CN106146701B - A kind of preparation method of halogen polymer - Google Patents
A kind of preparation method of halogen polymer Download PDFInfo
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- CN106146701B CN106146701B CN201510194429.3A CN201510194429A CN106146701B CN 106146701 B CN106146701 B CN 106146701B CN 201510194429 A CN201510194429 A CN 201510194429A CN 106146701 B CN106146701 B CN 106146701B
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Abstract
The invention discloses a kind of preparation methods of halogenation monoolefine alkylstyrene copolymers, it is included under the conditions of cationic polymerization, monoolefine shown in Formula II and the in the mixed solvent with ring-alkylated styrenes shown in formula III with each component in initiator system in alkane and halogenated alkane are contacted, halogenated alkane in the solution containing monoolefine alkylstyrene copolymers replaced with alkane, solution is contacted with halogen-containing compound after replacing carries out halogenation, the initiator system contains the compound for being capable of providing carbonium ion, lewis acid and activator, the activator is selected from 2 compound represented of 1 compound represented of Formulas I and Formulas I.The method of the present invention can significantly improve polymerization efficiency, and can obtain the polymer with higher molecular weight, be omitted and be redissolved process using polymer necessary to slurry polymerization process, simplify production technology.
Description
Technical field
The present invention relates to a kind of preparation methods of halogen polymer, more particularly, to a kind of halogenation monoolefine-alkylbenzene
The preparation method of ethylene copolymer.
Background technology
Butyl rubber is produced by the slurry polymerization process of diluent of monochloro methane currently, worldwide generally using,
Its reason essentially consists in：The production efficiency of slurry polymerization process is high, and the molecular weight of product is high, processing performance is good.It is poly- with slurry
Products molecule legal to compare, that polymerisation in solution rule is obtained without apparent advantage, especially solution polymerization process in these areas
It measures that low, processing performance is poor, therefore is difficult that the product obtained with slurry polymerization process mutually competes on the market.But polymerisation in solution
The development space of method than broader, such as：Solution polymerization process more meets environmental requirement than slurry polymerization process, and to polymerization temperature
Accommodation it is broader, especially to realize high temperature polymerization in terms of have better development prospect.
Halogenated butyl rubber generally use solwution method prepare, that is, by the butyl rubber being dissolved in alkane with it is halogen-containing
Compound contact carries out halogenation, when preparing butyl rubber using slurry polymerization process, needs in polymerization procedure and halogen
The solvent for changing the halogenated alkane being arranged in the mixture for being intended to be obtained with alkane displacement slurry polymerization process between reaction step is replaced
Step and polymer are redissolved step, and in solution polymerization process, if using the mixed solution conduct of halogenated alkane and alkane
Polymer solvent then can directly carry out halogenation after the halogenated alkane in the solution for obtaining polymerization is replaced with alkane,
It is redissolved step without polymer, it is clear that production of the solution polymerization process more suitable for solwution method halogenated butyl rubber.
However, main problem existing for solution polymerization process is：It needs to draw using the high activity for being adapted to solution polymerization system
Agent system is sent out, to obtain the product of high molecular weight.
US3361725 propose aluminum alkyl halide be the effective initiator for preparing butyl rubber in the solution, can compared with
The product of higher molecular weight is obtained at high temperature, but the molar ratio of dialkylaluminum halides in aluminum alkyl halide is required to reach
80% or more, and the molar ratio of monoalkyl dihalide aluminium is then less than 20%, thus the self-initiating of alkyl aluminum is leaned on to act on solution
In prepare butyl rubber in (such as hexane).But in fact, the efficiency of initiation of this initiator system is very low, and polymerization is fast
Rate is very slow, cannot be satisfied the needs of practical application.For this purpose, US6403747 improves this initiator system, i.e., with
On dialkylaluminum halides/monoalkyl dihalide aluminium mixed system in introduce micro water or aikyiaiurnirsoxan beta, make initiator system live
Property improve, so as to prepare the butyl rubber that weight average molecular weight reaches 400,000 or more at -60 DEG C to -80 DEG C.Although
The efficiency of initiation of initiator system and rate of polymerization disclosed in US6403747 are improved to some extent, but in practical operation
It is in journey or unsatisfactory, and the preparation of initiator system is relatively difficult, especially requires very the technology of preparing of aikyiaiurnirsoxan beta
It is high.
Halogenated isobutylene-p-methylstyrene copolymer is usually to carry out the copolymer of isobutene and p-methylstyrene
Part p-methylstyrene group transformations are obtained from halomethylstyrene group by halogenation.Since molecular backbone is complete
Saturated structures, therefore halogenated isobutylene-p-methylstyrene copolymer is with more better than halogenated isobutylene-isoprene rubber
Comprehensive performance, especially have better heat resistance；Also, the presence of the benzyl halogen functional group due to high activity, energy
It is enough that vulcanization and co-vulcanization are realized in wider range with various rubber, in addition also there is the modification advantage of wider range.The production
Product pass through is made dynamic vulcanization alloy for producing the inner liner of tire with nylon blending, can accomplish not only it is light but also thin,
It can be seen that halogenated isobutylene-p-methylstyrene copolymer can be used for producing the tire with higher performance, and
With quite wide market application prospect.Therefore, research and development are poly- suitable for the solution of isobutene-p-methylstyrene copolymer
Technique is closed for pushing the exploitation of halogenated isobutylene-p-methylstyrene copolymer to be had a very important significance with application.
Invention content
When isobutene-p-methylstyrene copolymer halogenation is prepared halogenated isobutylene-p-methylstyrene copolymer,
Unreacted p-methylstyrene monomer can also participate in halogenation, therefore it is required that methylbenzene in the glue of progress halogenation
The content of ethylene is low.It since the boiling point of p-methylstyrene is higher, is not easy to remove, therefore, it is desirable to by isobutene and to methylbenzene
When ethylene carries out combined polymerization, the monomer including p-methylstyrene can be made to convert completely as far as possible.However, the hair of the present invention
A person of good sense has found in the course of the research, and for isobutene when carrying out cationic solution polymerization, polymerization efficiency is to solvent polarity and unwise
Sense, but use C+Isobutene and ring-alkylated styrenes are passed through cation by (that is, carbonium ion)/lewis acid initiator system
When polymerization methods carry out combined polymerization in the solution, polymerization efficiency is very poor, and rate of polymerization is slow, and needing to carry out reaction for a long time can just make
Monomer completely or almost completely converts.Cationic polymerization usually carries out at low temperature, and polymerization time is longer, maintains low temperature institute
The energy expenditure needed is higher, and prolonged polymerization obviously cannot be satisfied the requirement of large-scale production.Moreover, using C+/ Louis
This acid initiator system usually requires that the isobutene-of high molecular weight could be prepared to methylbenzene under more harsh reaction condition
Ethylene copolymer.
The present inventor is studied regarding to the issue above, is found：Isobutene and ring-alkylated styrenes are passed through into sun
When the mode of ionic polymerization carries out combined polymerization in the solution, if in C+Quinoid chemical combination is introduced in/lewis acid initiator system
Object (the especially quinonoid compound with electron-withdrawing substituent) can significantly improve polymerization efficiency, can be with higher rate of polymerization
The monomer including ring-alkylated styrenes is set completely or almost completely to convert；Simultaneously, moreover it is possible to obtain that there is the poly- of higher molecular weight
Close object, especially rubber heavy polymer.It has thus completed the present invention.
The present invention provides a kind of preparation methods of halogenation monoolefine-alkylstyrene copolymers, and this method includes following
Step：
(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, and the polymerization is molten
Agent is made of at least one first polymer solvent and at least one second polymer solvent, and first polymer solvent is selected from alkyl halide
Hydrocarbon, second polymer solvent are selected from alkane, and the condition of the contact makes, by weight, described to contain monoolefine-alkylbenzene
The content of unreacted ring-alkylated styrenes is not higher than 1000ppm in the solution of ethylene copolymer；
The initiator system contain at least one compound for being capable of providing carbonium ion, at least one lewis acid and
At least one activator, the activator be selected from -2 compound represented of -1 compound represented of Formulas I and Formulas I,
In Formulas I -1 and Formulas I -2, R1、R2、R3、R4、R5、R6、R7And R8Respectively-H ,-X1、-NO2、With in-CN
One kind, X1And X2One kind respectively in halogen group；
The monoolefine be selected from Formula II compound represented,
In Formula II, R9And R10Respectively C1~C5Linear or branched alkyl group；Or R9For hydrogen, R10For C3~C5Branch
Alkyl；
The ring-alkylated styrenes be selected from formula III compound represented,
In formula III, R11For C1~C5Linear or branched alkyl group；
(2) at least one displacement solvent swap step (1) obtain containing the molten of monoolefine-alkylstyrene copolymers
Halogenated alkane in liquid, obtains solution after the displacement containing monoolefine-alkylstyrene copolymers, and the displacement solvent is selected from alkane
Hydrocarbon；
(3) solution and halogen-containingization after the displacement containing monoolefine-alkylstyrene copolymers for obtaining step (2)
Object contact is closed, so that the part hydrogen atom in the monoolefine-alkylstyrene copolymers strand is substituted with halogen atoms.
Polymerization procedure according to the method for the present invention, with the simple C of use+(that is, carbonium ion)/lewis acid draws
The polymerization technique of hair agent system is compared, and the polymerization efficiency significantly improved can be obtained, so as to be realized with higher rate of polymerization
Monomer completely or almost completely converts so that the glue containing monoolefine-alkylstyrene copolymers of preparation is de- without experience
Except the process of unreacted monomer can be directly used for halogenation；On the other hand the polymer with higher molecular weight can also be obtained,
Especially rubber heavy polymer.In addition, with simple C is used+/ lewis acid initiator system is compared, the present invention
Even if method implement that higher polymerization efficiency can be obtained if polymerization at higher temperatures and prepare with higher molecular weight
Polymer, so as to be effectively reduced the energy expenditure in polymerization process.
According to the method for the present invention, the solution polymerizeing can be sent directly into halogenation step, and use is omitted
Slurry polymerization process prepares polymer necessary to polymer and is redissolved process, effectively simplifies halogenation monoolefine-alkylbenzene
The production technology of ethylene copolymer.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is a kind of preferred embodiment according to the method for the present invention.
Fig. 2 is another preferred embodiment according to the method for the present invention.
