CN106146698B - A kind of preparation method of halogen polymer - Google Patents

Abstract

The invention discloses a kind of preparation methods of halogenation monoolefine conjugated diene copolymer, it is included under the conditions of cationic polymerization, monoolefine shown in Formula II and formula III conjugated diene are contacted with each component in initiator system in alkane, it removes in the obtained solution containing monoolefine conjugated diene copolymer after unreacted monoolefine and conjugated diene, it is contacted with halogen-containing compound, carry 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, obtain higher polymer yield；The polymer with higher molecular weight can also be obtained.This method is omitted to replace using solvent necessary to slurry polymerization process is redissolved process with polymer, simplifies 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-conjugation two The preparation method of olefin 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.

Compared with slurry polymerization process, polymerisation in solution rule is in these areas without apparent advantage, especially polymerisation in solution Molecular weight product that method obtains is low, processing performance is poor, therefore is difficult that the product that is obtained with slurry polymerization process is mutually competing on the market It strives.But the development space of solution polymerization process is than broader, such as：Solution polymerization process is than slurry polymerization process more meets environmental protection It asks, and broader to the accommodation of polymerization temperature, especially to realizing that high temperature polymerization aspect has better development prospect. In addition, prepared by halogenated butyl rubber generally use solwution method, that is, by the butyl rubber being dissolved in alkane and halogen-containingization It closes object contact and carries out halogenation, when preparing butyl rubber using slurry polymerization process, need in polymerization procedure and halogenation The solvent for the halogenated alkane that setting is intended in the mixture obtained with alkane displacement slurry polymerization process between reaction step replaces step Rapid and polymer is redissolved step, and in solution polymerization process, if being not necessarily to the solvent as polymer solvent using alkane Displacement step and polymer are redissolved step, it is clear that production of the solution polymerization process more suitable for solwution method halogenated butyl rubber.

However, for producing butyl rubber in the solution, main problems faced is that the efficiency of initiation of initiator system is low, Cause polymerization efficiency poor, it is difficult 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., upper It states in dialkylaluminum halides/monoalkyl dihalide aluminium mixed system and introduces micro water or aikyiaiurnirsoxan beta, keep initiator system active It improves, 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.

Therefore, for the cationic solution polymerization technique of butyl rubber, there is an urgent need for the height that exploitation is adapted to polymerisation in solution Active initiator system obtains the product of high molecular weight to improve efficiency of initiation and polymerization efficiency.

Invention content

The purpose of the present invention is to provide a kind of preparation method of halogenation monoolefine-conjugated diene copolymer, this method Monoolefine-conjugated diene copolymer is prepared using solution polymerization process, can be prepared with higher polymerization efficiency has higher molecular Monoolefine-conjugated diene copolymer of amount.

The present invention provides a kind of preparation methods of halogenation monoolefine-conjugated diene copolymer, and this method includes following Step：

(1) under the conditions of cationic polymerization, at least one polymer solvent, by least one monoolefine and at least one Conjugated diene is contacted with each component in initiator system, obtains the solution containing monoolefine-conjugated diene copolymer, institute It states polymer solvent and is selected from alkane；

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 conjugated diene is selected from formula III compound represented,

In formula III, R₁₁、R₁₂And R₁₃Respectively hydrogen or C₁~C₅Linear or branched alkyl group；

(2) unreacted monomer in the solution containing monoolefine-conjugated diene copolymer is removed, it is single to obtain removing Solution after body；

(3) solution after the removing monomer is contacted with halogen-containing compound, so that the monoolefine-conjugated diene Part hydrogen atom in copolymer molecule chain is substituted with halogen atoms.

Method using the present invention prepares monoolefine-conjugated diene copolymer, with the simple H of use⁺/ lewis acid draws Hair agent system is compared, and one side efficiency of initiation significantly improves, so as to obtain higher polymerization produce with higher rate of polymerization Rate；On the other hand the polymer with higher molecular weight, especially rubber heavy polymer can also be obtained.In addition, with Using simple H⁺/ lewis acid initiator system is compared, and method of the invention can be implemented to polymerize at higher temperatures, to The energy expenditure that can be effectively reduced in polymerization process.

According to the method for the present invention, after the unreacted monomer of solution removal polymerizeing, it is not necessarily to slurry polymerization legal system Solvent necessary to standby polymer is replaced and polymer redissolution process can be sent into halogenation step and carry out halogenation, is had Simplify to effect the production technology of halogenation monoolefine-conjugated diene copolymer.

Description of the drawings

Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.

Fig. 1 is used to illustrate a kind of preferred embodiment according to the method for the present invention.

Reference sign

1：Monoolefine 2 shown in Formula II：Conjugated diene shown in formula III

3：Polymer solvent 4：Initiator solution

5：Terminator 6：Solution containing monoolefine-conjugated diene copolymer

7：Polymer solvent steam 8：Unreacted monomer and polymer solvent steam

9：Solution 10 after removing monomer：Halogen-containing compound

11：The aqueous solution 12 of alkaline matter：Solution containing halogenation monoolefine-conjugated diene copolymer

I：Polymer reactor II：Monomer removal device

III：Halogenation reactor

Specific implementation mode

The present invention provides a kind of preparation methods of halogenation monoolefine-conjugated diene copolymer, and this method includes following Step：

(1) under the conditions of cationic polymerization, at least one polymer solvent, by least one monoolefine and at least one Conjugated diene is contacted with each component in initiator system, obtains the solution containing monoolefine-conjugated diene copolymer, institute It states polymer solvent and is selected from alkane；

(2) unreacted monomer in the solution containing monoolefine-conjugated diene copolymer is removed, it is single to obtain removing Solution after body；

(3) solution after the removing monomer is contacted with halogen-containing compound, so that the monoolefine-conjugated diene Part hydrogen atom in copolymer molecule chain is substituted with halogen atoms.

In the present invention, " optionally " expression includes or does not include, and "at least one" indicates one or more kinds of.

