CN106146700A - A kind of preparation method of halogen polymer - Google Patents

A kind of preparation method of halogen polymer Download PDF

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CN106146700A
CN106146700A CN201510195133.3A CN201510195133A CN106146700A CN 106146700 A CN106146700 A CN 106146700A CN 201510195133 A CN201510195133 A CN 201510195133A CN 106146700 A CN106146700 A CN 106146700A
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monoolefine
benzoquinone
solution
alkane
polymerization
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CN106146700B (en
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邱迎昕
张月红
孟伟娟
周新钦
张雷
龚惠勤
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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 ring-alkylated styrenes shown in formula III in the mixed solvent of halogenated alkane and 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 can carry protogenic compound, 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 can significantly improve polymerization efficiency, reduces the energy consumption needed for polymerization, 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 H+/ lewis acid initiator system, is gathered isobutene. by cation with ring-alkylated styrenes When conjunction mode carries out combined polymerization in the solution, polymerization efficiency extreme difference, rate of polymerization is slow, needs to react ability for a long time Monomer is made to convert completely or almost completely.Cationic polymerization is carried out the most at low temperatures, and polymerization time is the longest, maintains Energy expenditure needed for low temperature is the highest, and long polymerization obviously cannot meet the requirement of large-scale production.And, adopt Use H+/ lewis acid initiator system typically requires the isobutyl that could prepare high molecular under more harsh reaction condition Alkene-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 H+/ 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 can carry protogenic compound, at least one lewis acid and at least one Planting 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 H 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, reduces the energy expenditure in polymerization process, prepare containing monoolefine-alkylstyrene The process that the glue of thing removes unreacted monomer without experience i.e. can be directly used for halogenation.And, the H simple with employing+/ The polymerization technique of lewis acid initiator system is compared, and uses the method for the present invention to be polymerized, can obtain and have relatively high score The polymer of son amount, particularly rubber heavy polymer.It addition, the H 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 make Get everything ready 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 glue containing monoolefine-alkylstyrene copolymers prepared is without experience removing The process of unreacted monomer can carry out halogenation, and the method for the present invention is omitted and uses slurry polymerization process preparation poly-simultaneously During compound, necessary polymer re-dissolved process, simplifies the production of halogenation monoolefine-alkylstyrene copolymers effectively Technique.
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 system In each component contact in polymer solvent, obtain the solution containing monoolefine-alkylstyrene copolymers, described polymerization is molten Agent 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 halo Alkane, described second polymer solvent be selected from alkane, the condition of described contact makes, by weight, described containing monoolefine- In the solution of alkylstyrene copolymers, the content of unreacted ring-alkylated styrenes is not higher than 1000ppm, is preferably the highest In 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 Enough carry protogenic compound, at least one lewis acid and at least one 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 (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).
Method in accordance with the invention it is preferred that in Formulas I-1, R1、R2、R3And R4It is asynchronously-H, in Formulas I-2, R5、R6、R7And R8It is asynchronously-H.It is highly preferred that described activator selected from tetrachloroquinone (include chloranil and Monoethyl quinone), four cyano benzoquinone (including four cyano 1,4-benzoquinone and four cyano neighbour's benzoquinone) and DDQ (bag Include dichloro dicyano p-benzoquinone and dichloro dicyano neighbour's benzoquinone).It is further preferred that described activator is dichloro dicyanobenzenes Quinone (includes dichloro dicyano p-benzoquinone and dichloro dicyano neighbour's benzoquinone).
The content of described activator is to be obtained in that gratifying polymerization effect is as the criterion.Usually, described matter can be provided The compound of son can be 1: 0.01～5 with the mol ratio of described activator, preferably 1: 0.1～3, more preferably 1: 0.2～2.5, more preferably 1: 0.4～2, the most preferably 1: 0.5～1.8.
The method according to the invention, described lewis acid and described can to carry protogenic compound can be cationic polymerization The conventional selection in field, is not particularly limited, if described lewis acid and protogenic compound can be carried can be formed Cationic species, causes and 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 rate of polymerization There is the polymer of higher molecular weight.