Reference sign
1：Monoolefine 2 shown in Formula II：Ring-alkylated styrenes shown in formula III
31：First polymer solvent 32：Second polymer solvent
4：Initiator solution 5：Terminator
6：Solution 7 containing monoolefine-alkylstyrene copolymers：Replace solvent vapo(u)r
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：Mixture containing halogenation monoolefine-alkylstyrene copolymers
14：Light source I：Polymer reactor
II：Solvent displacer III：Halogenation reactor
IV：Mixer V：Photohalogenation reactor
VI：Neutralization reactor
Specific implementation mode
The present invention provides a kind of preparation methods of halogenation monoolefine-alkylstyrene copolymers, and this method includes following
Step：
(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, and the polymerization is molten
Agent is made of at least one first polymer solvent and at least one second polymer solvent, and first polymer solvent is selected from alkyl halide
Hydrocarbon, second polymer solvent are selected from alkane, and the condition of the contact makes, by weight, described to contain monoolefine-alkylbenzene
In the solution of ethylene copolymer the content of unreacted ring-alkylated styrenes be not higher than 1000ppm, preferably not higher than 500ppm,
More preferably not above 200ppm；
(2) at least one displacement solvent swap step (1) obtain containing the molten of monoolefine-alkylstyrene copolymers
Halogenated alkane in liquid, obtains solution after the displacement containing monoolefine-alkylstyrene copolymers, and the displacement solvent is selected from alkane
Hydrocarbon；
(3) solution and halogen-containingization after the displacement containing monoolefine-alkylstyrene copolymers for obtaining step (2)
Object contact is closed, so that the part hydrogen atom in the monoolefine-alkylstyrene copolymers strand is substituted with halogen atoms.
According to the method for the present invention, the initiator system (being referred to as initiator composition) contains at least one energy
Compound, at least one lewis acid and at least one activator of carbonium ion are enough provided.
The activator be selected from -2 compound represented of -1 compound represented of Formulas I and Formulas I,
In Formulas I -1 and Formulas I -2, R1、R2、R3、R4、R5、R6、R7And R8Respectively-H ,-X1、-NO2、With in-CN
One kind, X1And X2Respectively in halogen group one kind (such as：- F ,-Cl ,-Br or-I).
The specific example of the activator can include but is not limited to：Tetrahydrochysene 1,4-benzoquinone, tetrahydrochysene neighbour benzoquinones, three hydrogen pair of a fluorine
Benzoquinones, three hydrogen neighbour benzoquinones of a fluorine, difluoro dihydro 1,4-benzoquinone, difluoro dihydro neighbour benzoquinones, one hydrogen 1,4-benzoquinone of trifluoro, one hydrogen neighbour's benzene of trifluoro
Quinone, tetrafluoro 1,4-benzoquinone, tetrafluoro neighbour benzoquinones, three hydrogen 1,4-benzoquinone of a chlorine, three hydrogen neighbour benzoquinones of a chlorine, dichloro-dihydro 1,4-benzoquinone (including 2,
3- dichloros 1,4-benzoquinone, 2,5- dichloros 1,4-benzoquinone, 2,6- dichloros 1,4-benzoquinone), dichloro-dihydro neighbour benzoquinones (including 3,4- dichloro neighbour's benzene
Quinone, 3,5- dichloro neighbours benzoquinones, 3,6- dichloro neighbours benzoquinones), one hydrogen 1,4-benzoquinone of trichlorine, one hydrogen neighbour benzoquinones of trichlorine, chloranil, four
Chlorine neighbour benzoquinones, three hydrogen 1,4-benzoquinone of monobromo, three hydrogen neighbour benzoquinones of monobromo, dibromo dihydro 1,4-benzoquinone (including 2,3- dibromos 1,4-benzoquinone, 2,5-
Dibromo 1,4-benzoquinone, 2,6- dibromos 1,4-benzoquinone), dibromo dihydro neighbour benzoquinones (including 3,4- dibromo-os benzoquinones, 3,5- dibromo-os benzoquinones,
3,6- dibromo-o benzoquinones), one hydrogen 1,4-benzoquinone of tribromo, one hydrogen neighbour benzoquinones of tribromo, tetrabromo 1,4-benzoquinone, tetrabromo-phthalic quinone, three nitre of a fluorine
Base 1,4-benzoquinone, a fluorine trinitro- neighbour benzoquinones, difluoro dinitro 1,4-benzoquinone (including 2, bis- fluoro- 5,6- dinitros 1,4-benzoquinone of 3-, 2,5-
Two fluoro- 3,6- dinitros 1,4-benzoquinone, 2,6-, bis- fluoro- 3,5- dinitros 1,4-benzoquinone), difluoro dinitro o benzoquinones (including 3,4- bis-
Fluoro- 5,6- dinitro os benzoquinones, 3,5-, bis- fluoro- 4,6- dinitro os benzoquinones, 3,6-, bis- fluoro- 4,5- dinitro os benzoquinones), trifluoro
One nitro 1,4-benzoquinone, one nitro neighbour benzoquinones of trifluoro, a chlorine trinitro- 1,4-benzoquinone, a chlorine trinitro- neighbour benzoquinones, dichloro dinitro pair
Benzoquinones (including 2, bis- chloro- 5,6- dinitros 1,4-benzoquinone of 3-, 2,5-, bis- chloro- 3,6- dinitros 1,4-benzoquinone, 2,6-, bis- chloro- 3,5- bis-
Nitro 1,4-benzoquinone), dichloro dinitro o benzoquinones (including 3, bis- chloro- 5,6- dinitro os benzoquinones of 4-, 3,5-, bis- chloro- 4,6- dinitros
Base neighbour benzoquinones, 3,6-, bis- chloro- 4,5- dinitro os benzoquinones), one nitro 1,4-benzoquinone of trichlorine, one nitro neighbour benzoquinones of trichlorine, monobromo three
Nitro 1,4-benzoquinone, monobromo trinitro- neighbour benzoquinones, dibromo dinitro 1,4-benzoquinone (including 2, bis- bromo- 5,6- dinitros 1,4-benzoquinone of 3-, 2,
Bis- bromo- 3,6- dinitros 1,4-benzoquinone of 5-, 2,6-, bis- bromo- 3,5- dinitros 1,4-benzoquinone), dibromo dinitro o benzoquinones (including 3,4-
Two bromo- 5,6- dinitro os benzoquinones, 3,5-, bis- bromo- 4,6- dinitro os benzoquinones, 3,6-, bis- bromo- 4,5- dinitro os benzoquinones), three
Bromo- nitro 1,4-benzoquinone, one nitro neighbour benzoquinones of tribromo, tetranitro 1,4-benzoquinone, tetranitro neighbour benzoquinones, a fluorine tricyano 1,4-benzoquinone, one
Fluorine tricyano neighbour benzoquinones, difluoro dicyano p-benzoquinone (including 2, bis- fluoro- 5,6- dicyano p-benzoquinones of 3-, 2,5-, bis- fluoro- 3,6- bis-
Cyano 1,4-benzoquinone, 2,6-, bis- fluoro- 3,5- dicyano p-benzoquinones), difluoro dicyano neighbour benzoquinones (including 3, bis- fluoro- 5,6- dicyan of 4-
Base neighbour benzoquinones, 3,5-, bis- fluoro- 4,6- dicyanos neighbour benzoquinones, 3,6-, bis- fluoro- 4,5- dicyanos neighbour benzoquinones), one cyano of trifluoro is to benzene
Quinone, one cyano neighbour benzoquinones of trifluoro, a chlorine tricyano 1,4-benzoquinone, a chlorine tricyano neighbour benzoquinones, dichloro dicyano p-benzoquinone (including 2,
Bis- chloro- 5,6- dicyano p-benzoquinones of 3-, 2,5-, bis- chloro- 3,6- dicyano p-benzoquinones, 2,6-, bis- chloro- 3,5- dicyano p-benzoquinones),
Dichloro dicyano neighbour benzoquinones (including 3, bis- chloro- 5,6- dicyanos neighbour benzoquinones of 4-, 3,5-, bis- chloro- 4,6- dicyanos neighbour benzoquinones, 3,6-
Two chloro- 4,5- dicyanos neighbour benzoquinones), one cyano 1,4-benzoquinone of trichlorine, one cyano neighbour benzoquinones of trichlorine, monobromo tricyano 1,4-benzoquinone, one
Bromine tricyano neighbour benzoquinones, dibromo dicyano p-benzoquinone (including 2, bis- bromo- 5,6- dicyano p-benzoquinones of 3-, 2,5-, bis- bromo- 3,6- bis-
Cyano 1,4-benzoquinone, 2,6-, bis- bromo- 3,5- dicyano p-benzoquinones), dibromo dicyano neighbour benzoquinones (including 3, bis- bromo- 5,6- dicyan of 4-
Base neighbour benzoquinones, 3,5-, bis- bromo- 4,6- dicyanos neighbour benzoquinones, 3,6-, bis- bromo- 4,5- dicyanos neighbour benzoquinones), one cyano of tribromo is to benzene
Quinone, one cyano neighbour benzoquinones of tribromo, one cyano 1,4-benzoquinone of trinitro-, one cyano neighbour benzoquinones of trinitro-, dinitro dicyano p-benzoquinone
(including 2,3- dinitros -5,6- dicyano p-benzoquinone, 2,5- dinitros -3,6- dicyano p-benzoquinone, 2,6- dinitros -3,5-
Dicyano p-benzoquinone), dinitro dicyano neighbour benzoquinones (including 3,4- dinitro -5,6- dicyano neighbours benzoquinones, 3,5- dinitros -
4,6- dicyano neighbour benzoquinones, 3,6- dinitro -4,5- dicyano neighbours benzoquinones), a nitro tricyano 1,4-benzoquinone, a nitro tricyano
Adjacent benzoquinones, four cyano 1,4-benzoquinone, four cyano neighbour benzoquinones, a fluorine front three acid chloride group 1,4-benzoquinone, a fluorine front three acid chloride group neighbour benzoquinones, two
Fluorine dimethyl chloride base 1,4-benzoquinone (including 2, bis- fluoro- 5,6- dimethyl chlorides base 1,4-benzoquinone of 3-, 2,5-, bis- fluoro- 3,6- dimethyl chlorides bases
1,4-benzoquinone, 2,6-, bis- fluoro- 3,5- dimethyl chlorides base 1,4-benzoquinone), difluoro dimethyl chloride base neighbour benzoquinones (including 3,4- bis- fluoro- 5,6-
Dimethyl chloride base neighbour benzoquinones, 3,5-, bis- fluoro- 4,6- dimethyl chlorides base neighbour benzoquinones, 3,6-, bis- fluoro- 4,5- dimethyl chlorides base neighbour's benzene
Quinone), one formyl chloro 1,4-benzoquinone of trifluoro, one formyl chloro neighbour benzoquinones of trifluoro, a chlorine front three acid chloride group 1,4-benzoquinone, three formyl of a chlorine
Chloro neighbour benzoquinones, dichloro dimethyl chloride base 1,4-benzoquinone (including 2, bis- chloro- 5,6- dimethyl chlorides base 1,4-benzoquinone of 3-, 2,5- bis- chloro- 3,
6- dimethyl chloride bases 1,4-benzoquinone, 2,6-, bis- chloro- 3,5- dimethyl chlorides base 1,4-benzoquinone), dichloro dimethyl chloride base neighbour benzoquinones (including 3,
Bis- chloro- 5,6- dimethyl chlorides base neighbour benzoquinones of 4-, 3,5-, bis- chloro- 4,6- dimethyl chlorides base neighbour benzoquinones, 3,6-, bis- chloro- 4,5-, bis- formyls
Chloro neighbour benzoquinones), one formyl chloro 1,4-benzoquinone of trichlorine, one formyl chloro neighbour benzoquinones of trichlorine, monobromo front three acid chloride group 1,4-benzoquinone, one
Bromine front three acid chloride group neighbour benzoquinones, dibromo dimethyl chloride base 1,4-benzoquinone (including 2, bis- bromo- 5,6- dimethyl chlorides base 1,4-benzoquinone of 3-, 2,
Bis- bromo- 3,6- dimethyl chlorides base 1,4-benzoquinone of 5-, 2,6-, bis- bromo- 3,5- dimethyl chlorides base 1,4-benzoquinone), dibromo dimethyl chloride base neighbour's benzene
Quinone (including 3, bis- bromo- 5,6- dimethyl chlorides base neighbour benzoquinones of 4-, 3,5-, bis- bromo- 4,6- dimethyl chlorides base neighbour benzoquinones, 3,6- bis- are bromo-
4,5- dimethyl chloride base neighbour benzoquinones), one formyl chloro 1,4-benzoquinone of tribromo, one formyl chloro neighbour benzoquinones of tribromo, tetramethyl acid chloride group pair
Benzoquinones and tetramethyl acid chloride group neighbour's benzoquinones.
