CN105646757A - Cationic polymerization system and preparation method of high-unsaturation-degree isoolefin copolymer - Google Patents
Cationic polymerization system and preparation method of high-unsaturation-degree isoolefin copolymer Download PDFInfo
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Abstract
The invention relates to a cationic polymerization system and a preparation method of a high-unsaturation-degree isoolefin copolymer. The polymerization system and a polymerization method can improve the feeding amount of multiolefin copolymerization monomers in the system, high-molecular-weight, high-unsaturation-degree (high multiolefin content) and substantially gel-free copolymer product can be obtained, the monomer conversion rate is relatively high, the reaction efficiency of a catalyst and the copolymerization monomers is high, the catalyst cost is low, and industrial application value is achieved.
Description
Technical field
The present invention relates to a kind of cationic polymerization system and the preparation method of high degree of unsaturation isoolefin copolymers, in particular, be a kind of isoolefin monomer method of carrying out that under composite catalyst effect cationic polymerization prepares high degree of unsaturation isoolefin copolymers.
Background technology
Isoolefin copolymers containing unsaturated construction unit is usually formed by isoalkene and other olefinic monomer copolymerization, and its degree of unsaturation refers to the content of unsaturated construction unit (such as conjugated diene) in copolymer. If industrial products butyl rubber is a kind of important synthetic rubber, it it is the copolymer of isobutene. (IB) and a small amount of isoprene (IP), degree of unsaturation refers to the content of isoprene in copolymer, generally at 2.5mol% (molar fraction) below. Butyl rubber has air-tightness and the stretching/compressing damping property of excellence, is widely used in tire and pharmaceuticals industry. It is generally acknowledged that unsaturated construction unit in isoolefin copolymers (such as copolymerization alkadienes alkene) content is called high degree of unsaturation isoolefin copolymers more than the isoolefin copolymers of 2.5% (molar fraction). In order to other high undersaturated dience rubbers (such as natural rubber, isoprene rubber, butadiene rubber or butadiene-styrene rubber) better and with and improve cross-linked network density, it is desirable to increase unsaturated structural unit content in isoolefin copolymers. Generally, the degree of unsaturation of isoolefin copolymers can be improved by strengthening the inventory of polyene (second comonomer), but may result in the problems such as polymerisation conversion decline, molecular weight and molecular weight or gel content increase. The inventory of isoprene (IP) conjugated diene monomer can be strengthened such as butyl rubber (IIR) in preparing, a kind of chain-transferring agent and poisonous substance it is typically considered yet with conjugated diene, polyreaction can be had a negative impact (referring to: KennedyJP.CationicPolymerization.NewYork:Wiley-Interscie nce, 1972,337), cause polymerisation conversion and significant decrease of molecular weight and serious gelatin phenomenon, be difficult to prepare the heavy polymer product substantially without gel. Although polymer molecular weight can be improved by reducing reaction temperature, reduce the adverse effect of the molecular weight reduction caused because increasing alkadienes inventory, but reduce temperature further and can more promote the generation of gel, gelatin phenomenon is inevitable, and it is big to consume energy, product quality and performance all decline. Additionally, conjugated diene too much in polymerization process can cause other side reactions, referring to JournalofPolymerScience, PartA, 1987,27:107��124.These are to prepare the technical difficult points that high degree of unsaturation isoolefin copolymers exists.
