CN106146700B - A kind of preparation method of halogen polymer - Google Patents

A kind of preparation method of halogen polymer Download PDF

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CN106146700B
CN106146700B CN201510195133.3A CN201510195133A CN106146700B CN 106146700 B CN106146700 B CN 106146700B CN 201510195133 A CN201510195133 A CN 201510195133A CN 106146700 B CN106146700 B CN 106146700B
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monoolefine
solution
solvent
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compound
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CN106146700A (en
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邱迎昕
张月红
孟伟娟
周新钦
张雷
龚惠勤
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention discloses 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 halogenated alkane and 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 proton, lewis acid and activator, the activator is selected from 2 compound represented of 1 compound represented of Formulas I and Formulas I.This method can significantly improve polymerization efficiency, reduce the energy consumption needed for polymerization, 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

A kind of preparation method of halogen polymer
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 H+/ lewis acid initiator system, by isobutene and ring-alkylated styrenes by cationic polymerization mode in solution When middle progress combined polymerization, polymerization efficiency is very poor, and rate of polymerization is slow, and needing to carry out reaction for a long time just can make monomer wholly or substantially Conversion completely.Cationic polymerization usually carries out at low temperature, and polymerization time is longer, and the energy expenditure needed for maintenance low temperature is just Higher, prolonged polymerization obviously cannot be satisfied the requirement of large-scale production.Moreover, using H+/ lewis acid initiator system It is generally necessary to which isobutene-p-methylstyrene copolymer of high molecular weight could be prepared under more harsh reaction condition.
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 H+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 contains at least one compound for being capable of providing proton, at least one lewis acid and at least A kind of activator, the activator are 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 is 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 is 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 H of use+/ lewis acid initiator system is gathered Close technique compare, the polymerization efficiency significantly improved can be obtained, so as to higher rate of polymerization realize monomer completely or base This conversion completely, reduces the energy expenditure in polymerization process, and what is be prepared contains monoolefine-alkylstyrene copolymers Glue remove the process of unreacted monomer without undergoing and can be directly used for halogenation.Moreover, with simple H is used+/ Louis The polymerization technique of this acid initiator system is compared, and method using the present invention is polymerize, and can be obtained with higher molecular weight Polymer, especially rubber heavy polymer.In addition, with simple H is used+/ lewis acid initiator system is compared, Even if the method for the present invention is implemented to obtain higher polymerization efficiency if polymerization and prepare to have compared with high score at higher temperatures The polymer of son amount, so as to be effectively reduced the energy expenditure in polymerization process.
According to the method for the present invention, the glue containing monoolefine-alkylstyrene copolymers being prepared is without experience Halogenation can be carried out by removing the process of unreacted monomer, while the method for the present invention is omitted and is prepared using slurry polymerization process Polymer necessary to polymer is redissolved process, effectively simplifies the life of halogenation monoolefine-alkylstyrene copolymers Production. art.
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：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 the condition of the contact makes, by weight, described to contain monoolefine-alkylbenzene second The content of unreacted ring-alkylated styrenes is not higher than 1000ppm, preferably not higher than 500ppm, more in the solution of alkene copolymer Preferably not higher than 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 Enough carry protogenic compound, 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 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 One nitro 1,4-benzoquinone of bromine, 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).
Method in accordance with the invention it is preferred that in Formulas I -1, R1、R2、R3And R4It is asynchronously-H, in Formulas I -2, R5、R6、R7 And R8It is asynchronously-H.It is highly preferred that the activator is selected from tetrachloroquinone (including chloranil and monoethyl quinone), four Cyano benzoquinones (including four cyano 1,4-benzoquinone and four cyano neighbour benzoquinones) and dichlorocyanobenzoquinone (including dichloro dicyano p-benzoquinone With dichloro dicyano neighbour benzoquinones).It is further preferred that the activator is dichlorocyanobenzoquinone (including dichloro dicyano pair Benzoquinones and dichloro dicyano neighbour benzoquinones).
The content of the activator, which is subject to, can obtain satisfactory polymerization effect.Usually, described to be capable of providing The compound of proton and the molar ratio of the activator can be 1: 0.01~5, preferably 1: 0.1~3, more preferably 1: 0.2 ~2.5, further preferably 1: 0.4~2 are still more preferably 1: 0.5~1.8.
According to the method for the present invention, the lewis acid and the compound for being capable of providing proton can be that cation is poly- The conventional selection in conjunction field, is not particularly limited, as long as the lewis acid can be formed with the compound for being capable of providing proton Cationic species cause 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 ,-Br or-I) respectively in halogen group, 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 more preferably applied in combination with lewis acid shown in formula IV.That is, according to the present invention Method, the lewis acid is 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 rate and polymer molecular weight, can be obtained with higher rate of polymerization has higher molecular The polymer of amount.