Described lewis acidic content can be the conventional amount used in cationic polymerization field.Usually, described matter can be provided The compound of son and described lewis acidic mol ratio can be 0.01～1: 1, preferably 0.02～0.5: 1, more preferably 0.03～0.3: 1, more preferably 0.03～0.15: 1, more preferably 0.035～0.1: 1.
Described can carry protogenic compound can be in cationic polymerization field conventional various can carry protogenic Compound.It is usually, described that can to carry protogenic compound can be H2O and/or Bronsted acid, its instantiation is permissible Include but not limited to: H2O、HCl、HF、HBr、H2SO4、H2CO3、H3PO4And HNO3.Preferably, described Can carry protogenic compound is HCl.
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 can be less than 10 hours, preferably less than 5 hours, more It is preferably less than 2 hours.Preferably, the time of described ageing is 60 minutes to 120 minutes.
Described solvent can be various can to dissolve described Bronsted acid, described lewis acid and the liquids of described activator Matter.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～C10Aliphatic alkane and C3～C10Alicyclic alkanes.As solvent, described Halogenated alkane includes halogenated aliphatic alkane and halogenated cyclo alkane, such as C1～C10Halogenated alkane include C1～C10's Halogenated aliphatic alkane and C3～C10Halogenated cyclo alkane.Halogen atom in described halogenated alkane 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 10～60 volumes；The content of described second polymer solvent can be 20～99 volume %, It is preferably 40～90 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, 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 typically more than 30 minutes.Turn at monomer Under conditions of rate meets requirement, from the angle shortening polymerization time further, polymerization time can be typically 180 Below minute, preferably less than 120 minutes, more preferably less than 60 minutes.
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 monoolefine-alkylstyrene copolymers, so can obtain rubber monoolefine- Alkylstyrene copolymers.
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 solvent 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, more It is 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 %, more preferably 10～ 15 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 and/or chlorine element.It is highly preferred that described halogen-containing compound is bromine Element.
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 Carry out under part.Described radical initiator can be common various can to promote monoolefine-alkylstyrene copolymers and contain The radical initiator of halogen compounds reaction, preferably oleosoluble radical initiators, such as azo type free radical initiator, It is preferably selected from azo diisobutyl nitrile, AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile).The consumption of described radical initiator with Halogenation can be caused to be as the criterion.Usually, described radical initiator and the weight of monoolefine-alkylstyrene copolymers Ratio can be 0.01～1: 100, preferably 0.05～0.5: 100.Described radical initiator carries the most as a solution Confession, solvent can selected from one or more the combination in the aforementioned alkane being used as the second polymer solvent, be preferably with Second polymer solvent is identical.When carrying out described contact under the conditions of light-initiated, illumination condition is can cause monoolefine-alkyl Styrol copolymer generation halogenation is as the criterion, such as: light source can be that daylight lamp or electric filament lamp are (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 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.The time of described contact can be according to the temperature of contact and intended halogenation journey Degree selects, 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 carries out water vapor accumulation and is dried, 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 CDC13Making 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 1～32 is for illustrating the polymerization procedure in the inventive method.
Experimental example 1
(1) 0.133g chloranil is dissolved in 66.5g dichloromethane solution, obtains chloranil's solution.With Weight meter, in this solution, the concentration of chloranil is 2000ppm.At-80 DEG C, in 60mL Cornu Caprae seu Ovis bottle, order adds Enter that the pre-20mL being cooled to-80 DEG C contains the dichloromethane solution of HCl (concentration is 0.0038mol/L), 1.8mL contains two The hexane solution of chloroethyl aluminum (concentration is 0.9mol/L) and 0.5mL aforementioned chloranil solution, mix homogeneously After be aged 60min at-80 DEG C, thus obtain initiator solution.By weight, in this initiator solution, chloranil Concentration be 50ppm.