In order to solve these technological difficulties, this area is improved mainly through different initiator systems and corresponding polymerization. As: CA2441079 and CA2578679 is open a kind of by ZnR1R2Or RZnX (wherein R1, R2Most likely C6F5Group) Isobutylene Initiated and isoprene carry out combined polymerization altogether, wherein isoprene inventory is 7.0mol%, polyreaction 1h at-78 DEG C, and conversion ratio only has 6%, in polymerizate butyl rubber, isoprene content is 6.4mol%, gel content is 3.8%, and relevant research is reported referring also to GarrattS, GuerreroA, HughesDL, BochmannM, Angew.Chem.Int.Ed.2004,43:2166��2169. CN1316443 and EP-A-1122267 discloses a kind of method preparing low gel, high molecular polyisoolefines and copolymer (such as butyl rubber) under vfanadium compound and organic nitro-compound exist, gel content is substantially reduced after wherein adding Nitrocarbol., but still containing a certain amount of gel in polymerizate, polymerizate yield substantially reduces. CN1310980C discloses the production method of a kind of high-isoprene butyl rubber, and the method relates at least one organic nitro-compound and AlCl3Carrying out under/regimen condition, and do not need vfanadium compound, zirconium halide or halogenation hafnium and deposit and carry out in case, in polymer, multi-olefin content is more than 2.5mol%. The organic nitrating agent used in above-mentioned patented technology is poisonous and poor stability, as poisonous in Nitrocarbol., inflammable, have explosivity etc. CN1526745B and CN101775092A discloses a kind of employing AlCl3It is total to initiator system and under at least one multiolefin crosslinking agent divinylbenzene reagent existent condition, it it is the continuation method producing polymer under 50%-95% at conversion ratio, in polymerizate, gel content is less than 15wt%, degree of unsaturation is more than 4.1mol%, the method is to carry out when being absent from transistion metal compound and organic nitro-compound, but multiolefin crosslinking agent divinylbenzene is expensive, the existence of difunctional easilys lead to the formation of gel.
But, in order to other dience rubbers (such as polybutadiene rubber, polyisoprene rubber or natural rubber) more effectively composite crosslinking, need in butyl rubber containing higher isoprene content, namely need to prepare the butyl rubber product of high degree of unsaturation.
Summary of the invention
The present invention provides a kind of cationic polymerization system and the method preparing high degree of unsaturation isoolefin copolymers by cationic polymerization process, this polymerization system and polymerization can the inventorys of polyene comonomer in raising system, and high molecular can be obtained, high degree of unsaturation (high multiolefin content) and substantially without the isoolefin copolymers product of gel, and monomer conversion is higher, the reaction efficiency of catalyst and comonomer is high, catalyst cost is low, do not use the reagent such as organic nitro-compound or multiolefin crosslinking agent divinylbenzene, there is industrial application value.
A kind of cationic polymerization system provided by the invention, comprises isoolefin monomer, polyene comonomer, proton source compound, lewis acid, activator and organic diluent or solvent. In polymerization system, the concentration of isoolefin monomer is 1.0��6.0mol/L, and it is 2.2%��25% that polyene comonomer accounts for the molar content of total monomer. Preferably, the concentration of isoolefin monomer is 1.5��5.5mol/L, and it is 2.4%��21% that polyene comonomer accounts for the molar content of total monomer.
Described lewis acid is that (general structure is MX to metal halide common in cationic polymerizationn) or alkyl metal halide (general structure is MRn-mXm), selected from AlXn��AlRn-mXm��BCl3��TiX4��FeX3Or SnCl4In one or more, wherein, n=3; M=1��3; X=F, Cl or Br; R is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group; Preferred structure formula is AlXnOr AlRn-mXm(wherein, n=3; M=1��3; X=F, Cl or Br; R is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group) material in a kind of or their mixture, more preferably AlCl3��AlBr3��AlRCl2��AlR2Cl or their mixture, R is methyl, ethyl, propyl group, butyl or amyl group. The mol ratio of lewis acid and monomer (isoalkene and comonomer thereof) is 3.0 �� 10-4��3.0 �� 10-2: 1, it is preferable that 6.0 �� 10-4��1.0 �� 10-2: 1, more preferably 8.0 �� 10-4��8.0 �� 10-3: 1. In order to obtain high conversion, abundant lewis acid is required, but too much lewis acid can cause that polyreaction is difficult to control to, and side reaction increases.
Described proton source compound at least one in water, hydrogen halides, carboxylic acid, alcohol or phenolic compounds, more preferably cheap water and/or hydrogen chloride. Proton source compound is 1.0 �� 10 with the mol ratio of monomer (isoalkene and comonomer thereof) in polymerization system-5��5.0 �� 10-4: 1, it is preferable that 2.0 �� 10-5��3.0 �� 10-4: 1, more preferably 2.5 �� 10-5��2.0 �� 10-4: 1. In order to obtain the polymerizate of high molecular, proton source compound amount is the least possible. Along with proton source compound amount increases, polymerisation conversion improves, and polymer molecular weight declines. The proton source compound of q.s is necessary.