The activator be preferably selected from tetrahydrochysene benzoquinones (including tetrahydrochysene 1,4-benzoquinone and tetrahydrochysene neighbour benzoquinones), tetrachloroquinone (including
Chloranil and monoethyl quinone), four cyano benzoquinones (including four cyano 1,4-benzoquinone and four cyano neighbour benzoquinones) and dichloro dicyan
Base benzoquinones (including dichloro dicyano p-benzoquinone and dichloro dicyano neighbour benzoquinones).
The lewis acid and the compound for being capable of providing proton can be the conventional selection in cationic polymerization field,
It is not particularly limited, as long as the lewis acid can form cationic species with the compound for being capable of providing proton, causes
Polymerization.
Usually, the lewis acid can be selected from but not limited to：AlCl3、BF3、BCl3、TiCl4、SnCl4、ZnCl2, formula
Lewis acid and R shown in lewis acid, Formula V shown in IV15 3Al,
In formula IV, X31And X32One kind (such as-F ,-Cl ,-B respectively in halogen grouprOr-I), preferably-Cl；R12For
C1~C8Linear or branched alkyl group, preferably C1~C5Linear or branched alkyl group, more preferably ethyl；
In Formula V, X4For one kind (such as-F ,-Cl ,-Br or-I) in halogen group, preferably-Cl；R13And R14Respectively C1
~C8Linear or branched alkyl group, preferably C1~C5Linear or branched alkyl group, more preferably ethyl.
In Formula V, R13And R14It may be the same or different, it is preferably identical.
R15 3In Al, three R15Can be respectively C1~C8Linear or branched alkyl group, preferably C1~C5Straight chain or branch
Alkyl group.R15 3In Al, three R15Can be identical, or it is different, it is preferably identical.
In the present invention, C1~C8Linear or branched alkyl group include C1~C8Straight chained alkyl and C3~C8Branched alkyl,
Its specific example can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, 2- methyl butyls, 3- methyl butyls, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methyl amyls,
4- methyl amyls, 2,3- dimethylbutyls, 2,2- dimethylbutyls, 3,3- dimethylbutyls, 2- ethyl-butyls, n-heptyl, 2-
Methylhexyl, 3- methylhexyls, 4- methylhexyls, 5- methylhexyls, 2,2- dimethyl amyl groups, 2,3- dimethyl amyl groups, 2,4-
Dimethyl amyl group, 3,3- dimethyl amyl groups, 3,4- dimethyl amyl groups, 4,4- dimethyl amyl groups, 2- ethylpentyls, 3- ethyls penta
Base, n-octyl, 2- methylheptyls, 3- methylheptyls, 4- methylheptyls, 5- methylheptyls, 6- methylheptyls, 2,2- dimethyl oneself
Base, 2,3- dimethylhexanyls, 2,4- dimethylhexanyls, 2,5- dimethylhexanyls, 3,3- dimethylhexanyls, 3,4- dimethyl oneself
Base, 3,5- dimethylhexanyls, 4,4- dimethylhexanyls, 4,5- dimethylhexanyls, 5,5- dimethylhexanyls, 2- ethylhexyls, 3-
Ethylhexyl, 4- ethylhexyls, 2- n-propyls amyl and 2- isopropyl amyls.
In the present invention, lewis acidic specific example shown in formula IV can include but is not limited to：Dichloromethyl aluminium, dichloro
Aluminium ethide, dichloro n-propyl aluminium, two chloro isopropyl aluminium, dichloro n-butylaluminum and dichloro aluminium isobutyl.Preferably, shown in formula IV
Lewis acid is ethyl aluminum dichloride.
In the present invention, lewis acidic specific example shown in Formula V can include but is not limited to：Dimethylaluminum chloride, two
Ethylmercury chloride aluminium, diη-propyl aluminium chloride, diisopropyl aluminium chloride, di-n-butyl aluminium chloride and diisobutyl aluminum chloride.It is preferred that
Ground, lewis acid shown in Formula V are diethyl aluminum chloride.
In the present invention, R15 3The specific example of Al can include but is not limited to：Trimethyl aluminium and triethyl aluminum.
According to the method for the present invention, the lewis acid is preferably road shown in lewis acid and/or Formula V shown in formula IV
Lewis acid, more preferably ethyl aluminum dichloride and/or diethyl aluminum chloride.
Containing there are two alkyl in lewis acidic molecular structure shown in Formula V, it can play and inhibit cation activity center
Occur chain tra nsfer effect, so as to improve preparation polymer molecular weight.But lewis acidic shown in Formula V contain
It measures excessively high, can reduce polymerization rate, extend polymerization time.Therefore, according to the method for the present invention, Louis shown in Formula V
Acid is preferably applied in combination with other lewis acids, is preferably applied in combination with lewis acid shown in formula IV.That is, according to the present invention
Method, the lewis acid are preferably lewis acid shown in lewis acid and Formula V shown in formula IV.
According to the method for the present invention, it is Louis shown in lewis acid and Formula V shown in formula IV in the lewis acid
When sour, on the basis of lewis acidic total amount, lewis acidic content shown in Formula V is preferably 10~90 moles of %.More preferably
Ground, on the basis of lewis acidic total amount, lewis acidic content shown in Formula V is 30~70 moles of %, in this way can be poly-
It closes and obtains preferably balance between reaction speed and polymer molecular weight, can be obtained with higher polymerization speed has higher molecular
The polymer of amount.
The compound for being capable of providing carbonium ion, which can be various interacts with lewis acid, can be precipitated carbon just
The compound of ion.Specifically, the compound for being capable of providing carbonium ion can be selected from one or more hydrogen atom
Respectively quiltThe respective quilt of the above hydrogen atom of one or both of substituted alkane and arylSubstituted aromatic hydrocarbons,
R16、R17、R18And R19Respectively hydrogen, C1~C8Alkyl, phenyl, C7~C10Phenylalkyl, C7~C10Alkyl phenyl or C3
~C8Naphthenic base；X5And X6One kind respectively in halogen group, such as-F ,-Cl ,-Br or-I, preferably-Cl or-Br。
The C7~C10Phenylalkyl refer to C1~C4At least one of alkyl hydrogen atom is substituted by phenyl the base to be formed
Group, specific example can include but is not limited to：(wherein, propylidene can be sub- n-propyl for benzyl, phenethyl, phenylpropyl
Or isopropylidene) and benzene butyl (wherein, sub- normal-butyl can be sub- normal-butyl, sub- sec-butyl, isobutylidene or sub- tertiary butyl).
The C7~C10Alkyl phenyl refer at least one of phenyl hydrogen atom by C1~C4Alkyl replaces the base to be formed
Group, specific example can include but is not limited to：(wherein, propyl can be n-propyl or different for tolyl, ethylbenzene, propyl phenyl
Propyl), butylbenzene base (wherein, butyl can be normal-butyl, sec-butyl, isobutyl group or tertiary butyl).
The C3~C8The specific example of naphthenic base can include but is not limited to：Cyclopropyl, cyclobutyl, cyclopenta, hexamethylene
Base, suberyl and cyclooctyl.
In the present invention, C1~C8Alkyl include C1~C8Straight chained alkyl and C3~C8Branched alkyl, specific example
It can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl,
2- methyl butyls, 3- methyl butyls, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methyl amyls, 4- methyl amyls,
2,3- dimethylbutyls, 2,2- dimethylbutyls, 3,3- dimethylbutyls, 2- ethyl-butyls, n-heptyl, 2- methylhexyls, 3-
Methylhexyl, 4- methylhexyls, 5- methylhexyls, 2,2- dimethyl amyl groups, 2,3- dimethyl amyl groups, 2,4- dimethyl amyl groups,
3,3- dimethyl amyl groups, 3,4- dimethyl amyl groups, 4,4- dimethyl amyl groups, 2- ethylpentyls, 3- ethylpentyls, n-octyl, 2-
Methylheptyl, 3- methylheptyls, 4- methylheptyls, 5- methylheptyls, 6- methylheptyls, 2,2- dimethylhexanyls, 2,3- diformazans
Base hexyl, 2,4- dimethylhexanyls, 2,5- dimethylhexanyls, 3,3- dimethylhexanyls, 3,4- dimethylhexanyls, 3,5- dimethyl
Hexyl, 4,4- dimethylhexanyls, 4,5- dimethylhexanyls, 5,5- dimethylhexanyls, 2- ethylhexyls, 3- ethylhexyls, 4- second
Base hexyl, 2- n-propyls amyl and 2- isopropyl amyls.
The specific example of the compound for being capable of providing carbonium ion can include but is not limited to：To dibenzyl chlorine (that is,
Isosorbide-5-Nitrae-two (chloromethyl) benzene), to dibenzyl bromide (that is, Isosorbide-5-Nitrae-two (bromomethyl) benzene), to dicumyl chlorine (that is, (2- chlorine is different for Isosorbide-5-Nitrae-two
Propyl) benzene), to dicumyl bromine (that is, Isosorbide-5-Nitrae-two (2- bromines isopropyl) benzene), to dicumyl methyl ether (that is, (the 2- methoxyl groups of Isosorbide-5-Nitrae-two
Isopropyl) benzene), to two benzyl group methyl ethers (that is, Isosorbide-5-Nitrae-two (methoxy) benzene) and acetic acid to dicumyl ester (that is, Isosorbide-5-Nitrae-two
(2- acetoxyl groups isopropyl) benzene).