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 is 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-os 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 bis- fluoro- 5,6- dinitros 1,4-benzoquinone of 2,3-, 2,5- Two fluoro- 3,6- dinitros 1,4-benzoquinone, bis- fluoro- 3,5- dinitros 1,4-benzoquinone of 2,6-), difluoro dinitro o benzoquinones (including 3,4- bis- Fluoro- 5,6- dinitro os benzoquinones, bis- fluoro- 4,6- dinitro os benzoquinones of 3,5-, bis- fluoro- 4,5- dinitro os benzoquinones of 3,6-), 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 bis- chloro- 5,6- dinitros 1,4-benzoquinone of 2,3-, bis- chloro- 3,6- dinitros 1,4-benzoquinone of 2,5-, bis- chloro- 3,5- bis- of 2,6- Nitro 1,4-benzoquinone), dichloro dinitro o benzoquinones (including bis- chloro- 5,6- dinitro os benzoquinones of 3,4-, bis- chloro- 4,6- dinitros of 3,5- Base neighbour benzoquinones, bis- chloro- 4,5- dinitro os benzoquinones of 3,6-), 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 bis- bromo- 5,6- dinitros 1,4-benzoquinone of 2,3-, 2, Bis- bromo- 3,6- dinitros 1,4-benzoquinone of 5-, bis- bromo- 3,5- dinitros 1,4-benzoquinone of 2,6-), dibromo dinitro o benzoquinones (including 3,4- Two bromo- 5,6- dinitro os benzoquinones, bis- bromo- 4,6- dinitro os benzoquinones of 3,5-, bis- bromo- 4,5- dinitro os benzoquinones of 3,6-), 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 bis- fluoro- 5,6- dicyano p-benzoquinones of 2,3-, bis- fluoro- 3,6- bis- of 2,5- Cyano 1,4-benzoquinone, bis- fluoro- 3,5- dicyano p-benzoquinones of 2,6-), difluoro dicyano neighbour benzoquinones (including bis- fluoro- 5,6- dicyan of 3,4- Base neighbour benzoquinones, bis- fluoro- 4,6- dicyanos neighbour benzoquinones of 3,5-, bis- fluoro- 4,5- dicyanos neighbour benzoquinones of 3,6-), 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-, bis- chloro- 3,6- dicyano p-benzoquinones of 2,5-, bis- chloro- 3,5- dicyano p-benzoquinones of 2,6-), Dichloro dicyano neighbour benzoquinones (including bis- chloro- 5,6- dicyanos neighbour benzoquinones of 3,4-, bis- chloro- 4,6- dicyanos neighbour benzoquinones of 3,5-, 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 bis- bromo- 5,6- dicyano p-benzoquinones of 2,3-, bis- bromo- 3,6- bis- of 2,5- Cyano 1,4-benzoquinone, bis- bromo- 3,5- dicyano p-benzoquinones of 2,6-), dibromo dicyano neighbour benzoquinones (including bis- bromo- 5,6- dicyan of 3,4- Base neighbour benzoquinones, bis- bromo- 4,6- dicyanos neighbour benzoquinones of 3,5-, bis- bromo- 4,5- dicyanos neighbour benzoquinones of 3,6-), 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- dinitro -5,6- dicyano p-benzoquinones, 2,5- dinitro -3,6- dicyano p-benzoquinones, 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 neighbours 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 bis- fluoro- 5,6- dimethyl chlorides base 1,4-benzoquinone of 2,3-, bis- fluoro- 3,6- dimethyl chlorides bases of 2,5- 1,4-benzoquinone, bis- fluoro- 3,5- dimethyl chlorides base 1,4-benzoquinone of 2,6-), difluoro dimethyl chloride base neighbour benzoquinones (including bis- fluoro- 5,6- of 3,4- Dimethyl chloride base neighbour benzoquinones, bis- fluoro- 4,6- dimethyl chlorides base neighbour benzoquinones of 3,5-, bis- fluoro- 4,5- dimethyl chlorides base neighbour's benzene of 3,6- 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 bis- chloro- 5,6- dimethyl chlorides base 1,4-benzoquinone of 2,3-, 2,5- bis- chloro- 3, 6- dimethyl chloride bases 1,4-benzoquinone, bis- chloro- 3,5- dimethyl chlorides base 1,4-benzoquinone of 2,6-), dichloro dimethyl chloride base neighbour benzoquinones (including 3, Bis- chloro- 5,6- dimethyl chlorides base neighbour benzoquinones of 4-, bis- chloro- 4,6- dimethyl chlorides base neighbour benzoquinones of 3,5-, bis- chloro- 4,5- of 3,6-, 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 bis- bromo- 5,6- dimethyl chlorides base 1,4-benzoquinone of 2,3-, 2, Bis- bromo- 3,6- dimethyl chlorides base 1,4-benzoquinone of 5-, bis- bromo- 3,5- dimethyl chlorides base 1,4-benzoquinone of 2,6-), dibromo dimethyl chloride base neighbour's benzene Quinone (including bis- bromo- 5,6- dimethyl chlorides base neighbour benzoquinones of 3,4-, bis- bromo- 4,6- dimethyl chlorides base neighbour benzoquinones of 3,5-, 3,6- bis- are bromo- 4,5- dimethyl chloride base neighbours benzoquinones), one formyl chloro 1,4-benzoquinone of tribromo, one formyl chloro neighbour benzoquinones of tribromo, tetramethyl acid chloride group pair Benzoquinones and tetramethyl acid chloride group neighbour's benzoquinones.

The activator be preferably selected from tetrahydrochysene benzoquinones (including tetrahydrochysene 1,4-benzoquinone and tetrahydrochysene neighbour benzoquinones), tetrachloroquinone (including Chloranil and monoethyl quinone), four cyano benzoquinones (including four cyano 1,4-benzoquinone and four cyano neighbour benzoquinones) and dichloro dicyan Base benzoquinones (including dichloro dicyano p-benzoquinone and dichloro dicyano neighbour benzoquinones).