Described activator is R selected from formula1COOR2At least one in the halogenated carboxylic acid ester compounds represented, R in formula1For alkyl, aralkyl or thiazolinyl that alpha-carbon is optionally substituted by halogen, R2It is the alkyl of 1��10 carbon atom, aralkyl or thiazolinyl, activator preferably is selected from methyl chloroacetate, ethyl chloroacetate, vinyl chloroacetate, propyl chloroacetate, butyl chloroacetate, dichloroacetic acid pentyl ester, the own ester of dichloroacetic acid alkene, dichloroacetic acid isocyanate, dichloroacetic acid monooctyl ester, chloroacetic acid phenyl ester, chloroacetic acid benzyl ester, methyl dichloroacetate, ethyl dichloroacetate, dichloroacetic acid propyl ester, dichloroacetic acid allyl ester, dichloroacetic acid propyl ester, dichloroacetic acid butyl ester, dichloroacetic acid pentyl ester, the own ester of dichloroacetic acid alkene, dichloroacetic acid isocyanate, dichloroacetic acid monooctyl ester, dichloroacetic acid phenyl ester, dichloroacetic acid benzyl ester, ethyl trichloroacetate, trichloroacetic acid propyl ester, trichloroacetic acid isopropyl ester, butyl trichloroacetate, trichloroacetic acid pentyl ester, the own ester of trichloroacetic acid alkene, trichloroacetic acid isocyanate, trichloroacetic acid monooctyl ester, trichloroacetic acid phenyl ester, trichloroacetic acid benzyl ester, ��-allylmethyl, ��-chloroacrylic acid ethyl ester, ��-chloroacrylic acid propyl ester, ��-chloroacrylic acid butyl ester, ��-chloroacrylic acid pentyl ester, the own ester of ��-chloroacrylic acid alkene, ��-chloroacrylic acid isocyanate, ��-chloropropene monooctyl ester, ��-chloroacrylic acid benzyl ester, methyl bromoacetate, bromoacetate, acid propyl bromide, one or more in bromoacetic acid butyl ester, more preferably from one or more in ethyl chloroacetate, allyl chloroacetate, butyl chloroacetate, monoxone benzyl ester, dichloroacetic acid propyl ester, dichloroacetic acid allyl ester, dichloroacetic acid butyl ester, dichloroacetic acid benzyl ester, trichloroacetic acid propyl ester, allyl trichloroacetate, butyl trichloroacetate, the own ester of trichloroacetic acid, trichloroacetic acid benzyl ester, ��-chloroacrylic acid propyl ester, ��-chloroacrylic acid allyl ester, ��-chloroacrylic acid butyl ester or ��-chloroacrylic acid benzyl ester.The mol ratio of activator and monomer (isoalkene and comonomer thereof) is 6.0 �� 10-4��9.0 �� 10-3: 1, it is preferable that 8.0 �� 10-4��7.0 �� 10-3: 1, more preferably 1.0 �� 10-3��5.0 �� 10-3: 1. A certain amount of activator is necessary, but too much consumption activator may result in molecular weight and molecular weight.
In the present invention, isoalkene is not limited to specific isoolefin monomer, selected from well known to a person skilled in the art isoalkene, but it preferably is selected from one or more of isoalkene of 4��7 carbon atoms, such as isobutene., 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene or 4-methyl-1-pentene, more preferably from isobutene. or 2-methyl-1-butene alkene.
In the present invention, comonomer is not limited to special polyene selected from polyene, can with one or more polyenes of isoalkene combined polymerization selected from well known to a person skilled in the art, but preferably there is the polyene of 4-14 carbon atom, such as butadiene, isoprene, 2, 4-dimethyl butadiene, pentadiene, 3-methyl isophthalic acid, 3-pentadiene, 2, 4-hexadiene, 2-neopentyl butadiene, 2-methyl isophthalic acid, 5-hexadiene, 2, 5-dimethyl-2, 4-hexadiene, 2-methyl isophthalic acid, 4-pentadiene, 2-methyl isophthalic acid, 6-heptadiene, cyclopentadiene, methyl cyclopentadiene, cyclohexadiene, 1-vinyl cyclohex diene, ethylidene norbornene, one or more mixture in nopinene, especially conjugated diene, particularly preferably isoprene or cyclopentadiene.