Relative scale between the compound for being capable of providing carbonium ion, the lewis acid and the activator can
To be selected according to specific polymerizing condition.Specifically, the compound for being capable of providing carbonium ion and the activator
Molar ratio can be 0.3~100: 1, preferably 0.4~50: 1, more preferably 0.5~20: 1, further preferably 0.5~5
: 1, it is still more preferably 0.8~2.5: 1, such as 0.8~1.5: 1.The molar ratio of the lewis acid and the activator can be with
It is 4~1000: 1, preferably 5~250: 1, more preferably 5~50: 1, further preferably 8~25: 1, such as 10~20: 1.
May be used common various methods by the monoolefine and ring-alkylated styrenes with it is each in the initiator system
Component contacts, and to be polymerize, forms monoolefine-alkylstyrene copolymers.
In one embodiment of the invention, each component in the initiator system can be dissolved in solvent,
And be aged obtained mixture, obtain initiator solution；By the initiator solution and described in being dissolved in polymer solvent
Monoolefine and ring-alkylated styrenes mixing.
The purpose of the ageing is to make lewis acid in initiator system and is capable of providing compound and the work of proton
Agent forms stable complexing and causes activated centre, can carry out under normal conditions.Usually, the ageing can be -100
DEG C to 20 DEG C, preferably -100 DEG C to 0 DEG C, more preferably -100 DEG C to -50 DEG C, further preferred -90 DEG C to -70 DEG C of temperature range
Interior progress.The time of the ageing can be 10 minutes or more.The present inventor has found in the course of the research, the ageing
Time be preferably 30 minutes or more, polymerization efficiency can be further increased in this way, so as to be obtained in shorter polymerization time
Monoolefine-alkylstyrene copolymers with higher molecular weight.It is highly preferred that the time of the ageing is 60 minutes or more.
Under the premise of guaranteeing to obtain higher polymerization efficiency, from the angle of economy, the time of the ageing is 10 hours
Hereinafter, preferably 5 hours hereinafter, more preferably 2 hours or less.The time of the ageing is more preferably 30 minutes to 5 hours, into
One step is preferably 60 minutes to 120 minutes.
The solvent can be it is various can dissolve the compound for being capable of providing carbonium ion, the lewis acid and
The liquid substance of the activator.Usually, the solvent can be selected from alkane, halogenated alkane and aromatic hydrocarbons, be preferably selected from C3~
C10Alkane, C1~C10Halogenated alkane and C6~C12Aromatic hydrocarbons.
As solvent, the alkane includes aliphatic alkane and alicyclic alkanes, such as C3~C10Alkane include C3~C10
Aliphatic alkane and C3~C10Alicyclic alkanes.
As solvent, the halogenated alkane includes halogenated aliphatic alkane and halogenated cyclo alkane, such as C1~C10Halogen
Include C for alkane1~C10Halogenated aliphatic alkane and C3~C10Halogenated cyclo alkane.Halogen in the halogenated alkane
Atom can be chlorine, bromine or fluorine, preferably chlorine or fluorine.The halogenated alkane is preferably C1~C4Halogenated aliphatic alkane.
The specific example of the solvent can include but is not limited to：Propane, normal butane, iso-butane, pentane, isopentane,
Neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl cyclopentane,
Normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- dimethyl
Pentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2,
5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 2-
Methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4- bis-
Methyl heptane, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- trimethyls
Hexane, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyl cyclohexanes, 2,4,
4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- methyl -4-
Ethyl hexane, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- ethyls
Hexamethylene, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane (include the various isomers of trimethyl-cyclohexane, such as
1,2,3- trimethyl-cyclohexane, 1,2,4- trimethyl-cyclohexanes, 1,2,5- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes),
N-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl
Octane, 3- ethyls octane, 4- ethyls octane, 2,3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethyl heptan
Alkane, 2,4,5- trimethylheptanes, 2,4,6- trimethylheptanes, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5-
Trimethylheptane, 2,2,6- trimethylheptanes, 2,3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptan
Alkane, 2- methyl -4- ethyl heptanes, 2- methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5-
Methyl -3- ethyl heptanes, 4- methyl -4- ethyl heptanes, 4- propyl heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2-
Methyl -3,3- diethylpentane, 1,2- diethyl cyclohexanes, 1,3- diethyl cyclohexanes, Isosorbide-5-Nitrae-diethyl cyclohexane, normal-butyl
Hexamethylene, isobutyl butylcyclohexane, t-butylcyclohexane, tetramethyl-ring hexane (include the various isomers of tetramethyl-ring hexane, such as
1,2,3,4- tetramethyl-ring hexane, 1,2,4,5- tetramethyl-ring hexanes, 1,2,3,5- tetramethyl-ring hexanes), a fluoromethane, difluoro
Methane, fluoroform, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane, Difluoroethane,
Trifluoroethane, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethanes, tetrachloroethanes, pentachloro-
Ethane, carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoro-propane,
Octafluoropropane, a chloropropane, dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, eight chlorine
Propane, a fluorine butane, difluorobutane, 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 (including ortho-xylene, meta-xylene and to two
Toluene).
The concentration of the initiator solution can be conventional selection, be not particularly limited.The dosage of the initiator solution
It can be made appropriate choice according to specific polymerizing condition, polymerization can be caused by being subject to.Those skilled in the art can be
Under the introduction of the prior art, the initiator amount for being adequate to bring about polymerization is determined by the experiment of limited number of time.
According to the method for the present invention, the monoolefine can be the monoene that can carry out cationic polymerization commonly used in the art
Hydrocarbon.Usually, the monoolefine be selected from Formula II compound represented,
In Formula II, R9And R10Respectively C1~C5Linear or branched alkyl group；Or R9For hydrogen, R10For C3~C5Branch
Alkyl.
In the present invention, C1~C5Linear or branched alkyl group include C1~C5Straight chained alkyl and C3~C5Branched alkyl,
Its specific example can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
Specifically, the monoolefine can be selected from but not limited to：2- methyl-1-propylenes (that is, isobutene), 2- methyl-1s-
Butylene, 3-methyl-1-butene, 2,3- dimethyl -1- butylene, 2- Methyl-1-pentenes, 3- Methyl-1-pentenes, 4- methyl-1-pentenes
Alkene, 2,3- dimethyl -1- amylenes, 2,4- dimethyl -1- amylenes, 2- methyl-1s-hexene, 2,3- dimethyl -1- hexenes, 2,4- bis-
Methyl-1-hexene, 2,5- dimethyl-1- hexenes and 2,4,4- trimethyl-1- amylenes.
Preferably, the monoolefine is isobutene.
According to the method for the present invention, the ring-alkylated styrenes be selected from formula III compound represented,
In formula III, R11For C1~C5Linear or branched alkyl group.
The example of the ring-alkylated styrenes can include but is not limited to：P-methylstyrene, m-methyl styrene, to ethyl
Styrene and p-tert-butylstyrene.
Preferably, the ring-alkylated styrenes is selected from shown in Formula IV to alkylbenzene between shown in ring-alkylated styrenes and Formula VII
Ethylene,
In Formula IV, R11For C1~C5Linear or branched alkyl group；
In Formula VII, R11For C1~C5Linear or branched alkyl group.
It is highly preferred that the ring-alkylated styrenes is to ring-alkylated styrenes and/or ring-alkylated styrenes, such as p-methylstyrene
And/or m-methyl styrene.
It is further preferred that in the ring-alkylated styrenes, the content to ring-alkylated styrenes is 80 weight % or more, such as can
Think 80~100 weight %.It is highly preferred that in the ring-alkylated styrenes, the content to ring-alkylated styrenes is 90 weight % or more,
Such as can be 90~100 weight %.Most preferably, the ring-alkylated styrenes is preferably p-methylstyrene.
According to the method for the present invention, the relative usage of the monoolefine and the ring-alkylated styrenes can be prepared according to final
The concrete application occasion of polymer make appropriate choice.Usually, it is with the total amount of the monoolefine and ring-alkylated styrenes
The content of benchmark, the monoolefine can be 80~99 weight %, preferably 90~97 weight %；The ring-alkylated styrenes contains
Amount can be 1~20 weight %, preferably 3~10 weight %.
According to the method for the present invention, the polymer solvent is polymerize by least one first polymer solvent and at least one second
Solvent forms, and first polymer solvent is selected from halogenated alkane, and second polymer solvent is selected from alkane.It is molten as the first polymerization
Agent, the halogen atom in the halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.First polymer solvent is preferred
For C1~C10Halogenated alkane, more preferably C1~C4Halogenated alkane.As the second polymer solvent, the alkane includes fat
Race's alkane and alicyclic alkanes.The aliphatic alkane is preferably C3~C10Aliphatic alkane, more preferably C3~C8Fat
Race's alkane, further preferably C5~C8Aliphatic alkane；The alicyclic alkanes are preferably C3~C10Alicyclic alkanes,
Further preferably C5~C10Alicyclic alkanes.
The specific example of first polymer solvent can include but is not limited to：One fluoromethane, difluoromethane, fluoroform
Alkane, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane, Difluoroethane, trifluoroethane, four
Fluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethanes, tetrachloroethanes, pentachloroethane, chlordene
Carbon, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoro-propane, octafluoropropane, one
Chloropropane, dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, octachloropropane, a fluorine fourth
Alkane, difluorobutane, 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 and ten chlorobutanes.
The specific example of second polymer solvent can include but is not limited to：Propane, normal butane, iso-butane, pentane,
Isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl
Pentamethylene, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4-
Dimethyl pentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethyl
Hexane, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethyls
Pentane, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl-gs
Alkane, 2,4- dimethyl heptanes, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,
4,5- trimethyl cyclohexanes, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- front threes
Base hexane, 2,4,4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexyls
Alkane, 3- methyl -4- ethyl hexanes, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes,
1- methyl -4- ethyl cyclohexanes, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane, n-decane, 2- methylnonanes,
3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyls octane, 4-
Ethyl octane, 2,3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethylheptanes, 2,4,5- trimethylheptanes,
2,4,6- trimethylheptanes, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- trimethylheptanes, 2,2,6- tri-
Methyl heptane, 2,3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 2- methyl -4- ethyl heptan
Alkane, 2- methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyl heptanes, 4-
Methyl -4- ethyl heptanes, 4- propyl heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- diethyl penta
Alkane, 1,2- diethyl cyclohexanes, 1,3- diethyl cyclohexanes, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene
Alkane, t-butylcyclohexane and tetramethyl-ring hexane.
Preferably, first polymer solvent is selected from monochloro methane, dichloromethane and monochlorethane, and second polymerization is molten
Agent is selected from pentane, n-hexane and normal heptane.
According to the method for the present invention, the ratio between first polymer solvent and second polymer solvent can basis
Specific condition is selected.Usually, on the basis of the total amount of the polymer solvent, the content of the first polymer solvent can be
1~80 volume %, preferably 1~60 volume, more preferably 10~50 volume %；The content of second polymer solvent can be
20~99 volume %, preferably 40~99 volume %, more preferably 50~90 volume %.
