increasing molecular weight. Therefore, it is necessary to control the content of the high molecular weight fraction and the content of the low molecular weight fraction of the rubber simultaneously so that the rubber has both high green strength and a fast stress relaxation rate. The chinese patent publication No. CN1966537a discloses a method for preparing isoolefin polymer or copolymer, wherein a diluent compounded by methylene dichloride and n-hexane is mainly used, and alcohols, esters or ketones are added into a lewis acid catalyst system to regulate the molecular weight and distribution of butyl rubber. However, their alcohols, esters or ketones reduce the activity of the lewis acid catalysts, resulting in low gum yields.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides butyl rubber with wide molecular weight distribution and a synthesis method thereof, and aims to realize simultaneous regulation and control of a high molecular weight part and a low molecular weight part in the polymerization process of butyl rubber, so as to obtain butyl rubber with wider molecular weight distribution, and the obtained butyl rubber has high green rubber strength, high stress relaxation rate and the like, and is beneficial to application.
The invention provides a synthetic method of butyl rubber with wide molecular weight distribution, which comprises the following steps:
polymerizing a polymerization monomer in a mixed solvent, and carrying out slurry polymerization reaction in the presence of an initiator and a chain transfer agent to obtain the butyl rubber;
the polymerization monomer comprises isobutene and isoprene, the mixed solvent comprises a polarity regulator, a polymerization solvent of methyl chloride is optionally adopted, and the chain transfer agent is selected from C4-10 linear olefins, C4-10 branched olefins or cycloolefins; the polarity regulator is selected from fluorinated hydrocarbon with a general formula shown in a formula 1;
C x H y F z a formula 1;
the value of x is 1-10, the value of y is 1-20, the value of z is 1-8,x, and y and z are integers.
Preferably, the method comprises the steps of, the polarity modifier is difluoromethane, trifluoromethane, 1, 2-tetrafluoroethane, 1, 2-tetrafluoroethane 1, 2-pentafluoroethane, 1, 2-difluoroethylene, 1, 2-trifluoroethylene, 1-fluoropropene, 1-difluoropropylene 1, 2-pentafluoroethane, 1, 2-difluoroethylene 1, 2-trifluoroethylene, 1-fluoropropene, 1-difluoropropylene.
Preferably, the chain transfer agent is one or more of 1-butene, 1-pentene, 1-hexene, 2-octene, butadiene, 1, 3-pentadiene, 2, 5-dimethyl-2, 4-hexadiene, 2, 3-dimethyl-1, 3-butadiene, cyclohexadiene, cyclopentadiene, 2-methylcyclopentadiene, 2-methyl-1-pentene, 2-ethyl-1-hexene, 2, 4-trimethyl-1-pentene, 2, 4-trimethyl-2-pentene, 4-methyl-1-pentene, 3-dimethyl-1-butene and vinylcyclohexane.
Preferably, the mass ratio of the polymerization solvent to the polarity regulator is (0:100) to (90:10).
Preferably, the initiator is configured in accordance with the following system: mixing main initiator hydrogen chloride and auxiliary initiator aluminum dichloride, and aging preferably at-70 ℃ to-100 ℃; the molar ratio of the polymerized monomer to the main initiator is 1500-1000: 1, the molar ratio of the main initiator to the co-initiator is preferably (10:1) to (5:1).
Preferably, the concentration of the polymerized monomer in the mixed solvent is 8-30wt%; the molar ratio of the isobutene to the isoprene is preferably (2:98) - (12:88); the chain transfer agent is added into the mixed solution of the polymerized monomer and the mixed solvent, and the addition amount accounts for 20 ppm-1000 ppm.
Preferably, the slurry polymerization reaction time is 5 min-30 min, and the reaction temperature is-70 ℃ to-100 ℃.
Preferably, after the slurry polymerization reaction, alcohols are also added to stop and precipitate products, and the products are dried in a vacuum oven at 40-50 ℃ to obtain the dried butyl rubber.