Described organic diluent or solvent are known in those skilled in the art, including ethylene, alkane, cycloalkane or halogenated hydrocarbons (CaHbXc, wherein X represents halogen atom, such as Cl, F, a represents the number of carbon atom, selected from the integer of 1��10, b, c be at least 1 integer) or its isomer. organic diluent or solvent include but not limited to the one or more combination thing of following material: ethylene, ethane, propane, butane, pentane, hexane, heptane, isobutyltrimethylmethane., hexamethylene, hexahydrotoluene, chloromethanes, dichloromethane, ethyl chloride, dichloroethanes, fluoromethane, difluoromethane, fluoroform, fluoroethane, Difluoroethane, HFC-143a, tetrafluoroethane, pentafluoroethane, fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, Octafluorobutane., nine fluorine butane, fluorine Tetramethylene., difluoro Tetramethylene., trifluoro Tetramethylene., ptfe ring butane, five fluorine Tetramethylene., trans-1,1,2,2,3,4-Hexafluorocyclobutane. or seven fluorine Tetramethylene., more preferably from ethylene, butane, pentane, hexane, chloromethanes, dichloromethane, ethyl chloride, difluoromethane, tetrafluoroethane, the one or more combination thing of fluoro-propane. what it should be particularly mentioned is chloromethanes, dichloromethane, difluoromethane, tetrafluoroethane, the mixture of fluoro-propane or chloromethanes and dichloromethane, the mixture of chloromethanes and difluoromethane, the mixture of chloromethanes and tetrafluoromethane, the mixture of dichloromethane and difluoromethane, the mixture of dichloromethane and tetrafluoromethane, alkane is (such as butane, pentane, hexane or hexahydrotoluene) with alkyl chloride (such as chloromethanes, dichloromethane or ethyl chloride) mixture, alkane is (such as butane, pentane, hexane or hexahydrotoluene) with fluoric ether (such as difluoromethane, tetrafluoroethane, fluoro-propane) mixture.
The preparation method that present invention also offers a kind of high degree of unsaturation isoolefin copolymers, adopt above-mentioned polymerization system, isoalkene and multi-olefin monomer, under proton source compound, lewis acid and activator exist, prepare isoolefin copolymers by cationic polymerization process in organic diluent or solvent.
The preparation method of the present invention, cationic polymerization controls by common polymerization process, polymerization temperature, pressure and time adjust in known scope, polymerization temperature carries out at-120 DEG C��20 DEG C, it is preferable that carries out at-110 DEG C��10 DEG C, carries out at-104 DEG C��-10 DEG C, polymerization system pressure is in 0.1 bar��4 bar scope, polymerization time is 1 second��120 minutes, it is preferable that 30 seconds��60 minutes, more preferably 1 minute��40 minutes.Polyreaction completes, and adds the alcoholic solution containing antioxidant and polyreaction is terminated, for instance by 2,2-di-2-ethylhexylphosphine oxides (4-methyl-6 tert-butyl phenol), Inganox1010 or Inganox1076 dissolves in ethanol. Through deviating from solvent, the last handling process such as dry obtains polymerizate.
In the above-mentioned preparation method of the present invention, described cationic polymerization adopts known slurry process or solution polymerization technique to carry out, and depends on selected organic diluent or the solvent dissolubility to copolymer. Can be batchwise polymerization mode, it is also possible to be continuous polymerization mode. Monomer is mixed homogeneously with organic diluent or solvent, then can trigger monomer polyreaction after mixing with proton source compound, lewis acid and activator.