The dosage of the polymer solvent can be the conventional selection of this field.Usually, the dosage of the polymer solvent makes
It is 2~50 weight %, preferably 5~30 weight %, more preferably 5~20 weight % to obtain total monomer concentration.
According to the method for the present invention, the cationic polymerization condition can be the conventional selection of this field.Usually, monoene
Hydrocarbon and ring-alkylated styrenes and the contact of each component in initiator system can -120 DEG C to 20 DEG C, preferably -100 DEG C to 0 DEG C, more
It is preferred that being carried out within the temperature range of -100 DEG C to -50 DEG C, further preferably -90 DEG C to -60 DEG C.According to the method for the present invention, institute
The time for stating contact can be the conventional selection of this field, generally can be 10-180 minutes, preferably 30-120 minutes.
According to the method for the present invention, can also include adding polymerization in the solution obtained after completion of polymerization to polymerization
Agent come make polymerisation terminate (such as alcohol).The type and dosage of the polymerization terminator is not particularly limited in the present invention,
Can be the conventional selection of this field, polymerisation can be terminated by being subject to, and repeats no more herein.
According to the method for the present invention, the efficiency of initiation of used initiator system is high.On the one hand, method energy of the invention
Higher monomer conversion is obtained, content of monomer is low in the obtained solution containing monoolefine-alkylstyrene copolymers, especially
Be ring-alkylated styrenes content it is low, usually, the weight percentage of unreacted ring-alkylated styrenes in the solution polymerizeing
For 1000ppm hereinafter, usually 500ppm hereinafter, even 200ppm hereinafter, halogen can be directly used in monomer without isolation
The step of changing reaction, can also being omitted for removing unreacted monomer after halogenation completion.On the other hand, using this
The molecular weight of monoolefine-alkylstyrene copolymers prepared by the method for invention is high, and can especially obtain weight average molecular weight is
10×104Above, even weight average molecular weight is 40 × 104Above monoolefine-the alkylstyrene copolymers, and then rubber can be obtained
Glue monoolefine-alkylstyrene copolymers.
According to the method for the present invention, in step (2), contain monoolefine-alkyl with what displacement solvent swap step (1) obtained
Halogenated alkane in the solution of styrol copolymer obtains solution after the displacement containing monoolefine-alkylstyrene copolymers, institute
It states displacement solvent and is selected from alkane.The purpose for carrying out solvent displacement is to contain monoolefine-ring-alkylated styrenes by what step (1) obtained
The first polymer solvent (that is, halogenated alkane) for being unsuitable for halogenation in the solution of copolymer cements out, then to carry out halogen
Change reaction.
As displacement solvent, the alkane includes aliphatic alkane and alicyclic alkanes.The aliphatic alkane is preferably
C3~C10Aliphatic alkane, more preferably C3~C8Aliphatic alkane, further preferably C5~C8Aliphatic alkane；
The alicyclic alkanes are preferably C3~C10Alicyclic alkanes, further preferably C5~C10Alicyclic alkanes.
The specific example of the displacement solvent can include but is not limited to：Propane, normal butane, iso-butane, pentane, isoamyl
Alkane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl ring penta
Alkane, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- diformazans
Base pentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes,
2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes,
2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4-
Dimethyl heptane, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- front threes
Base hexane, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyl cyclohexanes, 2,
4,4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- methyl -
4- ethyl hexanes, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- second
Butylcyclohexane, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane, n-decane, 2- methylnonanes, 3- methylnonanes,
4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyls octane, 4- ethyls octane, 2,
3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethylheptanes, 2,4,5- trimethylheptanes, 2,4,6- front threes
Base heptane, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- trimethylheptanes, 2,2,6- trimethylheptanes, 2,
3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 2- methyl -4- ethyl heptanes, 2- methyl -5-
Ethyl heptane, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyl heptanes, 4- methyl -4- ethyls
Heptane, 4- propyl heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- diethylpentane, 1,2- diethyls
Butylcyclohexane, 1,3- diethyl cyclohexanes, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, tertiary butyl ring
Hexane and tetramethyl-ring hexane.
The displacement solvent is preferably selected from C3~C10Aliphatic alkane, be more preferably selected from C5~C8Aliphatic alkane, into
One step is preferably selected from pentane, n-hexane and normal heptane.
According to the method for the present invention, the type of the displacement solvent and the type of second polymer solvent can be phase
Together, or it is different, it is preferably identical, be conducive to subsequent isolate and purify in this way.
Method according to the invention it is possible to be contained what step (1) obtained with displacement solvent using common various methods
Halogenated alkane in the solution of monoolefine-alkylstyrene copolymers cements out, and such as flashes and/or strips.In a kind of implementation
In mode, the steam for replacing solvent is sent into the solution containing monoolefine-alkylstyrene copolymers that step (1) obtains,
The sensible heat and latent heat carried using the steam of displacement solvent contains monoolefine-alkylstyrene copolymers by what step (1) obtained
Solution in halogenated alkane steam, and at least partly replace solvent and be retained in containing monoolefine-alkylstyrene copolymers
In solution.The feeding amount of the steam of the displacement solvent is be enough will be in the solution containing monoolefine-alkylstyrene copolymers
Halogenated alkane steam subject to.In this embodiment, replace the steam of solvent temperature can replace as needed it is halogenated
It, generally can be in the range of 10~150 DEG C, preferably in the range of 30~100 DEG C, more preferably 50 depending on the boiling point of alkane
In the range of~90 DEG C；Can be 10~200kPa (absolute pressure), preferably 50~120kPa into the pressure in the container of line replacement
(absolute pressure), more preferably 80~100kPa (absolute pressure).In this embodiment, that replaces the steam of solvent is passed through the time with can
By the halogenated alkane in the solution containing monoolefine-alkylstyrene copolymers it is whole or it is substantially all steam subject to, usually,
Duration can be 10~300 minutes, preferably 30~200 minutes, more preferably 50~150 minutes, further preferably
100~150 minutes.
According to the method for the present invention, solution after the displacement containing monoolefine-alkylstyrene copolymers that step (2) obtains
It can be sent directly into step (3) and be contacted with halogen-containing compound, can also obtain step (2) contains monoolefine-alkane
It is sent into step (3) after solution is concentrated or diluted after the displacement of base styrol copolymer and is connect with halogen-containing compound
It touches.Usually, monoolefine-alkylbenzene in solution is sent into after the displacement containing monoolefine-alkylstyrene copolymers of step (3)
The content of ethylene copolymer can be 1~30 weight %, preferably 5~20 weight %.
According to the method for the present invention, in step (3), the halogen-containing compound can be that common various can make monoene
The compound that part hydrogen atom in hydrocarbon-alkylstyrene copolymers strand is replaced by halogen atom.Preferably, described to contain
The compound of halogen is halogen simple substance, as bromine (that is, bromine) and/or chlorine are plain (that is, chlorine).It is highly preferred that described contain halogen
Compound be bromine.
In step (3), solution and halogen-containing compound connects after the displacement containing monoolefine-alkylstyrene copolymers
Touch to carry out under normal conditions, as long as can make monoolefine-alkylstyrene copolymers that halogenation occur.Generally
Ground, the contact can carry out in the presence of at least one radical initiator, and the contact can also be in light-initiated condition
Under.The radical initiator can be it is common it is various can promote monoolefine-alkylstyrene copolymers with contain it is halogenated
The radical initiator of object reaction is closed, preferably oleosoluble radical initiators are preferably selected from such as azo type free radical initiator
Azo diisobutyl nitrile, azobisisovaleronitrile and azobisisoheptonitrile.The dosage of the radical initiator is can cause halogen
Change subject to reaction.Usually, the molar ratio of the radical initiator and the halogen contained compound can be 0.01~0.5:
1, preferably 0.02~0.2: 1, more preferable 0.03~0.1: 1.The radical initiator preferably provides as a solution, molten
Agent can be selected from the combination of one or more of aforementioned alkane for being used as the second polymer solvent, preferably polymerize with second
Solvent is identical.When carrying out the contact under the conditions of light-initiated, illumination condition is can cause monoolefine-alkylstyrene
Object occurs subject to halogenation, such as：Light source can be incandescent lamp (incandescent lamp of such as 80~200W).
In step (3), the amount of the halogen atom introduced in the strand of monoolefine-alkylstyrene copolymers can root
It is selected according to the use occasion of the halogenation monoolefine-alkylstyrene copolymers finally prepared.Usually, finally obtained list
The content of halogen atom can be in the range of 0.2~2 mole of % in olefm-alkyl styrol copolymer.Preferably, polymer
The content of middle halogen atom is in the range of 0.4~1.5 mole of %.
In step (3), the Contact Temperature of the solution containing monoolefine-alkylstyrene copolymers and halogen-containing compound
It can be conventional selection.Usually, the contact can carry out at a temperature of -10 DEG C to 80 DEG C, preferably at 0 DEG C to 60 DEG C
At a temperature of carry out, more preferably carried out at a temperature of 30 DEG C to 60 DEG C.The time of the contact can according to the temperature of contact with
And expected halogenation degree is selected, and generally can be 0.5~30 minute, preferably 1~15 minute.
According to the method for the present invention, in step (3), after the completion of halogenation, preferably the mixture that halogenation obtains is carried out
It neutralizes, the pH value for the mixture that halogenation obtains preferably is neutralized to 8~10.It can be by being added in the mixture that is obtained to halogenation
Alkaline matter and neutralized, the basic species for example can be NaOH and/or KOH, preferably NaOH.The basic species are of fine quality
Choosing provides as a solution, such as provides in form of an aqueous solutions.
Method according to the invention it is possible to the mixture after the mixture obtained from halogenation using conventional method or neutralization
In isolate halogenation monoolefine-alkylstyrene copolymers.For example, after can be by obtaining mixture or neutralizing halogenation
Mixture is condensed, to obtain halogenation monoolefine-alkylstyrene copolymers.
According to the method for the present invention, monoolefine-alkylbenzene with higher molecular weight can be prepared with higher polymerization efficiency
Ethylene copolymer, and then prepare halogenation monoolefine-alkylstyrene copolymers with higher molecular weight.Particularly, using this
The method of invention can be with higher polymerization efficiency, and it is 10 × 10 to prepare weight average molecular weight4Above, even weight average molecular weight be 40 ×
104Above monoolefine-the alkylstyrene copolymers, and then rubber halogenation monoolefine-alkylstyrene copolymers can be prepared.
According to the method for the present invention particularly suitable for preparing halogenated isobutylene-p-methylstyrene copolymer, especially rubber halogenation is different
Butylene-p-methylstyrene copolymer.