(2) in the 500mL glass reactor being furnished with strength constant speed stirring, order adds 100mL and is cooled to-60 DEG C in advance Monochloro methane, 80mL be cooled in advance-80 DEG C normal hexane, 32mL be cooled to isobutene. and the 1.3mL room temperature (25 of-80 DEG C in advance DEG C) p-methylstyrene (content is 98 weight %), mix homogeneously.In reactor, drip prepared by step (1) Initiator solution.Wherein, the addition of initiator solution is 16mL；Control at the temperature in drop rate makes reactor Within the scope of-90 DEG C to-85 DEG C.After being added dropwise to complete, keep the scope that the temperature in reactor is in-90 DEG C to-85 DEG C Within, carry out the polyreaction of 60min with stirring, in reactant mixture, then add 5mL contain 0.5 weight The methanol solution of %NaOH, to terminate polyreaction.The mixed solution obtained is placed in desolvation in hot bath, obtains Product after washing, be dried to constant weight in 60 DEG C in vacuum drying oven, thus obtain subject polymer.
Measure the weight of the polymer obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution of polymer Index, result is listed in Table 1.
Experimental example 2～4
Using the method identical with experimental example 1 to be polymerized, except for the difference that, in experimental example 2, step (1) obtains In initiator solution, by weight, the concentration of chloranil is 100ppm, the polymerization reaction time in step (2) For 50min；In experimental example 3, in the initiator solution that step (1) obtains, by weight, the concentration of chloranil For 300ppm, the polymerization reaction time in step (2) is 40min；In experimental example 4, the initiation that step (1) obtains In agent solution, by weight, the concentration of chloranil is 800ppm, and the polymerization reaction time in step (2) is 30min. Experimental result is listed in Table 1.
Experimental example 5
(1) 0.1596g chloranil is dissolved in 206g and contains the dichloromethane of HCl (concentration is 0.0032mol/L) In, then above-mentioned solution is cooled to-80 DEG C in advance, and adds and be cooled to the 11mL of-80 DEG C in advance and contain ethyl aluminum dichloride (concentration is Hexane solution 0.9mol/L), after mix homogeneously, is aged 31min at-80 DEG C, thus obtains initiator solution.Its In, by weight, in initiator solution, the concentration of tetrachloroquinone is 750ppm.
(2) in the 500mL glass reactor being furnished with strength constant speed stirring, order adds 60mL and is cooled to the one of-80 DEG C in advance Chloromethanes, 140mL be cooled in advance-80 DEG C normal hexane, 25mL be cooled to isobutene. and the 1.1mL room temperature (25 of-80 DEG C in advance DEG C) p-methylstyrene (content is 98 weight %), mix homogeneously.In reactor, drip prepared by step (1) Initiator solution.Wherein, the addition of initiator solution is 20mL, controls at the temperature in drop rate makes reactor Within the scope of-85 DEG C to-80 DEG C.After being added dropwise to complete, keep the scope that the temperature in reactor is in-85 DEG C to-80 DEG C Within, carry out the polyreaction of 50min with stirring, in reactant mixture, then add 5mL contain 0.5 weight The methanol solution of %NaOH, to terminate polyreaction.The mixed solution obtained is placed in desolvation in hot bath, obtains Product after washing, be dried to constant weight in 60 DEG C in vacuum drying oven, thus obtain subject polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtained are listed in Table 1.
Experimental example 6～8
The method identical with experimental example 5 is used to be polymerized, except for the difference that, in experimental example 6, old in step (1) The change time is 65min, and the polymerization reaction time in step (2) is 30min；In experimental example 7, old in step (1) The change time is 15min, and the polymerization reaction time in step (2) is 70min；In experimental example 8, old in step (1) The change time is 100min, and the polymerization reaction time in step (2) is 30min.Experimental result is listed in Table 1.
Experimental example 9
(1) by 0.072g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 120g and contains HCl (concentration is 0.0042mol/L) Dichloromethane solution in, then above-mentioned solution is cooled to-80 DEG C in advance, and add 5.6mL be cooled in advance-80 DEG C containing two The hexane solution of chloroethyl aluminum (concentration is 0.9mol/L), after mix homogeneously, is aged 60min at-80 DEG C, thus obtains To initiator solution.By weight, in initiator solution, 2,3-bis-chloro-5, the concentration of 6-dicyano p-benzoquinone is 580ppm.
