CN106146701A - A kind of preparation method of halogen polymer - Google Patents

A kind of preparation method of halogen polymer Download PDF

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CN106146701A
CN106146701A CN201510194429.3A CN201510194429A CN106146701A CN 106146701 A CN106146701 A CN 106146701A CN 201510194429 A CN201510194429 A CN 201510194429A CN 106146701 A CN106146701 A CN 106146701A
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monoolefine
benzoquinone
alkane
solution
compound
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CN106146701B (en
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张雷
邱迎昕
龚惠勤
周新钦
张月红
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention discloses the preparation method of a kind of halogenation monoolefine-alkylstyrene copolymers, under the conditions of being included in cationic polymerization, monoolefine shown in Formula II is contacted with each component in initiator system with the ring-alkylated styrenes shown in formula III in the mixed solvent of alkane and halogenated alkane, the halogenated alkane in the solution containing monoolefine-alkylstyrene copolymers obtained is replaced with alkane, solution after displacement is contacted with halogen-containing compound and carries out halogenation, described initiator system contains the compound that can provide carbonium ion, lewis acid and activator, described activator is selected from the compound shown in Formulas I-1 and the compound shown in Formulas I-2.The method of the present invention can significantly improve polymerization efficiency, and can obtain the polymer with higher molecular weight, necessary polymer re-dissolved process when being omitted employing slurry polymerization process, simplifies production technology.

Description

A kind of preparation method of halogen polymer
Technical field
The present invention relates to the preparation method of a kind of halogen polymer, more particularly, to a kind of halogenation monoolefine-alkylbenzene second The preparation method of alkene copolymer.
Background technology
At present, the most commonly used slurry polymerization process with monochloro methane as diluent produces butyl rubber, its Reason essentially consists in: the production efficiency of slurry polymerization process is high, and the molecular weight of product is high, good processability.With slurry Polymerization is compared, and polymerisation in solution rule does not has the product that obvious advantage, especially solution polymerization process obtain in these areas Molecular weight is low, processing characteristics is poor, and the product being the most commercially difficult to obtain with slurry polymerization process is competed mutually.But, The development space ratio of solution polymerization process is broader, such as: solution polymerization process more meets environmental requirement than slurry polymerization process, and And broader to the subject range of polymerization temperature, especially there is more preferable DEVELOPMENT PROSPECT to realizing high temperature polymerization aspect.
Halogenated butyl rubber generally uses solwution method to prepare, namely by the butyl rubber being dissolved in alkane and halogen-containingization Compound contact carries out halogenation, when using slurry polymerization process to prepare butyl rubber, needs at polymerization procedure and halogen Arrange the solvent being intended to replace the halogenated alkane in the mixture that slurry polymerization process obtains with alkane between change reactions steps to replace Step and polymer re-dissolved step, and in solution polymerization process, if using the mixed solution of halogenated alkane and alkane to make For polymer solvent, then can directly carry out halogenation after the halogenated alkane alkane in solution polymerization obtained is replaced Reaction, and without polymer re-dissolved step, it is clear that solution polymerization process is more suitable for the production of solwution method halogenated butyl rubber.
But, the subject matter that solution polymerization process exists is: need to use the high activity being adapted to solution polymerization system to cause Agent system, to obtain the product of high molecular.
It is the effective initiator preparing butyl rubber in the solution that US3361725 proposes aluminum alkyl halide, can be higher At a temperature of obtain the product of higher molecular weight, but require that in aluminum alkyl halide, the molar ratio of dialkylaluminum halides reaches More than 80%, the molar ratio of monoalkyl dihalide aluminum is then less than 20%, and thus the self-initiating by alkyl aluminum acts on molten In liquid (such as hexane) in prepare butyl rubber.But, it practice, the efficiency of initiation of this initiator system is the lowest, and And rate of polymerization is the slowest, it is impossible to meet the needs of reality application.To this end, this initiator system is carried out by US6403747 Improve, in above dialkylaluminum halides/monoalkyl dihalide aluminum mixed system, i.e. introduce water or the aikyiaiurnirsoxan beta of trace, Initiator system activity is made to improve, such that it is able to prepare weight average molecular weight at-60 DEG C to-80 DEG C to reach more than 400,000 Butyl rubber.Although the efficiency of initiation of initiator system disclosed in US6403747 and rate of polymerization are improved to some extent, But the most unsatisfactory in actual mechanical process, and initiator system preparation is relatively difficult, especially to aikyiaiurnirsoxan beta Technology of preparing require the highest.
Halogenated isobutylene-p-methylstyrene copolymer is usually and the copolymer of isobutene. Yu p-methylstyrene is carried out halogen Change, part p-methylstyrene group transformations is halomethylstyrene group and obtains.Owing to molecular backbone is complete Saturated structures, therefore halogenated isobutylene-p-methylstyrene copolymer has more excellent than halogenated isobutylene-isoprene rubber Combination property, especially there is more preferable heat resistance；Further, due to the existence of highly active benzyl halogen functional group, Sulfuration and co-vulcanization can be realized in broader scope with various rubber, the most also there is the modified advantage of wider range. This product through and nylon blending make dynamic vulcanization alloy for producing the inner liner of tire, can accomplish the lightest but also thin,
As can be seen here, halogenated isobutylene-p-methylstyrene copolymer can be used for producing the tire with higher performance, and has There is the most wide market application foreground.Therefore, research and development be suitable to isobutene .-p-methylstyrene copolymer solution gather Close technique for promoting the exploitation of halogenated isobutylene-p-methylstyrene copolymer to be of great significance with application tool.
Summary of the invention
When halogenated isobutylene-p-methylstyrene copolymer is prepared in isobutene .-p-methylstyrene copolymer halogenation, not The p-methylstyrene monomer of reaction also can participate in halogenation, therefore it is required that carry out in the glue of halogenation methylbenzene The content of ethylene is low.Owing to the boiling point of p-methylstyrene is higher, it is difficult to removing, it is desirable to by isobutene. and to first When base styrene carries out combined polymerization, the monomer including p-methylstyrene can be made to convert the most completely.But, this The inventor of invention finds in research process, and isobutene. is when carrying out cationic solution polymerization, and its polymerization efficiency is to solvent Polarity is the most insensitive, but uses C+(that is, carbonium ion)/lewis acid initiator system, by isobutene. and alkylbenzene When ethylene carries out combined polymerization in the solution by cationic polymerization mode, polymerization efficiency extreme difference, rate of polymerization is slow, need into The long-time reaction of row just can make monomer convert completely or almost completely.Cationic polymerization is carried out the most at low temperatures, poly- The conjunction time is the longest, and the energy expenditure needed for maintaining low temperature is the highest, and long polymerization obviously cannot meet large-scale production Requirement.And, use C+/ lewis acid initiator system typically requires could be prepared under more harsh reaction condition The isobutene. of high molecular-p-methylstyrene copolymer.
The present inventor is studied for the problems referred to above, finds: by isobutene. and ring-alkylated styrenes by sun from When the mode of son polymerization carries out combined polymerization in the solution, if at C+/ lewis acid initiator system introduces quinonoid compound (particularly having the quinonoid compound of electron-withdrawing substituent) can significantly improve polymerization efficiency, can be with higher polymerization speed Rate makes the monomer including ring-alkylated styrenes convert completely or almost completely；Simultaneously, moreover it is possible to obtain that there is higher molecular weight Polymer, particularly rubber heavy polymer.This completes the present invention.
The invention provides the preparation method of a kind of halogenation monoolefine-alkylstyrene copolymers, the method includes following step Rapid:
(1) under the conditions of cationic polymerization, by least one monoolefine and at least one ring-alkylated styrenes and initiator body Each component in system contacts in polymer solvent, obtains the solution containing monoolefine-alkylstyrene copolymers, described polymerization Solvent is made up of at least one first polymer solvent and at least one second polymer solvent, and described first polymer solvent is selected from halogen For alkane, described second polymer solvent is selected from alkane, and the condition of described contact makes, by weight, described containing monoene In the solution of hydrocarbon-alkylstyrene copolymers, the content of unreacted ring-alkylated styrenes is not higher than 1000ppm；
Described initiator system contains at least one compound that can provide carbonium ion, at least one lewis acid and extremely Few a kind of activator, described activator is selected from the compound shown in Formulas I-1 and the compound shown in Formulas I-2,
In Formulas I-1 and Formulas I-2, R1、R2、R3、R4、R5、R6、R7And R8It is respectively-H ,-X1、-NO2、 With the one in-CN, X1And X2It is respectively the one in halogen group；
Described monoolefine is selected from the compound shown in Formula II,
In Formula II, R9And R10It is respectively C1～C5Straight or branched alkyl；Or R9For hydrogen, R10For C3～C5 Branched alkyl；
Described ring-alkylated styrenes is selected from the compound shown in formula III,
In formula III, R11For C1～C5Straight or branched alkyl；
(2) molten containing monoolefine-alkylstyrene copolymers obtained by least one replacement solvent displacement step (1) Halogenated alkane in liquid, obtains solution after the displacement containing monoolefine-alkylstyrene copolymers, and described replacement solvent is selected from Alkane；
(3) solution and halogen-containingization after the displacement containing monoolefine-alkylstyrene copolymers that step (2) is obtained Compound contacts, so that the part hydrogen atom in described monoolefine-alkylstyrene copolymers strand is substituted with halogen atoms.
According to the polymerization procedure in the inventive method, the C simple with employing+(that is, carbonium ion)/lewis acid The polymerization technique of initiator system is compared, it is possible to obtain the polymerization efficiency significantly improved, it is thus possible to higher rate of polymerization Realize monomer to convert completely or almost completely so that the glue containing monoolefine-alkylstyrene copolymers of preparation is without warp Go through and remove the process of unreacted monomer and i.e. can be directly used for halogenation；On the other hand can also obtain and there is the poly-of higher molecular weight Compound, particularly rubber heavy polymer.It addition, the C simple with employing+/ lewis acid initiator system is compared, Even if the method for the present invention implements polymerization at higher temperatures, also can obtain higher polymerization efficiency and preparation has higher The polymer of molecular weight, it is thus possible to the energy expenditure being effectively reduced in polymerization process.
The method according to the invention, the solution that polymerization obtains can be sent directly in halogenation step, eliminates employing and becomes silted up Slurry polymerization prepares necessary polymer re-dissolved process during polymer, effectively simplifies halogenation monoolefine-alkylbenzene second The production technology of alkene copolymer.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, concrete with following Embodiment is used for explaining the present invention together, but is not intended that limitation of the present invention.
Fig. 1 is a kind of preferred implementation of the method according to the invention.
Fig. 2 is the another kind of preferred implementation of the method according to the invention.