Fig. 1 shows that method using the present invention prepares a kind of preferred implementation side of monoolefine-alkylstyrene copolymers
Formula.The preferred embodiment is described in detail below in conjunction with Fig. 1.As shown in Figure 1, monoolefine shown in Formula II is (excellent
Be selected as isobutene) 1, ring-alkylated styrenes 2, the first polymer solvent 31 shown in formula III and the second polymer solvent 32 with prepare in advance
And aged initiator solution 4 is sent into polymer reactor I, and polymerisation is carried out under the conditions of cationic polymerization.Into
After the polymerisation of row predetermined time, terminator 5 is sent into polymer reactor I, terminates polymerisation.Polymer reactor I is defeated
The solution 6 containing monoolefine-alkylstyrene copolymers gone out subsequently enters in solvent displacer II, will replace solvent vapo(u)r 7
It is sent into from the bottom of solvent displacer II, the halogenated alkane in the solution 6 containing monoolefine-alkylstyrene copolymers is steamed
Go out, the halogenated alkane 8 to be displaced at the top of solvent displacer II.Solution 9 is replaced from solvent after obtained displacement
The bottom of device II exports, subsequently into halogenation reactor III with halogen-containing compound 10 and radical initiator solution 11
Haptoreaction, so that at least partly hydrogen atom in monoolefine-alkylstyrene copolymers strand is replaced by halogen atom.
When the content of halogen atom meets pre-provisioning request in monoolefine-alkylstyrene copolymers strand, to halogenation reactor III
The middle aqueous solution 12 for being sent into alkaline matter, is neutralized.Finally, contain halogenation monoolefine-ring-alkylated styrenes by what neutralization obtained
The mixture 13 of copolymer exports, and is sent into subsequent handling and is detached and purified, to finally obtain halogenation monoolefine-alkyl
Styrol copolymer.
Fig. 2 shows another preferred embodiment according to the method for the present invention.Embodiment shown in Fig. 2 and figure
Difference lies in halogenation steps for embodiment shown in 1, below only to the halogenation step of Fig. 2 illustrated embodiments into
Row is described in detail.As shown in Fig. 2, solution 9 enters in mixer IV after the displacement of solvent displacer II outputs, with halogen-containingization
It closes object 10 to be uniformly mixed, then obtained mixture is sent into photohalogenation reactor V, halogenation is carried out under the irradiation of light source 14
Reaction.After the completion of halogenation, the mixture in photohalogenation reactor V is sent into neutralization reactor VI and alkaline matter
The contact of aqueous solution 12 is neutralized.Finally, the mixture containing halogenation monoolefine-alkylstyrene copolymers neutralization obtained
13 outputs, and be sent into subsequent handling and detached and purified, to finally obtain halogenation monoolefine-alkylstyrene copolymers.
Below in conjunction with experimental example and embodiment, the present invention will be described in detail.
In following experimental example and contrast experiment's example, polymer yield is measured using weight method,
Polymer yield (%)=(weight/total monomer weight of obtained polymer) × 100%.
In following experimental example, contrast experiment's example, embodiment and comparative example, the molecular weight and molecular weight distributing index of polymer
It is measured using Japanese Shimadzu Corporation production LC-20A type gel permeation chromatographs, using single aperture chromatographic column WithFour columns are combined.Mobile phase is tetrahydrofuran, flow velocity 0.7mL/min；A concentration of 2mg/ of sample solution
ML, sample size are 200 μ L；Test temperature is 35 DEG C；Using single distribution polystyrene as standard sample.
In following embodiment and comparative example, using the AVANCE400 Nuclear Magnetic Resonance commercially available from Bruker companies of Switzerland, with
CDCl3Make solvent, TMS is internal standard, measure the content of p-methylstyrene in monoolefine-alkylstyrene copolymers of preparation with
And in halogenation monoolefine-alkylstyrene copolymers halogen content.
Following experimental example, contrast experiment's example, the solvent used in embodiment and comparative example and monomer before use, using
Method commonly used in the art is refined.
Experimental example 1~25 is used to illustrate the polymerization procedure in the method for the present invention.
Experimental example 1
(1) by 0.128g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- are dissolved in 160g and containing (a concentration of to dicumyl chlorine
In dichloromethane 0.0064mol/L), obtained solution is cooled to -85 DEG C in advance, it is dense that 8mL is then sequentially added into the solution
Degree is that obtained mixed liquor is placed in -85 DEG C of cryostat by the hexane solution of the ethyl aluminum dichloride of 0.9mol/L after mixing
Middle ageing 60min, to obtain initiator solution.
(2) 500mL is sequentially added in the stainless steel reactor of the 2000mL stirred equipped with strength constant speed and is cooled to -80 DEG C in advance
N-hexane, 500mL is cooled to -80 DEG C of monochloro methane in advance, to be cooled to -80 DEG C of isobutene and 12mL room temperature in advance (be 25 to 250mL
DEG C) p-methylstyrene (98 weight % of content), be uniformly mixed.The initiator that into reactor prepared by a dropping step (1) is molten
Liquid.Wherein, the addition of initiator solution be 100mL, control rate of addition make the temperature in reactor be in -85 DEG C to -
Within the scope of 90 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be within the scope of -85 DEG C to -90 DEG C, and carry out
Then the dichloromethane solution that 100g contains 3 weight % triethylene glycols is added in the polymerisation of 60min into reaction mixture, with
Polymerisation is terminated, to obtain the solution containing monoolefine-alkylstyrene copolymers.Then, contain monoene by what is obtained
The solution of hydrocarbon-alkylstyrene copolymers, which is placed in hot bath, removes solvent, is dried extremely in 60 DEG C in vacuum drying oven after washing
Constant weight obtains monoolefine-alkylstyrene copolymers.
Polymer yield, obtained polymer molecular weight and molecualr weight distribution index listed in table 1.
Experimental comparison's example 1
It is polymerize using with 1 identical method of experimental example, unlike, in step (1), 2,3- bis- chloro- 5 is not used,
6- dicyano p-benzoquinones.Experimental result is listed in table 1.
Experimental example 2
It is polymerize using with 1 identical method of experimental example, unlike, in step (1), digestion time 100min；
In step (2), the time of polymerisation is 40min.Experimental result is listed in table 1.
Experimental example 3
It is polymerize using with 1 identical method of experimental example, unlike, in step (1), digestion time 30min；Step
Suddenly in (2), the time of polymerisation is 70min.Experimental result is listed in table 1.
Experimental example 4
It is polymerize using with 1 identical method of experimental example, unlike, in step (1), digestion time 10min；Step
Suddenly in (2), the time of polymerisation is 100min.Experimental result is listed in table 1.
Experimental example 5
It is polymerize using with 1 identical method of experimental example, unlike, in step (1), 2,3- bis- chloro- 5,6- dicyan
The tetrahydrochysene 1,4-benzoquinone of base 1,4-benzoquinone equimolar amounts replaces；In step (2), the time of polymerisation is 60min.Experimental result exists
It is listed in table 1.
Experimental example 6
It is polymerize using with 1 identical method of experimental example, unlike, in step (1), 2,3- bis- chloro- 5,6- dicyan
The chloranil of base 1,4-benzoquinone equimolar amounts replaces；In step (2), the time of polymerisation is 50min.Experimental result exists
It is listed in table 1.
Experimental example 7
It is polymerize using with 1 identical method of experimental example, unlike, in step (1), 2,3- bis- chloro- 5,6- dicyan
The four cyano 1,4-benzoquinone of base 1,4-benzoquinone equimolar amounts replaces；In step (2), the time of polymerisation is 120min.Experiment knot
Fruit is listed in table 1.
Experimental example 8
It is polymerize using with 1 identical method of experimental example, unlike, in step (2), the dosage of n-hexane is
The dosage of 800mL, monochloro methane are 200mL, polymerization reaction time 80min.Experimental result is listed in table 1.
Experimental example 9
It is polymerize using with 1 identical method of experimental example, unlike, in step (1), by 0.163g chloranils
It is dissolved in 200g and containing in the dichloromethane of dicumyl bromine (a concentration of 0.0052mol/L), obtained solution is cooled to -85 in advance
DEG C, the hexane solution of the ethyl aluminum dichloride of a concentration of 0.9mol/L of 10mL is then sequentially added into the solution, is uniformly mixed
Afterwards, obtained mixed liquor is placed in -85 DEG C of cryostat and is aged 80min, to obtain initiator solution；
In step (2), the time of polymerisation is 50min.Experimental result is listed in table 1.
Experimental example 10
Polymerize using with 1 identical method of experimental example, unlike, in step (2), be added dropwise initiator solution and
In polymerization process, the temperature in reactor is set to be within the scope of -60 DEG C to -70 DEG C, polymerization reaction time is
120min.Experimental result is listed in table 1.
Experimental example 11
It is polymerize using with 9 identical method of experimental example, unlike, in step (2), the dosage of n-hexane is
The dosage of 700mL, monochloro methane are 300mL, polymerization reaction time 60min.Experimental result is listed in table 1.
Experimental example 12
It is polymerize using with 9 identical method of experimental example, unlike, in step (2), the dosage of n-hexane is
The dosage of 200mL, monochloro methane are 800mL, polymerization reaction time 40min.Experimental result is listed in table 1.
Experimental example 13
(1) by 0.152g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- are dissolved in 200g and containing (a concentration of to dicumyl chlorine
In dichloromethane 0.006mol/L), obtained solution is cooled to -85 DEG C in advance, 6mL concentration is then sequentially added into the solution
For the aluminium diethyl monochloride of the hexane solution and a concentration of 1.0mol/L of 6mL of the ethyl aluminum dichloride (EADC) of 0.9mol/L
(DEAC) n-heptane solution (molar ratio of EADC/DEAC is 4.7/5.3), after mixing, obtained mixed liquor is set
It is aged 80min in -85 DEG C of cryostat, to obtain initiator solution.
(2) 600mL is sequentially added in the stainless steel reactor of the 2000mL stirred equipped with strength constant speed and is cooled to -80 DEG C in advance
N-hexane, 400mL is cooled to -80 DEG C of monochloro methane in advance, to be cooled to -80 DEG C of isobutene and 12mL room temperature in advance (be 25 to 250mL
DEG C) p-methylstyrene (98 weight % of content), be uniformly mixed.The initiator that into reactor prepared by a dropping step (1) is molten
Liquid.Wherein, the addition of initiator solution is 90mL, and control rate of addition makes the temperature in reactor be in -85 DEG C to -90
Within the scope of DEG C.After being added dropwise to complete, the temperature in reactor is kept to be within the scope of -85 DEG C to -90 DEG C, and carry out
Then the dichloromethane solution that 100g contains 3 weight % triethylene glycols is added in the polymerisation of 60min into reaction mixture, with
Polymerisation is terminated, to obtain the solution containing monoolefine-alkylstyrene copolymers.Then, contain monoene by what is obtained
The solution of hydrocarbon-alkylstyrene copolymers, which is placed in hot bath, removes solvent, is dried extremely in 60 DEG C in vacuum drying oven after washing
Constant weight obtains monoolefine-alkylstyrene copolymers.
Polymer yield, obtained polymer molecular weight and molecualr weight distribution index listed in table 2.
Experimental example 14
It is polymerize using with 13 identical method of experimental example, unlike, in step (2), initiator solution is being added dropwise
And in the range of in polymerization process the temperature in reactor being maintained at -60 DEG C to -70 DEG C, polymerization reaction time is
100min.Experimental result is listed in table 2.