The lewis acidic content can be the conventional amount used in cationic polymerization field.Usually, described to be capable of providing The compound of proton can be 0.01~1: 1, preferably 0.02~0.5: 1 with the lewis acidic molar ratio, more preferably 0.03~0.3: 1, more preferably 0.03~0.15: 1, further preferably 0.035~0.1: 1.
The compound for being capable of providing proton can be capable of providing proton to be commonly various in cationic polymerization field Compound.Usually, the compound for being capable of providing proton can be H2O and/or Bronsted acid, specific example can wrap It includes but is not limited to：H2O、HCl、HF、HBr、H2SO4、H2CO3、H3PO4And HNO3.Preferably, the chemical combination for being capable of providing proton Object is HCl.
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 30 minutes or more, polymerization efficiency can be further increased, so as in shorter polymerization time obtain have higher Monoolefine-alkylstyrene copolymers of molecular weight.For example, the digestion time can be 30 minutes to 5 hours.More preferably The time on ground, the ageing is 60 minutes or more.Under the premise of guaranteeing to obtain higher polymerization efficiency, from the angle of economy Degree sets out, and the time of the ageing can be for 10 hours hereinafter, preferably 5 hours hereinafter, more preferably 2 hours or less.It is preferred that The time on ground, the ageing is 60 minutes to 120 minutes.
The solvent can be the various liquids that can dissolve the Bronsted acid, the lewis acid and the activator Matter.Usually, the solvent can be selected from alkane, halogenated alkane and aromatic hydrocarbons, be preferably selected from C3~C10Alkane, C1~C10Halogen For alkane and C6~C12Aromatic hydrocarbons.As solvent, the alkane includes aliphatic alkane and alicyclic alkanes, such as C3~C10Alkane Hydrocarbon includes C3~C10Aliphatic alkane and C3~C10Alicyclic alkanes.As solvent, the halogenated alkane includes halogenated fat Fat race alkane and halogenated cyclo alkane, such as C1~C10Halogenated alkane include C1~C10Halogenated aliphatic alkane and C3~C10 Halogenated cyclo alkane.Halogen atom in the halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.The halogen It is preferably C for alkane1~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 10~60 volumes；The content of second polymer solvent can be 20~99 volume %, preferably 40~90 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, it polymerize It can be at -120 DEG C to 20 DEG C, preferably -100 DEG C to 0 DEG C, more preferably -100 DEG C to -40 DEG C, further preferably -90 DEG C to -60 DEG C Within the temperature range of carry out.According to the method for the present invention, polymerization time generally can be 30 minutes or more.It is full in monomer conversion Under conditions of foot requires, from the further angle for shortening polymerization time, polymerization time generally can be 180 minutes hereinafter, Preferably 120 minutes hereinafter, more preferably 60 minutes or less.
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 monoolefine-the alkylstyrene copolymers, and then rubber monoolefine-alkylstyrene copolymers can be obtained.
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 solvent for being unsuitable for halogenation in the solution of copolymer cements out, then to carry out halogenation.
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.It is described to set The specific example for changing solvent can include but is not limited to：Propane, normal butane, iso-butane, pentane, isopentane, neopentane, ring penta Alkane, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl cyclopentane, normal heptane, 2- first Base hexane, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- dimethyl pentanes, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2,5- dimethyl oneself Alkane, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 2- methyl -3- second Base pentane, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 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- trimethyl cyclohexanes, 2,4,4- trimethyls Hexane, 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- ethyl cyclohexanes, just Propyl cyclohexane, 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- trimethyl heptan Alkane, 2,3,5- trimethylheptanes, 2,3,6- trimethylheptanes, 2,4,5- trimethylheptanes, 2,4,6- trimethylheptanes, 2,2,3- Trimethylheptane, 2,2,4- trimethylheptanes, 2,2,5- trimethylheptanes, 2,2,6- trimethylheptanes, 2,3,3- trimethyl heptan Alkane, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 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, n-butyl cyclohexane, isobutyl butylcyclohexane, t-butylcyclohexane and tetramethyl Butylcyclohexane.The displacement solvent is preferably selected from C3~C10Aliphatic alkane, be more preferably selected from C5~C8Aliphatic alkane, Further preferably it is 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 %, more preferably 10~15 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, such as bromine and/or chlorine element.It is highly preferred that the halogen-containing compound is 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 Lower progress.The radical initiator can be it is common it is various can promote monoolefine-alkylstyrene copolymers with it is halogen The radical initiator of plain compound reaction, preferably oleosoluble radical initiators, such as azo type free radical initiator, preferably Selected from azo diisobutyl nitrile, azobisisovaleronitrile and azobisisoheptonitrile.The dosage of the radical initiator is can draw It sends out subject to halogenation.Usually, the weight ratio of the radical initiator and monoolefine-alkylstyrene copolymers can be 0.01~1: 100, preferably 0.05~0.5: 100.The radical initiator preferably provides as a solution, and solvent can be with Combination selected from one or more of the aforementioned alkane for being used as the second polymer solvent, preferably with the second polymer solvent phase Together.When carrying out the contact under the conditions of light-initiated, illumination condition is occurred with that can cause monoolefine-alkylstyrene copolymers Subject to halogenation, such as：Light source can be fluorescent lamp or 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 within the temperature range of -10 DEG C to 80 DEG C, preferably at 0 DEG C to 60 It is carried out within the temperature range of DEG C.The time of the contact can carry out according to the temperature of contact and expected halogenation degree Selection 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 carries out water vapor accumulation and drying, 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 CDC13Make 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 1~32 is used to illustrate the polymerization procedure in the method for the present invention.
