CN106146699A

CN106146699A - A kind of preparation method of halogen polymer

Info

Publication number: CN106146699A
Application number: CN201510194428.9A
Authority: CN
Inventors: 张雷; 邱迎昕; 龚惠勤; 周新钦; 张月红
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2015-04-22
Filing date: 2015-04-22
Publication date: 2016-11-23
Anticipated expiration: 2035-04-22
Also published as: CN106146699B

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 alkane, the solution containing monoolefine-alkylstyrene copolymers obtained is contacted with halogen-containing compound and carries out halogenation, described initiator system contains, and can to provide the compound of carbonium ion, lewis acid and activator, described activator be 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, it is thus achieved that higher polymer yield；The polymer with higher molecular weight can also be obtained.When the method for the present invention eliminates employing slurry polymerization process, necessary solvent is replaced and polymer re-dissolved 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 Change to arrange between reactions steps and be intended to the solvent swap step with the halogenated alkane in alkane displacement slurry mixture and polymerization Thing re-dissolved step, and in solution polymerization process, if using alkane as polymer solvent, then walk without the displacement of described solvent Rapid and 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, at least one polymer solvent, by least one monoolefine and at least one Kind of ring-alkylated styrenes contacts with each component in initiator system, and obtain containing monoolefine-alkylstyrene copolymers is molten Liquid, described polymer solvent is selected from alkane, and the condition of described contact makes, by weight, described containing monoolefine-alkylbenzene In the solution of ethylene copolymer, 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) solution containing monoolefine-alkylstyrene copolymers that step (1) obtains is connect with halogen-containing compound Touch, 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⁺The polymerization of/lewis acid initiator system Technique is compared, it is possible to obtain the polymerization efficiency that significantly improves, it is thus possible to realize monomer completely or base with higher rate of polymerization This converts completely so that the glue containing monoolefine-alkylstyrene copolymers of preparation removes unreacted list without experience The process of body i.e. can be directly used for halogenation；On the other hand the polymer with higher molecular weight, particularly rubber can also be obtained Use heavy polymer.It addition, the C simple with employing⁺/ lewis acid initiator system is compared, and the method for the present invention is i.e. Make to implement at higher temperatures polymerization, also can obtain higher polymerization efficiency and preparation has the polymer of higher 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 is prepared necessary solvent during polymer and is replaced and polymer re-dissolved process, effectively simplifies halogenation monoene The production technology of hydrocarbon-alkylstyrene copolymers.

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 be the one of the method according to the invention preferred embodiment.

Fig. 2 is another preferred embodiment 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

3: polymer solvent 4: initiator solution

5: terminator 6: containing the solution of monoolefine-alkylstyrene copolymers

7: halogen-containing compound 8: radical initiator solution

9: the aqueous solution 10 of alkaline matter: containing the mixture of halogenation monoolefine-alkylstyrene copolymers

11: light source I: polymer reactor

II: halogenation reactor III: blender

IV: photohalogenation reactor V: neutralization reactor

Detailed description of the invention

(1) under the conditions of cationic polymerization, at least one polymer solvent, by least one monoolefine and at least one Kind of ring-alkylated styrenes contacts with each component in initiator system, and obtain containing monoolefine-alkylstyrene copolymers is molten Liquid, described polymer solvent is selected from alkane, and the condition of described contact makes, by weight, described containing monoolefine-alkylbenzene In the solution of ethylene copolymer, the content of unreacted ring-alkylated styrenes is not higher than 1000ppm, is preferably not higher than 500ppm, more preferably not above 200ppm；