Description of reference numerals
1: the monoolefine 2 shown in Formula II: the ring-alkylated styrenes shown in formula III
31: the first polymer solvent 32: the second polymer solvents
4: initiator solution 5: terminator
6: the solution 7 containing monoolefine-alkylstyrene copolymers: replacement solvent steam
8: the halogenated alkane 9 displaced: solution after displacement
10: halogen-containing compound 11: radical initiator solution
12: the aqueous solution 13 of alkaline matter: containing the mixture of halogenation monoolefine-alkylstyrene copolymers
14: light source I: polymer reactor
II: solvent displacer III: halogenation reactor
IV: blender V: photohalogenation reactor
VI: neutralization reactor
Detailed description of the invention
The invention provides the preparation method of a kind of halogenation monoolefine-alkylstyrene copolymers, the method includes following step Rapid:
(1) under the conditions of cationic polymerization, by least one monoolefine and at least one ring-alkylated styrenes and initiator body Each component in system contacts in polymer solvent, obtains the solution containing monoolefine-alkylstyrene copolymers, described polymerization Solvent is made up of at least one first polymer solvent and at least one second polymer solvent, and described first polymer solvent is selected from halogen For alkane, described second polymer solvent is selected from alkane, and the condition of described contact makes, by weight, described containing monoene In the solution of hydrocarbon-alkylstyrene copolymers, the content of unreacted ring-alkylated styrenes is not higher than 1000ppm, is preferably not Higher than 500ppm, more preferably not above 200ppm；
(2) molten containing monoolefine-alkylstyrene copolymers obtained by least one replacement solvent displacement step (1) Halogenated alkane in liquid, obtains solution after the displacement containing monoolefine-alkylstyrene copolymers, and described replacement solvent is selected from Alkane；
(3) solution and halogen-containingization after the displacement containing monoolefine-alkylstyrene copolymers that step (2) is obtained Compound contacts, so that the part hydrogen atom in described monoolefine-alkylstyrene copolymers strand is substituted with halogen atoms.
The method according to the invention, described initiator system (being referred to as initiator composition) contains at least one energy The compound of carbonium ion, at least one lewis acid and at least one activator are enough provided.
Described activator is selected from the compound shown in Formulas I-1 and the compound shown in Formulas I-2,
In Formulas I-1 and Formulas I-2, R1、R2、R3、R4、R5、R6、R7And R8It is respectively-H ,-X1、-NO2、 With the one in-CN, X1And X2It is respectively the one (such as :-F ,-Cl ,-Br or-I) in halogen group.
The instantiation of described activator can include but not limited to: tetrahydrochysene 1,4-benzoquinone, tetrahydrochysene neighbour's benzoquinone, fluorine three hydrogen pair Benzoquinone, fluorine three hydrogen neighbour's benzoquinone, difluoro dihydro 1,4-benzoquinone, difluoro dihydro neighbour's benzoquinone, trifluoro one hydrogen 1,4-benzoquinone, trifluoro one Hydrogen neighbour's benzoquinone, tetrafluoro 1,4-benzoquinone, tetrafluoro neighbour's benzoquinone, a chlorine three hydrogen 1,4-benzoquinone, chlorine three hydrogen neighbour's benzoquinone, dichloro-dihydro pair Benzoquinone (include 2,3-dichloro 1,4-benzoquinone, 2,5-dichloro 1,4-benzoquinone, 2,6-dichloro 1,4-benzoquinone), dichloro-dihydro neighbour's benzoquinone (include 3,4-dichloro neighbour's benzoquinone, 3,5-dichloro neighbour's benzoquinone, 3,6-dichloro neighbour's benzoquinone), trichlorine one hydrogen 1,4-benzoquinone, trichlorine one hydrogen neighbour's benzoquinone, Chloranil, monoethyl quinone, monobromo three hydrogen 1,4-benzoquinone, monobromo three hydrogen neighbour's benzoquinone, dibromo dihydro 1,4-benzoquinone (include 2,3-dibromo 1,4-benzoquinone, 2,5-dibromo 1,4-benzoquinone, 2,6-dibromo 1,4-benzoquinone), dibromo dihydro neighbour's benzoquinone (include 3,4-dibromo-o Benzoquinone, 3,5-dibromo-o benzoquinone, 3,6-dibromo-o benzoquinone), tribromo one hydrogen 1,4-benzoquinone, tribromo one hydrogen neighbour's benzoquinone, tetrabromo is to benzene Quinone, tetrabromo-phthalic quinone, a fluorine trinitro-1,4-benzoquinone, fluorine trinitro-neighbour's benzoquinone, difluoro dinitro 1,4-benzoquinone (include 2,3- Two fluoro-5,6-dinitro 1,4-benzoquinone, 2,5-bis-fluoro-3,6-dinitro 1,4-benzoquinone, 2,6-bis-fluoro-3,5-dinitro 1,4-benzoquinone), difluoro Dinitro o benzoquinone (include 3,4-bis-fluoro-5,6-dinitro o benzoquinone, 3,5-bis-fluoro-4,6-dinitro o benzoquinone, 3,6-bis-fluoro-4,5- Dinitro o benzoquinone), trifluoro one nitro 1,4-benzoquinone, trifluoro one nitro neighbour's benzoquinone, a chlorine trinitro-1,4-benzoquinone, chlorine three nitre Base neighbour's benzoquinone, dichloro dinitro 1,4-benzoquinone (include 2,3-bis-chloro-5,6-dinitro 1,4-benzoquinone, 2,5-bis-chloro-3,6-dinitro pair Benzoquinone, 2,6-bis-chloro-3,5-dinitro 1,4-benzoquinone), dichloro dinitro o benzoquinone (include 3,4-bis-chloro-5,6-dinitro o benzoquinone, 3,5-bis-chloro-4,6-dinitro o benzoquinone, 3,6-bis-chloro-4,5-dinitro o benzoquinone), trichlorine one nitro 1,4-benzoquinone, trichlorine one nitre Base neighbour's benzoquinone, monobromo trinitro-1,4-benzoquinone, monobromo trinitro-neighbour's benzoquinone, dibromo dinitro 1,4-benzoquinone (include 2,3-bis-bromo-5,6- Dinitro 1,4-benzoquinone, 2,5-bis-bromo-3,6-dinitro 1,4-benzoquinone, 2,6-bis-bromo-3,5-dinitro 1,4-benzoquinone), dibromo dinitro o Benzoquinone (include 3,4-bis-bromo-5,6-dinitro o benzoquinone, 3,5-bis-bromo-4,6-dinitro o benzoquinone, 3,6-bis-bromo-4,5-dinitro Adjacent benzoquinone), three bromo-nitro 1,4-benzoquinone, tribromo one nitro neighbour's benzoquinone, tetranitro 1,4-benzoquinone, tetranitro neighbour's benzoquinone, a fluorine Tricyano 1,4-benzoquinone, fluorine tricyano neighbour's benzoquinone, difluoro dicyano p-benzoquinone (include 2,3-bis-fluoro-5,6-dicyano p-benzoquinone, 2,5-bis-fluoro-3,6-dicyano p-benzoquinone, 2,6-bis-fluoro-3,5-dicyano p-benzoquinone), difluoro dicyano neighbour's benzoquinone (include 3,4- Two fluoro-5,6-dicyano neighbour's benzoquinone, 3,5-bis-fluoro-4,6-dicyano neighbour's benzoquinone, 3,6-bis-fluoro-4,5-dicyano neighbour's benzoquinone), trifluoro One cyano group 1,4-benzoquinone, trifluoro one cyano group neighbour's benzoquinone, a chlorine tricyano 1,4-benzoquinone, chlorine tricyano neighbour's benzoquinone, dichloro dicyan Base 1,4-benzoquinone (include 2,3-bis-chloro-5,6-dicyano p-benzoquinone, 2,5-bis-chloro-3,6-dicyano p-benzoquinone, 2,6-bis-chloro-3,5- Dicyano p-benzoquinone), dichloro dicyano neighbour's benzoquinone (include 3,4-bis-chloro-5,6-dicyano neighbour's benzoquinone, 3,5-bis-chloro-4,6-dicyan Base neighbour's benzoquinone, 3,6-bis-chloro-4,5-dicyano neighbour's benzoquinone), trichlorine one cyano group 1,4-benzoquinone, trichlorine one cyano group neighbour's benzoquinone, monobromo Tricyano 1,4-benzoquinone, monobromo tricyano neighbour's benzoquinone, dibromo dicyano p-benzoquinone (include 2,3-bis-bromo-5,6-dicyano p-benzoquinone, 2,5-bis-bromo-3,6-dicyano p-benzoquinone, 2,6-bis-bromo-3,5-dicyano p-benzoquinone), dibromo dicyano neighbour's benzoquinone (include 3,4- Two bromo-5,6-dicyano neighbour's benzoquinone, 3,5-bis-bromo-4,6-dicyano neighbour's benzoquinone, 3,6-bis-bromo-4,5-dicyano neighbour's benzoquinone), tribromo One cyano group 1,4-benzoquinone, tribromo one cyano group neighbour's benzoquinone, trinitro-one cyano group 1,4-benzoquinone, trinitro-one cyano group neighbour's benzoquinone, dinitro Base dicyano p-benzoquinone (include 2,3-dinitro-5,6-dicyano p-benzoquinone, 2,5-dinitro-3,6-dicyano p-benzoquinone, 2,6- Dinitro-3,5-dicyano p-benzoquinone), dinitro dicyano neighbour's benzoquinone (include 3,4-dinitro-5,6-dicyano neighbour's benzoquinone, 3,5-dinitro-4,6-dicyano neighbour's benzoquinone, 3,6-dinitro-4,5-dicyano neighbour's benzoquinone), a nitrotrimethylolmethane cyano group 1,4-benzoquinone, one Nitrotrimethylolmethane cyano group neighbour's benzoquinone, four cyano 1,4-benzoquinone, four cyano neighbour's benzoquinone, a fluorine front three acid chloride group 1,4-benzoquinone, a fluorine front three Acid chloride group neighbour's benzoquinone, difluoro dimethyl chloride base 1,4-benzoquinone (include 2,3-bis-fluoro-5,6-dimethyl chloride base 1,4-benzoquinone, 2,5-difluoro -3,6-dimethyl chloride base 1,4-benzoquinone, 2,6-bis-fluoro-3,5-dimethyl chloride base 1,4-benzoquinone), difluoro dimethyl chloride base neighbour's benzoquinone (bag Include 3,4-bis-fluoro-5,6-dimethyl chloride base neighbour's benzoquinone, 3,5-bis-fluoro-4,6-dimethyl chloride base neighbour's benzoquinone, 3,6-bis-fluoro-4,5-bis-formyl Chloro neighbour's benzoquinone), trifluoro one formyl chloro 1,4-benzoquinone, trifluoro one formyl chloro neighbour's benzoquinone, a chlorine front three acid chloride group 1,4-benzoquinone, One chlorine front three acid chloride group neighbour's benzoquinone, dichloro dimethyl chloride base 1,4-benzoquinone (include 2,3-bis-chloro-5,6-dimethyl chloride base 1,4-benzoquinone, 2,5-bis-chloro-3,6-dimethyl chloride base 1,4-benzoquinone, 2,6-bis-chloro-3,5-dimethyl chloride base 1,4-benzoquinone), dichloro dimethyl chloride base neighbour's benzene Quinone (include 3,4-bis-chloro-5,6-dimethyl chloride base neighbour's benzoquinone, 3,5-bis-chloro-4,6-dimethyl chloride base neighbour's benzoquinone, 3,6-bis-chloro-4,5- Dimethyl chloride base neighbour's benzoquinone), trichlorine one formyl chloro 1,4-benzoquinone, trichlorine one formyl chloro neighbour's benzoquinone, monobromo front three acid chloride group 1,4-benzoquinone, monobromo front three acid chloride group neighbour's benzoquinone, dibromo dimethyl chloride base 1,4-benzoquinone (include 2,3-bis-bromo-5,6-dimethyl chloride base 1,4-benzoquinone, 2,5-bis-bromo-3,6-dimethyl chloride base 1,4-benzoquinone, 2,6-bis-bromo-3,5-dimethyl chloride base 1,4-benzoquinone), dibromo two formyl Chloro neighbour's benzoquinone (include 3,4-bis-bromo-5,6-dimethyl chloride base neighbour's benzoquinone, 3,5-bis-bromo-4,6-dimethyl chloride base neighbour's benzoquinone, 3,6- Two bromo-4,5-dimethyl chloride base neighbour's benzoquinone), tribromo one formyl chloro 1,4-benzoquinone, tribromo one formyl chloro neighbour's benzoquinone, four formyls Chloro 1,4-benzoquinone and tetramethyl acid chloride group neighbour's benzoquinone.