Experimental example 1
(1) 0.133g chloranils are dissolved in 66.5g dichloromethane solutions, obtain chloranil's solution.With weight Gauge, in the solution, a concentration of 2000ppm of chloranil.At -80 DEG C, into 60mL goat's horn bottles sequentially be added be cooled in advance - 80 DEG C of 20mL contains that the dichloromethane solution of HCl (a concentration of 0.0038mol/L), that 1.8mL contains ethyl aluminum dichloride is (a concentration of The aforementioned chloranil's solution of hexane solution and 0.5mL 0.9mol/L) is aged 60min at -80 DEG C after mixing, To obtain initiator solution.By weight, in the initiator solution, a concentration of 50ppm of chloranil.
(2) 100mL is cooled to -60 DEG C in advance one is sequentially added in the 500mL glass reactors stirred equipped with strength constant speed Chloromethanes, 80mL are cooled to -80 DEG C of n-hexane in advance, 32mL be cooled in advance -80 DEG C isobutene and 1.3mL room temperature (25 DEG C) to first Base styrene (content is 98 weight %), is uniformly mixed.The initiator solution that into reactor prepared by a dropping step (1).Wherein, The addition of initiator solution is 16mL；Control drop rate makes the temperature in reactor be in -90 DEG C to -85 DEG C of range Within.After being added dropwise to complete, keeps the temperature in reactor to be within the scope of -90 DEG C to -85 DEG C, carried out with stirring Then the methanol solution that 5mL contains 0.5 weight %NaOH is added in the polymerisation of 60min into reaction mixture, poly- to terminate Close reaction.Obtained mixed solution is placed in hot bath and removes solvent, obtained product after washing, in vacuum drying oven in 60 DEG C of dryings are to constant weight, to obtain subject polymer.
The weight of obtained polymer is measured, polymer yield is calculated, and measures the molecular weight and molecular weight point of polymer As a result cloth index is listed in table 1.
Experimental example 2~4
It is polymerize using with 1 identical method of experimental example, unlike, in experimental example 2, initiation that step (1) obtains In agent solution, by weight, a concentration of 100ppm of chloranil, the polymerization reaction time in step (2) is 50min；It is real It tests in example 3, in the initiator solution that step (1) obtains, by weight, a concentration of 300ppm of chloranil, in step (2) Polymerization reaction time be 40min；In experimental example 4, in the initiator solution that step (1) obtains, by weight, chloranil A concentration of 800ppm, the polymerization reaction time in step (2) is 30min.Experimental result is listed in table 1.
Experimental example 5
(1) 0.1596g chloranils are dissolved in the dichloromethane that 206g contains HCl (a concentration of 0.0032mol/L), Then above-mentioned solution is cooled to -80 DEG C in advance, and the pre- 11mL for being cooled to -80 DEG C is added and contains ethyl aluminum dichloride (a concentration of 0.9mol/ L hexane solution) is aged 31min at -80 DEG C, to obtain initiator solution after mixing.Wherein, by weight, In initiator solution, a concentration of 750ppm of tetrachloroquinone.
(2) chlorine that 60mL is cooled to -80 DEG C in advance is sequentially added in the 500mL glass reactors stirred equipped with strength constant speed Methane, 140mL are cooled to -80 DEG C of n-hexane in advance, 25mL be cooled in advance -80 DEG C isobutene and 1.1mL room temperature (25 DEG C) to first Base styrene (content is 98 weight %), is uniformly mixed.The initiator solution that into reactor prepared by a dropping step (1).Wherein, The addition of initiator solution is 20mL, and control drop rate makes the temperature in reactor be in -85 DEG C to -80 DEG C of range Within.After being added dropwise to complete, keeps the temperature in reactor to be within the scope of -85 DEG C to -80 DEG C, carried out with stirring Then the methanol solution that 5mL contains 0.5 weight %NaOH is added in the polymerisation of 50min into reaction mixture, poly- to terminate Close reaction.Obtained mixed solution is placed in hot bath and removes solvent, obtained product after washing, in vacuum drying oven in 60 DEG C of dryings are to constant weight, to obtain subject polymer.