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), tribromo one 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).It is highly preferred that described activator is dichloro Dicyano 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 (such as-F ,-Cl ,-Br or-I) in halogen group, 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 more 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) and 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, it is specifically as follows 1～2: 1.Described lewis acid and described work The mol ratio of agent can be 4～1000: 1, preferably 5～250: 1, more preferably 5～50: 1, further preferably It is 8～25: 1, the most preferably 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 more than 30 minutes, can improve polymerization efficiency further, it is thus possible to obtain in shorter polymerization time There is the monoolefine-alkylstyrene copolymers of higher molecular weight.Such as, described digestion time can be 30 minutes to 5 Hour.It is highly preferred that the time of described ageing is more than 60 minutes.Guaranteeing to obtain the premise of higher polymerization efficiency Under, from the angle of economy, the time of described ageing is less than 10 hours, preferably less than 5 hours, more preferably It it is less than 2 hours.Preferably, the time of described ageing is 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 can be selected from alkane.As polymer solvent, described alkane can be Aliphatic alkane and/or alicyclic alkanes, as selected from C₃～C₁₀Aliphatic alkane and C₃～C₁₀Alicyclic alkanes. Described aliphatic alkane is preferably C₃～C₈Aliphatic alkane, more preferably C₅～C₈Aliphatic alkane.Described fat Ring race alkane is preferably C₅～C₁₀Alicyclic alkanes.

In the present invention, the instantiation of described 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-diformazan Base hexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3-ethyl hexane, 2，2，3-trimethyl-pentane, 2,3,3-trimethyls Pentane, 2,4,4-trimethylpentanes, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-first Base octane, 2,3-dimethyl heptane, 2,4-dimethyl heptane, 3-ethyl heptane, 4-ethyl heptane, 2,3,4-trimethyl cyclohexanes, 2,3,5-trimethyl cyclohexanes, 2,4,5-trimethyl cyclohexanes, 2,2,3-trimethyl cyclohexanes, 2,2,4-trimethyl cyclohexanes, 2,2,5-trimethyls Hexane, 2,3,3-trimethyl cyclohexanes, 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, just Decane, 2-methylnonane, 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-trimethylheptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethyls Heptane, 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-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-first Base-3,3-diethylpentane, 1,2-diethyl cyclohexane, 1,3-diethyl cyclohexane, Isosorbide-5-Nitrae-diethyl cyclohexane, normal-butyl ring Hexane, isobutyl group hexamethylene, t-butylcyclohexane and tetramethyl-ring hexane.

Described polymer 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 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, polymerization Can be at-120 DEG C to 20 DEG C, preferably-100 DEG C to 0 DEG C, more preferably-100 DEG C to-40 DEG C, further preferably-90 DEG C to-60 Carry out within the temperature range of DEG C.The method according to the invention, polymerization time can be the conventional selection of this area, typically may be used Think 10～180 minutes, preferably 30～120 minutes.

The method according to the invention, it is also possible to be included in and be polymerized in the mixture that backward polymerization obtains interpolation polymerization Agent makes polyreaction 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 20 × 10⁴Above, particularly weight average molecular weight is 40 × 10⁴Above monoolefine-ring-alkylated styrenes Copolymer, and then rubber monoolefine-alkylstyrene copolymers can be obtained.

The method according to the invention, the solution containing monoolefine-alkylstyrene copolymers that step (1) obtains can be straight Pick in step (2) and contact with halogen-containing compound, it is also possible to step (1) is obtained containing monoolefine-alkyl The solution of styrol copolymer is sent in step (2) after concentrating or diluting and is contacted with halogen-containing compound.Typically Ground, sends into monoolefine-alkylstyrene copolymers in the solution containing monoolefine-alkylstyrene copolymers of step (2) Content can be 1～30 weight %, preferably 5～20 weight %.

The method according to the invention, in step (2), 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 (2), the solution containing monoolefine-alkylstyrene copolymers is permissible with contacting of halogen-containing compound Carry out under normal conditions, as long as monoolefine-alkylstyrene copolymers generation halogenation can be made.Usually, institute Stating contact to carry out in the presence of at least one radical initiator, described contact can also be under the conditions of light-initiated. Described radical initiator can be common various can promote monoolefine-alkylstyrene copolymers with containing halogen chemical combination The radical initiator of thing reaction, preferably oleosoluble radical initiators, such as azo type free radical initiator, preferably selects From azo diisobutyl nitrile, AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile).The consumption of described radical initiator is drawing Send out halogenation to be as the criterion.Usually, the mol ratio of described radical initiator and described halogen contained compound can be 0.01～ 0.5: 1, preferably 0.02～0.2: 1, more preferably 0.02～0.1: 1.Described radical initiator is preferably with solution Form provides, and solvent can be selected from the aforementioned combination as one or more in the alkane of polymer solvent, is preferably Identical with polymer solvent.When carrying out described contact under the conditions of light-initiated, illumination condition is can cause monoolefine-alkylbenzene Ethylene copolymer generation halogenation is as the criterion, such as: light source can be electric filament lamp (electric filament lamp such as 80～200W).