(2) in being furnished with the glass reactor of 500mL of strength constant speed stirring, order adds 100mL and is cooled to-80 DEG C in advance Monochloro methane, 100mL be cooled in advance-80 DEG C normal hexane, 25mL be cooled to isobutene. and the 1.1mL room temperature (25 of-80 DEG C in advance DEG C) p-methylstyrene (content is 98 weight %), mix homogeneously.In reactor, drip prepared by step (1) Initiator solution.Wherein, the addition of initiator solution is 25mL, controls at the temperature in drop rate makes reactor Within the scope of-90 DEG C to-85 DEG C.After being added dropwise to complete, keep the scope that the temperature in reactor is in-90 DEG C to-85 DEG C Within, carry out the polyreaction of 30min with stirring, in reactant mixture, then add 5mL contain 0.5 weight % The methanol solution of NaOH, to terminate polyreaction.The mixed solution obtained is placed in desolvation in hot bath, obtains Solid after washing, be dried to constant weight in 60 DEG C in vacuum drying oven, thus obtain subject polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtained are listed in Table 1.
Experimental example 10～11
Use and be polymerized with the same procedure of experimental example 9, except for the difference that, in the step (2) of experimental example 10, a chlorine The consumption of methane is 60mL, and the consumption of normal hexane is 140mL；In the step (2) of experimental example 11, the use of monochloro methane Amount is 20mL, and the consumption of normal hexane is 180mL.Experimental result is listed in Table 1.
Experimental example 12
The method identical with experimental example 9 is used to be polymerized, except for the difference that, the initiator solution that step (1) obtains In, by weight, 2,3-bis-chloro-5, the concentration of 6-dicyano p-benzoquinone is 300ppm；In step (2), monochloro methane Consumption is 80mL, and the consumption of normal hexane is 120mL, and the addition of initiator solution is 24mL；Initiator solution drips After completing, the temperature in reactor is controlled as being within the scope of-70 DEG C to-65 DEG C, and carries out the polymerization of 50min.
Experimental result is listed in Table 1.
Experimental example 13
(1) by 0.0532g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 66.3g and (concentration is containing HCl In dichloromethane 0.0027mol/L), then above-mentioned solution is cooled to-85 DEG C in advance, and adds 4mL and be cooled to-85 DEG C in advance Containing the hexane solution of ethyl aluminum dichloride (concentration is 0.9mol/L), after mix homogeneously, it is aged 60min at-85 DEG C, Thus obtain initiator solution.Wherein, by weight, in initiator solution, 2,3-bis-chloro-5,6-dicyano p-benzoquinone's is dense Degree is 770ppm.
(2) using the method identical with experimental example 9 to be polymerized, except for the difference that, initiator solution is experimental example 13 step Suddenly the initiator solution that prepared by (1)；The consumption of monochloro methane is 40mL, and the consumption of normal hexane is 160mL；Initiator The addition of solution is 15mL, and polymerization time is 30min.Experimental result is listed in Table 1.
Experimental example 14～15
The method identical with experimental example 9 is used to be polymerized, except for the difference that, in experimental example 14, old in step (1) The change time is 10min, and the polymerization reaction time in step (2) is 60min；In experimental example 15, in step (1) Digestion time is 30min, and the polymerization reaction time in step (2) is 40min.Experimental result is listed in Table 1.
Experimental example 16～17
Use the method identical with experimental example 9 to be polymerized, except for the difference that, in experimental example 16, in step (1), use Replacing 2 etc. the four cyano 1,4-benzoquinone of weight, 3-bis-chloro-5,6-dicyano p-benzoquinone, in step (2), polymerization reaction time is 60min；In experimental example 17, in step (1), the tetrahydrochysene 1,4-benzoquinone replacement 2 of the weight such as use, 3-bis-chloro-5,6-dicyano pair Benzoquinone；In step (2), polymerization reaction time is 30min.Experimental result is listed in Table 1.