Polymer yield, obtained polymer molecular weight and molecualr weight distribution index listed in table 1.
Experimental example 6~8
It is polymerize using with 5 identical method of experimental example, unlike, in experimental example 6, when ageing in step (1) Between be 65min, the polymerization reaction time in step (2) is 30min；In experimental example 7, the digestion time in step (1) is 15min, the polymerization reaction time in step (2) are 70min；In experimental example 8, the digestion time in step (1) is 100min, step Suddenly the polymerization reaction time in (2) is 30min.Experimental result is listed in table 1.
Experimental example 9
(1) by 0.072g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- are dissolved in 120g and contain HCl (a concentration of 0.0042mol/ L in dichloromethane solution), above-mentioned solution is then cooled to -80 DEG C in advance, and 5.6mL is added is cooled to -80 DEG C in advance and contains dichloro The hexane solution of aluminium ethide (a concentration of 0.9mol/L) is aged 60min at -80 DEG C, to obtain initiator after mixing Solution.By weight, in initiator solution, a concentration of 580ppm of 2,3- bis- chloro- 5,6- dicyano p-benzoquinones.
(2) 100mL is sequentially added in the glass reactor of the 500mL stirred equipped with strength constant speed and is cooled to -80 DEG C in advance Monochloro methane, 100mL are cooled to -80 DEG C of n-hexane in advance, 25mL is cooled to -80 DEG C of isobutene and 1.1mL room temperature (25 DEG C) in advance P-methylstyrene (content is 98 weight %), is uniformly mixed.The initiator solution that into reactor prepared by a dropping step (1). Wherein, the addition of initiator solution is 25mL, and control drop rate makes the temperature in reactor be in -90 DEG C to -85 DEG C Within the scope of.After being added dropwise to complete, the temperature in reactor is kept to be within the scope of -90 DEG C to -85 DEG C, it is adjoint stir into Then the methanol solution that 5mL contains 0.5 weight %NaOH is added in the polymerisation of row 30min into reaction mixture, to terminate Polymerisation.Obtained mixed solution is placed in hot bath and removes solvent, obtained solid after washing, in vacuum drying oven It is dry to constant weight in 60 DEG C, to obtain subject polymer.
Polymer yield, obtained polymer molecular weight and molecualr weight distribution index listed in table 1.
Experimental example 10~11
It is polymerize using with the same procedure of experimental example 9, unlike, the step of experimental example 10 in (2), monochloro methane Dosage be 60mL, the dosage of n-hexane is 140mL；In the step of experimental example 11 (2), the dosage of monochloro methane is 20mL, just The dosage of hexane is 180mL.Experimental result is listed in table 1.
Experimental example 12
It is polymerize using method identical with experimental example 9, unlike, in the initiator solution that step (1) obtains, By weight, a concentration of 300ppm of 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones；In step (2), the dosage of monochloro methane is The dosage of 80mL, n-hexane are 120mL, and the addition of initiator solution is 24mL；After initiator solution is added dropwise to complete, it will react Temperature control in device carries out the polymerization of 50min within the scope of -70 DEG C to -65 DEG C.
Experimental result is listed in table 1.
Experimental example 13
(1) by 0.0532g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- be dissolved in 66.3g and containing HCl it is (a concentration of In dichloromethane 0.0027mol/L), above-mentioned solution is then cooled to -85 DEG C in advance, and 4mL is added is cooled to -85 DEG C in advance and contain The hexane solution of ethyl aluminum dichloride (a concentration of 0.9mol/L) is aged 60min at -85 DEG C, to be drawn after mixing Send out agent solution.Wherein, by weight, in initiator solution, a concentration of 770ppm of 2,3- bis- chloro- 5,6- dicyano p-benzoquinones.
(2) it uses and is polymerize with 9 identical method of experimental example, unlike, initiator solution is 13 step of experimental example (1) initiator solution prepared；The dosage of monochloro methane is 40mL, and the dosage of n-hexane is 160mL；The addition of initiator solution Amount is 15mL, polymerization time 30min.Experimental result is listed in table 1.
Experimental example 14~15
It is polymerize using with 9 identical method of experimental example, unlike, in experimental example 14, when ageing in step (1) Between be 10min, the polymerization reaction time in step (2) is 60min；In experimental example 15, the digestion time in step (1) is 30min, the polymerization reaction time in step (2) are 40min.Experimental result is listed in table 1.
Experimental example 16~17
Polymerize using with 9 identical method of experimental example, unlike, in experimental example 16, in step (1), with etc. weight The four cyano 1,4-benzoquinone of amount replaces 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones, in step (2), polymerization reaction time 60min； In experimental example 17, in step (1), with etc. the tetrahydrochysene 1,4-benzoquinone of weight replace 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones；Step (2) in, polymerization reaction time 30min.Experimental result is listed in table 1.