In preparation method of the present invention, proton source compound, lewis acid and activator can be directly added into polymerization system, can also with use after organic solvent wiring solution-forming, compound concentration is in lewis acid, it is generally 0.01mol//L��1.5mol//L, preferred 0.02mol//L��0.8mol//L, more preferably 0.03mol//L��0.5mol//L, described organic solvent is a kind of in alkane, cycloalkane or halogenated hydrocarbons or their mixture. Described activator can adopt various ways to add, as: proton source compound, activator are used by after directly using after the mixing of different feed way or placing a period of time from lewis acid three; Or add immediately after first proton source compound and activator being added the monomer mixture with reaction medium or placement a period of time adds lewis acid; Or before polymerization proton source compound is added in polymerization system, add the mixed liquor placing a period of time after lewis acid mixes with activator moment or mixes. The mixing of above-mentioned each component or placement temperature are at-100 DEG C��10 DEG C, it is preferable that-95 DEG C��0 DEG C, more preferably-90 DEG C��-10 DEG C standing times are 1 minute��100 days, it is preferable that 2 minutes��20 days, more preferably 5 minutes��10 days.
The application of the invention method, it is possible to reaching the efficient copolymerization of isoalkene and multi-olefin monomer, monomer conversion may be up to 100%, and can prepare have simultaneously raising double bond content, substantially without the high molecular isoolefin copolymers of gel. Weight average molecular weight (the M of isoolefin copolymersw), it is preferable that more than 100kg/mol, more preferably greater than 300kg/mol, it is even more preferably greater than 400kg/mol, is even more preferably greater than 600kg/mol; In isoolefin copolymers, polyene structure unit content (degree of unsaturation) is higher than commercially produced product, multi-olefin content is more than 2.5mol%, more preferably greater than 4.0mol%, is even more preferably greater than 6.0mol%, but it is even more preferably greater than 10mol%, reach more than 20mol%. Gel content in isoolefin copolymers is typically smaller than 1wt%, it is preferable that less than 0.5wt%, is even more preferably less than 0.1wt%, but even more preferably still can't check gel content.
Particularly, pass through the inventive method, the copolyreaction activity of multi-olefin monomer can be improved, degree of unsaturation in copolymer is significantly improved, even up to polyene structure unit content in copolymer more than monomeric charge content, such that it is able to utilize polyene comonomer efficiently, simplify the last handling processes such as separation and recovery, reduce energy consumption, reduce cost, have industrial application value.
The present invention adopts GPC (gel permeation chromatography) method to measure weight average molecular weight (Mw) and the molecular weight distributing index (MWD) of polymerizate;With PS standard specimen for calibration trace. Automatic viscosity instrument is adopted to measure the viscosity-average molecular weight (M ��) of polymerizate; Testing at 30 DEG C, using toluene as solvent, computing formula is [��]=[2 (��sp-ln��r)]1/2/ c, wherein ��r=t/t0, ��sp=��r-1, t is concentration is the flowing time of polymer toluene solution of c, t0Flowing time for toluene. Adopt1H-NMR detects the degree of unsaturation of polymerizate, sample cell diameter 5mm, and sample dissolves with deuterochloroform at normal temperatures, with TMS for interior mark, tests at 25 DEG C. The mensuration of gel content adopts " People's Republic of China's petroleum chemical industry standard " SH/T1050-91.
Detailed description of the invention:
Example is set forth below and illustrates in greater detail the present invention, but protection scope of the present invention should not be limited only to these examples.
Embodiment 1
Under-40 DEG C and high pure nitrogen protection, with CH2Cl2For reaction medium, by H2O, HCl and AlCl3Reaction 1 hour, is subsequently adding butyl chloroacetate in advance, places 2 hours, obtain homogeneous phase solution after mix homogeneously.