Experimental comparison's example 1
Using the method identical with experimental example 9 to be polymerized, except for the difference that, do not use 2,3-bis-chloro-5,6-dicyano is to benzene Quinone.Experimental result is listed in Table 1.
Experimental example 18
(1) by 0.0652g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 80g and containing HCl (concentration is 0.003mol/L) Dichloromethane in, the solution obtained is cooled to-85 DEG C in advance, then in this solution order add 2.8mL concentration be The hexane solution of the ethyl aluminum dichloride (EADC) of 0.9mol/L and the diethyl chlorination that 1.2mL concentration is 0.9mol/L The toluene solution (molar ratio of EADC Yu DEAC is 7/3) of aluminum (DEAC), after mix homogeneously, by obtain Mixed liquor is placed in the cryostat of-85 DEG C ageing 60min.Wherein, by weight, in initiator solution 2,3-bis-chloro-5,6-bis- The content of cyano group 1,4-benzoquinone is 800ppm.
(2) two mouthfuls of flasks of 200mL are placed in the low temperature cryostat that temperature control is-80 DEG C to-85 DEG C, successively to two mouthfuls Flask adds 85mL and is cooled to normal hexane/monochloro methane mixed solution (wherein, normal hexane/monochloro methane of-85 DEG C Volume ratio is 9/1), 15mL be cooled to isobutene. and the p-methylstyrene of 0.62mL room temperature (25 DEG C) of-85 DEG C, mixed Close uniformly, obtain monomer solution.Adding initiator solution prepared by 10mL step (1) in monomer solution, mixing is all Even rear standing and reacting 40min, controlling cryostat temperature in dropping initiator solution and course of reaction is to be in-85 DEG C to-80 DEG C Within the scope of.Reaction terminates to add in backward reactant mixture the methanol solution that 5mL contains 0.5 weight %NaOH, with Terminate polyreaction.Then mixed solution is placed in desolvation in hot bath, after the solid obtained is washed, Vacuum drying oven is dried to constant weight in 60 DEG C, obtains subject polymer.
Measure the weight of the polymer obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution of polymer Index, result is listed in table 2.
Experimental example 19
The method identical with experimental example 18 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant, the molar ratio making EADC Yu DEAC is 5/5.Experimental result result is listed in table 2.
Experimental comparison's example 2
Use the method preparation initiator solution identical with experimental example 19 and be polymerized, except for the difference that, in step (1) Do not use 2,3-bis-chloro-5,6-dicyano p-benzoquinone.Experimental result result is listed in table 2.
Experimental example 20
Using the method identical with experimental example 19 to be polymerized, except for the difference that, in step (1), the time of ageing is 30min； 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 19 to be polymerized, except for the difference that, in step (1), the time of ageing is 15min； In step (2), polymerization reaction time is 60min.Experimental result is listed in table 2.
Experimental example 22
The method identical with experimental example 18 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant, the molar ratio making EADC Yu DEAC is 3/7；In step (2), polymerization reaction time is 60min. Experimental result is listed in table 2.
Experimental example 23
The method identical with experimental example 18 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant, the molar ratio making EADC Yu DEAC is 1/9；In step (2), polymerization reaction time is 140min. Experimental result is listed in table 2.
Experimental example 24
The method identical with experimental example 23 is used to be polymerized, except for the difference that, in step (2), normal hexane and a chloromethane The total amount of alkane is constant, and making normal hexane is 8/2 with the volume ratio of monochloro methane, and polymerization reaction time is 100min.
Experimental result is listed in table 2.
Experimental example 25
The method identical with experimental example 23 is used to be polymerized, except for the difference that, in step (2), normal hexane and a chloromethane The total amount of alkane is constant, and making normal hexane is 7/3 with the volume ratio of monochloro methane, and polymerization reaction time is 80min.Experimental result List in table 2.