Experimental comparison's example 1
It is polymerize using with 9 identical method of experimental example, unlike, do not use 2,3-, bis- chloro- 5,6- dicyanos pair Benzoquinones.Experimental result is listed in table 1.
Experimental example 18
(1) by 0.0652g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- be dissolved in 80g and containing HCl it is (a concentration of In dichloromethane 0.003mol/L), obtained solution is cooled to -85 DEG C in advance, it is dense that 2.8mL is then sequentially added into the solution Degree is the diethyl aluminum chloride of the hexane solution and a concentration of 0.9mol/L of 1.2mL of the ethyl aluminum dichloride (EADC) of 0.9mol/L (DEAC) toluene solution (molar ratio of EADC and DEAC are 7/3), after mixing, -85 is placed in by obtained mixed liquor DEG C cryostat in be aged 60min.Wherein, by weight, in initiator solution 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones content For 800ppm.
(2) 200mL two mouth flasks are placed in temperature control in -80 DEG C to -85 DEG C of low temperature cryostat, to be burnt successively to two mouthfuls N-hexane/monochloro methane mixed solution (wherein, volume ratio of n-hexane/monochloro methane that 85mL is cooled to -85 DEG C is added in bottle For 9/1), 15mL be cooled to -85 DEG C isobutene and 0.62mL room temperature (25 DEG C) p-methylstyrene, be uniformly mixed, obtain Monomer solution.Initiator solution prepared by 10mL steps (1) is added into monomer solution, stands reaction 40min after mixing, It is within the scope of -85 DEG C to -80 DEG C that control cryostat temperature in initiator solution and reaction process, which is added dropwise,.After reaction The methanol solution that 5mL contains 0.5 weight %NaOH is added into reaction mixture, to terminate polymerisation.Then it will mix molten Liquid, which is placed in hot bath, removes solvent, dry to constant weight in 60 DEG C in vacuum drying oven after obtained solid is washed, and obtains To subject polymer.
The weight of obtained polymer is measured, polymer yield is calculated, and measures the molecular weight and molecular weight point of polymer As a result cloth index is listed in table 2.
Experimental example 19
It is polymerize using with 18 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC Constant, it is 5/5 to make the molar ratio of EADC and DEAC.Experimental result result is listed in table 2.
Experimental comparison's example 2
Initiator solution and it is polymerize using being prepared with 19 identical method of experimental example, unlike, in step (1) not Use 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones.Experimental result result is listed in table 2.
Experimental example 20
It is polymerize using with 19 identical method of experimental example, unlike, in step (1), the time of ageing is 30min；In step (2), polymerization reaction time 50min.Experimental result is listed in table 2.
Experimental example 21
It is polymerize using with 19 identical method of experimental example, unlike, in step (1), the time of ageing is 15min；In step (2), polymerization reaction time 60min.Experimental result is listed in table 2.
Experimental example 22
It is polymerize using with 18 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC Constant, it is 3/7 to make the molar ratio of EADC and DEAC；In step (2), polymerization reaction time 60min.Experimental result is in table 2 In list.
Experimental example 23
It is polymerize using with 18 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC Constant, it is 1/9 to make the molar ratio of EADC and DEAC；In step (2), polymerization reaction time 140min.Experimental result is in table 2 In list.
Experimental example 24
It is polymerize using with 23 identical method of experimental example, unlike, in step (2), n-hexane and monochloro methane Total amount it is constant, make the volume ratio of n-hexane and monochloro methane be 8/2, polymerization reaction time 100min.
Experimental result is listed in table 2.
Experimental example 25
It is polymerize using with 23 identical method of experimental example, unlike, in step (2), n-hexane and monochloro methane Total amount it is constant, make the volume ratio of n-hexane and monochloro methane be 7/3, polymerization reaction time 80min.Experimental result is in table 2 In list.
Experimental example 26
It is polymerize using with 23 identical method of experimental example, unlike, in step (2), n-hexane and monochloro methane Total amount it is constant, make the volume ratio of n-hexane and monochloro methane be 6/4, polymerization reaction time 60min.Experimental result is in table 2 In list.
Experimental example 27
It is polymerize using with 23 same procedure of experimental example, unlike, in step (2), n-hexane and monochloro methane Total amount is constant, and it is 5/5 to make the volume ratio of n-hexane and monochloro methane, polymerization reaction time 60min.Experimental result is in table 2 It lists.
Experimental example 28
It is polymerize using with 19 identical method of experimental example, unlike, in step (1)；By 0.0651g tetrachloro-p-phenylenes Quinone be dissolved in 80g and containing HCl (a concentration of 0.0042mol/L) dichloromethane solution in, obtained solution is cooled to -85 in advance DEG C, hexane solution and the 1.1mL that the EADC of a concentration of 0.9mol/L of 2.8mL is then sequentially added into the solution are a concentration of The n-heptane solution (EADC/DEAC molar ratios are 7/3) of the DEAC of 1.0mol/L, after mixing, the mixed liquor that will be obtained It is placed in -85 DEG C of ageing 60min.Wherein, by weight, the content of chloranil is 800ppm in initiator solution；Step (2), the total amount of n-hexane and monochloro methane is constant, and it is 6/4 to make the volume ratio of n-hexane and monochloro methane.Experimental result is in table 2 In list.