The present invention provides butyl rubber obtained by the synthesis process as described hereinbefore, having a molecular weight distribution Mw/Mn of greater than 3.7, preferably greater than 4.5.
Preferably, the butyl rubber molecular weight distribution Mw/Mn is greater than 5.0.
Compared with the prior art, the method comprises the steps of polymerizing monomers including isobutene and isoprene in a mixed solvent, wherein the mixed solvent comprises a polarity regulator and a polymerization solvent of methyl chloride, and slurry polymerization is carried out in the presence of an initiator and a chain transfer agent to obtain the butyl rubber with wide molecular weight distribution; the chain transfer agent is selected from C4-10 linear olefins, C4-10 branched olefins or cycloolefins; the polarity modifier is selected from fluorinated hydrocarbons with a general formula shown in a formula 1. In the slurry polymerization system of the present invention, one or more of said polar modifier is mainly introduced to control the high molecular weight fraction and said chain transfer agent is introduced to control the low molecular weight fraction. The butyl rubber obtained by the invention has wide molecular weight distribution, and the high molecular weight part and the low molecular weight part are controlled simultaneously. The raw rubber of the butyl rubber obtained by the invention has high strength, and simultaneously has high stress relaxation rate, thereby improving the processability of the butyl rubber.
Furthermore, the invention does not relate to the configuration of the using agent of the mixed initiation system, has simple process and easy control, and the use of the polarity regulator is beneficial to improving the activity of the initiator. The invention preferably uses an aluminum alkyl initiation system, does not use aluminum alkoxide and has low cost.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
The invention provides a synthetic method of butyl rubber with wide molecular weight distribution, which comprises the following steps:
polymerizing a polymerization monomer in a mixed solvent, and carrying out slurry polymerization reaction in the presence of an initiator and a chain transfer agent to obtain the butyl rubber;
the polymerization monomer comprises isobutene and isoprene, the mixed solvent comprises a polarity regulator, a polymerization solvent of methyl chloride is optionally adopted, and the chain transfer agent is selected from C4-10 linear olefins, C4-10 branched olefins or cycloolefins; the polarity regulator is selected from fluorinated hydrocarbon with a general formula shown in a formula 1;
C x H y F z a formula 1;
the value of x is 1-10, the value of y is 1-20, the value of z is 1-8,x, and y and z are integers.
The synthetic method of the invention can obtain butyl rubber with wider molecular weight distribution, so that the obtained butyl rubber has high green rubber strength, fast stress relaxation rate and the like, and is beneficial to application.
In the specific implementation steps of the synthesis method of the butyl rubber with wide molecular weight distribution, the polymerization monomer and the mixed solvent are mixed to obtain a polymerization monomer solution, and then a trace of chain transfer agent is added. Wherein the monomers comprise isobutene and isoprene, and the molar ratio of the isobutene to the isoprene is preferably (2:98) - (12:88); the monomer solution concentration may be 8wt% to 30wt%, further 10wt% to 30wt%, for example, 12%, 15%, 20%, 28%, etc.
In the present invention, the mixed solvent includes a polar modifier fluorocarbon, and optionally a polymerization solvent of methyl chloride; the molecular general formula of the polarity regulator is C x H y F z Mainly comprises one or more fluorine substituted short-chain alkane and alkene. In the formula 1, x, y and z are integers; x is 1 to 10, y is 1 to 20, and z is 1 to 8, preferably 1 to 5. The polarity modifier is preferably difluoromethane, trifluoromethane 1, 2-tetrafluoroethane, 1, 2-tetrafluoroethane 1, 2-pentafluoroethane 1, 2-difluoroethylene, 1, 2-trifluoroethylene, 1-fluoropropene, 1-difluoropropylene, 1, 2-difluoropropylene, 1, 3-difluoropropylene, 2, 3-difluoropropylene,one or more of 3-difluoropropene, 1, 2-trifluoropropene, 1, 3-trifluoropropene, 1,2, 3-trifluoropropene, 2, 3-trifluoropropene and 2, 3-tetrafluoro-1-propene, more preferably 1, 2-tetrafluoroethane and/or dichloromethane.