In step (2), 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 (2), 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 within the temperature range of-10 DEG C to 80 DEG C, preferably at 0 DEG C Carry out within the temperature range of 60 DEG C, more preferably carry out within the temperature range of 20 DEG C to 60 DEG C.The time of described contact can Select with the temperature according to contact and intended halogenation degree, can be typically 0.5～30 minute, be preferably 1～15 minute.

The method according to the invention, in step (2), 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 20 × 10⁴Above, particularly 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, the ring-alkylated styrenes 2 shown in formula III and polymer solvent 3 and preparation in advance aged initiator Solution 4 is sent in polymer reactor I, carries out polyreaction under the conditions of cationic polymerization.Carry out the scheduled time After polyreaction, terminator 5 is sent in polymer reactor I, terminate polyreaction.Containing of polymer reactor I output The solution 6 of monoolefine-alkylstyrene copolymers subsequently enter in halogenation reactor II with halogen-containing compound 7 and freely Base initiator solution 8 haptoreaction, so that at least part of hydrogen atom quilt in monoolefine-alkylstyrene copolymers strand Halogen atom is replaced.In monoolefine-alkylstyrene copolymers strand, the content of halogen atom meets pre-provisioning request Time, in halogenation reactor II, send into the aqueous solution 9 of alkaline matter, be neutralized.Finally, neutralization obtained contains The mixture 10 of halogenation monoolefine-alkylstyrene copolymers exports, and sends into and carry out in subsequent handling separating 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, the solution containing monoolefine-alkylstyrene copolymers of polymer reactor I output 6 enter in blender III, mix homogeneously with halogen-containing compound 7, then the mixture obtained are sent into photohalogenation anti- Answer in device IV, under the irradiation of light source 11, carry out halogenation.After halogenation completes, by photohalogenation reactor IV In mixture send in neutralization reactor V and contact to be neutralized with the aqueous solution 9 of alkaline matter.Finally, will neutralize The mixture 10 containing halogenation monoolefine-alkylstyrene copolymers obtained exports, and sends into and carry out in subsequent handling point From 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 1～20 is for illustrating the polymerization procedure in the inventive method.

Experimental example 1

(1) by 0.142g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 200g and containing (concentration is to dicumyl chlorine In dichloromethane 0.005mol/L), the solution obtained being cooled to-85 DEG C in advance, then in this solution, order adds 5mL Concentration is the hexane solution of the ethyl aluminum dichloride (EADC) of 0.9mol/L and 4.5mL concentration is the diethyl of 1.0mol/L The n-heptane solution (molar ratio of EADC Yu DEAC is 5/5) of base aluminum chloride (DEAC), after mix homogeneously, The mixed liquor obtained is placed in the cryostat of-85 DEG C ageing 100min, thus obtains initiator solution.

(2) in being furnished with the stainless steel reactor of 2000mL of strength constant speed stirring, order adds 800g and is cooled to-80 in advance DEG C normal hexane, 100g be cooled to isobutene. and the p-methylstyrene (content 98 of 6g room temperature (being 25 DEG C) of-80 DEG C in advance Weight %), mix homogeneously.Initiator solution prepared by step (1) is dripped in reactor.Wherein, initiator solution Addition be 120mL, control rate of addition and the temperature in reactor be within the scope of-85 DEG C to-90 DEG C. After being added dropwise to complete, keep the temperature in reactor to be within the scope of-85 DEG C to-90 DEG C, and the polymerization carrying out 50min is anti- Should, in reactant mixture, then add the dichloromethane solution that 100g contains 3 weight % 2,2'-ethylenedioxybis(ethanol) .s, anti-to terminate polymerization Should, thus obtain the solution containing monoolefine-alkylstyrene copolymers.Then, by obtain containing monoolefine-alkylbenzene The solution of ethylene copolymer is placed in desolvation in hot bath, is dried to constant weight in 60 DEG C after washing in vacuum drying oven, To 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