Experimental example 29
It is polymerize using with 28 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC Constant, it is 5/5 to make the molar ratio of EADC/DEAC.Experimental result is listed in table 2.
Experimental example 30
It is polymerize using with 28 identical method of experimental example, unlike, in step (1), the total amount of EADC and DEAC Constant, it is 3/7 to make the molar ratio of EADC/DEAC.Experimental result is listed in table 2.
Experimental example 31
It is polymerize using with 29 identical method of experimental example, unlike, in step (2), n-hexane and monochloro methane Total amount it is constant, make the volume ratio of n-hexane and monochloro methane be 9/1.Experimental result is listed in table 2.
Experimental example 32
It is polymerize using with 29 identical method of experimental example, unlike, in step (2), n-hexane and monochloro methane Total amount it is constant, make the volume ratio of n-hexane and monochloro methane be 8/2.Experimental result is listed in table 2.
Experimental comparison's example 3
It is polymerize using with 28 identical method of experimental example, unlike, chloranil is not used in step (1). Experimental result is listed in table 2.
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 H of use+/ lewis acid initiator system is compared, and can enable polymer yield within the shorter time Reach 100%, the content of unreacted ring-alkylated styrenes can reach in the monoolefine-alkylstyrene copolymers being prepared 200ppm (by weight) is hereinafter, can directly to carry out halogenation anti-without undergoing the step of detaching unreacted ring-alkylated styrenes It answers.On the contrary, the polymerization efficiency of Experimental comparison's example 1~3 is poor, and it is identical in remaining condition, with identical polymerization time Polymer yield can not be made to reach 99% or more, and then unreacted alkyl in the monoolefine-alkylstyrene copolymers prepared The content of styrene 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) by 0.128g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- be dissolved in 160g and containing HCl it is (a concentration of In dichloromethane 0.0054mol/L), obtained solution is cooled to -85 DEG C in advance, it is a concentration of that 8mL is then added into the solution Obtained mixed liquor is placed in -85 DEG C of cryostat and is aged after mixing by the ethyl aluminum dichloride hexane solution of 0.9mol/L 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 drop rate make the temperature in reactor be in -90 DEG C to - Within the scope of 85 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be within the scope of -90 DEG C to -85 DEG C, and carry out 100g is then added into reaction mixture and contains 3 weight % tri- for the polymerisation (polymer yield reaches 100%) of 60min The dichloromethane solution of glycol obtains the polymer solution containing monoolefine-alkylstyrene copolymers to terminate polymerisation (weight content of unreacted p-methylstyrene is 200ppm or less in the polymer solution), monoolefine-alkyl of preparation The content of the molecular weight of styrol copolymer, molecular weight distributing index and the structural unit formed by p-methylstyrene is in table It is listed in 3.
(3) polymer solution that step (2) obtains is pressed into nitrogen in the solvent displacer vacuumized, from solvent The bottom of displacer is passed through 70 DEG C of n-hexane steam, and control operating pressure is 90kPa (absolute pressure), and being passed through for n-hexane steam is held The continuous time is 150min, to which (wherein, the content of monoolefine-alkylstyrene copolymers is 13.2 weights to solution after replace Measure %).
(4) referring to Fig.1 shown in mode, solution after displacement that step (3) 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.
(5) obtained mixture water vapour removing solvent will be neutralized and be condensed, obtained aqueous bromination glue is being opened In 110 DEG C of dry 10min in mill, to obtain bromination monoolefine-alkylstyrene copolymers, bromine content arranges in table 3 Go out.
Embodiment 2
Bromination monoolefine-alkylstyrene copolymers are prepared using method same as Example 1, difference is as follows：
In step (2), the dosage using n-hexane is 800mL, and the dosage of monochloro methane is 200mL, to be contained Polymer solution (the weight of unreacted p-methylstyrene in the polymer solution of monoolefine-alkylstyrene copolymers Content is 200ppm or less)；
In step (3), the duration that is passed through of n-hexane steam is 120min, monoolefine-in solution after obtained displacement The content of alkylstyrene copolymers is 12.6 weight %；
Step (4) is carried out using mode shown in Fig. 2：Solution nitrogen indentation mixing after the displacement that step (3) is obtained In device, 1min is mixed with 4g bromines, then mixture is sent into tablet photohalogenation reactor, opens light source (power 200W) It irradiates 2min and carries out photohalogenation reaction.Then, obtained bromination glue is sent into neutralization reactor, and into neutralization reactor It is sent into the neutralization that the aqueous solution that 90g contains 2 weight %NaOH carries out 20min.