The 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 1：0.01~3, preferably 1：0.1~2.5, more preferably 1： 0.2~2, further preferably 1：0.5~1.8, it is still more preferably 1：0.7~1.5.

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 IV¹⁷ ₃Al,

In formula IV, X³¹And X³²One kind (such as-F ,-Cl ,-Br or-I) respectively in halogen group, preferably-Cl；R₁₄For 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；R₁₅And R₁₆Respectively C₁ ~C₈Linear or branched alkyl group, preferably C₁~C₅Linear or branched alkyl group, more preferably ethyl.

In Formula V, R₁₅And R₁₆It may be the same or different, it is preferably identical.

R¹⁷ ₃In Al, three R¹⁷Can be respectively C₁~C₈Linear or branched alkyl group, preferably C₁~C₅Straight chain or branch Alkyl group.R¹⁷ ₃In Al, three R¹⁷Can 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, R¹⁷ 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 %, such energy It is enough that good balance is obtained between polymerization rate and polymer molecular weight, can be obtained with higher polymerization speed have compared with The polymer of high molecular weight.It is highly preferred that on the basis of lewis acidic total amount, lewis acidic content shown in Formula V is 20 ~80 moles of %.It is further preferred that on the basis of lewis acidic total amount, lewis acidic content shown in Formula V is 30~ 70 moles of %.

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 with the lewis acidic molar ratio：1, preferably 0.02~0.5：1, more preferably 0.03~0.3：1, further preferably 0.05~0.15：1.

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、H₂CO_3、H₃PO₄And HNO₃.Preferably, the chemical combination for being capable of providing proton Object is HCl.

May be used common various methods by the monoolefine and conjugated diene with it is each in the initiator system Component contacts, and to be polymerize, forms monoolefine-conjugated diene copolymer.

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 conjugated diene 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 to 10 hours.Preferably, the time of the ageing is 30 minutes or more, Such as 30 minutes to 5 hours.It is highly preferred that the time of the ageing is 60 minutes or more, such as 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 include C₃~C₁₀ Aliphatic alkane and C₃~C₁₀Alicyclic alkanes.

As solvent, the halogenated alkane includes halogenated aliphatic alkane and halogenated cyclo alkane, such as C₁~C₁₀Halogen Include C for alkane₁~C₁₀Halogenated aliphatic alkane and C₃~C₁₀Halogenated cyclo alkane.Halogen in the halogenated alkane Atom can be chlorine, bromine or fluorine, preferably chlorine or fluorine.The halogenated alkane is preferably C₁~C₄Halogenated aliphatic alkane.

The specific example of the solvent can include but is not limited to：Propane, normal butane, iso-butane, pentane, isopentane, Neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl cyclopentane, Normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- dimethyl Pentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2, 5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 2- Methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4- bis- Methyl heptane, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- trimethyls Hexane, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyl cyclohexanes, 2,4, 4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- methyl -4- Ethyl hexane, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- ethyls Hexamethylene, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane (include the various isomers of trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 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- trimethyls 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- diethylpentanes, 1,2- diethyl cyclohexanes, 1,3- diethyl cyclohexanes, 1,4- diethyl cyclohexanes, 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-rings hexane, 1,2,4,5- tetramethyl-rings hexane, 1,2,3,5- tetramethyl-rings hexane), 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 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.

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 conjugated diene refers to the compound containing conjugated double bond in molecular structure.It is excellent Selection of land, the conjugated diene are selected from conjugated diene shown in formula III,

In formula III, R₁₁、R₁₂And R₁₃It is identical or different, respectively hydrogen or C₁~C₅Linear or branched alkyl group.

The specific example of the conjugated diene can include but is not limited to isobutene and isoprene.It is highly preferred that institute It is isoprene to state conjugated diene.

According to the method for the present invention, the relative usage of the monoolefine and the conjugated diene 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 conjugated diene The content of benchmark, the monoolefine can be 80~99.5 weight %, preferably 90~98 weight %；The conjugated diene Content can be 0.5~20 weight %, preferably 2~10 weight %.

According to the method for the present invention, the polymer solvent is selected from alkane.As polymer solvent, the alkane can be fat Race's alkane and/or alicyclic alkanes are such as selected from C₃~C₁₀Aliphatic alkane and C₃~C₁₀Alicyclic alkanes.The aliphatic Alkane is preferably C₃~C₈Aliphatic alkane, more preferably C₅~C₈Aliphatic alkane.The alicyclic alkanes are preferably C₅ ~C₁₀Alicyclic alkanes.

In the present invention, the specific example of the polymer solvent can include but is not limited to：Propane, normal butane, iso-butane, just 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 pentanes, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- bis- Methyl hexane, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- tri- Methylpentane, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl Heptane, 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- tri- Methyl 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 cyclohexane, 1,3- diethyl cyclohexanes, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene Alkane, t-butylcyclohexane and tetramethyl-ring hexane.

The polymer solvent is preferably selected from C₃~C₁₀Aliphatic alkane, be more preferably selected from C₅~C₈Aliphatic alkane, into One step is preferably selected from pentane, isopentane, n-hexane, hexamethylene, normal heptane and isooctane.

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.Monoolefine and altogether Yoke alkadienes and the contact of each component in initiator system can -120 DEG C to 20 DEG C, preferably -100 DEG C to 0 DEG C, it is more excellent It is carried out within the temperature range of selecting -100 DEG C to -40 DEG C, further preferably -90 DEG C to -60 DEG C.According to the method for the present invention, described The duration of contact can be the conventional selection of this field, generally can be 10~180 minutes, preferably 30~120 minutes.