Described activator is preferably selected from tetrahydrochysene benzoquinone (including tetrahydrochysene 1,4-benzoquinone and tetrahydrochysene neighbour's benzoquinone), tetrachloroquinone (includes Chloranil and monoethyl quinone), four cyano benzoquinone (including four cyano 1,4-benzoquinone and four cyano neighbour's benzoquinone) and dichloro two Cyano group benzoquinone (includes dichloro dicyano p-benzoquinone and dichloro dicyano neighbour's benzoquinone).
Described lewis acid and described can propose the conventional selection that protogenic compound can be cationic polymerization field, does not has It is particularly limited to, as long as described lewis acid and protogenic compound can be carried can form cationic species, causes It is polymerized.
Usually, described lewis acid can be selected from, but not limited to: AlCl3、BF3、BCl3、TiCl4、SnCl4、ZnCl2、 Lewis acid shown in lewis acid shown in formula IV, Formula V and R15 3Al,
In formula IV, X31And X32It is respectively the one in halogen group (such as-F ,-Cl ,-BrOr-I), it is preferably-Cl； R12For C1～C8Straight or branched alkyl, preferably C1～C5Straight or branched alkyl, more preferably ethyl；
In Formula V, X4For the one (such as-F ,-Cl ,-Br or-I) in halogen group, it is preferably-Cl；R13And R14Respectively From for C1～C8Straight or branched alkyl, preferably C1～C5Straight or branched alkyl, more preferably ethyl.
In Formula V, R13And R14Can be identical, it is also possible to different, the most identical.
R15 3In Al, three R15Can be each C1～C8Straight or branched alkyl, preferably C1～C5Straight chain Or branched alkyl.R15 3In Al, three R15Can be identical, it is also possible to for difference, the most identical.
In the present invention, C1～C8Straight or branched alkyl include C1～C8Straight chained alkyl and C3～C8Branched alkyl, Its instantiation can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, the tert-butyl group, n-pentyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethyl fourth Base, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,2-dimethyl amyl group, 2,3- Dimethyl amyl group, 2,4-dimethyl amyl group, 3,3-dimethyl amyl group, 3,4-dimethyl amyl group, 4,4-dimethyl amyl group, 2-second Base amyl group, 3-ethyl pentyl group, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6- Methylheptyl, 2,2-dimethylhexanyl, 2,3-dimethylhexanyl, 2,4-dimethylhexanyl, 2,5-dimethylhexanyl, 3,3-bis- Methylhexyl, 3,4-dimethylhexanyl, 3,5-dimethylhexanyl, 4,4-dimethylhexanyl, 4,5-dimethylhexanyl, 5,5-bis- Methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-n-pro-pyl amyl group and 2-isopropyl amyl group.
In the present invention, the lewis acidic instantiation shown in formula IV can include but not limited to: dichloromethyl aluminum, two Chloroethyl aluminum, dichloro n-pro-pyl aluminum, two chloro isopropyl aluminum, dichloro n-butylaluminum and dichloro aluminium isobutyl.Preferably, formula Lewis acid shown in IV is ethyl aluminum dichloride.
In the present invention, the lewis acidic instantiation shown in Formula V can include but not limited to: dimethylaluminum chloride, two Ethylmercury chloride aluminum, diη-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl aluminum chloride and diisobutyl aluminum chloride. Preferably, the lewis acid shown in Formula V is diethyl aluminum chloride.
In the present invention, R15 3The instantiation of Al can include but not limited to: trimethyl aluminium and triethyl aluminum.
The method according to the invention, described lewis acid is preferably the lewis acid shown in formula IV and/or the road shown in Formula V Lewis acid, more preferably ethyl aluminum dichloride and/or diethyl aluminum chloride.
Containing two alkyl in lewis acidic molecular structure shown in Formula V, it is possible to play suppression cation activity center and send out The effect of raw chain tra nsfer such that it is able to improve the molecular weight of the polymer of preparation.But, lewis acidic shown in Formula V Too high levels, can reduce polymerization rate, extends polymerization time.Therefore, the method according to the invention, shown in Formula V Lewis acid be preferably applied in combination with other lewis acid, be preferably applied in combination with the lewis acid shown in formula IV.That is, The method according to the invention, described lewis acid is preferably the lewis acid shown in formula IV and the lewis acid shown in Formula V.
The method according to the invention, is the lewis acid shown in formula IV and the Louis shown in Formula V at described lewis acid During acid, on the basis of lewis acidic total amount, the lewis acidic content shown in Formula V is preferably 10～90 moles of %.More Preferably, on the basis of lewis acidic total amount, the lewis acidic content shown in Formula V is 30～70 moles of %, so Preferably balance can be obtained between polymerization rate and polymer molecular weight, tool can be obtained with higher polymerization speed There is the polymer of higher molecular weight.
Described carbonium ion can be provided compound can be various interact with lewis acid can separate out carbon just from The compound of son.Specifically, the described compound that can provide carbonium ion can be selected from one or more hydrogen atom Each quiltOne or more hydrogen atom each quilt in substituted alkane and arylSubstituted virtue Hydrocarbon, R16、R17、R18And R19It is respectively hydrogen, C1～C8Alkyl, phenyl, C7～C10Phenylalkyl, C7～C10 Alkyl phenyl or C3～C8Cycloalkyl；X5And X6It is respectively the one in halogen group, such as-F ,-Cl ,-Br or-I, It is preferably-Cl or-Br。
Described C7～C10Phenylalkyl refer to C1～C4At least one hydrogen atom in alkyl is substituted by phenyl the base of formation Group, its instantiation can include but not limited to: (wherein, propylidene can be sub-for benzyl, phenethyl, phenylpropyl N-pro-pyl or isopropylidene) and benzene butyl (wherein, sub-normal-butyl can be sub-normal-butyl, Asia sec-butyl, isobutylidene Or the Asia tert-butyl group).
Described C7～C10Alkyl phenyl refer to that at least one hydrogen atom in phenyl is by C1～C4Alkyl replaces the base formed Group, its instantiation can include but not limited to: (wherein, propyl group can be positive third for tolyl, ethylbenzene, propyl phenyl Base or isopropyl), butylbenzene base (wherein, butyl can be normal-butyl, sec-butyl, isobutyl group or the tert-butyl group).
Described C3～C8The instantiation of cycloalkyl can include but not limited to: cyclopropyl, cyclobutyl, cyclopenta, Cyclohexyl, suberyl and ring octyl group.
In the present invention, C1～C8Alkyl include C1～C8Straight chained alkyl and C3～C8Branched alkyl, it is specifically real Example can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth Base, n-pentyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl Amyl group, 4-methyl amyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethyl-butyl, just Heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,2-dimethyl amyl group, 2,3-dimethyl Amyl group, 2,4-dimethyl amyl group, 3,3-dimethyl amyl group, 3,4-dimethyl amyl group, 4,4-dimethyl amyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2,2-dimethylhexanyl, 2,3-dimethylhexanyl, 2,4-dimethylhexanyl, 2,5-dimethylhexanyl, 3,3-dimethylhexanyl, 3,4-dimethylhexanyl, 3,5-dimethylhexanyl, 4,4-dimethylhexanyl, 4,5-dimethylhexanyl, 5,5-dimethylhexanyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-n-pro-pyl amyl group and 2-isopropyl amyl group.
The instantiation of the described compound that can provide carbonium ion can include but not limited to: to dibenzyl chlorine (i.e., Isosorbide-5-Nitrae-two (chloromethyl) benzene), to dibenzyl bromide (that is, Isosorbide-5-Nitrae-two (bromomethyl) benzene), to dicumyl chlorine (that is, Isosorbide-5-Nitrae-two (2-chlorine Isopropyl) benzene), to dicumyl bromine (that is, Isosorbide-5-Nitrae-two (2-bromine isopropyl) benzene), to dicumyl methyl ether (that is, Isosorbide-5-Nitrae-two (2-first Epoxide isopropyl) benzene), to two benzyl group methyl ethers (that is, Isosorbide-5-Nitrae-two (methoxy) benzene) with acetic acid is to dicumyl ester (i.e., Isosorbide-5-Nitrae-two (2-acetoxyl group isopropyl) benzene).
The described relative scale that can provide between the compound of carbonium ion, described lewis acid and described activator is permissible Select according to concrete polymerizing condition.Specifically, the described compound that carbonium ion can be provided and described activator Mol ratio can be 0.3～100: 1, preferably 0.4～50: 1, more preferably 0.5～20: 1, more preferably 0.5～5: 1, the most preferably 0.8～2.5: 1, such as 0.8～1.5: 1.Described lewis acid and described activator Mol ratio can be 4～1000: 1, preferably 5～250: 1, more preferably 5～50: 1, more preferably 8～ 25: 1, such as 10～20: 1.
Conventional various methods can be used each group in described monoolefine and ring-alkylated styrenes and described initiator system Tap is touched, and to be polymerized, forms monoolefine-alkylstyrene copolymers.
In one embodiment of the invention, each component in described initiator system can be dissolved in solvent, and The mixture ageing that will obtain, obtains initiator solution；By described initiator solution be dissolved in polymer solvent described in Monoolefine and the mixing of described ring-alkylated styrenes.
The lewis acid that the purpose of described ageing is to make in initiator system with can propose protogenic compound and activation Agent forms stable complexation initiating activity center, can carry out under normal conditions.Usually, described ageing can be-100 DEG C to 20 DEG C, preferably-100 DEG C to the temperature models of 0 DEG C, more preferably-100 DEG C to-50 DEG C, further preferably-90 DEG C to-70 DEG C Carry out in enclosing.The time of described ageing can be more than 10 minutes.The present inventor finds in research process, institute The time stating ageing is preferably more than 30 minutes, so can improve polymerization efficiency further, it is thus possible to when shorter polymerization Interior acquisition has the monoolefine-alkylstyrene copolymers of higher molecular weight.It is highly preferred that the time of described ageing is 60 More than minute.On the premise of guaranteeing to obtain higher polymerization efficiency, from the angle of economy, described ageing Time is less than 10 hours, preferably less than 5 hours, more preferably less than 2 hours.The time of described ageing is more preferably It is 30 minutes to 5 hours, more preferably 60 minutes to 120 minutes.