In an embodiment of the present invention, the mass ratio of the polar modifier to the polymerization solvent is (100:0) to (10:90). The amount of polymerization solvent may be 0; the ratio of the two reagents mainly affects the ratio of the large molecular weight, and the ratio of the two reagents can be adjusted according to the requirement on the molecular weight. The invention mainly introduces one or more of the polar regulators to regulate the high molecular weight part. The increase in polarity of the system of the invention increases on the one hand the initiator activity and gives faster polymers of higher molecular weight at the same reaction temperature. On the other hand, the swelling of the polymer in the diluent is reduced, the dispersion state of the polymerized monomer during polymerization is improved, the polymerization heat is timely withdrawn, the reaction temperature is controlled, and the negative influence of temperature rise on a macromolecular part is reduced; and can solve the industrialization problem of agglomeration and gum hanging of butyl rubber caused by the temperature rise in the reaction process.
Meanwhile, the system of the invention introduces a certain chain transfer agent to control the low molecular weight part. In the invention, a small amount or a trace amount of chain transfer agent has better regulation capability on a low molecular weight part; the chain transfer agent is selected depending on its poisoning ability and chain transfer ability, and preferably, an olefin having low poisoning ability and high chain transfer ability is selected from among C4-10 linear olefins, C4-10 branched olefins and cycloolefins. Preferably, the chain transfer agent of the present invention is added in an amount of 20ppm to 1000ppm based on the monomer solution.
The chain transfer agent according to embodiments of the present invention may be one or more of 1-butene, 1-pentene, 1-hexene, 2-octene, butadiene, 1, 3-pentadiene, 2, 5-dimethyl-2, 4-hexadiene, 2, 3-dimethyl-1, 3-butadiene, cyclohexadiene, cyclopentadiene, 2-methylcyclopentadiene, 2-methyl-1-pentene, 2-ethyl-1-hexene, 2, 4-trimethyl-1-pentene, 2, 4-trimethyl-2-pentene, 4-methyl-1-pentene, 3-dimethyl-1-butene and vinylcyclohexane, for example, 2, 4-trimethyl-1-pentene may be used.
In the embodiment of the invention, the initiator consists of a main initiator and a co-initiator, and can be specifically configured according to the following system: mixing main initiator hydrogen chloride (HCl) and auxiliary initiator aluminum ethyl chloride, wherein n-hexane can be used as a solvent; preferably aging is carried out at-70 to-100 ℃ for 5 to 30 minutes. Preferably, the molar ratio of the polymerization monomer to the main initiator is 1500-1000: 1, a step of; the molar ratio of the main initiator to the co-initiator is preferably (10:1) to (5:1). The invention preferably uses the alkyl aluminum initiator, and has low cost and high safety. The invention does not relate to the configuration of the using agent of the mixed initiation system, has simple process and easy control, and the use of the polarity regulator is beneficial to improving the activity of the initiator.
The embodiment of the invention belongs to slurry polymerization, the diluent is mainly chloromethane, and the monomer concentration is high. The operation of the polymerization reaction comprises the following steps: the initiator is slowly dripped into the mixed solution of the polymerized monomer and the mixed solvent, etc., preferably for 5 min-30 min, and the reaction temperature is minus 70 ℃ to minus 100 ℃.
The polymerization termination and post-treatment in the embodiment of the invention comprises the following steps: adding alcohol such as ethanol to terminate and precipitate a product, and drying the product in a vacuum oven at 45 ℃ to obtain the butyl rubber with excellent performance.
The examples of the present invention provide butyl rubber obtained by the synthesis process as described hereinbefore, having a molecular weight distribution Mw/Mn of greater than 3.7, preferably greater than 4.5, more preferably greater than 5.0. The butyl rubber has wide molecular weight distribution, the high molecular weight part and the low molecular weight part are controlled simultaneously, the raw rubber strength is improved, and meanwhile, the butyl rubber has fast stress relaxation rate, and the processability of the butyl rubber is improved.