According to the method for the present invention, in a kind of preferred embodiment of step (1), the activator is four cyano benzene Quinone (including four cyano 1,4-benzoquinone and four cyano neighbour benzoquinones) and/or dichlorocyanobenzoquinone (including dichloro dicyano p-benzoquinone and Dichloro dicyano neighbour benzoquinones), the lewis acid is shown in lewis acid shown in formula IV (preferably ethyl aluminum dichloride) and Formula V Lewis acid (preferably diethyl aluminum chloride), on the basis of the lewis acidic total amount, lewis acid shown in formula IV Content be 30~70 moles of %, lewis acidic content shown in Formula V is 30~70 moles of %, and the polymer solvent is alkane Hydrocarbon.According to the preferred embodiment, even if can be with if higher temperature is polymerize (as being not higher than -60 DEG C to -70 DEG C) Higher polymerization efficiency preparation has higher molecular weight, and (such as weight average molecular weight is 2.5 × 10⁵More than) monoolefine-conjugated diene Hydrocarbon copolymer.It is highly preferred that the activator is dichlorocyanobenzoquinone (including dichloro dicyano p-benzoquinone and dichloro dicyano Adjacent benzoquinones), higher polymerization efficiency can be obtained in this way.According to the preferred embodiment, polymerisation is at -60 DEG C to -120 DEG C, carry out within the temperature range of preferably -80 DEG C to -90 DEG C.In the preferred embodiment, each group divides it in initiator system Between ratio be not particularly limited, can be previously described ratio, still, the compound for being capable of providing proton with it is described The molar ratio of activator is preferably 1：0.8~1.5；The compound for being capable of providing proton and the lewis acidic molar ratio Preferably 0.04~0.1：1.In the preferred embodiment, remaining reaction condition can be previously described condition.

According to the method for the present invention, can also include that polymerization is added in the mixture obtained after completion of polymerization to polymerization eventually Only agent come make polymerisation terminate (such as alcohol).The present invention does not limit the type and dosage of the polymerization terminator especially It is fixed, 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, it in step (2), removes out described containing the molten of monoolefine-conjugated diene copolymer Unreacted monomer (that is, step (2)), then carries out halogenation (that is, step (3)) again in liquid.Conventional method may be used Unreacted monomer in the removing solution containing monoolefine-conjugated diene copolymer, as long as polymer will not be settled out Come.

In a kind of preferred embodiment of the present invention, by stripping or flashing, unreacted monomer is removed.Specifically Contain monoolefine-conjugated diene by what the steam feeding step (1) of at least one polymer solvent obtained in step (2) in ground In the solution of copolymer, to steam unreacted monomer, the polymer solution after removing monomer is obtained.The polymer solvent Steam feeding amount be enough will unreacted monomer whole or base in the solution containing monoolefine-conjugated diene copolymer Subject to this whole steams.In this embodiment, the boiling for the monomer that the temperature of the steam of polymer solvent can steam as needed It, generally can be in the range of 10 DEG C~150 DEG C, preferably in the range of 30 DEG C~100 DEG C, more preferably 50~90 depending on point In the range of DEG C；The pressure carried out in the container of monomer removal can be 10~200kPa (absolute pressure), preferably 50~120kPa (absolute pressure).In this embodiment, the steam of polymer solvent be passed through the time with can will contain monoolefine-conjugated diene it is total Unreacted monomer in the solution of polymers it is whole or it is substantially all steam subject to, usually, the duration can be 10~300 points Clock, preferably 30~200 minutes, more preferably 50~150 minutes.In step (2), the type of the polymer solvent of steam is formed It can be identical or different with polymer solvent described in step (1)；Under the premise of being enough to steam unreacted monomer, from advantageous It is preferably identical in the angle of later separation purifying.

According to the method for the present invention, solution can be sent directly into step (3) and contain after the removing monomer that step (2) obtains The compound of halogen contacts, and is sent into step (3) after can also being concentrated or being diluted and is contacted with halogen-containing compound.One As, it is sent into monoolefine-conjugated diene copolymer in the solution containing monoolefine-conjugated diene copolymer of step (3) Content can be 1~30 weight %, preferably 5~20 weight %.

According to the method for the present invention, in step (3), the halogen-containing compound can be that common various can make monoene The compound that part hydrogen atom in hydrocarbon-conjugated diene copolymer strand is replaced by halogen atom.Preferably, described to contain The compound of halogen is halogen simple substance, as bromine (that is, bromine) and/or chlorine are plain (that is, chlorine).

In step (3), the amount of the halogen atom introduced in the strand of monoolefine-conjugated diene copolymer can root It is selected according to the use occasion of the halogenation monoolefine-conjugated diene copolymer finally prepared.Usually, finally obtained list The content of halogen atom can be in the range of 0.2~3 mole of %, preferably 0.5~2 in alkene-conjugated diene copolymer Within the scope of mole %.

In step (3), the Contact Temperature of the solution containing monoolefine-conjugated diene copolymer and halogen-containing compound It can be conventional selection.Usually, the contact can carry out within the temperature range of 0 DEG C to 80 DEG C, preferably at 10 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 1~30 minute, preferably 3~15 minutes.

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 control for the mixture for more preferably obtaining halogenation is in the range of 8~10.It can be by being obtained to halogenation Mixture in addition alkaline matter and neutralized, the basic species for example can be NaOH and/or KOH, preferably NaOH. The alkaline matter preferably 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-conjugated diene copolymer.For example, after can be by obtaining mixture or neutralizing halogenation Mixture carries out water vapor accumulation, to obtain halogenation monoolefine-conjugated diene copolymer.

According to the method for the present invention, the efficiency of initiation of initiator system is high, can with higher polymerization efficiency, prepare have compared with Monoolefine-conjugated diene copolymer of high molecular weight, and then prepare halogenation monoolefine-conjugated diene with higher molecular weight Hydrocarbon copolymer.Particularly, method using the present invention can be with higher polymerization efficiency, and it is 10 × 10 to prepare weight average molecular weight⁴With Above, even 30 × 10⁴Above rubber monoolefine-conjugated diene copolymer, and then rubber halogenation monoolefine-can be prepared Conjugated diene copolymer.According to the method for the present invention particularly suitable for preparing halogenated isobutylene-isoprene copolymer, especially Rubber halogenated isobutylene-isoprene copolymer.