Under-102 DEG C and High Purity Nitrogen protection; polymer reactor adds 20mL mixed solution ([IB]=5.0mol/L containing isobutene. (IB), isoprene (IP) and tetrafluoroethane; IP inventory accounts for the 3.0mol% of monomer total amount); it is subsequently adding above-mentioned homogeneous phase solution trigger monomer and carries out polyreaction, wherein AlCl3It is 1.1 �� 10 with the mol ratio of monomer total amount-3, H2The mol ratio of O and monomer total amount is 2.4 �� 10-5, the mol ratio of HCl and monomer total amount is 2.2 �� 10-5, the mol ratio of butyl chloroacetate and monomer (IB+IP) is 1.8 �� 10-3. Polyreaction adds the 5mL alcoholic solution containing 1wt% antioxidant 1010 and terminates reaction after 0.5 hour, put into after drying 48h in the vacuum drying oven of 50 DEG C, test after polymerizate desolvation. The yield of isobutene. and isoprene copolymer is 94%, weight average molecular weight (Mw) it is 6.5 �� 105G/mol, molecular weight distributing index (Mw/Mn) it is 4.9, isoprene content is 3.1mol%, and gel content can't check.
Embodiment 2
Under-50 DEG C and high pure nitrogen protection, with CH2Cl2For reaction medium, by H2O, HCl and AlCl3Reaction 0.5 hour, is subsequently adding chloroacetic acid tert-butyl ester and isopropyl chloracetate in advance, places 4 hours, prepare homogeneous phase solution after mix homogeneously.
Polymerization is with embodiment 1, and simply solvent is dichloromethane, and [IB] is 7.5mol%, AlCl for 3.9mol/L, IP inventory3It is 6.2 �� 10 with the mol ratio of monomer total amount-3, H2The mol ratio of O and monomer total amount is 6.2 �� 10-5, the mol ratio of HCl and monomer total amount is 1.0 �� 10-5, the mol ratio of chloroacetic acid tert-butyl ester and monomer total amount is 2.0 �� 10-3, the mol ratio of isopropyl chloracetate and monomer total amount is 2.0 �� 10-4. Polyreaction terminated after 1 hour, terminates and post-processing approach is with embodiment 1. Isobutene. and isoprene copolymer yield are 67%, MwIt is 1.5 �� 105G/mol, Mw/MnBeing 4.0, isoprene content is 7.3mol%, and gel content can't check.
Embodiment 3
Under-90 DEG C and high pure nitrogen protection, with CH2Cl2For reaction medium, by H2O, HCl and AlCl3Reaction 1 hour, is subsequently adding butyl chloroacetate in advance, places 168 hours, obtain homogeneous phase solution after mix homogeneously.
Polymerization with embodiment 1, [IB] for 3.0mol/L, IP inventory account for monomer total amount for 2.5mol%, AlCl3It is 1.3 �� 10 with the mol ratio of monomer total amount-3, H2The mol ratio of O and monomer total amount is 6.0 �� 10-5, the mol ratio of butyl chloroacetate and monomer total amount is 1.4 �� 10-3.Polyreaction terminated after 2 hours, terminates and post-processing approach is with embodiment 1. The yield of isobutene. and isoprene copolymer is 28%, MwIt is 3.2 �� 105G/mol, Mw/MnBeing 2.7, isoprene content is 2.6%, and gel content can't check.
Embodiment 4
Experimental technique with embodiment 1, simply [IB] for 2.1mol/L, IP inventory account for monomer total amount for 20mol%, AlCl3It is 2.8 �� 10 with the mol ratio of monomer total amount-3, H2The mol ratio of O and monomer total amount is 3.5 �� 10-5, the mol ratio of butyl chloroacetate and monomer total amount is 4.0 �� 10-3. Polyreaction terminated after 0.5 hour, terminates and post-processing approach is with embodiment 1. The yield of isobutene. and isoprene copolymer is 86%, MwIt is 1.2 �� 105G/mol, Mw/MnBeing 6.1, isoprene content is 21.4mol%, and gel content can't check.
Embodiment 5
Experimental technique with embodiment 1, simply [IB] for 3.4mol/L, IP inventory account for monomer total amount for 4mol%, AlCl3It is 1.5 �� 10 with the mol ratio of monomer total amount-3, H2The mol ratio of O and monomer total amount is 3.1 �� 10-5, the mol ratio of butyl chloroacetate and monomer total amount is 2.2 �� 10-3, the mol ratio of ethyl trichloroacetate and monomer total amount is 2.0 �� 10-4. Polyreaction terminated after 1 hour, terminates and post-processing approach is with embodiment 1. The yield of isobutene. and isoprene copolymer is 99%, MwIt is 2.3 �� 105G/mol, Mw/MnBeing 4.3, isoprene content is 4.5mol%, and gel content can't check.