Experiment is listed in table 3.
Embodiment 3
Bromination monoolefine-alkylstyrene copolymers are prepared using method same as Example 1, difference is as follows：
In step (1), 0.163g chloranils are dissolved in 200g and contain the two of HCl (a concentration of 0.0052mol/L) In chloromethanes, obtained solution is cooled to -85 DEG C in advance, the two of a concentration of 0.9mol/L of 10mL are then sequentially added into the solution Obtained mixed liquor is placed in -85 DEG C of cryostat after mixing and is aged 80min by chloroethyl aluminium (EADC) hexane solution, To obtain initiator solution；In the polymer solution containing monoolefine-alkylstyrene copolymers that step (2) obtains, not The weight content of the p-methylstyrene of reaction is 200ppm or less.
In step (3), the content of monoolefine-alkylstyrene copolymers is 12.4 weights in solution after obtained displacement Measure %；
In step (4), the dosage of bromine is 4.2g.Experimental result is listed in table 3.
Embodiment 4
(1) by 0.152g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- be dissolved in 200g and containing HCl it is (a concentration of 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 diethyl aluminum chloride n-heptane solution of a concentration of 1.0mol/L of ethyl aluminum dichloride hexane solution and 6mL of 0.9mol/L (molar ratio of EADC/DEAC is 4.7/5.3), after mixing, obtained mixed liquor is placed in -85 DEG C of cryostat and is aged 80min, 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 drop rate makes the temperature in reactor be in -90 DEG C to -85 Within the scope of DEG C.After being added dropwise to complete, the temperature in reactor is kept to be within the scope of -90 DEG C to -85 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, the polymer solution (unreacted in the polymer solution containing monoolefine-alkylstyrene copolymers is obtained P-methylstyrene weight content be 200ppm or less).The molecular weight of monoolefine-alkylstyrene copolymers of preparation, The content of molecular weight distributing index and the structural unit formed by p-methylstyrene is listed in table 3.
(3) polymer solution that step (2) obtains is pressed into nitrogen in the solvent displacer vacuumized, from solvent The bottom of displacer is passed through 80 DEG C of n-hexane steam, and control operating pressure is 95kPa (absolute pressure), and being passed through for n-hexane steam is held The continuous time is 150min, to which (wherein, the content of monoolefine-alkylstyrene copolymers is 12.8 weights to solution after replace Measure %).
(4) referring to Fig.1 shown in mode, solution after displacement that step (3) 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.
(5) obtained mixture water vapour removing solvent will be neutralized and be condensed, obtained aqueous bromination glue is being opened In 110 DEG C of dry 10min in mill, to obtain bromination monoolefine-alkylstyrene copolymers, bromine content arranges in table 3 Go out.
Table 3
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 (46)

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 the condition of the contact makes, by weight, described to contain monoolefine-alkylbenzene second The content of unreacted ring-alkylated styrenes is not higher than 1000ppm in the solution of alkene copolymer；
The initiator system contains at least one compound for being capable of providing proton, at least one lewis acid and at least one Activator, the activator are 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 one in-CN Kind, X1And X2One kind respectively in halogen group；
The compound for being capable of providing proton and the molar ratio of the activator are 1：0.01~5, it is described to be capable of providing proton Compound and the lewis acidic molar ratio be 0.01~1：1；
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 compound for being capable of providing proton is H2O and/or Bronsted acid；
The monoolefine is 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 is 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, mole of the compound for being capable of providing proton and the activator Than being 1：0.1~3.
3. according to the method described in claim 2, wherein, mole of the compound for being capable of providing proton and the activator Than being 1：0.2~2.5.
4. according to the method described in claim 3, wherein, mole of the compound for being capable of providing proton and the activator Than being 1：0.4~2.
5. according to the method described in claim 1, wherein, the compound for being capable of providing proton lewis acidic is rubbed with described You are than being 0.02~0.5：1.
6. according to the method described in claim 5, wherein, the compound for being capable of providing proton lewis acidic is rubbed with described You are than being 0.03~0.3：1.
7. according to the method described in claim 6, wherein, the compound for being capable of providing proton lewis acidic is rubbed with described You are than being 0.03~0.15：1.
8. according to the method described in claim 7, wherein, the compound for being capable of providing proton lewis acidic is rubbed with described You are than being 0.035~0.1：1.
9. the method according to any one of claim 1~8, wherein the activator is selected from tetrahydrochysene benzoquinones, tetrachlorobenzene Quinone, four cyano benzoquinones and dichlorocyanobenzoquinone.
10. the method according to any one of claim 1~8, wherein in Formulas I -1, R1、R2、R3And R4Be asynchronously- H, in Formulas I -2, R5、R6、R7And R8It is asynchronously-H.