Fig. 1 shows that method using the present invention prepares a kind of preferred reality of halogenation monoolefine-conjugated diene copolymer Apply mode.The preferred embodiment is described in detail below in conjunction with Fig. 1.As shown in Figure 1, by monoolefine shown in Formula II Conjugated diene (preferably isoprene) 2 and polymer solvent 3 shown in (preferably isobutene) 1, formula III are prepared simultaneously with prior Aged initiator solution 4 is sent into polymer reactor I, and polymerisation is carried out under the conditions of cationic polymerization.It carries out After the polymerisation of predetermined time, terminator 5 is sent into polymer reactor I, terminates polymerisation.Polymer reactor I outputs Solution 6 containing monoolefine-conjugated diene copolymer be sent into monomer removal device II, by polymer solvent steam 7 from monomer The bottom of remover II is sent into, and the unreacted monomer in the solution 6 containing monoolefine-conjugated diene copolymer is (including different Butylene and/or isoprene) it steams, the unreacted monomer and polymer solvent steam deviate from the top of monomer removal device II 8.After obtained removing monomer solution 9 from the bottom of monomer removal device II export, subsequently enter in halogenation reactor III with it is halogen 10 haptoreaction of compound of element, so that at least partly hydrogen atom in monoolefine-conjugated diene copolymer strand is by halogen Plain atom is replaced.When the content of halogen atom meets pre-provisioning request in monoolefine-conjugated diene copolymer strand, to It is sent into the aqueous solution 11 of alkaline matter in halogenation reactor III, is neutralized.Finally, contain halogenation monoene by what neutralization obtained The solution 12 of hydrocarbon-conjugated diene copolymer exports, and is sent into subsequent handling and is detached, purified and dried, and is obtained with final To halogenation monoolefine-conjugated diene copolymer.

Below in conjunction with experimental example and embodiment, the present invention will be described in detail.

In following experimental example and Experimental comparison's example, polymer yield is measured using weight method,

Polymer yield (%)=(total weight of the monomer of weight/addition of obtained polymer) × 100%.

In following experimental example, Experimental comparison'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 experimental example, Experimental comparison's example, embodiment and comparative example, using commercially available from Bruker companies of Switzerland AVANCE400 Nuclear Magnetic Resonance, with CDC1₃Make solvent, TMS is internal standard, measures monoolefine-conjugated diene copolymer of preparation Degree of unsaturation (that is, the content of structural unit formed by isoprene in the monoolefine-conjugated diene copolymer prepared), And prepare halogenation monoolefine-conjugated diene copolymer in halogen content.

Following experimental example, Experimental comparison's example, the solvent used in embodiment and comparative example and monomer before use, using Method commonly used in the art is refined.

In following embodiment and comparative example, pressure is absolute pressure.

Experimental example 1~28 is used to illustrate the preparation method of halogenation monoolefine-conjugated diene copolymer according to the present invention In polymerization procedure.

Experimental example 1

(1) 0.0662g chloranils are dissolved in 80g and the dichloromethane for containing HCl (a concentration of 0.0036mol/L) is molten In liquid, obtained solution is cooled to -80 DEG C in advance, the dichloro of a concentration of 0.9mol/L of 2.6mL is then sequentially added into the solution The n-heptane solution of the hexane solution of aluminium ethide (EADC) and the diethyl aluminum chloride (DEAC) of a concentration of 1.0mol/L of 1mL, After mixing, obtained mixed liquor is aged to 80min at -80 DEG C, to obtain initiator solution.Wherein, by weight, draw The content for sending out chloranil in agent solution is 800ppm.

(2) 250mL three-necked flasks are placed in temperature control in -80 DEG C to -85 DEG C of low temperature cryostat, to be burnt successively to three mouthfuls It is added that 85mL is cooled to -80 DEG C of n-hexane, 15mL is cooled to -80 DEG C of isobutene and 0.5mL is cooled to -20 DEG C different in advance in bottle Pentadiene is uniformly mixed, obtains monomer solution.Initiator solution prepared by 10mL steps (1), mixing are added into monomer solution Reaction 30min is stood after uniformly, control cryostat temperature is within the scope of -80 DEG C to -85 DEG C in reaction process.Reaction knot The methanol solution that 5mL contains 0.5 weight %NaOH is added in Shu Houxiang reaction mixtures, to terminate polymerisation.Then it will mix Conjunction solution, which is placed in hot bath, removes solvent, dry to perseverance in 60 DEG C in vacuum drying oven after obtained solid is washed Weight, obtains monoolefine-conjugated diene copolymer.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 2

It polymerize using with 1 identical side of experimental example, unlike, in step (2), initiator solution and polymerization is added dropwise In reaction process, by the temperature control of cryostat within the scope of -40 DEG C to -50 DEG C, the dosage of initiator solution is 15mL, polymerization reaction time 50min.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 3

It is polymerize using with 1 identical method of experimental example, unlike, in step (1), the hexane solution of EADC A concentration of 0.9mol/L, a concentration of 1.0mol/L of the n-heptane solution of dosage 1.9mL, DEAC, dosage 1.7mL.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 4

It is polymerize using with 3 identical method of experimental example, unlike, in step (2), initiator solution is added dropwise and gathers It closes in reaction process, by the temperature control of cryostat within the scope of -60 DEG C to -70 DEG C, polymerization reaction time is 40min。

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 5

It is polymerize using with 1 identical method of experimental example, unlike, in step (1), the hexane solution of EADC A concentration of 0.9mol/L, a concentration of 1.0mol/L of the n-heptane solution of dosage 1.1mL, DEAC, dosage 2.3mL.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 6

(1) by bis- chloro- 5,6- dicyano p-benzoquinones of 0.0602g 2,3- be dissolved in 80g and containing HCl it is (a concentration of In dichloromethane solution 0.0040mol/L), obtained solution is cooled to -85 DEG C in advance, is then sequentially added into the solution The diethyl chlorination of the hexane solution and a concentration of 1.0mol/L of 1.1mL of the ethyl aluminum dichloride of a concentration of 0.9mol/L of 2.8mL Obtained mixed liquor is placed in -85 DEG C of cryostat after mixing and is aged 100min by the n-heptane solution of aluminium, to obtain Initiator solution.Wherein, by weight, the content of 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones is 730ppm in initiator solution.