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, digestion time is 60min；In step (2), polymerization reaction time is 60min.Experimental result is listed in Table 1.

Experimental example 3

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, digestion time is 30min；In step (2), polymerization reaction time is 80min.Experimental result is listed in Table 1.

Experimental example 4

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, digestion time is 10min；In step (2), polymerization reaction time is 100min.

Experimental result is listed in Table 1.

Experimental example 5

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, do not use diethyl aluminum chloride, but replace with the ethyl aluminum dichloride of equimolar amounts.Experimental result is listed in Table 1.

Experimental example 6

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, under conditions of the total amount of EADC and DEAC is constant, the molar ratio making EADC Yu DEAC is 1/9；Step (2), in, polymerization reaction time is 90min.Experimental result is listed in Table 1.

Experimental example 7

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, under conditions of the total amount of EADC and DEAC is constant, the molar ratio making EADC Yu DEAC is 3/7；Step (2), in, polymerization reaction time is 70min.Experimental result is listed in Table 1.

Experimental example 8

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, the tetrahydrochysene 1,4-benzoquinone of 2,3-bis-chloro-5,6-dicyano p-benzoquinone's equimolar amounts replaces；In step (2), polyreaction Time is 50min.Experimental result is listed in Table 1.

Experimental example 9

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, the chloranil of 2,3-bis-chloro-5,6-dicyano p-benzoquinone's equimolar amounts replaces；In step (2), polyreaction Time is 60min.Experimental result is listed in Table 1.

Experimental example 10

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1) In, the four cyano 1,4-benzoquinone of 2,3-bis-chloro-5,6-dicyano p-benzoquinone's equimolar amounts replaces；In step (2), polymerization is anti- It is 80min between Ying Shi.Experimental result is listed in Table 1.

Experimental example 11

The method identical with experimental example 1 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (2) In, the temperature in reactor is all maintained at the model of-60 DEG C to-70 DEG C by dropping initiator solution and polymerization process In enclosing, polymerization reaction time is 100min.Experimental result is listed in Table 1.

Experimental comparison's example 2

The method identical with experimental example 11 is used to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, step (1), in, 2 are not used, 3-bis-chloro-5,6-dicyano p-benzoquinone.Experimental result is listed in Table 1.

Experimental example 12

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 chlorine (concentration is 0.0052mol/L), the solution that will obtain Being cooled to-85 DEG C in advance, then in this solution, order adds the ethyl aluminum dichloride (EADC) that 10mL concentration is 0.9mol/L Hexane solution, after mix homogeneously, the mixed liquor obtained is placed in the cryostat of-85 DEG C ageing 80min, thus obtains Initiator solution；

In step (2), polymerization reaction time is 60min.

Experimental result is listed in Table 1.

Experimental comparison's example 3

Use the method identical with experimental example 12 to be polymerized, except for the difference that, in step (1), do not use tetrachloro-p-phenylene Quinone.Experimental result is listed in Table 1.

Experimental example 13

Using the method identical with experimental example 12 to be polymerized, except for the difference that, in step (1), digestion time is 60min； In step (2), polymerization reaction time is 70min.

Experimental result is listed in Table 1.

Experimental example 14

Using the method identical with experimental example 12 to be polymerized, except for the difference that, in step (1), digestion time is 30min； In step (2), polymerization reaction time is 90min.Experimental result is listed in Table 1.

Experimental example 15

Using the method identical with experimental example 12 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 1.