Experimental example 26
The method identical with experimental example 23 is used to be polymerized, except for the difference that, in step (2), normal hexane and a chloromethane The total amount of alkane is constant, and making normal hexane is 6/4 with the volume ratio of monochloro methane, and polymerization reaction time is 60min.Experimental result List in table 2.
Experimental example 27
Use and be polymerized with experimental example 23 same procedure, except for the difference that, in step (2), normal hexane and monochloro methane Total amount constant, the volume ratio making normal hexane and monochloro methane is 5/5, and polymerization reaction time is 60min.Experimental result exists Table 2 is listed.
Experimental example 28
The method identical with experimental example 19 is used to be polymerized, except for the difference that, in step (1)；By 0.0651g tetrachloro 1,4-benzoquinone is dissolved in 80g and containing in the dichloromethane solution of HCl (concentration is 0.0042mol/L), by pre-for the solution obtained Be cooled to-85 DEG C, then in this solution order add 2.8mL concentration be 0.9mol/L EADC hexane solution and 1.1mL concentration is the n-heptane solution (EADC/DEAC molar ratio is 7/3) of the DEAC of 1.0mol/L, and mixing is all After even, the mixed liquor obtained is placed in-85 DEG C of ageing 60min.Wherein, by weight, tetrachloro-p-phenylene in initiator solution The content of quinone is 800ppm；Step (2), the total amount of normal hexane and monochloro methane is constant, makes normal hexane and monochloro methane Volume ratio is 6/4.Experimental result is listed in table 2.
Experimental example 29
The method identical with experimental example 28 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant, the mol ratio making EADC/DEAC is 5/5.Experimental result is listed in table 2.
Experimental example 30
The method identical with experimental example 28 is used to be polymerized, except for the difference that, in step (1), EADC and DEAC Total amount constant, the mol ratio making EADC/DEAC is 3/7.Experimental result is listed in table 2.
Experimental example 31
The method identical with experimental example 29 is used to be polymerized, except for the difference that, in step (2), normal hexane and a chloromethane The total amount of alkane is constant, and making normal hexane is 9/1 with the volume ratio of monochloro methane.Experimental result is listed in table 2.
Experimental example 32
The method identical with experimental example 29 is used to be polymerized, except for the difference that, in step (2), normal hexane and a chloromethane The total amount of alkane is constant, and making normal hexane is 8/2 with the volume ratio of monochloro methane.Experimental result is listed in table 2.
Experimental comparison's example 3
Using the method identical with experimental example 28 to be polymerized, except for the difference that, step does not use chloranil in (1). Experimental result is listed in table 2.
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 H simple with employing+/ lewis acid initiator system is compared, and can make polymer yield within the shorter time 100% can be reached, the content energy of unreacted ring-alkylated styrenes in the 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 1～4 is used for the present invention is described.
Embodiment 1
(1) by 0.128g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 160g and (concentration is containing HCl In dichloromethane 0.0054mol/L), the solution obtained is cooled to-85 DEG C in advance, in this solution, then adds 8mL dense Degree is the ethyl aluminum dichloride hexane solution of 0.9mol/L, after mix homogeneously, the mixed liquor obtained is placed in the cryostat of-85 DEG C Middle ageing 60min, thus obtain 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 drop rate makes reactor Temperature be within the scope of-90 DEG C to-85 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be in-90 DEG C to-85 Within the scope of DEG C, and carry out the polyreaction (polymer yield reaches 100%) of 60min, then to reactant mixture Middle addition 100g contains the dichloromethane solution of 3 weight % 2,2'-ethylenedioxybis(ethanol) .s, to terminate polyreaction, obtain containing monoolefine- (in this polymer solution, the weight content of unreacted p-methylstyrene is the polymer solution of alkylstyrene copolymers Below 200ppm), the molecular weight of monoolefine-alkylstyrene copolymers of preparation, molecular weight distributing index and by first The content of the construction unit that base styrene is formed is listed in table 3.