Experimental comparison's example 2
It is polymerize using with 14 identical method of experimental example, unlike, in step (1), 2,3- bis- chloro- 5 is not used,
6- dicyano p-benzoquinones.Experimental result is listed in table 2.
Experimental example 15
It is polymerize using with 13 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC
Under conditions of constant, it is 7/3 to make the molar ratio of EADC/DEAC；In step (2), polymerization reaction time 40min.Experiment knot
Fruit is listed in table 2.
Experimental example 16
It is polymerize using with 13 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC
Under conditions of constant, it is 3/7 to make the molar ratio of EADC/DEAC；In step (2), polymerization reaction time 80min.Experiment knot
Fruit is listed in table 2.
Experimental example 17
It is polymerize using with 13 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC
Under conditions of constant, it is 1/9 to make the molar ratio of EADC/DEAC；In step (2), polymerization reaction time 120min.Experiment knot
Fruit is listed in table 2.
Experimental example 18
It is polymerize using with 13 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC
Under conditions of constant, it is 9/1 to make the molar ratio of EADC/DEAC；In step (2), polymerization reaction time 40min.Experiment knot
Fruit is listed in table 2.
Experimental example 19
It is polymerize using with 13 identical method of experimental example, unlike, in step (1), diethyl aluminum chloride is used etc.
The ethyl aluminum dichloride of mole replaces, that is, the initiator solution prepared is free of diethyl aluminum chloride；In step (2), polymerisation
Time is 30min.Experimental result is listed in table 2.
Experimental example 20
It is polymerize using with 13 identical method of experimental example, unlike, in step (1), digestion time 60min；
In step (2), polymerization reaction time 50min.Experimental result is listed in table 2.
Experimental example 21
It is polymerize using with 13 identical method of experimental example, unlike, in step (1), digestion time 30min；
In step (2), polymerization reaction time 80min.Experimental result is listed in table 2.
Experimental example 22
It is polymerize using with 13 identical method of experimental example, unlike, in step (1), digestion time 15min；
In step (2), polymerization reaction time 120min.Experimental result is listed in table 2.
Experimental example 23
(1) 0.0497g chloranils and 0.0422g are dissolved in 62.1g dichloromethane dibenzyl chlorine, by what is obtained
Solution is cooled to -85 DEG C in advance, and the hexane solution of the ethyl aluminum dichloride of a concentration of 0.9mol/L of 1.7mL is then added into the solution
It is made into initiator solution with the toluene solution of the diethyl aluminum chloride of a concentration of 0.9mol/L of 1.7mL, is uniformly mixed and is placed on -80
DEG C cryostat in be aged 100min.By weight, in initiator solution chloranil content 800ppm, to dibenzyl chlorine
Content is 680ppm.
(2) into the polymerization bottle of 250mL, 60mL is cooled to -80 DEG C of n-hexane, 40mL is cooled to -80 DEG C for addition successively
Monochloro methane, 11mL are cooled to -80 DEG C of isobutene and the p-methylstyrene (content is 98 weight %) of 0.46mL room temperature, mix
Monomer solution is formed after conjunction.Polymerization bottle is placed in -80 DEG C of low temperature cryostat, 10mL steps (1) are added into monomer solution and match
The initiator solution of system is then allowed to stand reaction 80min, and control cryostat temperature is in -80 DEG C to -85 DEG C of range in reaction process
It is interior.After reaction, 5mL is added into reaction mixture and contains the methanol solution of 0.5 weight %NaOH to terminate polymerisation,
To obtain the solution containing monoolefine-alkylstyrene copolymers.Then, contain monoolefine-ring-alkylated styrenes by what is obtained
The solution of copolymer, which is placed in hot bath, removes solvent, dry to constant weight in 60 DEG C in vacuum drying oven after washing, obtains monoene
Hydrocarbon-alkylstyrene copolymers.
Polymer yield, obtained polymer molecular weight and molecualr weight distribution index listed in table 2.
Experimental example 24
(1) 0.0497g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- and 0.0422g are dissolved in 62.1g bis- to dibenzyl chlorine
In chloromethanes, obtained solution is cooled to -85 DEG C in advance, the dichloro of a concentration of 0.9mol/L of 1.7mL is then added into the solution
It is molten that the toluene solution of the diethyl aluminum chloride of a concentration of 0.9mol/L of hexane solution and 1.7mL of aluminium ethide is made into initiator
Liquid, uniformly mixed be placed in -80 DEG C of cryostat are aged 60min.By weight, 2,3-, bis- chloro- 5,6- bis- in initiator solution
The content 800ppm of cyano 1,4-benzoquinone, the content to dibenzyl chlorine are 680ppm.
(2) into the polymerization bottle of 250mL, 60mL is cooled to -80 DEG C of n-hexane, 40mL is cooled to -80 DEG C for addition successively
Monochloro methane, 11mL are cooled to -80 DEG C of isobutene and the p-methylstyrene (content is 98 weight %) of 0.46mL room temperature, mix
Monomer solution is formed after conjunction.Polymerization bottle is placed in -80 DEG C of low temperature cryostat, 10mL steps (1) are added into monomer solution and match
The initiator solution of system is then allowed to stand reaction 60min, and control cryostat temperature is in -80 DEG C to -85 DEG C of range in reaction process
It is interior.After reaction, 5mL is added into reaction mixture and contains the methanol solution of 0.5 weight %NaOH to terminate polymerisation,
To obtain the solution containing monoolefine-alkylstyrene copolymers.Then, contain monoolefine-ring-alkylated styrenes by what is obtained
The solution of copolymer, which is placed in hot bath, removes solvent, dry to constant weight in 60 DEG C in vacuum drying oven after washing, obtains monoene
Hydrocarbon-alkylstyrene copolymers.
Polymer yield, obtained polymer molecular weight and molecualr weight distribution index listed in table 2.
Experimental example 25
It is polymerize using with 24 identical method of experimental example, unlike, in step (2), the dosage of n-hexane is
The dosage of 90mL, monochloro methane are 10mL, polymerization reaction time 100min.Experimental result is listed in table 2.
Tables 1 and 2 as a result, it was confirmed that polymerize using the method for the present invention, higher polymerization efficiency can be obtained, monomer turns
Rate is high, with the simple C of use+/ lewis acid initiator system is compared, and polymer yield can be made to reach within the shorter time
100%, the content energy of unreacted ring-alkylated styrenes in the solution containing monoolefine-alkylstyrene copolymers being prepared
Reach 200ppm (by weight) hereinafter, the solution without undergo detach unreacted ring-alkylated styrenes the step of can directly into
Row halogenation.On the contrary, the polymerization efficiency of Experimental comparison's example 1~2 is poor, and it is identical in remaining condition, with identical
Polymerization time can not make polymer yield reach 99% or more, and then not anti-in the monoolefine-alkylstyrene copolymers prepared
The content for the ring-alkylated styrenes answered is far above 1000ppm (by weight), can not directly carry out halogenation.
Examples 1 to 4 is for illustrating the present invention.
Embodiment 1
(1) solution containing monoolefine-alkylstyrene copolymers that will be prepared using method identical with experimental example 1
The solvent that (wherein, the weight content of unreacted p-methylstyrene is 200ppm or less) has been vacuumized with nitrogen indentation is set
In parallel operation, be passed through 70 DEG C of n-hexane steam from the bottom of solvent displacer, control operating pressure is 90kPa (absolute pressure), just oneself
The duration that is passed through of alkane steam is 150min, to the solution (content of monoolefine-alkylstyrene copolymers after being replaced
For 13.2 weight %).
(2) referring to Fig.1 shown in mode, solution after displacement that step (1) obtains is pressed into nitrogen and has been vacuumized
In halogenation reactor, and 54 DEG C are heated to, 14g is then added into halogenation reactor successively contains two different heptan of 2 weight % azos
The hexane solution and 6g bromines of nitrile, react 10min at a temperature of 54 DEG C.Then, it is added and contains 2 weight % containing 120g
The aqueous solution of NaOH carries out the neutralization of 20min.
(3) obtained mixture water vapour removing solvent will be neutralized and be condensed, obtained aqueous bromination glue is being opened
It is 10 minutes dry in 110 DEG C in mill, to obtain bromination monoolefine-alkylstyrene copolymers, measure bromination monoolefine-alkane
As a result bromine content in base styrol copolymer is listed in table 3.
Embodiment 2
Bromination monoolefine-alkylstyrene copolymers are prepared using method same as Example 1, unlike, step
(1) in, the solution containing monoolefine-alkylstyrene copolymers used is to be prepared using method identical with experimental example 8
(wherein, the weight content of unreacted p-methylstyrene is 200ppm to solution containing monoolefine-alkylstyrene copolymers
Below), the duration that is passed through of n-hexane steam is 120min, and monoolefine-ring-alkylated styrenes is total in solution after obtained displacement
The content of polymers is 12.6 weight %；
Step (2) is carried out using mode shown in Fig. 2：Solution nitrogen indentation mixing after the displacement that step (1) is obtained
In device, 1min is mixed with 4g bromines, then mixture is sent into tablet photohalogenation reactor, light source irradiation 2min is opened and carries out
Photohalogenation reacts.Then, obtained bromination glue is sent into neutralization reactor, and is sent into 90g into neutralization reactor and contains 2
The aqueous solution of weight %NaOH carries out the neutralization of 20min.
The bromine content of bromination monoolefine-alkylstyrene copolymers of preparation is listed in table 3.
Embodiment 3
Bromination monoolefine-alkylstyrene copolymers are prepared using method same as Example 1, unlike, step
(1) in, using method identical with experimental example 9 prepare the solution containing monoolefine-alkylstyrene copolymers (wherein, not
The weight content of the p-methylstyrene of reaction is 200ppm or less), monoolefine-ring-alkylated styrenes in solution after obtained displacement
The content of copolymer is 12.4 weight %；
In step (2), the dosage of bromine is 4.2g.
The bromine content of bromination monoolefine-alkylstyrene copolymers of preparation is listed in table 3.
Embodiment 4
(1) solution containing monoolefine-alkylstyrene copolymers that will be prepared using method identical with experimental example 13
The solvent that (wherein, the weight content of unreacted p-methylstyrene is 200ppm or less) has been vacuumized with nitrogen indentation is set
In parallel operation, be passed through 80 DEG C of n-hexane steam from the bottom of solvent displacer, control operating pressure is 95kPa (absolute pressure), just oneself
The duration that is passed through of alkane steam is 150min, to the solution (content of monoolefine-alkylstyrene copolymers after being replaced
For 12.8 weight %).
(2) referring to Fig.1 shown in mode, solution after displacement that step (1) obtains is pressed into nitrogen and has been vacuumized
In halogenation reactor, and 52 DEG C are heated to, 15g is then added into halogenation reactor successively contains two different heptan of 2 weight % azos
The hexane solution and 6g bromines of nitrile, react 14min at a temperature of 52 DEG C.Then, it is added and contains 2 weight % containing 120g
The aqueous solution of NaOH carries out the neutralization of 20min.