Experimental example 16

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 containing in the dichloromethane to dicumyl bromine (concentration is 0.006mol/L), by pre-for the solution obtained Being cooled to-85 DEG C, then in this solution, order adds the hexane solution of the ethyl aluminum dichloride that 12mL concentration is 0.9mol/L, After mix homogeneously, the mixed liquor obtained is placed in the cryostat of-85 DEG C ageing 80min, thus obtains initiator solution；

In step (2), polymerization reaction time is 50min.Experimental result is listed in Table 1.

Experimental example 17

Using the method identical with experimental example 1 to be polymerized, except for the difference that, the initiator solution of employing is and experimental example 12 Identical initiator solution.Experimental result is listed in Table 1.

Experimental example 18

The method identical with experimental example 17 is used to be polymerized, except for the difference that, in initiator solution, EADC and DEAC Total amount constant under conditions of, the molar ratio making EADC Yu DEAC is 7/3；In step (2), polyreaction Time is 80min.Experimental result is listed in Table 1.

Experimental example 19

The method identical with experimental example 17 is used to be polymerized, except for the difference that, in initiator solution, EADC and DEAC Total amount constant under conditions of, the molar ratio making EADC Yu DEAC is 9/1；In step (2), polyreaction Time is 70min.Experimental result is listed in Table 1.

Experimental example 20

Use the method identical with experimental example 1 to be polymerized, except for the difference that, in initiator solution, dicumyl bromine is used Mole dibenzyl chloro is replaced；In step (2), the time of polyreaction is 60min.

Experimental result is listed in Table 1.

Table 1 as a result, it was confirmed that use the inventive method be polymerized, higher polymerization efficiency, monomer conversion can be obtained Height, the C simple with employing⁺/ lewis acid initiator system is compared, and polymer yield can be made to reach within the shorter time 100%, the content energy of unreacted ring-alkylated styrenes in the solution containing monoolefine-alkylstyrene copolymers prepared Reach 200ppm (by weight) below, it is not necessary to experience separates the step of unreacted ring-alkylated styrenes and can directly carry out Halogenation.On the contrary, the polymerization efficiency of Experimental comparison's example 1～3 is poor, in the case of remaining condition is identical, with identical Polymerization time polymer yield cannot be made to reach more than 99%, and then in the monoolefine-alkylstyrene copolymers of preparation not The content of the ring-alkylated styrenes of reaction is far above 1000ppm (by weight), it is impossible to directly carry out halogenation.

Embodiment 1～5 is for the method that the present invention is described.

Embodiment 1

With reference to the mode shown in Fig. 1, whole solution containing monoolefine-alkylstyrene copolymers prepared by experimental example 1 (should be containing in the solution of monoolefine-alkylstyrene copolymers, the content of monoolefine-alkylstyrene copolymers is 15 weights Amount %, the weight content of unreacted p-methylstyrene is below 200ppm) halogenation of evacuation it is pressed into nitrogen In reactor, and it is heated to 54 DEG C, in halogenation reactor, adds 10g the most successively contained for 2 weight % azo two different heptan The hexane solution of nitrile and 6g bromine, react 10min at a temperature of 54 DEG C.Then, addition contains 2 containing 120g The aqueous solution of weight %NaOH carries out the neutralization of 20min.

The mixture water vapour desolvation that neutralization obtained also is condensed, and the aqueous bromination glue obtained is on a mill until It is dried 10 minutes in 110 DEG C, thus obtains bromination monoolefine-alkylstyrene copolymers, measure bromination monoolefine-alkyl Bromine content in styrol copolymer, result is listed in table 2.

Embodiment 2

Using method same as in Example 1 to prepare bromination monoolefine-alkylstyrene copolymers, except for the difference that, halogenation is anti- The mode shown in Fig. 2 that should refer to is carried out: be pressed into by the solution nitrogen containing monoolefine-alkylstyrene copolymers of preparation In blender, mix 1min with 5.5g bromine, then mixture is sent in flat board photohalogenation reactor, open light source (merit Rate is the electric filament lamp of 200W) irradiate 2min carry out photohalogenation reaction.Then, the bromination glue obtained is sent into neutralization anti- Answer in device, and the aqueous solution that feeding 90g contains 2 weight %NaOH in neutralization reactor carries out the neutralization of 20min. The bromine content of the bromination monoolefine-alkylstyrene copolymers of preparation is listed in table 2.