Embodiment 6
Under 20 DEG C and high pure nitrogen protection, with CH2Cl2It is organic solvent with normal hexane, HCl is reacted 10 minutes with ethyl aluminum dichloride (EADC), obtains [EADC] for 0.21mol/L homogeneous phase solution.
Under-98 DEG C and High Purity Nitrogen protection; polymer reactor adds 20mL mixed solution ([IB]=3.0mol/L containing isobutene., isoprene, chloroacetic acid tert-butyl ester, monoxone benzyl ester and tetrafluoroethane; that IP inventory accounts for monomer total amount is 5.8mol%), it is subsequently adding above-mentioned homogeneous phase solution trigger monomer and carries out polyreaction. Wherein, EADC is 6.3 �� 10 with the mol ratio of monomer total amount-3, the mol ratio of HCl and monomer total amount is 1.2 �� 10-4, the mol ratio of chloroacetic acid tert-butyl ester and monomer total amount is 3.1 �� 10-4, the mol ratio of monoxone benzyl ester and monomer total amount is 1.0 �� 10-5. Polyreaction terminated after 1 hour, terminates and post-processing approach is with embodiment 1. The yield of isobutene. and isoprene copolymer is 96%, MwIt is 2.2 �� 105G/mol, Mw/MnBeing 4.6, isoprene content is 4.5mol%, and gel content can't check.
Claims (10)
1. a cationic polymerization system, comprises isoolefin monomer, polyene comonomer, lewis acid, proton source compound, activator and organic diluent or solvent, it is characterized in that:
Isoalkene is the isoalkene of 4��7 carbon atoms, and its concentration is 1.0mol/L��6.0mol/L;
Polyene is the polyene of 4-14 carbon atom, and the molar content accounting for total monomer is 2.2%��25%;
Lewis acid is metal halide or alkyl metal halide, and its mol ratio with monomer is 3.0 �� 10-4��3.0 �� 10-2: 1;
Proton source compound is at least one in water, hydrogen halides, carboxylic acid, alcohol or phenolic compounds, and its mol ratio with monomer is 1.0 �� 10-5��5.0 �� 10-4: 1;
Activator is R selected from formula1COOR2At least one in the halogenated carboxylic acid ester compounds represented, R in formula1For alkyl, aralkyl or thiazolinyl that alpha-carbon is optionally substituted by halogen, R2Being the alkyl of 1��10 carbon atom, aralkyl or thiazolinyl, the mol ratio of activator and monomer is 6.0 �� 10-4��9.0 �� 10-3: 1;
Organic diluent or solvent are ethylene, alkane, cycloalkane or halogenated hydrocarbons or its isomer.
2. polymerization system according to claim 1, is characterized in that: described isoalkene is one or more in isobutene., 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene or 4-methyl-1-pentene; Described polyene be butadiene, isoprene, 2,4-dimethyl butadiene, pentadiene, 3-methyl isophthalic acid, 3-pentadiene, 2,4-hexadiene, 2-neopentyl butadiene, 2-methyl isophthalic acid, 5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl isophthalic acid, 4-pentadiene, 2-methyl isophthalic acid, one or more in 6-heptadiene, cyclopentadiene, methyl cyclopentadiene, cyclohexadiene, 1-vinyl cyclohex diene, ethylidene norbornene, nopinene.