(3) obtained mixture water vapour removing solvent will be neutralized and be condensed, obtained aqueous bromination glue is being opened
It is 10 minutes dry in 110 DEG C in mill, to obtain bromination monoolefine-alkylstyrene copolymers, measure bromination monoolefine-alkane
As a result bromine content in base styrol copolymer is listed in table 3.
Table 3
| Number | Content of halogen (mol%) |
| Embodiment 1 | 1.24 |
| Embodiment 2 | 1.16 |
| Embodiment 3 | 0.91 |
| Embodiment 4 | 1.26 |
Examples 1 to 4 as a result, it was confirmed that method using the present invention prepares the copolymerization of halogenated isobutylene-p-methylstyrene
Object can realize that monomer completely or almost completely converts, the glue polymerizeing in polymerization procedure with higher rate of polymerization
Liquid can directly carry out halogenation without undergoing the operation of removing unreacted monomer, be effectively improved production efficiency, reduce energy
Consumption.Also, method using the present invention can prepare the isobutene with higher molecular weight-p-methylstyrene copolymer, to
Rubber isobutene-p-methylstyrene copolymer can be obtained, and then obtains halogenated isobutylene-p-methylstyrene rubber.Together
When, method of the invention is prepared without slurry polymerization process to be polymerize necessary to isobutene-p-methylstyrene copolymer
Object is redissolved process.Therefore, method of the invention is suitable for large-scale production, is with a wide range of applications.
Claims (43)
1. a kind of preparation method of halogenation monoolefine-alkylstyrene copolymers, this approach includes the following steps：
It (1), will be at least one monoolefine and at least one ring-alkylated styrenes and initiator system under the conditions of cationic polymerization
Each component contacted in polymer solvent, obtain the solution containing monoolefine-alkylstyrene copolymers, the polymer solvent by
At least one first polymer solvent and at least one second polymer solvent form, and first polymer solvent is selected from halogenated alkane,
Second polymer solvent is selected from alkane, and on the basis of the total amount of the polymer solvent, the content of first polymer solvent is 1
~80 volume %；The content of second polymer solvent is 20~99 volume %, and the condition of the contact makes, by weight,
In the solution containing monoolefine-alkylstyrene copolymers the content of unreacted ring-alkylated styrenes be not higher than
1000ppm；
The initiator system contains at least one compound for being capable of providing carbonium ion, at least one lewis acid and at least
The molar ratio of a kind of activator, the compound for being capable of providing carbonium ion and the activator is 0.3~100：1, it is described
The molar ratio of lewis acid and the activator is 4~1000：1, the activator is selected from -1 compound represented of Formulas I and formula
I-2 compounds represented,
In Formulas I -1 and Formulas I -2, R1、R2、R3、R4、R5、R6、R7And R8Respectively-H ,-X1、-NO2、With one in-CN
Kind, X1And X2One kind respectively in halogen group；
The compound for being capable of providing carbonium ion is selected from quiltSubstituted aromatic hydrocarbons, R18And R19Respectively hydrogen, C1~C8
Alkyl, phenyl, C7~C10Phenylalkyl, C7~C10Alkyl phenyl or C3~C8Naphthenic base X6For in halogen group
It is a kind of；
The lewis acid is lewis acid shown in lewis acid and/or Formula V shown in formula IV,
In formula IV, X31And X32One kind respectively in halogen group；R12For C1~C8Linear or branched alkyl group；
In Formula V, X4For one kind in halogen group；R13And R14Respectively C1~C8Linear or branched alkyl group；
The monoolefine be selected from Formula II compound represented,
In Formula II, R9And R10Respectively C1~C5Linear or branched alkyl group；Or R9For hydrogen, R10For C3~C5Branched alkyl；
The ring-alkylated styrenes be selected from formula III compound represented,
In formula III, R11For C1~C5Linear or branched alkyl group；
(2) it is replaced in the solution containing monoolefine-alkylstyrene copolymers that solvent swap step (1) obtains at least one
Halogenated alkane, obtain solution after the displacement containing monoolefine-alkylstyrene copolymers, the displacement solvent is selected from alkane；
(3) solution and halogen-containing compound after the displacement containing monoolefine-alkylstyrene copolymers for obtaining step (2)
Or the contact of halogen simple substance, so that the part hydrogen atom in the monoolefine-alkylstyrene copolymers strand is by halogen original
Son substitution.
2. according to the method described in claim 1, wherein, the compound for being capable of providing carbonium ion and the activator
Molar ratio is 0.4~50：1.
3. according to the method described in claim 2, wherein, the compound for being capable of providing carbonium ion and the activator
Molar ratio is 0.5~20：1.
4. according to the method described in claim 3, wherein, the compound for being capable of providing carbonium ion and the activator
Molar ratio is 0.5~5：1.
5. according to the method described in claim 4, wherein, the compound for being capable of providing carbonium ion and the activator
Molar ratio is 0.8~2.5：1.
6. according to the method described in claim 1, wherein, the molar ratio of the lewis acid and the activator is 5~250：
1。
7. according to the method described in claim 6, wherein, the molar ratio of the lewis acid and the activator is 5~50：1.
8. according to the method described in claim 7, wherein, the molar ratio of the lewis acid and the activator is 8~25：1.
9. according to the method described in claim 1, wherein, by least one monoolefine and at least one ring-alkylated styrenes with it is described
In initiator system each component contact method include：Each component in the initiator system is dissolved in solvent, and
Obtained mixture is aged, initiator solution is obtained；By the initiator solution and the list being dissolved in polymer solvent
Alkene and ring-alkylated styrenes mixing.
10. according to the method described in claim 9, wherein, the time of the ageing is 10 minutes to 10 hours.
11. according to the method described in claim 10, wherein, the time of the ageing is 30 minutes to 5 hours.
12. according to the method for claim 11, wherein the time of the ageing is 60 minutes to 120 minutes.
13. the method according to any one of claim 9~12, wherein temperature of the ageing at -100 DEG C to 20 DEG C
It spends in range and carries out.
14. according to the method for claim 13, wherein the ageing carries out within the temperature range of -100 DEG C to 0 DEG C.
15. according to the method for claim 14, wherein the ageing carries out within the temperature range of -100 DEG C to -50 DEG C.
16. according to the method for claim 15, wherein the ageing carries out within the temperature range of -90 DEG C to -70 DEG C.
17. the method according to any one of claim 9~12, wherein the solvent is selected from alkane, halogenated alkane
With it is one or more in aromatic hydrocarbons.
18. the method according to any one of claim 1~12, wherein the activator is selected from tetrachloroquinone, dichloro
Dicyano benzoquinone, tetrahydrochysene benzoquinones and four cyano benzoquinones.
19. the method according to any one of claim 1~12, wherein in formula IV, X31And X32Respectively-Cl；R12
For ethyl.
20. the method according to any one of claim 1~12, wherein in Formula V, X4For-Cl；R13And R14Respectively
Ethyl.
21. the method according to any one of claim 1~12, wherein the lewis acid is road shown in formula IV
Lewis acid shown in Lewis acid and Formula V, in the lewis acid, the lewis acid of 10~90 moles of % is road shown in Formula V
Lewis acid.
22. according to the method for claim 21, wherein in the lewis acid, the lewis acid of 30~70 moles of % is
Lewis acid shown in Formula V.
23. the method according to any one of claim 1~12, wherein X6For-Cl or-Br.
24. the method according to any one of claim 1~12, wherein the chemical combination for being capable of providing carbonium ion
Object is selected to 1,4- bis- (chloromethyl) benzene, 1,4- bis- (bromomethyl) benzene, (2- chloro isopropyls) benzene of 1,4- bis- and 1,4- bis-, (2- bromines are different
Propyl) benzene.
25. according to the method described in claim 1, wherein, on the basis of the total amount of the monoolefine and the ring-alkylated styrenes,
The content of the monoolefine is 80~99 weight %；The content of the ring-alkylated styrenes is 1~20 weight %.
26. according to the method for claim 25, wherein using the total amount of the monoolefine and the ring-alkylated styrenes as base
The content of standard, the monoolefine is 90~97 weight %；The content of the ring-alkylated styrenes is 3~10 weight %.
27. according to the method described in any one of claim 1~12,25 and 26, wherein the ring-alkylated styrenes is to first
Base styrene and/or m-methyl styrene；
The monoolefine is isobutene.
28. according to the method described in any one of claim 1~12,25 and 26, wherein in step (1), the contact
It is carried out within the temperature range of -120 DEG C to 20 DEG C.
29. according to the method for claim 28, wherein in step (1), temperature model of the contact at -100 DEG C to 0 DEG C
Enclose interior progress.
30. according to the method for claim 29, wherein in step (1), temperature of the contact at -100 DEG C to -50 DEG C
It is carried out in range.
31. according to the method for claim 30, wherein in step (1), temperature model of the contact at -90 DEG C to -60 DEG C
Enclose interior progress.
32. according to the method described in claim 1, wherein, the halogen simple substance is bromine and/or chlorine element.
33. according to the method for claim 32, wherein the halogen simple substance is bromine.
34. the method according to claim 32 or 33, wherein in step (3), contact the depositing in radical initiator
It is lower progress or it is light-initiated under the conditions of carry out.
35. according to the method for claim 34, wherein the contact carries out in the presence of radical initiators, described
The molar ratio of radical initiator and the halogen contained compound is 0.01~0.5：1.
36. according to the method for claim 35, wherein mole of the radical initiator and the halogen contained compound
Than being 0.02~0.2：1.
37. according to the method described in any one of claim 1,32 and 33, wherein in step (3), the contact is -10
DEG C to carrying out within the temperature range of 80 DEG C, the time of the contact is 0.5~30 minute.
38. according to the method for claim 37, wherein in step (3), temperature range of the contact at 0 DEG C to 60 DEG C
The time of interior progress, the contact is 1~15 minute.
39. according to the method described in claim 1, wherein, on the basis of the total amount of the polymer solvent, first polymerization is molten
The content of agent is 1~60 volume %；The content of second polymer solvent is 40~99 volume %.
40. according to the method for claim 39, wherein on the basis of the total amount of the polymer solvent, first polymerization
The content of solvent is 10~50 volume %；The content of second polymer solvent is 50~90 volume %.
41. according to the method described in any one of claim 1~12,25,26,32,33,39 and 40, wherein described first
Polymer solvent is selected from C1~C10Halogenated alkane；
Second polymer solvent and the displacement solvent are identical or different, each are selected from C3~C10Aliphatic alkane.
42. according to the method for claim 41, wherein second polymer solvent and the displacement solvent each are selected from C5
~C8Aliphatic alkane.
43. according to the method for claim 42, wherein second polymer solvent and the displacement solvent each are selected from just
Pentane, n-hexane and normal heptane.
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