Described solvent described can provide the compound of carbonium ion, described lewis acid and institute for various can dissolving State the liquid substance of activator.Usually, described solvent can be selected from alkane, halogenated alkane and aromatic hydrocarbons, is preferably selected from C3~ C10Alkane, C1～C10Halogenated alkane and C6～C12Aromatic hydrocarbons.
As solvent, described alkane includes aliphatic alkane and alicyclic alkanes, such as C3～C10Alkane include C3～C10 Aliphatic alkane and C3～C10Alicyclic alkanes.
As solvent, described halogenated alkane includes halogenated aliphatic alkane and halogenated cyclo alkane, such as C1～C10Halogen C is included for alkane1～C10Halogenated aliphatic alkane and C3～C10Halogenated cyclo alkane.In described halogenated alkane Halogen atom can be chlorine, bromine or fluorine, preferably chlorine or fluorine.Described halogenated alkane is preferably C1～C4Halogenated aliphatic Alkane.
The instantiation of described solvent can include but not limited to: propane, normal butane, iso-butane, pentane, isopentane, Neopentane, Pentamethylene., normal hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, hexamethylene, methyl ring Pentane, normal heptane, 2-methyl hexane, 3-methyl hexane, 2-ethylpentane, 3-ethylpentane, 2,3-dimethyl pentane, 2,4-dimethyl pentanes, normal octane, 2-methyl heptane, 3-methyl heptane, 4-methyl heptane, 2,3-dimethylhexane, 2,4- Dimethylhexane, 2,5-dimethylhexane, 3-ethyl hexane, 2，2，3-trimethyl-pentane, 2,3,3-trimethylpentanes, 2,4,4- Trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3- Dimethyl heptane, 2,4-dimethyl heptane, 3-ethyl heptane, 4-ethyl heptane, 2,3,4-trimethyl cyclohexanes, 2,3,5-front threes Base hexane, 2,4,5-trimethyl cyclohexanes, 2,2,3-trimethyl cyclohexanes, 2,2,4-trimethyl cyclohexanes, 2,2,5-trimethyl cyclohexanes, 2,3,3- Trimethyl cyclohexane, 2,4,4-trimethyl cyclohexanes, 2-methyl-3-ethyl hexane, 2-methyl-4-ethyl hexane, 3-methyl-3-ethyl Hexane, 3-methyl-4-ethyl hexane, 3,3-diethylpentane, 1-methyl-2-ethyl cyclohexane, 1-methyl-3-ethyl cyclohexane, 1-methyl-4-ethyl cyclohexane, n-pro-pyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane (include 3-methyl cyclohexanol The various isomers of alkane, such as 1,2,3-trimethyl-cyclohexanes, 1,2,4-trimethyl-cyclohexanes, 1,2,5-trimethyl-cyclohexanes, 1,3,5- Trimethyl-cyclohexane), n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2,3-diformazan Base octane, 2,4-dimethyl octane, 3-ethyl octane, 4-ethyl octane, 2,3,4-trimethylheptane, 2,3,5-trimethyl heptan Alkane, 2,3,6-trimethylheptane, 2,4,5-trimethylheptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4- Trimethylheptane, 2,2,5-trimethylheptane, 2,2,6-trimethylheptane, 2,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethyl heptane, 2-methyl-4-ethyl heptane, 2-methyl-5-ethyl heptane, 3-methyl-3-ethyl heptane, 4-first Base-3-ethyl heptane, 5-methyl-3-ethyl heptane, 4-methyl-4-ethyl heptane, 4-propyl group heptane, 3,3-diethylhexane, 3,4-diethylhexane, 2-methyl-3,3-diethylpentane, 1,2-diethyl cyclohexane, 1,3-diethyl cyclohexane, Isosorbide-5-Nitrae-two Ethyl cyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, t-butylcyclohexane, tetramethyl-ring hexane (include tetramethyl The various isomers of butylcyclohexane, such as 1,2,3,4-tetramethyl-ring hexanes, 1,2,4,5-tetramethyl-ring hexanes, 1,2,3,5-tetramethyls Hexamethylene), a fluoromethane, difluoromethane, fluoroform, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, Carbon tetrachloride, a fluoroethane, Difluoroethane, HFC-143a, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, a chloroethene Alkane, dichloroethanes, trichloroethane, sym-tetrachloroethane, Pentalin., carbon hexachloride, a fluoro-propane, difluoropropane, three Fluoro-propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoropropane, a chloropropane, dichloropropane, Trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, octachloropropane, a fluorine butane, difluoro fourth Alkane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, Octafluorobutane., nine fluorine butane, ten Fluorine butane, a chlorobutane, dichloroetane, three chlorobutanes, four chlorobutanes, pentachlorobutane, chlordene butane, heptachlor butane, Telodrine alkane, nine chlorobutanes, ten chlorobutanes, toluene, ethylbenzene and dimethylbenzene (include o-Dimethylbenzene, meta-xylene and right Dimethylbenzene).
The concentration of described initiator solution can be conventional selection, is not particularly limited.The consumption of described initiator solution can To carry out suitable selection according to concrete polymerizing condition, so that polymerization can be caused to be as the criterion.Those skilled in the art can be Under the teaching of prior art, determined the initiator amount being adequate to bring about polymerization by the experiment of limited number of time.
The method according to the invention, described monoolefine can be the commonly used in the art monoene that can carry out cationic polymerization Hydrocarbon.Usually, described monoolefine is selected from the compound shown in Formula II,
In Formula II, R9And R10It is respectively C1～C5Straight or branched alkyl；Or R9For hydrogen, R10For C3～C5 Branched alkyl.
In the present invention, C1～C5Straight or branched alkyl include C1～C5Straight chained alkyl and C3～C5Branched alkyl, Its instantiation can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
Specifically, described monoolefine can be selected from, but not limited to: 2-methyl-1-propylene (that is, isobutene .), 2-methyl isophthalic acid- Butylene, 3-methyl-1-butene, 2,3-dimethyl-1-butylene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2,3-dimethyl-1-amylenes, 2,4-dimethyl-1-amylene, 2-methyl isophthalic acid-hexene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1- Hexene, 2,5-dimethyl-1-hexene and 2,4,4-trimethyl-1-amylenes.
Preferably, described monoolefine is isobutene..
The method according to the invention, described ring-alkylated styrenes is selected from the compound shown in formula III,
In formula III, R11For C1～C5Straight or branched alkyl.
The example of described ring-alkylated styrenes can include but not limited to: p-methylstyrene, a methyl styrene, to ethyl Styrene and p-tert-butylstyrene.
Preferably, described ring-alkylated styrenes shown in the Formula IV to alkylbenzene between shown in ring-alkylated styrenes and Formula VII Ethylene,
In Formula IV, R11For C1～C5Straight or branched alkyl；
In Formula VII, R11For C1～C5Straight or branched alkyl.
It is highly preferred that described ring-alkylated styrenes is to ring-alkylated styrenes and/or a ring-alkylated styrenes, such as p-methylstyrene and / or a methyl styrene.
It is further preferred that in described ring-alkylated styrenes, the content to ring-alkylated styrenes is more than 80 weight %, such as may be used Think 80～100 weight %.It is highly preferred that in described ring-alkylated styrenes, the content to ring-alkylated styrenes is 90 weight % Above, can be such as 90～100 weight %.Most preferably, described ring-alkylated styrenes is preferably p-methylstyrene.
The method according to the invention, described monoolefine can be according to final preparation with the relative usage of described ring-alkylated styrenes The concrete application scenario of polymer carries out suitable selection.Usually, with the total amount of described monoolefine and ring-alkylated styrenes it is Benchmark, the content of described monoolefine can be 80～99 weight %, preferably 90～97 weight %；Described ring-alkylated styrenes Content can be 1～20 weight %, preferably 3～10 weight %.
The method according to the invention, described polymer solvent is molten by least one first polymer solvent and at least one the second polymerization Agent forms, and described first polymer solvent is selected from halogenated alkane, and described second polymer solvent is selected from alkane.As the first polymerization Solvent, the halogen atom in described halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.Described first polymerization is molten Agent is preferably C1～C10Halogenated alkane, more preferably C1～C4Halogenated alkane.As the second polymer solvent, described Alkane includes aliphatic alkane and alicyclic alkanes.Described aliphatic alkane is preferably C3～C10Aliphatic alkane, more excellent Elect C as3～C8Aliphatic alkane, more preferably C5～C8Aliphatic alkane；Described alicyclic alkanes is preferred For C3～C10Alicyclic alkanes, more preferably C5～C10Alicyclic alkanes.
The instantiation of described first polymer solvent can include but not limited to: a fluoromethane, difluoromethane, fluoroform, Carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane, Difluoroethane, trifluoro second Alkane, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethane, sym-tetrachloroethane, five Ethyl chloride, carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, Heptafluoro-propane, octafluoropropane, a chloropropane, dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene third Alkane, heptachloropropane, octachloropropane, a fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, six Fluorine butane, seven fluorine butane, Octafluorobutane., nine fluorine butane, ten fluorine butane, a chlorobutane, dichloroetane, three chlorobutanes, Four chlorobutanes, pentachlorobutane, chlordene butane, heptachlor butane, telodrine alkane, nine chlorobutanes and ten chlorobutanes.
The instantiation of described second polymer solvent can include but not limited to: propane, normal butane, iso-butane, pentane, Isopentane, neopentane, Pentamethylene., normal hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, hexamethylene, Methyl cyclopentane, normal heptane, 2-methyl hexane, 3-methyl hexane, 2-ethylpentane, 3-ethylpentane, 2,3-dimethyl Pentane, 2,4-dimethyl pentane, normal octane, 2-methyl heptane, 3-methyl heptane, 4-methyl heptane, 2,3-dimethylhexane, 2,4-dimethylhexanes, 2,5-dimethylhexane, 3-ethyl hexane, 2，2，3-trimethyl-pentane, 2,3,3-trimethylpentanes, 2,4,4- Trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3- Dimethyl heptane, 2,4-dimethyl heptane, 3-ethyl heptane, 4-ethyl heptane, 2,3,4-trimethyl cyclohexanes, 2,3,5-front threes Base hexane, 2,4,5-trimethyl cyclohexanes, 2,2,3-trimethyl cyclohexanes, 2,2,4-trimethyl cyclohexanes, 2,2,5-trimethyl cyclohexanes, 2,3,3- Trimethyl cyclohexane, 2,4,4-trimethyl cyclohexanes, 2-methyl-3-ethyl hexane, 2-methyl-4-ethyl hexane, 3-methyl-3-ethyl Hexane, 3-methyl-4-ethyl hexane, 3,3-diethylpentane, 1-methyl-2-ethyl cyclohexane, 1-methyl-3-ethyl cyclohexane, 1-methyl-4-ethyl cyclohexane, n-pro-pyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane, n-decane, 2-methyl Nonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2,3-dimethyl octane, 2,4-dimethyl octane, 3-ethyl Octane, 4-ethyl octane, 2,3,4-trimethylheptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane, 2,4,5-front threes Base heptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6- Trimethylheptane, 2,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethyl heptane, 2-methyl-4-ethyl heptan Alkane, 2-methyl-5-ethyl heptane, 3-methyl-3-ethyl heptane, 4-methyl-3-ethyl heptane, 5-methyl-3-ethyl heptane, 4-methyl-4-ethyl heptane, 4-propyl group heptane, 3,3-diethylhexane, 3,4-diethylhexane, 2-methyl-3,3-diethyl penta Alkane, 1,2-diethyl cyclohexane, 1,3-diethyl cyclohexane, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl basic ring Hexane, t-butylcyclohexane and tetramethyl-ring hexane.