In order to further illustrate and understand the present invention, a method for synthesizing a wide molecular weight distribution butyl rubber, etc. provided by the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention. In the following examples, all the raw materials used are commercially available.
Example 1
110.5g of chloromethane and 27.6g of 1, 2-tetrafluoroethane were taken in a cold bath at-90℃in a reactor;
then 19.5g of isobutene and 0.607g of isoprene are added to obtain a polymerization monomer solution, and stirring is started;
mixing 0.22g of 20wt% ethyl aluminum dichloride n-hexane solution and 5g of 0.025wt% HCl n-hexane solution to obtain a catalyst solution, and aging in a cold bath at-90 ℃ for 10min;
slowly dripping the catalyst solution into a polymerization monomer solution, and reacting for 10min in a cold bath at the temperature of minus 90 ℃;
adding 50g of ethanol into the reaction vessel to terminate and separate out a product;
the product was placed in a vacuum oven and dried at 45 ℃.
17.09g of butyl rubber was obtained, the conversion was 85%; nuclear magnetic analysis, mooney viscosity analysis, GPC test were performed. The obtained butyl rubber had a degree of unsaturation of 1.5mol%, a Mooney viscosity ML (1+8) at 125℃of 43 and a number average molecular weight Mn of 13.2X10 4 g/mol, weight average molecular weight Mw of 49.1X10 4 g/mol, molecular weight distribution Mw/Mn is 3.72.
Example 2
69.1g of chloromethane and 69.1g of 1, 2-tetrafluoroethane are taken in a cold bath at the temperature of-90 ℃ in a reactor;
then 19.5g of isobutene and 0.607 isoprene are added to obtain a polymerized monomer solution, and stirring is started;
mixing 0.22g of 20wt% ethyl aluminum dichloride n-hexane solution and 5g of 0.025wt% HCl n-hexane solution to obtain a catalyst solution, and aging in a cold bath at-90 ℃ for 10min;
slowly dripping the catalyst solution into the polymerization monomer solution, and reacting for 10min;
adding 50g of ethanol into the reaction vessel to terminate and separate out a product;
the product was placed in a vacuum oven and dried at 45 ℃.
18.09g of butyl rubber was obtained, the conversion was 90%; nuclear magnetic analysis, mooney viscosity analysis, GPC test were performed. The obtained butyl rubber had a degree of unsaturation of 1.62mol%, a Mooney viscosity ML (1+8) at 125℃of 45 and a number average molecular weight Mn of 13.8X10 4 g/mol, weight average molecular weight Mw of 55.3X10 4 g/mol, molecular weight distribution Mw/Mn is 4.0.
Example 3
138.1g of 1, 2-tetrafluoroethane were taken in a reactor at-90℃in a cold bath;
then 19.5g of isobutene and 0.607g of isoprene are added to obtain a polymerization monomer solution, and stirring is started;
mixing 0.22g of 20wt% ethyl aluminum dichloride n-hexane solution and 5g of 0.025wt% HCl n-hexane solution to obtain a catalyst solution, and aging in a cold bath at-90 ℃ for 10min;
slowly dripping the catalyst solution into the polymerization monomer solution, and reacting for 10min;
adding 50g of ethanol into the reaction vessel to terminate and separate out a product;
the product was placed in a vacuum oven and dried at 45 ℃.
19.5g of butyl rubber was obtained, the conversion was 97%; nuclear magnetic analysis, mooney viscosity analysis, GPC test were performed. The obtained butyl rubber has a degree of unsaturation of 1.78mol%, a Mooney viscosity ML (1+8) at 125℃of 55 and a number average molecular weight Mn of 15.21X 10 4 g/mol, weight average molecular weight Mw of 62.2X10 4 g/mol, molecular weight distribution Mw/Mn is 4.1.