(2) 250mL three-necked flasks are placed in temperature control in -80 DEG C to -85 DEG C of low temperature cryostat, to be burnt successively to three mouthfuls It is added that 85mL is cooled to -80 DEG C of n-hexane, 15mL is cooled to -80 DEG C of isobutene and 0.5mL is cooled to -20 DEG C different in advance in bottle Pentadiene is uniformly mixed, obtains monomer solution.Initiator solution prepared by 10mL steps (1), mixing are added into monomer solution Reaction 30min is stood after uniformly, it is in -80 DEG C to -85 DEG C that control cryostat temperature in initiator solution and reaction process, which is added dropwise, Within the scope of.The methanol solution that 5mL contains 0.5 weight %NaOH is added into reaction mixture after reaction, to terminate Polymerisation.Then mixed solution is placed in hot bath and removes solvent, after obtained solid is washed, in vacuum drying oven In it is dry to constant weight in 60 DEG C, obtain monoolefine-conjugated diene copolymer.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Contrast experiment's example 1

Initiator solution and it is polymerize using being prepared with 6 identical method of experimental example, unlike, in step (1) not Use bis- chloro- 5,6- dicyano p-benzoquinones of 2,3-.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 7

Initiator solution and it is polymerize using being prepared with 6 identical method of experimental example, unlike, in step (1), two The ethyl aluminum dichloride of ethylmercury chloride aluminium equimolar amounts replaces.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 8

It is polymerize using with 6 identical method of experimental example, unlike, in step (2), initiator solution is added dropwise and gathers It closes in reaction process, by the control of cryostat temperature within the scope of -60 DEG C to -70 DEG C, the dosage of initiator solution is 15mL, polymerization reaction time 40min.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 9

It is polymerize using with 6 identical method of experimental example, unlike, in step (1), the n-hexane of ethyl aluminum dichloride A concentration of 0.9mol/L of solution, dosage 2mL；A concentration of 1.0mol/L of the n-heptane solution of diethyl aluminum chloride, dosage For 1.8mL.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 10

It is polymerize using with 9 identical method of experimental example, unlike, in step (2), initiator solution is added dropwise and gathers It closes in reaction process, by the temperature control of cryostat within the scope of -60 DEG C to -70 DEG C, polymerization reaction time is 40min。

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 11

It is polymerize using with 9 identical method of experimental example, unlike, in step (2), initiator solution is added dropwise and gathers It closes in reaction process, by the temperature control of cryostat within the scope of -40 DEG C to -50 DEG C, polymerization reaction time is 50min。

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 12

It is polymerize using with 6 identical method of experimental example, unlike, in step (1), the n-hexane of ethyl aluminum dichloride A concentration of 0.9mol/L of solution, dosage 1.2mL；A concentration of 1.0mol/L of the n-heptane solution of diethyl aluminum chloride is used Amount is 2.5mL.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 13

It is polymerize using with 6 identical method of experimental example, unlike, in step (1), digestion time 60min.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 14

It is polymerize using with 6 identical method of experimental example, unlike, in step (1), digestion time 30min.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 15

It is polymerize using with 6 identical method of experimental example, unlike, in step (1), the time of ageing is 10min.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 16

It is polymerize using with 6 identical method of experimental example, unlike, unlike, in step (1), 2,3- bis- is chloro- 5,6- dicyanos with etc. the tetrahydrochysene 1,4-benzoquinone of weight replace.The weight of obtained polymer is measured, calculates polymer yield, and survey The molecular weight, molecular weight distributing index and degree of unsaturation for determining polymer, are as a result listed in table 1.

Experimental example 17

It is polymerize using with 6 identical method of experimental example, unlike, unlike, in step (1), 2,3- bis- is chloro- 5,6- dicyanos with etc. the four cyano 1,4-benzoquinone of weight replace.

The weight of obtained polymer is measured, calculates polymer yield, and measure the molecular weight of polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Experimental example 18

(1) 0.0632g chloranils are dissolved in 80g and the dichloromethane for containing HCl (a concentration of 0.0038mol/L) is molten In liquid, above-mentioned solution is then cooled to -85 DEG C in advance, it is (a concentration of that the pre- 4mL for being cooled to -85 DEG C of addition contains ethyl aluminum dichloride Hexane solution 0.9mol/L) is aged 100min at -85 DEG C, to obtain initiator solution after mixing.With weight It counts, in obtained initiator solution, a concentration of 760ppm of chloranil.

(2) two mouthfuls of glass reaction bottles of 250mL are placed in the low temperature cryostat that temperature control is -80 DEG C to -85 DEG C, to glass Sequentially be added in reaction bulb 85mL is cooled to -80 DEG C of n-hexane in advance, 15mL is cooled to -80 DEG C of isobutene in advance, 0.5mL be cooled in advance - Initiator solution prepared by 15mL steps (1) is added dropwise after mixing in 20 DEG C of isoprene, is then allowed to stand reaction 30min, It is added dropwise in reaction process, control cryostat temperature is within the scope of -80 DEG C to -85 DEG C.After reaction, mixed to reaction It closes and the methanol solution that 5mL contains 0.5 weight %NaOH is added in object, to terminate polymerisation.Obtained mixed solution is placed in Solvent is removed in hot bath, obtained solid is after washing, dry to constant weight in 60 DEG C in vacuum drying oven, to obtain monoene Hydrocarbon-conjugated diene copolymer.