Preferably, described first polymer solvent is selected from monochloro methane, dichloromethane and monochlorethane, and described second polymerization is molten Agent is selected from pentane, normal hexane and normal heptane.
The method according to the invention, the ratio between described first polymer solvent and described second polymer solvent can be according to tool The condition of body selects.Usually, on the basis of the total amount of described polymer solvent, the content of the first polymer solvent is permissible It is 1～80 volume %, preferably 1～60 volumes, more preferably 10～50 volume %；Containing of described second polymer solvent Amount can be 20～99 volume %, preferably 40～99 volume %, more preferably 50～90 volume %.
The consumption of described polymer solvent can be the conventional selection of this area.Usually, the consumption of described polymer solvent makes Total monomer concentration is 2～50 weight %, preferably 5～30 weight %, more preferably 5～20 weight %.
The method according to the invention, described cationic polymerization condition can be the conventional selection of this area.Usually, monoene Hydrocarbon and ring-alkylated styrenes component each with initiator system contact can-120 DEG C to 20 DEG C, preferably-100 DEG C to 0 DEG C, Carry out within the temperature range of more preferably-100 DEG C to-50 DEG C, further preferably-90 DEG C to-60 DEG C.The method according to the invention, The time of described contact can be the conventional selection of this area, can be typically 10-180 minute, preferably 30-120 minute.
The method according to the invention, it is also possible to be included in and be polymerized in the solution that backward polymerization obtains interpolation polymerization terminator Polyreaction is made to terminate (such as alcohol).The present invention is not particularly limited for kind and the consumption of described polymerization terminator, Can be the conventional selection of this area, be as the criterion so that polyreaction can be terminated, repeat no more herein.
The method according to the invention, the efficiency of initiation of the initiator system used is high.On the one hand, the method energy of the present invention Obtaining higher monomer conversion, in the solution containing monoolefine-alkylstyrene copolymers obtained, content of monomer is low, special The content not being ring-alkylated styrenes is low, usually, and the weight percent of unreacted ring-alkylated styrenes in the solution that polymerization obtains Content is below 1000ppm, usually below 500ppm, even below 200ppm, can monomer without isolation And it is directly used in halogenation, the step for removing unreacted monomer can also be omitted after halogenation completes. On the other hand, the molecular weight of monoolefine-alkylstyrene copolymers prepared by the method for the employing present invention is high, particularly can Obtaining weight average molecular weight is 10 × 104Above, even weight average molecular weight is 40 × 104Above monoolefine-ring-alkylated styrenes is common Polymers, and then rubber monoolefine-alkylstyrene copolymers can be obtained.
The method according to the invention, in step (2), with replacement solvent displacement step (1) obtain containing monoolefine- Halogenated alkane in the solution of alkylstyrene copolymers, molten after obtaining the displacement containing monoolefine-alkylstyrene copolymers Liquid, described replacement solvent is selected from alkane.Carry out that the purpose of solvent displacement is to obtain step (1) containing monoolefine- The first polymer solvent (that is, halogenated alkane) being unsuitable for halogenation in the solution of alkylstyrene copolymers cements out, To carry out halogenation subsequently.
As replacement solvent, described alkane includes aliphatic alkane and alicyclic alkanes.Described aliphatic alkane is preferably C3～C10Aliphatic alkane, more preferably C3～C8Aliphatic alkane, more preferably C5～C8Aliphatic Alkane；Described alicyclic alkanes is preferably C3～C10Alicyclic alkanes, more preferably C5～C10Alicyclic alkane Hydrocarbon.
The instantiation of described replacement solvent can include but not limited to: propane, normal butane, iso-butane, pentane, different Pentane, neopentane, Pentamethylene., normal hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, hexamethylene, Methyl cyclopentane, normal heptane, 2-methyl hexane, 3-methyl hexane, 2-ethylpentane, 3-ethylpentane, 2,3-dimethyl Pentane, 2,4-dimethyl pentane, normal octane, 2-methyl heptane, 3-methyl heptane, 4-methyl heptane, 2,3-dimethylhexane, 2,4-dimethylhexanes, 2,5-dimethylhexane, 3-ethyl hexane, 2，2，3-trimethyl-pentane, 2,3,3-trimethylpentanes, 2,4,4- Trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3- Dimethyl heptane, 2,4-dimethyl heptane, 3-ethyl heptane, 4-ethyl heptane, 2,3,4-trimethyl cyclohexanes, 2,3,5-front threes Base hexane, 2,4,5-trimethyl cyclohexanes, 2,2,3-trimethyl cyclohexanes, 2,2,4-trimethyl cyclohexanes, 2,2,5-trimethyl cyclohexanes, 2,3,3- Trimethyl cyclohexane, 2,4,4-trimethyl cyclohexanes, 2-methyl-3-ethyl hexane, 2-methyl-4-ethyl hexane, 3-methyl-3-ethyl Hexane, 3-methyl-4-ethyl hexane, 3,3-diethylpentane, 1-methyl-2-ethyl cyclohexane, 1-methyl-3-ethyl cyclohexane, 1-methyl-4-ethyl cyclohexane, n-pro-pyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane, n-decane, 2-methyl Nonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2,3-dimethyl octane, 2,4-dimethyl octane, 3-ethyl Octane, 4-ethyl octane, 2,3,4-trimethylheptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane, 2,4,5-front threes Base heptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6- Trimethylheptane, 2,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethyl heptane, 2-methyl-4-ethyl heptan Alkane, 2-methyl-5-ethyl heptane, 3-methyl-3-ethyl heptane, 4-methyl-3-ethyl heptane, 5-methyl-3-ethyl heptane, 4-methyl-4-ethyl heptane, 4-propyl group heptane, 3,3-diethylhexane, 3,4-diethylhexane, 2-methyl-3,3-diethyl penta Alkane, 1,2-diethyl cyclohexane, 1,3-diethyl cyclohexane, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl basic ring Hexane, t-butylcyclohexane and tetramethyl-ring hexane.
Described replacement solvent is preferably selected from C3～C10Aliphatic alkane, be more preferably selected from C5～C8Aliphatic alkane, Further preferably selected from pentane, normal hexane and normal heptane.
The method according to the invention, the kind of described replacement solvent and the kind of described second polymer solvent can be identical, Can also be different, the most identical, so beneficially follow-up be isolated and purified.
Method according to the invention it is possible to use conventional various method replacement solvent by containing that step (1) obtains Halogenated alkane in the solution of monoolefine-alkylstyrene copolymers cements out, such as flash distillation and/or stripping.Implement in one In mode, the steam of replacement solvent is sent into the solution containing monoolefine-alkylstyrene copolymers that step (1) obtains In, utilize that step (1) obtains by sensible heat that the steam of replacement solvent carries and latent heat containing monoolefine-ring-alkylated styrenes Halogenated alkane in the solution of copolymer steams, and at least partly replacement solvent is retained in containing monoolefine-ring-alkylated styrenes common In the solution of polymers.The feeding amount of the steam of described replacement solvent is be enough to containing monoolefine-alkylstyrene copolymers Halogenated alkane in solution steams and is as the criterion.In this embodiment, the temperature of the steam of replacement solvent can be put as required Depending on the boiling point of the halogenated alkane changed, typically can be in the range of 10～150 DEG C, preferably in the range of 30～100 DEG C, More preferably in the range of 50～90 DEG C；Carrying out the pressure in the container replaced can be 10～200kPa (absolute pressures), excellent Elect 50～120kPa (absolute pressures), more preferably 80～100kPa (absolute pressure) as.In this embodiment, replacement solvent The time that is passed through of steam is with can by the halogenated alkane in the solution containing monoolefine-alkylstyrene copolymers all or base This all steams and is as the criterion, and usually, the persistent period can be 10～300 minutes, preferably 30～200 minutes, more excellent Elect 50～150 minutes as, more preferably 100～150 minutes.
The method according to the invention, solution after the displacement containing monoolefine-alkylstyrene copolymers that step (2) obtains Can be sent directly in step (3) and contact with halogen-containing compound, it is also possible to step (2) is obtained containing monoene Send into after after the displacement of hydrocarbon-alkylstyrene copolymers, solution concentrates or dilutes in step (3) with halogen-containingization Compound contacts.Usually, single in solution after the displacement containing monoolefine-alkylstyrene copolymers of feeding step (3) The content of olefm-alkyl styrol copolymer can be 1～30 weight %, preferably 5～20 weight %.
The method according to the invention, in step (3), described halogen-containing compound can be common various to make list The compound that part hydrogen atom in olefm-alkyl styrol copolymer strand is replaced by halogen atom.Preferably, institute Stating halogen-containing compound is halogen simple substance, such as bromine (that is, bromine) and/or chlorine element (that is, chlorine).It is highly preferred that Described halogen-containing compound is bromine.
In step (3), after the displacement containing monoolefine-alkylstyrene copolymers, solution and halogen-containing compound connects Touch and can carry out under normal conditions, as long as monoolefine-alkylstyrene copolymers generation halogenation can be made.Typically Ground, described contact can be carried out in the presence of at least one radical initiator, and described contact can also be at light-initiated bar Under part.Described radical initiator can be common various can promote monoolefine-alkylstyrene copolymers with containing halogen The radical initiator of compound reaction, preferably oleosoluble radical initiators, such as azo type free radical initiator, excellent Choosing is selected from azo diisobutyl nitrile, AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile).The consumption of described radical initiator is with energy Halogenation is enough caused to be as the criterion.Usually, described radical initiator with the mol ratio of described halogen contained compound can be 0.01～0.5: 1, preferably 0.02～0.2: 1, more preferably 0.03～0.1: 1.Described radical initiator is preferably with molten The form of liquid provides, and solvent can be selected from one or more the combination in the aforementioned alkane being used as the second polymer solvent, It is preferably identical with the second polymer solvent.When carrying out described contact under the conditions of light-initiated, illumination condition is can cause list Olefm-alkyl styrol copolymer generation halogenation is as the criterion, such as: light source can be that electric filament lamp is (such as 80～200W Electric filament lamp).
In step (3), the amount of the halogen atom introduced in the strand of monoolefine-alkylstyrene copolymers can root Select according to the use occasion of the halogenation monoolefine-alkylstyrene copolymers of final preparation.Usually, finally give In monoolefine-alkylstyrene copolymers, the content of halogen atom can be in the range of 0.2～2 mole of %.Preferably, poly- In compound, the content of halogen atom is in the range of 0.4～1.5 mole of %.