Embodiment 3

Using method same as in Example 1 to prepare bromination monoolefine-alkylstyrene copolymers, difference is as follows:

The solution containing monoolefine-alkylstyrene copolymers using experimental example 12 preparation (should be containing monoolefine-alkylbenzene In the solution of ethylene copolymer, the content of monoolefine-alkylstyrene copolymers is 17 weight %, unreacted to methylbenzene The weight content of ethylene is below 200ppm), the addition of bromine is 4.2g.Experimental result is listed in table 2.

Embodiment 4

The solution containing monoolefine-alkylstyrene copolymers using experimental example 16 preparation (should be containing monoolefine-alkylbenzene In the solution of ethylene copolymer, the content of monoolefine-alkylstyrene copolymers is 14 weight %, unreacted to methylbenzene The weight content of ethylene is below 200ppm), the consumption of bromine is 4.2g.Experimental result is listed in table 2.

Embodiment 5

Using method same as in Example 2 to prepare bromination monoolefine-alkylstyrene copolymers, difference is as follows:

The solution containing monoolefine-alkylstyrene copolymers using experimental example 17 preparation contains monoolefine-alkylbenzene second The solution of alkene copolymer (should contain in the solution of monoolefine-alkylstyrene copolymers, monoolefine-alkylstyrene copolymers Content be 11 weight %, the weight content of unreacted p-methylstyrene is below 200ppm), the consumption of bromine is 3g.Experimental result is listed in table 2.

Table 2

Numbering	Content of halogen (mol%)
		Embodiment 1	1.21
Embodiment 2	1.27
		Embodiment 3	0.85
Embodiment 4	0.85
		Embodiment 5	0.85

Embodiment 1～5 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, when the method for the present invention is without using slurry polymerization process to prepare isobutene .-p-methylstyrene copolymer necessary molten Agent replacement and polymer re-dissolved process.Therefore, the method for the present invention is suitable to large-scale production, before having a wide range of applications Scape.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, in the technology concept of the present invention, can carry out multiple simple variant to technical scheme, These simple variant belong to protection scope of the present invention.

It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in not contradiction In the case of, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is to various Possible compound mode illustrates the most separately.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this Bright thought, it should be considered as content disclosed in this invention equally.

Claims

1. a preparation method for halogenation monoolefine-alkylstyrene copolymers, the method comprises the following steps:

Described monoolefine is selected from the compound shown in Formula II,

In formula III, R₁₁For C₁～C₅Straight or branched alkyl；

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, the most excellent Elect 10～20:1 as.

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 the temperature range of-100 DEG C to 20 DEG C Inside carry out, preferably carry out within the temperature range of-100 DEG C to 0 DEG C, more preferably enter within the temperature range of-100 DEG C to-50 DEG C OK, further preferably carry out within the temperature range of-90 DEG C to-70 DEG C.

Method the most according to claim 3, 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 carbonium ion can be provided selected from Isosorbide-5-Nitrae-two (chloromethyl) benzene, Isosorbide-5-Nitrae-two (bromomethyl) benzene, 1,4-bis-(2-bromine isopropyl) benzene and 1,4-bis-(2-chloro 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. methods according to claim 1, wherein, in step (1), described contact-120 DEG C to 20 DEG C, Preferably-100 DEG C are carried out within the temperature range of-40 DEG C, further preferably-90 DEG C to-60 DEG C to 0 DEG C, more preferably-100 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 (2), 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 (2), 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. according to the method described in any one in Claims 1 to 5,7,11 and 13～16, wherein, and step (1) In, described polymer solvent is selected from C₃～C₁₀Aliphatic alkane, be preferably selected from C₅～C₈Aliphatic alkane, more preferably Selected from pentane, normal hexane and normal heptane.