(3) the polymer solution nitrogen that step (2) obtains is pressed in the solvent displacer of evacuation, from molten The bottom of agent displacer is passed through the normal hexane steam of 70 DEG C, and controlling operation pressure is 90kPa (absolute pressure), normal hexane steam Being passed through the persistent period is 150min, thus solution (wherein, the content of monoolefine-alkylstyrene copolymers after being replaced It is 13.2 weight %).
(4) with reference to the mode shown in Fig. 1, after the displacement obtain step (3), 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.
(5) the mixture water vapour desolvation that neutralization obtained also is condensed, and the aqueous bromination glue obtained is being opened In 110 DEG C of dry 10min on refining machine, thus obtaining bromination monoolefine-alkylstyrene copolymers, its bromine content is at table 3 In list.
Embodiment 2
Using method same as in Example 1 to prepare bromination monoolefine-alkylstyrene copolymers, difference is as follows:
In step (2), the consumption using normal hexane is 800mL, and the consumption of monochloro methane is 200mL, thus obtains Polymer solution containing monoolefine-alkylstyrene copolymers (unreacted p-methylstyrene in this polymer solution Weight content is below 200ppm)；
In step (3), the persistent period that is passed through of normal hexane steam is 120min, monoolefine in solution after the displacement obtained- The content of alkylstyrene copolymers is 12.6 weight %；
Step (4) uses the mode shown in Fig. 2 to carry out: after the displacement obtain step (3), 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 (merit Rate is 200W) irradiate 2min carry out photohalogenation reaction.Then, the bromination glue obtained is sent in neutralization reactor, And the aqueous solution that feeding 90g contains 2 weight %NaOH in neutralization reactor carries out the neutralization of 20min.
Experiment is listed in table 3.
Embodiment 3
Using method same as in Example 1 to prepare bromination monoolefine-alkylstyrene copolymers, difference is as follows:
In step (1), 0.163g chloranil is dissolved in 200g and containing HCl (concentration is 0.0052mol/L) Dichloromethane in, the solution obtained is cooled to-85 DEG C in advance, then in this solution order add 10mL concentration be Ethyl aluminum dichloride (EADC) hexane solution of 0.9mol/L, after mix homogeneously, is placed in-85 DEG C by the mixed liquor obtained Cryostat in be aged 80min, thus obtain initiator solution；It is common containing monoolefine-ring-alkylated styrenes that step (2) obtains In the polymer solution of polymers, the weight content of unreacted p-methylstyrene is below 200ppm.
In step (3), after the displacement obtained, in solution, the content of monoolefine-alkylstyrene copolymers is 12.4 weight %；
In step (4), the consumption of bromine is 4.2g.Experimental result is listed in table 3.
Embodiment 4
(1) by 0.152g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 200g and containing HCl (concentration is 0.006mol/L) Dichloromethane in, the solution obtained is cooled to-85 DEG C in advance, then in this solution order add 6mL concentration be The ethyl aluminum dichloride hexane solution of 0.9mol/L and the diethyl aluminum chloride n-heptane solution that 6mL concentration is 1.0mol/L (molar ratio of EADC/DEAC is 4.7/5.3), after mix homogeneously, is placed in the cryostat of-85 DEG C by the mixed liquor obtained Middle ageing 80min, thus obtain 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 drop rate makes reactor Temperature is within the scope of-90 DEG C to-85 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be in-90 DEG C to-85 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, obtains the polymer containing monoolefine-alkylstyrene copolymers molten Liquid (in this polymer solution, the weight content of unreacted p-methylstyrene is below 200ppm).The monoolefine of preparation Containing of the molecular weight of-alkylstyrene copolymers, molecular weight distributing index and the construction unit that formed by p-methylstyrene Amount is listed in table 3.
(3) the polymer solution nitrogen that step (2) obtains is pressed in the solvent displacer of evacuation, from molten The bottom of agent displacer is passed through the normal hexane steam of 80 DEG C, and controlling operation pressure is 95kPa (absolute pressure), normal hexane steam Being passed through the persistent period is 150min, thus solution (wherein, the content of monoolefine-alkylstyrene copolymers after being replaced It is 12.8 weight %).