In step (3), the solution containing monoolefine-alkylstyrene copolymers and the Contact Temperature of halogen-containing compound Can be conventional selection.Usually, described contact can be carried out at a temperature of-10 DEG C to 80 DEG C, preferably at 0 DEG C to 60 Carry out at a temperature of DEG C, more preferably carry out at a temperature of 30 DEG C to 60 DEG C.The time of described contact can be according to contact Temperature and intended halogenation degree select, and can be typically 0.5～30 minute, preferably 1～15 minute.
The method according to the invention, in step (3), after halogenation completes, the mixture preferably obtained halogenation enters Row neutralizes, and the pH value of the mixture preferably halogenation obtained is neutralized to 8～10.Can be by the mixture obtained to halogenation Middle interpolation alkaline matter and be neutralized, described basic species can be such as NaOH and/or KOH, preferably NaOH. Described alkaline matter provides the most as a solution, as provided in form of an aqueous solutions.
Method according to the invention it is possible to mixture after using the mixture that obtains from halogenation of conventional method or neutralizing Isolate halogenation monoolefine-alkylstyrene copolymers.For example, it is possible to after by halogenation being obtained mixture or neutralizing Mixture is condensed, thus obtains halogenation monoolefine-alkylstyrene copolymers.
The method according to the invention, can prepare the monoolefine-alkylbenzene second with higher molecular weight with higher polymerization efficiency Alkene copolymer, and then prepare the halogenation monoolefine-alkylstyrene copolymers with higher molecular weight.Especially, this is used The method of invention can be with higher polymerization efficiency, and preparing weight average molecular weight is 10 × 104Above, even weight average molecular weight is 40×104Above monoolefine-alkylstyrene copolymers, and then rubber halogenation monoolefine-alkylstyrene can be prepared Thing.The method according to the invention is particularly suitable for preparing halogenated isobutylene-p-methylstyrene copolymer, particularly rubber halogen Change isobutene .-p-methylstyrene copolymer.
Fig. 1 shows a kind of preferred implementation using the method for the present invention to prepare monoolefine-alkylstyrene copolymers. Below in conjunction with Fig. 1, this is preferred embodiment described in detail.As it is shown in figure 1, by (excellent for the monoolefine shown in Formula II Elect isobutene. as) 1, ring-alkylated styrenes the 2, first polymer solvent 31 shown in formula III and the second polymer solvent 32 be with in advance Preparation aged initiator solution 4 are sent in polymer reactor I, are polymerized under the conditions of cationic polymerization Reaction.After carrying out the polyreaction of the scheduled time, terminator 5 is sent in polymer reactor I, terminate polyreaction. The solution 6 containing monoolefine-alkylstyrene copolymers of polymer reactor I output subsequently enters in solvent displacer II, Replacement solvent steam 7 is sent into from the bottom of solvent displacer II, by the solution containing monoolefine-alkylstyrene copolymers Halogenated alkane in 6 steams, thus obtains the halogenated alkane 8 displaced at the top of solvent displacer II.The displacement obtained Rear solution 9 from the bottom of solvent displacer II export, subsequently in halogenation reactor III with halogen-containing compound 10 With radical initiator solution 11 haptoreaction so that at least part of in monoolefine-alkylstyrene copolymers strand Hydrogen atom is replaced by halogen atom.In monoolefine-alkylstyrene copolymers strand, the content of halogen atom meets pre- During provisioning request, in halogenation reactor III, send into the aqueous solution 12 of alkaline matter, be neutralized.Finally, neutralization is obtained The mixture 13 containing halogenation monoolefine-alkylstyrene copolymers export, and send into subsequent handling is carried out separate and Purification, to finally give halogenation monoolefine-alkylstyrene copolymers.
Fig. 2 shows another preferred embodiment of the method according to the invention.Embodiment shown in Fig. 2 and figure The difference of the embodiment shown in 1 is halogenation step, the most only the halogenation step to Fig. 2 illustrated embodiment It is described in detail.As in figure 2 it is shown, solution 9 enters in blender IV after the displacement of solvent displacer II output, and contain Compound 10 mix homogeneously of halogen, then sends in photohalogenation reactor V by the mixture obtained, at light source 14 Halogenation is carried out under irradiation.After halogenation completes, the mixture in photohalogenation reactor V is sent into and neutralizes reaction Device VI contacts with the aqueous solution 12 of alkaline matter and is neutralized.Finally, neutralization is obtained containing halogenation monoolefine-alkane The mixture 13 of base styrol copolymer exports, and sends into and carry out in subsequent handling separating and purification, to finally give halogenation Monoolefine-alkylstyrene copolymers.
The present invention is described in detail below in conjunction with experimental example and embodiment.
In following experimental example and contrast experiment's example, weight method is used to measure polymer yield,
Polymer yield (%)=(weight/total monomer weight of the polymer obtained) × 100%.
In following experimental example, contrast experiment's example, embodiment and comparative example, the molecular weight of polymer and molecular weight distributing index Use Shimadzu Corporation of Japan to produce LC-20A type chromatograph of gel permeation to measure, use single aperture chromatographic column WithFour post combinations.Flowing is oxolane mutually, and flow velocity is 0.7mL/min；Sample solution concentration is 2mg/mL, sample size is 200 μ L；Test temperature is 35 DEG C；Using single distribution polystyrene as standard sample.
In following example and comparative example, use the AVANCE400 nuclear magnetic resonance analyser commercially available from Bruker company of Switzerland, With CDCl3Making solvent, TMS is internal standard, measures p-methylstyrene in the monoolefine-alkylstyrene copolymers of preparation Content and halogenation monoolefine-alkylstyrene copolymers in the content of halogen.
Solvent used in following experimental example, contrast experiment's example, embodiment and comparative example and monomer before use, use Method commonly used in the art refines.
Experimental example 1～25 is for illustrating the polymerization procedure in the inventive method.
Experimental example 1
(1) by 0.128g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 160g and containing (concentration is to dicumyl chlorine In dichloromethane 0.0064mol/L), the solution obtained being cooled to-85 DEG C in advance, then in this solution, order adds 8mL Concentration is the hexane solution of the ethyl aluminum dichloride of 0.9mol/L, after mix homogeneously, the mixed liquor obtained is placed in-85 DEG C Cryostat is aged 60min, thus obtains initiator solution.
(2) in being furnished with the stainless steel reactor of 2000mL of strength constant speed stirring, order adds 500mL and is cooled to-80 in advance DEG C normal hexane, 500mL is cooled to the monochloro methane of-80 DEG C in advance, 250mL is cooled to the isobutene. of-80 DEG C in advance and 12mL is normal The p-methylstyrene (content 98 weight %) of temperature (being 25 DEG C), mix homogeneously.Step (1) is dripped in reactor The initiator solution of preparation.Wherein, the addition of initiator solution is 100mL, in control rate of addition makes reactor Temperature be within the scope of-85 DEG C to-90 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be in-85 DEG C to-90 Within the scope of DEG C, and carry out the polyreaction of 60min, in reactant mixture, then add 100g contain 3 weight % The dichloromethane solution of 2,2'-ethylenedioxybis(ethanol)., to terminate polyreaction, thus obtain containing monoolefine-alkylstyrene copolymers molten Liquid.Then, the solution containing monoolefine-alkylstyrene copolymers obtained is placed in desolvation in hot bath, washing After be dried to constant weight in 60 DEG C in vacuum drying oven, obtain monoolefine-alkylstyrene copolymers.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtained are listed in Table 1.
Experimental comparison's example 1
Use the method identical with experimental example 1 to be polymerized, except for the difference that, in step (1), do not use 2,3-bis-chloro-5,6- Dicyano p-benzoquinone.Experimental result is listed in Table 1.
Experimental example 2
Using the method identical with experimental example 1 to be polymerized, except for the difference that, in step (1), digestion time is 100min； In step (2), the time of polyreaction is 40min.Experimental result is listed in Table 1.
Experimental example 3
Using the method identical with experimental example 1 to be polymerized, except for the difference that, in step (1), digestion time is 30min； In step (2), the time of polyreaction is 70min.Experimental result is listed in Table 1.
Experimental example 4
Using the method identical with experimental example 1 to be polymerized, except for the difference that, in step (1), digestion time is 10min； In step (2), the time of polyreaction is 100min.Experimental result is listed in Table 1.
Experimental example 5
The method identical with experimental example 1 is used to be polymerized, except for the difference that, in step (1), 2,3-bis-chloro-5,6-dicyan The tetrahydrochysene 1,4-benzoquinone of base 1,4-benzoquinone equimolar amounts replaces；In step (2), the time of polyreaction is 60min.Experiment Result is listed in Table 1.
Experimental example 6
The method identical with experimental example 1 is used to be polymerized, except for the difference that, in step (1), 2,3-bis-chloro-5,6-dicyan The chloranil of base 1,4-benzoquinone equimolar amounts replaces；In step (2), the time of polyreaction is 50min.Experiment Result is listed in Table 1.
Experimental example 7
The method identical with experimental example 1 is used to be polymerized, except for the difference that, in step (1), 2,3-bis-chloro-5,6-dicyan The four cyano 1,4-benzoquinone of base 1,4-benzoquinone equimolar amounts replaces；In step (2), the time of polyreaction is 120min. Experimental result is listed in Table 1.
Experimental example 8
Using the method identical with experimental example 1 to be polymerized, except for the difference that, in step (2), the consumption of normal hexane is 800mL, the consumption of monochloro methane is 200mL, and polymerization reaction time is 80min.Experimental result is listed in Table 1.
Experimental example 9
The method identical with experimental example 1 is used to be polymerized, except for the difference that, in step (1), by 0.163g tetrachloro pair Benzoquinone is dissolved in 200g and contains in the dichloromethane to dicumyl bromine (concentration is 0.0052mol/L), the solution that will obtain Being cooled to-85 DEG C in advance, the normal hexane then sequentially adding the ethyl aluminum dichloride that 10mL concentration is 0.9mol/L in this solution is molten Liquid, after mix homogeneously, is placed in the mixed liquor obtained in the cryostat of-85 DEG C ageing 80min, thus obtains initiator solution；
In step (2), the time of polyreaction is 50min.Experimental result is listed in Table 1.
Experimental example 10
The method identical with experimental example 1 is used to be polymerized, except for the difference that, in step (2), molten at dropping initiator In liquid and polymerization process, making the temperature in reactor be within the scope of-60 DEG C to-70 DEG C, polymerization reaction time is 120min.Experimental result is listed in Table 1.
Experimental example 11
Using the method identical with experimental example 9 to be polymerized, except for the difference that, in step (2), the consumption of normal hexane is 700mL, the consumption of monochloro methane is 300mL, and polymerization reaction time is 60min.Experimental result is listed in Table 1.
Experimental example 12
Using the method identical with experimental example 9 to be polymerized, except for the difference that, in step (2), the consumption of normal hexane is 200mL, the consumption of monochloro methane is 800mL, and polymerization reaction time is 40min.Experimental result is listed in Table 1.