Example 4
138.1g of 1, 2-tetrafluoroethane were taken in a reactor at-90℃in a cold bath;
then, 19.5g of isobutylene and 0.607g of isoprene were added to obtain a polymerization monomer solution, and 0.79g of a 1wt% methylene chloride solution of 2, 4-trimethyl-1-pentene was added thereto, followed by stirring;
mixing 0.22g of 20wt% ethyl aluminum dichloride n-hexane solution and 5g of 0.025wt% HCl n-hexane solution to obtain a catalyst solution, and aging in a cold bath at-90 ℃ for 10min;
slowly dripping the catalyst solution into the polymerization monomer solution, and reacting for 10min;
adding 50g of ethanol into the reaction vessel to terminate and separate out a product;
the product was placed in a vacuum oven and dried at 45 ℃.
19.62g of butyl rubber were obtainedThe conversion rate is 97.6%; nuclear magnetic analysis, mooney viscosity analysis, GPC test were performed. The obtained butyl rubber had a degree of unsaturation of 1.77mol%, a Mooney viscosity ML (1+8) at 125℃of 53 and a number average molecular weight Mn of 13.7X10 4 g/mol, weight average molecular weight Mw of 61.6X10 4 g/mol, molecular weight distribution Mw/Mn is 4.5.
Example 5
138.1g of 1, 2-tetrafluoroethane were taken in a reactor at-90℃in a cold bath;
then, 19.5g of isobutylene and 0.607g of isoprene were added to obtain a polymerization monomer solution, and 1.58g of a 1wt% methylene chloride solution of 2, 4-trimethyl-1-pentene was added thereto, followed by stirring;
mixing 0.22g of 20wt% ethyl aluminum dichloride n-hexane solution and 5g of 0.025wt% HCl n-hexane solution to obtain a catalyst solution, and aging in a cold bath at-90 ℃ for 10min;
slowly dripping the catalyst solution into the polymerization monomer solution, and reacting for 10min;
adding 50g of ethanol into the reaction vessel to terminate and separate out a product;
the product was placed in a vacuum oven and dried at 45 ℃.
19.6g of butyl rubber was obtained, the conversion was 97.5%; nuclear magnetic analysis, mooney viscosity analysis, GPC test were performed. The obtained butyl rubber has a degree of unsaturation of 1.78mol%, a Mooney viscosity ML (1+8) at 125℃of 52 and a number average molecular weight Mn of 12.3X10 4 g/mol, weight average molecular weight Mw of 57.8X10 4 g/mol, molecular weight distribution Mw/Mn is 4.7.
Example 6
69.1g of chloromethane and 69.1g of 1, 2-tetrafluoroethane are taken in a cold bath at the temperature of-90 ℃ in a reactor;
then, 19.5g of isobutylene and 0.607g of isoprene were added to obtain a polymerization monomer solution, and 3.16g of a 1wt% methylene chloride solution of 2, 4-trimethyl-1-pentene was added thereto, followed by stirring;
mixing 0.22g of 20wt% ethyl aluminum dichloride n-hexane solution and 5g of 0.025wt% HCl n-hexane solution to obtain a catalyst solution, and aging in a cold bath at-90 ℃ for 10min;
slowly dripping the catalyst solution into the polymerization monomer solution, and reacting for 10min;
adding 50g of ethanol into a reaction vessel to terminate and separate out a product;
the product was placed in a vacuum oven and dried at 45 ℃.
19.3g of butyl rubber were obtained, the conversion was 96%; the obtained butyl rubber was subjected to nuclear magnetic resonance analysis, mooney viscosity analysis and GPC measurement to obtain a butyl rubber having a degree of unsaturation of 1.72mol%, a Mooney viscosity ML (1+8) at 125℃of 50 and a number average molecular weight Mn of 11.4X10 4 g/mol, weight average molecular weight Mw of 59.3X10 4 g/mol, molecular weight distribution Mw/Mn is 5.2.