(4) with reference to the mode shown in Fig. 1, after the displacement obtain step (3), 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.
(5) the mixture water vapour desolvation that neutralization obtained also is condensed, and the aqueous bromination glue obtained is being opened In 110 DEG C of dry 10min on refining machine, thus obtaining bromination monoolefine-alkylstyrene copolymers, its bromine content is at table 3 In list.
Table 3
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 (18)

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 can carry protogenic compound, at least one lewis acid and at least one Planting 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, described protogenic compound and the described activator of can carrying Mol ratio be 1:0.01～5, preferably 1:0.1～3, more preferably 1:0.2～2.5, more preferably 1:0.4～ 2。
Method the most according to claim 1, wherein, described can carry protogenic compound and described Louis Acid mol ratio be 0.01～1:1, preferably 0.02～0.5:1, more preferably 0.03～0.3:1, more preferably 0.03～ 0.15:1, more preferably 0.035～0.1:1.
4. according to the method described in any one in claims 1 to 3, wherein, described activator selected from tetrahydrochysene benzoquinone, Tetrachloroquinone, four cyano benzoquinone and DDQ；
Preferably, in Formulas I-1, R1、R2、R3And R4It is asynchronously-H, in Formulas I-2, R5、R6、R7And R8No It is-H simultaneously；
It is highly preferred that described activator is selected from tetrachloroquinone, four cyano benzoquinone and DDQ.
5. according to the method described in any one in claims 1 to 3, wherein, described lewis acid is shown in formula IV Lewis acid and/or Formula V shown in lewis acid,
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.
6. according to the method described in any one in claims 1 to 3, wherein, described can carry protogenic compound For H2O and/or Bronsted acid, preferably HCl.
Method the most 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.
8. according to the method described in any one in claims 1 to 3 and 7, wherein, in step (1), will at least A kind of method that monoolefine contacts with each component in described initiator system with at least one ring-alkylated styrenes includes: by institute The each component stated in initiator system is dissolved in solvent, and the mixture ageing that will obtain, and obtains initiator solution；Will Described initiator solution mixes with the described monoolefine being dissolved in polymer solvent and described ring-alkylated styrenes.
Method the most according to claim 8, 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.
Method the most according to claim 8, wherein, described ageing is at-100 DEG C to 20 DEG C, preferably-100 DEG C extremely 0 DEG C, more preferably-100 DEG C are carried out within the temperature range of-50 DEG C, further preferably-90 DEG C to-70 DEG C.
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 3,7 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, described halogen-containing compound is halogen simple substance, is preferably Bromine and/or chlorine element, more preferably bromine.
14. methods according to claim 13, wherein, in step (3), described contact is at radical initiator In the presence of carry out or carry out under the conditions of light-initiated.
15. methods according to claim 14, wherein, described contact is carried out in the presence of radical initiators, The weight ratio of described radical initiator and monoolefine-alkylstyrene copolymers is 0.01～1:100, preferably 0.05～ 0.5:100.
16. according to the method described in any one in claim 1 and 13～15, wherein, in step (3), described Contact is carried out at a temperature 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 minute, It is preferably 1～15 minute.
17. according to the method described in any one in claims 1 to 3,7,11 and 13～15, wherein, with described On the basis of the total amount of polymer solvent, the content of described first polymer solvent is 1～80 volume %, preferably 10～60 volumes %；The content of described second polymer solvent is 20～99 volume %, preferably 40～90 volume %.
18. according to the method described in any one in claims 1 to 3,7,11 and 13～15, 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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CN111285948A (en) * 2020-02-11 2020-06-16 北京石油化工学院 Method for preparing halogenated polyisobutenyl special elastomer by one-step method and application

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CN106582858A (en) * 2016-12-20 2017-04-26 沈阳化工研究院有限公司 Catalyst for preparing alpha-olefin oligomer and polymerization method thereof
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CN111285948A (en) * 2020-02-11 2020-06-16 北京石油化工学院 Method for preparing halogenated polyisobutenyl special elastomer by one-step method and application
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