Experimental example 13
(1) by 0.152g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 200g and containing (concentration is to dicumyl chlorine In dichloromethane 0.006mol/L), the solution obtained being cooled to-85 DEG C in advance, then in this solution, order adds 6mL Concentration is the hexane solution of the ethyl aluminum dichloride (EADC) of 0.9mol/L and a chlorine two that 6mL concentration is 1.0mol/L The n-heptane solution (molar ratio of EADC/DEAC is 4.7/5.3) of aluminium ethide (DEAC), after mix homogeneously, will The mixed liquor obtained is placed in the cryostat of-85 DEG C ageing 80min, thus obtains initiator solution.
(2) in being furnished with the stainless steel reactor of 2000mL of strength constant speed stirring, order adds 600mL and is cooled to-80 in advance DEG C normal hexane, 400mL is cooled to the monochloro methane of-80 DEG C in advance, 250mL is cooled to the isobutene. of-80 DEG C in advance and 12mL is normal The p-methylstyrene (content 98 weight %) of temperature (being 25 DEG C), mix homogeneously.Step (1) is dripped in reactor The initiator solution of preparation.Wherein, the addition of initiator solution is 90mL, in control rate of addition makes reactor Temperature is within the scope of-85 DEG C to-90 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be in-85 DEG C to-90 DEG C Within the scope of, and carry out the polyreaction of 60min, in reactant mixture, then add 100g contain 3 weight % tri- The dichloromethane solution of glycol, to terminate polyreaction, thus obtains the solution containing monoolefine-alkylstyrene copolymers. Then, the solution containing monoolefine-alkylstyrene copolymers obtained is placed in desolvation in hot bath, after washing Vacuum drying oven is dried to constant weight in 60 DEG C, obtains monoolefine-alkylstyrene copolymers.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtained are listed in table 2.
Experimental example 14
The method identical with experimental example 13 is used to be polymerized, except for the difference that, in step (2), molten at dropping initiator Temperature in reactor is all maintained in the range of-60 DEG C to-70 DEG C by liquid and polymerization process, polymerization reaction time For 100min.Experimental result is listed in table 2.
Experimental comparison's example 2
Use the method identical with experimental example 14 to be polymerized, except for the difference that, in step (1), do not use 2,3-dichloro -5,6-dicyano p-benzoquinone.Experimental result is listed in table 2.
Experimental example 15
The method identical with experimental example 13 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant under conditions of, the molar ratio making EADC/DEAC is 7/3；In step (2), polymerization reaction time For 40min.Experimental result is listed in table 2.
Experimental example 16
The method identical with experimental example 13 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant under conditions of, the molar ratio making EADC/DEAC is 3/7；In step (2), polymerization reaction time For 80min.Experimental result is listed in table 2.
Experimental example 17
The method identical with experimental example 13 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant under conditions of, the molar ratio making EADC/DEAC is 1/9；In step (2), polymerization reaction time For 120min.Experimental result is listed in table 2.
Experimental example 18
The method identical with experimental example 13 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant under conditions of, the molar ratio making EADC/DEAC is 9/1；In step (2), polymerization reaction time For 40min.Experimental result is listed in table 2.
Experimental example 19
Using the method identical with experimental example 13 to be polymerized, except for the difference that, in step (1), diethyl aluminum chloride is used The ethyl aluminum dichloride of equimolar amounts replaces, and the initiator solution i.e. prepared does not contains diethyl aluminum chloride；In step (2), poly- The conjunction response time is 30min.Experimental result is listed in table 2.
Experimental example 20
Using the method identical with experimental example 13 to be polymerized, except for the difference that, in step (1), digestion time is 60min； In step (2), polymerization reaction time is 50min.Experimental result is listed in table 2.
Experimental example 21
Using the method identical with experimental example 13 to be polymerized, except for the difference that, in step (1), digestion time is 30min； In step (2), polymerization reaction time is 80min.Experimental result is listed in table 2.
Experimental example 22
Using the method identical with experimental example 13 to be polymerized, except for the difference that, in step (1), digestion time is 15min； In step (2), polymerization reaction time is 120min.Experimental result is listed in table 2.
Experimental example 23
(1) dibenzyl chlorine is dissolved in 62.1g dichloromethane, by obtain by 0.0497g chloranil and 0.0422g Solution is cooled to-85 DEG C in advance, and the normal hexane then adding the ethyl aluminum dichloride that 1.7mL concentration is 0.9mol/L in this solution is molten The toluene solution of liquid and diethyl aluminum chloride that 1.7mL concentration is 0.9mol/L is made into initiator solution, and mix homogeneously is rearmounted 100min it is aged in the cryostat of-80 DEG C.By weight, in initiator solution, the content 800ppm of chloranil, right The content of dibenzyl chlorine is 680ppm.
(2) successively in the polymerization bottle of 250mL add 60mL be cooled to-80 DEG C normal hexane, 40mL be cooled to-80 DEG C monochloro methane, 11mL is cooled to the p-methylstyrene of the isobutene. of-80 DEG C and 0.46mL room temperature (content is 98 Weight %), form monomer solution after mixing.Polymerization bottle is placed in the low temperature cryostat of-80 DEG C, adds in monomer solution The initiator solution that 10mL step (1) is prepared, then standing and reacting 80min, course of reaction controls at cryostat temperature In the range of-80 DEG C to-85 DEG C.After reaction terminates, in reactant mixture, add 5mL contain 0.5 weight %NaOH Methanol solution to terminate polyreaction, thus obtain the solution containing monoolefine-alkylstyrene copolymers.Then, will The solution containing monoolefine-alkylstyrene copolymers obtained is placed in desolvation in hot bath, at vacuum drying oven after washing In be dried to constant weight in 60 DEG C, obtain monoolefine-alkylstyrene copolymers.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtained are listed in table 2.
Experimental example 24
(1) by 0.0497g 2,3-bis-chloro-5,6-dicyano p-benzoquinone and 0.0422g are dissolved in 62.1g dichloromethane to dibenzyl chlorine In alkane, the solution obtained is cooled to-85 DEG C in advance, in this solution, then adds two chloroethenes that 1.7mL concentration is 0.9mol/L It is molten that the toluene solution of the hexane solution of base aluminum and diethyl aluminum chloride that 1.7mL concentration is 0.9mol/L is made into initiator Liquid, mix homogeneously is placed in the cryostat of-80 DEG C ageing 60min.By weight, in initiator solution 2,3-bis-chloro-5,6- The content 800ppm of dicyano p-benzoquinone, the content to dibenzyl chlorine is 680ppm.
(2) successively in the polymerization bottle of 250mL add 60mL be cooled to-80 DEG C normal hexane, 40mL be cooled to-80 DEG C monochloro methane, 11mL is cooled to the p-methylstyrene of the isobutene. of-80 DEG C and 0.46mL room temperature (content is 98 Weight %), form monomer solution after mixing.Polymerization bottle is placed in the low temperature cryostat of-80 DEG C, adds in monomer solution The initiator solution that 10mL step (1) is prepared, then standing and reacting 60min, course of reaction controls at cryostat temperature In the range of-80 DEG C to-85 DEG C.After reaction terminates, in reactant mixture, add 5mL contain 0.5 weight %NaOH Methanol solution to terminate polyreaction, thus obtain the solution containing monoolefine-alkylstyrene copolymers.Then, will The solution containing monoolefine-alkylstyrene copolymers obtained is placed in desolvation in hot bath, at vacuum drying oven after washing In be dried to constant weight in 60 DEG C, obtain monoolefine-alkylstyrene copolymers.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtained are listed in table 2.
Experimental example 25
Using the method identical with experimental example 24 to be polymerized, except for the difference that, in step (2), the consumption of normal hexane is 90mL, the consumption of monochloro methane is 10mL, and polymerization reaction time is 100min.Experimental result is listed in table 2.
Tables 1 and 2 as a result, it was confirmed that use the inventive method be polymerized, higher polymerization efficiency, monomer can be obtained Conversion ratio is high, the C simple with employing+/ lewis acid initiator system is compared, and can make polymer yield within the shorter time Reach 100%, unreacted ring-alkylated styrenes in the solution containing monoolefine-alkylstyrene copolymers prepared Content can reach 200ppm (by weight) below, and this solution separates the step of unreacted ring-alkylated styrenes without experience Can directly carry out halogenation.On the contrary, the polymerization efficiency of Experimental comparison's example 1～2 is poor, in the feelings that remaining condition is identical Under condition, polymer yield cannot be made to reach more than 99%, and then the monoolefine-alkylbenzene second of preparation with identical polymerization time In alkene copolymer, the content of unreacted ring-alkylated styrenes is far above 1000ppm (by weight), it is impossible to directly carry out halogenation Reaction.
Embodiment 1～4 is used for the present invention is described.
Embodiment 1
(1) solution (its containing monoolefine-alkylstyrene copolymers that the method identical with experimental example 1 will be used to prepare In, the weight content of unreacted p-methylstyrene is below 200ppm) solvent of evacuation it is pressed into nitrogen In displacer, being passed through the normal hexane steam of 70 DEG C from the bottom of solvent displacer, controlling operation pressure is 90kPa (absolute pressure), The persistent period that is passed through of normal hexane steam is 150min, thus solution (monoolefine-alkylstyrene copolymers after being replaced Content be 13.2 weight %).
(2) with reference to the mode shown in Fig. 1, after the displacement obtain step (1), solution nitrogen is pressed into evacuation Halogenation reactor in, and be heated to 54 DEG C, in halogenation reactor, add 14g the most successively contain 2 weight % azos The hexane solution of two different heptonitriles and 6g bromine, react 10min at a temperature of 54 DEG C.Then, add containing 120g Aqueous solution containing 2 weight %NaOH carries out the neutralization of 20min.
(3) the mixture water vapour desolvation that neutralization obtained also is condensed, and the aqueous bromination glue obtained is being opened It is dried 10 minutes in 110 DEG C on refining machine, thus obtains bromination monoolefine-alkylstyrene copolymers, measure bromination monoolefine Bromine content in-alkylstyrene copolymers, result is listed in table 3.
Embodiment 2
Method same as in Example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, the solution containing monoolefine-alkylstyrene copolymers of use is to use the method identical with experimental example 8 containing of preparing (wherein, the weight content of unreacted p-methylstyrene is 200ppm the solution of monoolefine-alkylstyrene copolymers Below), the persistent period that is passed through of normal hexane steam is 120min, monoolefine-ring-alkylated styrenes in solution after the displacement obtained The content of copolymer is 12.6 weight %；
Step (2) uses the mode shown in Fig. 2 to carry out: after the displacement obtain step (1), the press-in of solution nitrogen is mixed In clutch, mix 1min with 4g bromine, then mixture is sent in flat board photohalogenation reactor, open light source and irradiate 2min carries out photohalogenation reaction.Then, the bromination glue obtained is sent in neutralization reactor, and in neutralization reactor The aqueous solution that feeding 90g contains 2 weight %NaOH carries out the neutralization of 20min.
The bromine content of the bromination monoolefine-alkylstyrene copolymers of preparation is listed in table 3.