Example 7
The amplification experiments were performed in a 4L kettle.
69.1g of chloromethane and 69.1g of 1, 2-tetrafluoroethane are taken in a reaction kettle, and the temperature in the kettle is set to be minus 90 ℃;
273g of isobutene and 8.5g of isoprene are added to obtain a solution of the polymerization monomer and 45g of a 1wt% solution of 2, 4-trimethyl-1-pentene in methylene chloride, and stirring is started;
mixing 3.08g of 20wt% of aluminum ethyl dichloride n-hexane solution and 70g of 0.025wt% of HCl n-hexane solution to obtain a catalyst solution, and aging in a cold bath at-90 ℃ for 10min;
slowly adding the catalyst solution into a reaction kettle, and reacting for 40min;
adding 500g of ethanol into the reaction vessel to terminate and separate out a product;
the product was placed in a vacuum oven and dried at 45 ℃.
268.83g of butyl rubber was obtained, and the conversion was 95.5%; nuclear magnetic analysis, mooney viscosity analysis, GPC test were performed. The obtained butyl rubber had a degree of unsaturation of 1.75mol%, a Mooney viscosity ML (1+8) at 125℃of 50 and a number average molecular weight Mn of 11.3X10 4 g/mol, weight average molecular weight Mw of 59.9X10 4 g/mol, molecular weight distribution Mw/Mn is 5.3.
In the above examples, example 6 and example 7 are the optimal ratios, wherein example 7 is an equal scale enlargement of example 6.
Comparative example
1940g of chloromethane is taken and placed in a reaction kettle, and the temperature in the kettle is set at-85 ℃;
then 273g of isobutene and 8.5 isoprene are added to obtain a polymerized monomer solution, and stirring is started;
mixing 3.08g of 20wt% of aluminum ethyl dichloride n-hexane solution and 70g of 0.025wt% of HCl n-hexane solution to obtain a catalyst solution, and aging in a cold bath at-90 ℃ for 10min;
slowly adding the catalyst solution into a reaction kettle, and reacting for 40min;
adding 500g of ethanol into the reaction vessel to terminate and separate out a product;
the product was placed in a vacuum oven and dried at 45 ℃.
225.2g of butyl rubber was obtained, the conversion was 85%; nuclear magnetic analysis, mooney viscosity analysis, GPC test were performed. The obtained butyl rubber had a degree of unsaturation of 1.52mol%, a Mooney viscosity ML (1+8) at 125℃of 49 and a number average molecular weight Mn of 13.1X10 4 g/mol, weight average molecular weight Mw of 48.3X10 4 g/mol, molecular weight distribution Mw/Mn is 3.7.
The products obtained in example 7 and comparative example were each conventionally kneaded according to the following table formulation:
table 1 mixing formulation
Material | Parts by weight |
Butyl rubber | 100 |
Carbon black N660 | 50 |
Hard acid | 1 |
Sulfur, sulfur and its preparation method | 1.75 |
Zinc oxide | 3 |
TMTD | 1 |
Remarks: vulcanization conditions: 150 ℃, T 90 +3min, pressure 40Ton. Vulcanization accelerator TMTD (tetramethylthiuram disulfide).
The performance of the mixed product is tested as follows:
TABLE 2 Properties of the kneaded product
Example 7 | Comparative example | |
T 90 /min | 24.37 | 24.41 |
ML(1+4)@100℃ | 49 | 48 |
MSR | 0.7139 | 0.5778 |
TX80/S | 17.10 | 19.40 |
Area | 329 | 487 |
Shrinkage/% | 16.9 | 22.5 |
24h shrinkage/% | 25 | 29.7 |
5min/24h | 67.6% | 76.77% |
hardness/Shore A | 50 | 46 |
Tensile Strength/MPa | 18.9 | 16.42 |
Elongation at break/% | 547.12 | 553.78 |
100% elongation/MPa | 15.26 | 14.87 |
Remarks: mooney relaxation is as per standard: GB/T1232-2016; rubber shrinkage test standard GJB5873-2006; tensile property test criteria: GB/T528-2009.