The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index arrange in table 2 Go out.

Experimental example 19

It is polymerize using with 18 identical method of experimental example, unlike, initiator solution and polymerisation mistake is added dropwise Cheng Zhong, controlled within the scope of -60 DEG C to -70 DEG C, polymerization reaction time 40min.Polymer yield and The degree of unsaturation of obtained polymer, molecular weight and molecualr weight distribution index are listed in table 2.

Experimental example 20

It is polymerize using with 18 identical method of experimental example, unlike, initiator solution and polymerisation mistake is added dropwise Cheng Zhong, controlled within the scope of -40 DEG C to -50 DEG C, polymerization reaction time 50min.Polymer yield and The degree of unsaturation of obtained polymer, molecular weight and molecualr weight distribution index are listed in table 2.

Experimental example 21

(1) 0.0484g chloranils are dissolved in 60g and the dichloromethane for containing HCl (a concentration of 0.0044mol/L) is molten In liquid, above-mentioned solution is then cooled to -85 DEG C in advance, 3mL is added and is cooled to -85 DEG C and (a concentration of containing ethyl aluminum dichloride in advance N-hexane 0.9mol/L) is aged 70min at -85 DEG C, to obtain initiator solution after mixing.Wherein, with weight It counts, in initiator solution, a concentration of 780ppm of tetrachloroquinone.

(2) 200mL is sequentially added in the 500mL glass reactors stirred equipped with strength constant speed and is being cooled to -85 DEG C in advance just Hexane, 40mL are cooled to -85 DEG C of isobutene in advance and 1mL is cooled to -20 DEG C of isoprene in advance, after mixing, 30mL steps are added dropwise Suddenly the initiator solution that prepared by (1) then reacts 20min, in dropwise addition and reaction process, controlled in -80 DEG C to -85 Within the scope of DEG C.After reaction, the methanol solution that 10mL contains 0.5 weight %NaOH is added into reaction mixture, with Terminate polymerisation.Obtained mixed solution is placed in hot bath and removes solvent, obtained solid after washing, is dried in vacuum It is dry to constant weight in 60 DEG C in case, to obtain monoolefine-conjugated diene copolymer.

The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index arrange in table 2 Go out.

Experimental example 22

It is polymerize using with 21 identical method of experimental example, unlike, the four cyano 1,4-benzoquinone generation of weight such as use For chloranil.The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index are in table 2 In list.

Contrast experiment's example 2

It is polymerize using with 21 identical method of experimental example, unlike, initiator solution prepared by step (1) is free of Chloranil.The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index are in table 2 It lists.

Experimental example 23

(1) by bis- chloro- 5,6- dicyano p-benzoquinones of 0.0634g 2,3- be dissolved in 84.6g and containing HCl it is (a concentration of In dichloromethane solution 0.0041mol/L), above-mentioned solution is then cooled to -85 DEG C in advance, the pre- 4mL for being cooled to -85 DEG C is added and contains The hexane solution of ethyl aluminum dichloride (a concentration of 0.9mol/L) is aged 100min at -85 DEG C, to obtain after mixing Initiator solution.Wherein, by weight, in initiator solution, 2,3- bis- chloro- 5,6- dicyano p-benzoquinones' is a concentration of 730ppm。

(2) two mouthfuls of glass reaction bottles of 250mL are placed in the low temperature cryostat that temperature control is -80 DEG C to -85 DEG C, to glass Sequentially be added in reaction bulb 85mL is cooled to -80 DEG C of n-hexane in advance, 15mL is cooled to -80 DEG C of isobutene in advance, 0.5mL be cooled in advance - Initiator solution prepared by 10mL steps (1) is added dropwise after mixing in 20 DEG C of isoprene, is then allowed to stand reaction 30min, It is added dropwise in reaction process, control cryostat temperature is within the scope of -80 DEG C to -85 DEG C.After reaction, mixed to reaction It closes and the methanol solution that 5mL contains 0.5 weight %NaOH is added in object, to terminate polymerisation.Obtained mixed solution is placed in Solvent is removed in hot bath, obtained solid is after washing, dry to constant weight in 60 DEG C in vacuum drying oven, to obtain monoene Hydrocarbon-conjugated diene copolymer.The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution refer to Number is listed in table 2.

Experimental example 24

It is polymerize using with 23 identical method of experimental example, unlike, in step (2), the addition of initiator solution Amount is 15mL, and initiator solution is added dropwise within -60 DEG C to -70 DEG C of temperature range and is reacted, polymerization reaction time is 40min.The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index are listed in table 2.

Experimental example 25

It is polymerize using with 23 identical method of experimental example, unlike, in step (2), the addition of initiator solution Amount is 15mL, within the temperature range of -40 DEG C to -50 DEG C, initiator solution is added dropwise and is reacted, polymerization reaction time is 50min.The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index are listed in table 2.

Experimental example 26

It is polymerize using with 23 identical method of experimental example, unlike, in step (1), digestion time 60min. The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index are listed in table 2.

Experimental example 27

It is polymerize using with 23 identical method of experimental example, unlike, in step (1), digestion time 30min. The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index are listed in table 2.

Experimental example 28

It is polymerize using with 23 identical method of experimental example, unlike, in step (1), digestion time 10min. The degree of unsaturation of polymer yield and obtained polymer, molecular weight and molecualr weight distribution index are listed in table 2.

Examples 1 to 4 is for illustrating the present invention.

Embodiment 1

(1) under the conditions of -80 DEG C, into 150mL goat's horn bottles, it is (dense to contain HCl by the sequentially pre- 120mL for being cooled to -80 DEG C of addition Degree be 0.0056mol/L) and dichloromethane solution, the 5mL of chloranil (0.0044mol/L) contain ethyl aluminum dichloride Hexane solution, the 3mL of (EADC, a concentration of 0.9mol/L) are containing diethyl aluminum chloride (DEAC, a concentration of 1mol/L) just N-heptane solution is aged 60min, to obtain initiator solution at -80 DEG C after mixing.