3. polymerization system according to claim 1, is characterized in that: lewis acid is AlXnOr AlRn-mXm(wherein, n=3; M=1��3; X=F, Cl or Br; R is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group) material in a kind of or their mixture, its mol ratio with monomer is 6.0 �� 10-4��1.0 �� 10-2:1��
4. polymerization system according to claim 1, is characterized in that: proton source compound is water and/or hydrogen chloride, and it is 2.0 �� 10 with the mol ratio of monomer in polymerization system-5��3.0 �� 10-4:1��
5. polymerization system according to claim 1, is characterized in that: activator is selected from methyl chloroacetate, ethyl chloroacetate, vinyl chloroacetate, propyl chloroacetate, butyl chloroacetate, dichloroacetic acid pentyl ester, the own ester of dichloroacetic acid alkene, dichloroacetic acid isocyanate, dichloroacetic acid monooctyl ester, chloroacetic acid phenyl ester, chloroacetic acid benzyl ester, methyl dichloroacetate, ethyl dichloroacetate, dichloroacetic acid propyl ester, dichloroacetic acid allyl ester, dichloroacetic acid propyl ester, dichloroacetic acid butyl ester, dichloroacetic acid pentyl ester, the own ester of dichloroacetic acid alkene, dichloroacetic acid isocyanate, dichloroacetic acid monooctyl ester, dichloroacetic acid phenyl ester, dichloroacetic acid benzyl ester, ethyl trichloroacetate, trichloroacetic acid propyl ester, trichloroacetic acid isopropyl ester, butyl trichloroacetate, trichloroacetic acid pentyl ester, the own ester of trichloroacetic acid alkene, trichloroacetic acid isocyanate, trichloroacetic acid monooctyl ester, trichloroacetic acid phenyl ester, trichloroacetic acid benzyl ester, ��-allylmethyl, ��-chloroacrylic acid ethyl ester, ��-chloroacrylic acid propyl ester, ��-chloroacrylic acid butyl ester, ��-chloroacrylic acid pentyl ester, the own ester of ��-chloroacrylic acid alkene, ��-chloroacrylic acid isocyanate, ��-chloropropene monooctyl ester, ��-chloroacrylic acid benzyl ester, methyl bromoacetate, bromoacetate, acid propyl bromide, one or more in bromoacetic acid butyl ester, its mol ratio with monomer is 8.0 �� 10-4��7.0 �� 10-3:1��
6. polymerization system according to claim 1, it is characterized in that: organic diluent or solvent are ethylene, ethane, propane, butane, pentane, hexane, heptane, isobutyltrimethylmethane., hexamethylene, hexahydrotoluene, chloromethanes, dichloromethane, ethyl chloride, dichloroethanes, fluoromethane, difluoromethane, fluoroform, fluoroethane, Difluoroethane, HFC-143a, tetrafluoroethane, pentafluoroethane, fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, Octafluorobutane., nine fluorine butane, fluorine Tetramethylene., difluoro Tetramethylene., trifluoro Tetramethylene., ptfe ring butane, five fluorine Tetramethylene., trans-1,1,2,2,3,4-Hexafluorocyclobutane. or seven fluorine Tetramethylene., more preferably from ethylene, butane, pentane, hexane, chloromethanes, dichloromethane, ethyl chloride, difluoromethane, tetrafluoroethane, the one or more combination thing of fluoro-propane.
7. the preparation method of one kind high degree of unsaturation isoolefin copolymers, adopt any polymerization system of claim 1-6, isoalkene and multi-olefin monomer are under proton source compound, lewis acid and activator exist, organic diluent or solvent prepare isoolefin copolymers by cationic polymerization process, polymerization temperature is-120 DEG C��20 DEG C, polymerization system pressure is at 0.1��4 bar scope, polymerization time 1 second��120 minutes.
8. preparation method according to claim 7, is characterized in that: isoalkene concentration is 1.5mol/L��5.5mol/L; It is 2.4%��22% that polyene accounts for the molar content of total monomer; Polymerization temperature is-110 DEG C��10 DEG C, and polymerization reaction time is 30 seconds��60 minutes.
9. preparation method according to claim 7, is characterized in that: in polymerization system, lewis acid is 8.0 �� 10 with the mol ratio of monomer-4��8.0 �� 10-3: 1, the mol ratio of proton source compound and monomer is 2.5 �� 10-5��2.0 �� 10-4: 1, the mol ratio of activator and monomer is 1.0 �� 10-3��5.0 �� 10-3:1��
10. preparation method according to claim 7, is characterized in that: polymerization temperature is-104 DEG C��-10 DEG C, and polymerization reaction time is 1 minute��40 minutes.
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