As can be seen from the above examples and comparative examples, the combined action of the polar modifier and the chain transfer agent can give butyl rubber having a broad molecular weight distribution (preferably Mw/Mn of more than 5.0) and is excellent in processability and advantageous for application.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for synthesizing butyl rubber with wide molecular weight distribution, which is characterized by comprising the following steps:
polymerizing a polymerization monomer in a mixed solvent, and carrying out slurry polymerization reaction in the presence of an initiator and a chain transfer agent to obtain the butyl rubber;
the polymerization monomer comprises isobutene and isoprene, the mixed solvent comprises a polarity regulator, a polymerization solvent of methyl chloride is optionally adopted, and the chain transfer agent is selected from C4-10 linear olefins, C4-10 branched olefins or cycloolefins; the polarity regulator is selected from fluorinated hydrocarbon with a general formula shown in a formula 1;
C x H y F z a formula 1;
the value of x is 1-10, the value of y is 1-20, the value of z is 1-8,x, and y and z are integers.
2. The synthesis method according to claim 1, wherein, the polarity modifier is difluoromethane, trifluoromethane, 1, 2-tetrafluoroethane, 1, 2-tetrafluoroethane 1, 2-pentafluoroethane, 1, 2-difluoroethylene, 1, 2-trifluoroethylene, 1-fluoropropene, 1-difluoropropylene 1, 2-pentafluoroethane, 1, 2-difluoroethylene 1, 2-trifluoroethylene, 1-fluoropropene, 1-difluoropropylene.
3. The synthetic method of claim 1 wherein the chain transfer agent is one or more of 1-butene, 1-pentene, 1-hexene, 2-octene, butadiene, 1, 3-pentadiene, 2, 5-dimethyl-2, 4-hexadiene, 2, 3-dimethyl-1, 3-butadiene, cyclohexadiene, cyclopentadiene, 2-methylcyclopentadiene, 2-methyl-1-pentene, 2-ethyl-1-hexene, 2, 4-trimethyl-1-pentene, 2, 4-trimethyl-2-pentene, 4-methyl-1-pentene, 3-dimethyl-1-butene and vinylcyclohexane.
4. A synthetic method according to any one of claims 1 to 3 wherein the mass ratio of the polymerization solvent to the polarity modifier is (0:100) to (90:10).
5. A synthetic method according to any one of claims 1 to 3, characterized in that the initiator is configured according to the following system: mixing main initiator hydrogen chloride and auxiliary initiator aluminum dichloride, and aging preferably at-70 ℃ to-100 ℃; the molar ratio of the polymerized monomer to the main initiator is 1500-1000: 1, the molar ratio of the main initiator to the co-initiator is preferably (10:1) to (5:1).
6. A synthetic method according to any one of claims 1 to 3 wherein the concentration of the polymerized monomer in the mixed solvent is 8 to 30wt%; the molar ratio of the isobutene to the isoprene is preferably (2:98) - (12:88); the chain transfer agent is added into the mixed solution of the polymerized monomer and the mixed solvent, and the addition amount accounts for 20 ppm-1000 ppm.
7. The method according to claim 6, wherein the slurry polymerization is carried out for a period of 5 to 30 minutes at a reaction temperature of-70 to-100 ℃.
8. The method according to claim 7, wherein after the slurry polymerization, alcohols are further added to terminate and precipitate the product, and the product is dried in a vacuum oven at 40to 50 ℃ to obtain the dried butyl rubber.
9. Butyl rubber obtained by the synthetic process according to any one of claims 1 to 8, having a molecular weight distribution Mw/Mn greater than 3.7, preferably greater than 4.5.
10. The butyl rubber according to claim 9, wherein the butyl rubber molecular weight distribution Mw/Mn is greater than 5.0.
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