Embodiment 3
Method same as in Example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, use the solution containing monoolefine-alkylstyrene copolymers prepared by the method identical with experimental example 9 (wherein, not The weight content of the p-methylstyrene of reaction is below 200ppm), monoolefine-alkylbenzene second in solution after the displacement obtained The content of alkene copolymer is 12.4 weight %；
In step (2), the consumption of bromine is 4.2g.
The bromine content of the bromination monoolefine-alkylstyrene copolymers of preparation is listed in table 3.
Embodiment 4
(1) solution containing monoolefine-alkylstyrene copolymers that the method identical with experimental example 13 will be used to prepare (wherein, the weight content of unreacted p-methylstyrene is below 200ppm) is pressed into evacuation with nitrogen In solvent displacer, being passed through the normal hexane steam of 80 DEG C from the bottom of solvent displacer, controlling operation pressure is that 95kPa is (exhausted Pressure), the persistent period that is passed through of normal hexane steam is 150min, thus solution (monoolefine-ring-alkylated styrenes after being replaced The content of copolymer is 12.8 weight %).
(2) with reference to the mode shown in Fig. 1, after the displacement obtain step (1), solution nitrogen is pressed into evacuation Halogenation reactor in, and be heated to 52 DEG C, in halogenation reactor, add 15g the most successively contain 2 weight % azos The hexane solution of two different heptonitriles and 6g bromine, react 14min at a temperature of 52 DEG C.Then, add containing 120g Aqueous solution containing 2 weight %NaOH carries out the neutralization of 20min.
(3) the mixture water vapour desolvation that neutralization obtained also is condensed, and the aqueous bromination glue obtained is being opened It is dried 10 minutes in 110 DEG C on refining machine, thus obtains bromination monoolefine-alkylstyrene copolymers, measure bromination monoolefine Bromine content in-alkylstyrene copolymers, result is listed in table 3.
Table 3
Numbering Content of halogen (mol%)
Embodiment 1 1.24
Embodiment 2 1.16
Embodiment 3 0.91
Embodiment 4 1.26
Embodiment 1～4 as a result, it was confirmed that use the present invention method prepare halogenated isobutylene-p-methylstyrene copolymer, Monomer can be realized with higher rate of polymerization in polymerization procedure to convert completely or almost completely, the glue that polymerization obtains Operation without experience removing unreacted monomer can directly carry out halogenation, is effectively improved production efficiency, reduces energy Consumption.Further, the method for the present invention is used can to prepare the isobutene .-p-methylstyrene copolymer with higher molecular weight, from And rubber isobutene .-p-methylstyrene copolymer can be obtained, and then obtain halogenated isobutylene-p-methylstyrene rubber. Meanwhile, without using, slurry polymerization process is necessary when preparing isobutene .-p-methylstyrene copolymer gathers the method for the present invention Compound re-dissolved process.Therefore, the method for the present invention is suitable to large-scale production, is with a wide range of applications.

Claims (19)

1. a preparation method for halogenation monoolefine-alkylstyrene copolymers, the method comprises the following steps:
(1) under the conditions of cationic polymerization, by least one monoolefine and at least one ring-alkylated styrenes and initiator body Each component in system contacts in polymer solvent, obtains the solution containing monoolefine-alkylstyrene copolymers, described polymerization Solvent is made up of at least one first polymer solvent and at least one second polymer solvent, and described first polymer solvent is selected from halogen For alkane, described second polymer solvent is selected from alkane, and the condition of described contact makes, by weight, described containing monoene In the solution of hydrocarbon-alkylstyrene copolymers, the content of unreacted ring-alkylated styrenes is not higher than 1000ppm；
Described initiator system contains at least one compound that can provide carbonium ion, at least one lewis acid and extremely Few a kind of activator, described activator is selected from the compound shown in Formulas I-1 and the compound shown in Formulas I-2,
In Formulas I-1 and Formulas I-2, R1、R2、R3、R4、R5、R6、R7And R8It is respectively-H ,-X1、-NO2、 With the one in-CN, X1And X2It is respectively the one in halogen group；
Described monoolefine is selected from the compound shown in Formula II,
In Formula II, R9And R10It is respectively C1～C5Straight or branched alkyl；Or R9For hydrogen, R10For C3～C5 Branched alkyl；
Described ring-alkylated styrenes is selected from the compound shown in formula III,
In formula III, R11For C1～C5Straight or branched alkyl；
(2) molten containing monoolefine-alkylstyrene copolymers obtained by least one replacement solvent displacement step (1) Halogenated alkane in liquid, obtains solution after the displacement containing monoolefine-alkylstyrene copolymers, and described replacement solvent is selected from Alkane；
(3) solution and halogen-containingization after the displacement containing monoolefine-alkylstyrene copolymers that step (2) is obtained Compound contacts, so that the part hydrogen atom in described monoolefine-alkylstyrene copolymers strand is substituted with halogen atoms.
Method the most according to claim 1, wherein, the described compound that carbonium ion can be provided and described work The mol ratio of agent is 0.3～100:1, preferably 0.4～50:1, more preferably 0.5～20:1, more preferably 0.5～5:1, the most preferably 0.8～2.5:1.
Method the most according to claim 1, wherein, the mol ratio of described lewis acid and described activator be 4～ 1000:1, preferably 5～250:1, more preferably 5～50:1, more preferably 8～25:1.
Method the most according to claim 1, wherein, by least one monoolefine and at least one ring-alkylated styrenes The method contacted with each component in described initiator system includes: be dissolved in molten by each component in described initiator system In agent, and the mixture ageing that will obtain, obtain initiator solution；By described initiator solution be dissolved in polymer solvent In described monoolefine and described ring-alkylated styrenes mixing.
Method the most according to claim 4, wherein, the time of described ageing be 10 minutes to 10 hours, excellent Elect more than 30 minutes as, more preferably more than 60 minutes, more preferably 60 minutes to 120 minutes.
6. according to the method described in claim 4 or 5, wherein, described ageing is at-100 DEG C to 20 DEG C, preferably-100 DEG C carry out to-50 DEG C, further preferably-90 DEG C to-70 DEG C to 0 DEG C, more preferably-100 DEG C.
Method the most according to claim 4, wherein, described solvent is in alkane, halogenated alkane and aromatic hydrocarbons One or more.
8. according to the method described in any one in Claims 1 to 5 and 7, wherein, described activator is selected from tetrachlorobenzene Quinone, DDQ, tetrahydrochysene benzoquinone and four cyano benzoquinone.
9. according to the method described in any one in Claims 1 to 5 and 7, wherein, described lewis acid is formula IV Lewis acid shown in shown lewis acid and/or Formula V,
In formula IV, X31And X32It is respectively the one in halogen group, is preferably-Cl；R12For C1～C8Straight chain or Branched alkyl, preferably ethyl；
In Formula V, X4For the one in halogen group, it is preferably-Cl；R13And R14It is respectively C1～C8Straight chain or Alkyl group, preferably ethyl；
Preferably, described lewis acid is the lewis acid shown in formula IV and the lewis acid shown in Formula V, described Louis In this acid, the lewis acid of 10～90 moles of %, preferably 30～70 moles of % is the lewis acid shown in Formula V.
10. according to the method described in any one in Claims 1 to 5 and 7, wherein, described can provide carbon just from The compound of son is selected from quiltSubstituted aromatic hydrocarbons, R18And R19It is respectively hydrogen, C1～C8Alkyl, phenyl, C7~ C10Phenylalkyl, C7～C10Alkyl phenyl or C3～C8Cycloalkyl, X6For the one in halogen group, preferably For-Cl or-Br；
Preferably, the described compound that can provide carbonium ion is selected from Isosorbide-5-Nitrae-two (chloromethyl) benzene, Isosorbide-5-Nitrae-two (bromomethyl) Benzene, 1,4-bis-(2-chloro isopropyl) benzene and 1,4-bis-(2-bromine isopropyl) benzene.
11. methods according to claim 1, wherein, with the total amount of described monoolefine and described ring-alkylated styrenes be Benchmark, the content of described monoolefine is 80～99 weight %, preferably 90～97 weight %；Containing of described ring-alkylated styrenes Amount is 1～20 weight %, preferably 3～10 weight %.
12. according to the method described in any one in Claims 1 to 5,7 and 11, wherein, described ring-alkylated styrenes For p-methylstyrene and/or a methyl styrene；
Described monoolefine is isobutene..
13. according to the method described in any one in Claims 1 to 5,7 and 11, wherein, in step (1), and institute State contact at-120 DEG C to 20 DEG C, preferably-100 DEG C to 0 DEG C, more preferably-100 DEG C to-50 DEG C, further preferably-90 DEG C extremely Carry out within the temperature range of-60 DEG C.
14. methods according to claim 1, wherein, described halogen-containing compound is halogen simple substance, is preferably Bromine and/or chlorine element, more preferably bromine.
15. methods according to claim 14, wherein, in step (3), described contact is at radical initiator In the presence of carry out or be light-initiated under the conditions of carry out.
16. methods according to claim 15, wherein, described contact is carried out in the presence of radical initiators, Described radical initiator is 0.01～0.5:1 with the mol ratio of described halogen contained compound, preferably 0.02～0.2:1.
17. according to the method described in any one in claim 1 and 14～16, wherein, in step (3), described Contact is carried out within the temperature range of-10 DEG C to 80 DEG C, preferably 0 DEG C to 60 DEG C, and the time of described contact is 0.5～30 point Clock, preferably 1～15 minute.
18. methods according to claim 1, wherein, on the basis of the total amount of described polymer solvent, described first The content of polymer solvent is 1～80 volume %, preferably 1～60 volume %, more preferably 10～50 volume %；Described The content of the second polymer solvent is 20～99 volume %, preferably 40～99 volume %, more preferably 50～90 volume %.
19. according to the method described in any one in Claims 1 to 5,11,14～16 and 18, wherein, and described One polymer solvent is selected from C1～C10Halogenated alkane；
Described second polymer solvent and described replacement solvent are identical or different, each are selected from C3～C10Aliphatic alkane, Preferably it each is selected from C5～C8Aliphatic alkane, each more preferably be selected from pentane, normal hexane and normal heptane.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1735643A (en) * 2002-11-05 2006-02-15 阿肯马公司 Synthesis method for polydimethylketene by friedel - craft cationic polymerization of dimethylketene
CN102399311A (en) * 2010-08-19 2012-04-04 中国石油化工股份有限公司 Cationic polymerization initiation system and cationic polymerization method
CN102702409A (en) * 2012-06-07 2012-10-03 北京石油化工学院 Technology for directly producing halogenated butyl rubber using butyl glue prepared by solution method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1735643A (en) * 2002-11-05 2006-02-15 阿肯马公司 Synthesis method for polydimethylketene by friedel - craft cationic polymerization of dimethylketene
CN102399311A (en) * 2010-08-19 2012-04-04 中国石油化工股份有限公司 Cationic polymerization initiation system and cationic polymerization method
CN102702409A (en) * 2012-06-07 2012-10-03 北京石油化工学院 Technology for directly producing halogenated butyl rubber using butyl glue prepared by solution method

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