11. according to the method described in claim 10, wherein, the activator is selected from tetrachloroquinone, four cyano benzoquinones and dichloro Dicyano benzoquinone.
12. according to the method described in claim 1, wherein, in formula IV, X31And X32Respectively-Cl.
13. according to the method described in claim 1, wherein, in formula IV, R12For ethyl.
14. according to the method described in claim 1, wherein, in Formula V, X4For-Cl.
15. according to the method described in claim 1, wherein, R13And R14Respectively ethyl.
16. according to the method described in any one of claim 1 and 12~15, wherein the lewis acid is shown in formula IV Lewis acid and Formula V shown in lewis acid, in the lewis acid, the lewis acid of 10~90 moles of % is shown in Formula V Lewis acid.
17. according to the method for claim 16, wherein in the lewis acid, the lewis acid of 30~70 moles of % is Lewis acid shown in Formula V.
18. according to the method described in any one of claim 1~8 and 12~15, wherein the change for being capable of providing proton Conjunction object is HCl.
19. according to the method described in claim 1, wherein, in step (1), temperature model of the contact at -120 DEG C to 20 DEG C Enclose interior progress.
20. according to the method for claim 19, wherein in step (1), temperature model of the contact at -100 DEG C to 0 DEG C Enclose interior progress.
21. according to the method for claim 20, wherein in step (1), temperature of the contact at -100 DEG C to -40 DEG C It is carried out in range.
22. according to the method for claim 21, wherein in step (1), temperature model of the contact at -90 DEG C to -60 DEG C Enclose interior progress.
23. according to the method described in any one of claim 1~8 and 12~15, wherein, will be at least one in step (1) The method that monoolefine and at least one ring-alkylated styrenes are contacted with each component in the initiator system includes：By the initiation Each component in agent system is dissolved in solvent, and obtained mixture is aged, and obtains initiator solution；By the initiator Solution is mixed with the monoolefine and the ring-alkylated styrenes being dissolved in polymer solvent.
24. according to the method for claim 23, wherein the time of the ageing is 10 minutes to 10 hours.
25. according to the method for claim 24, wherein the time of the ageing is 30 minutes to 5 hours.
26. according to the method for claim 25, wherein the time of the statement is 60 minutes to 120 minutes.
27. according to the method for claim 23, wherein the ageing carries out within the temperature range of -100 DEG C to 20 DEG C.
28. according to the method for claim 27, wherein the ageing carries out within the temperature range of -100 DEG C to 0 DEG C.
29. according to the method for claim 28, wherein the ageing carries out within the temperature range of -100 DEG C to -50 DEG C.
30. according to the method for claim 29, wherein the ageing carries out within the temperature range of -90 DEG C to -70 DEG C.
31. 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 %.
32. according to the method for claim 31, 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 %.
33. according to the method described in any one of claim 1~8,12~15,31 and 32, wherein the ring-alkylated styrenes For p-methylstyrene and/or m-methyl styrene；
The monoolefine is isobutene.
34. according to the method described in claim 1, wherein, the halogen simple substance is bromine and/or chlorine element.
35. according to the method for claim 34, wherein the halogen simple substance is bromine.
36. the method according to claim 34 or 35, wherein in step (3), the contact exists in radical initiator Lower progress carries out under the conditions of light-initiated.
37. according to the method for claim 36, wherein the contact carries out in the presence of radical initiators, described The weight ratio of radical initiator and monoolefine-alkylstyrene copolymers is 0.01~1：100.
38. according to the method for claim 37, wherein the radical initiator and monoolefine-alkylstyrene The weight ratio of object is 0.05~0.5：100.
39. according to the method described in any one of claim 1,34 and 35, wherein in step (3), the contact is -10 DEG C to carrying out at a temperature of 80 DEG C, the time of the contact is 0.5~30 minute.
40. according to the method for claim 39, wherein in step (3), it is described contact at a temperature of 0 DEG C to 60 DEG C into Row.
41. according to the method for claim 39, wherein in step (3), the time of the contact is 1~15 minute.
42. according to the method described in any one of claim 1~8,12~15,31,32,34 and 35, wherein with described poly- On the basis of the total amount of bonding solvent, the content of first polymer solvent is 1~80 volume %；The content of second polymer solvent For 20~99 volume %.
43. according to the method for claim 42, wherein on the basis of the total amount of the polymer solvent, first polymerization The content of solvent is 10~60 volume %；The content of second polymer solvent is 40~90 volume %.
44. according to the method described in any one of claim 1~8,12~15,31,32,34 and 35, 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.
45. according to the method for claim 44, wherein second polymer solvent and the displacement solvent each are selected from C5 ~C8Aliphatic alkane.
46. according to the method for claim 45, wherein second polymer solvent and the displacement solvent each are selected from just Pentane, n-hexane and normal heptane.
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