(2) 1000mL is sequentially added in the 2000mL stainless steel reactors stirred equipped with strength constant speed and is cooled to -80 DEG C in advance N-hexane, 250mL is cooled to -80 DEG C of isobutene in advance and 7.6mL is cooled to -60 DEG C of isoprene in advance, be uniformly mixed.To reaction The initiator solution that in device prepared by a dropping step (1).Wherein, the addition of initiator solution is 100mL；Control rate of addition makes The temperature obtained in reactor is within the scope of -80 DEG C to -85 DEG C.After being added dropwise to complete, keep reactor in temperature be in- Within the scope of 80 DEG C to -85 DEG C, the polymerisation of 50min is carried out with stirring, 40mL is then added into reaction mixture Methanol solution containing 0.5 weight %NaOH, to terminate polymerisation.It is total that the monoolefine-conjugated diene prepared is measured by sampling Molecular weight, molecular weight distributing index and the degree of unsaturation of polymers, are as a result listed in table 3.

(3) after polymerisation, the list of evacuated 2000mL is pressed into the glue that nitrogen obtains step (1) In body remover, it is passed through the n-hexane steam that temperature is 80 DEG C from the bottom of monomer removal device under agitation, to remove glue Unreacted isobutene and isoprene and dichloromethane in liquid.The time that is passed through of n-hexane steam is 1h, monomer removal device Interior operating pressure is 98kPa, and the mixed gas of removing is discharged by the exhaust outlet at the top of monomer removal device, and is condensed back to It receives.

(4) glue (wherein, a concentration of 16.5 weight % of monoolefine-conjugated diene copolymer) after monomer is removed to use In the stainless steel reactor for the 2000mL that nitrogen indentation has vacuumized.Start agitating device, the temperature controlled in reactor is 40 DEG C, into reactor, addition 3.8g bromines are quickly stirred to react 5min, and it is water-soluble containing 2 weight %NaOH that 70mL is then added Liquid carries out the neutralization reaction of 5min.

(5) by the glue that step (4) obtains set with water vapour remove n-hexane, obtained product after washing, in mill It is dry to constant weight in 110 DEG C on machine, to obtain 143g brominations monoolefine-conjugated diene copolymer.Measure the bromination prepared As a result bromine content in monoolefine-conjugated diene copolymer is listed in table 3.

Embodiment 2

Bromination monoolefine-conjugated diene copolymer is prepared using method same as Example 1, unlike, step (1) in, chloranil is replaced with 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones, wherein for preparing containing for initiator solution Bis- chloro- 5,6- dicyano p-benzoquinones' of 2,3- is a concentration of in the dichloromethane of bis- chloro- 5,6- dicyano p-benzoquinones of HCl and 2,3- 0.0044mol/L。

Molecular weight, molecular weight distributing index and the unsaturation of monoolefine-conjugated diene copolymer prepared by step (2) Degree is listed in table 3, and the bromine content of the bromination monoolefine finally prepared-conjugated diene copolymer (135.2g) arranges in table 3 Go out.

Embodiment 3

Bromination monoolefine-conjugated diene copolymer is prepared using method same as Example 1, unlike, step (1) following methods are used to carry out：

Under the conditions of -80 DEG C, into 150mL goat's horn bottles, it is (a concentration of to contain HCl by the sequentially pre- 120mL for being cooled to -80 DEG C of addition 0.0048mol/L) and dichloromethane solution, the 8mL of bis- chloro- 5,6- dicyano p-benzoquinones (0.0041mol/L) of 2,3- contain two The hexane solution of chloroethyl aluminium (EADC, a concentration of 0.9mol/L) is aged 60min, to obtain at -80 DEG C after mixing Initiator solution.

Molecular weight, molecular weight distributing index and the unsaturation of monoolefine-conjugated diene copolymer prepared by step (2) Degree is listed in table 3, and the bromine content of the bromination monoolefine finally prepared-conjugated diene copolymer (148.2g) arranges in table 3 Go out.

Embodiment 4

(1) using identical method prepares initiator solution with 1 step of embodiment (1).

(2) polymerisation is carried out using the identical method with 1 step of embodiment (2).

(3) unreacted monomer and two in the glue polymerizeing is removed using method identical with 1 step of embodiment (3) Chloromethanes.

(4) glue (wherein, a concentration of 16.5 weight % of monoolefine-conjugated diene copolymer) after monomer is removed to use In the stainless steel reactor for the 2000mL that nitrogen indentation has vacuumized.Start agitating device, the temperature controlled in reactor is 45 DEG C, it is slowly introducing 3.0g chlorine into reactor and is quickly stirred to react 10min, 70mL is then added and contains 2 weight %NaOH's Aqueous solution carries out the neutralization reaction of 5min.

(5) by the glue that step (4) obtains set with water vapour remove n-hexane, obtained product after washing, in mill It is dry to constant weight in 110 DEG C on machine, to obtain chlorination monoolefine-conjugated diene copolymer.

The molecular weight of monoolefine-conjugated diene copolymer prepared by step (2), molecular weight distributing index, degree of unsaturation And polymer yield is listed in table 3, the chlorine of the chlorination monoolefine finally prepared-conjugated diene copolymer (144.5g) contains Amount is listed in table 3.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (34)

1. a kind of preparation method of halogenation monoolefine-conjugated diene copolymer, this approach includes the following steps：

(1) under the conditions of cationic polymerization, at least one polymer solvent, by least one monoolefine and at least one conjugation Alkadienes is contacted with each component in initiator system, obtains the solution containing monoolefine-conjugated diene copolymer, described poly- Bonding solvent is selected from alkane；

The initiator system contains at least one compound for being capable of providing proton, at least one lewis acid and at least one The molar ratio of activator, the compound for being capable of providing proton and the activator is 1：0.01~3, it is described to be capable of providing matter The compound of son is 0.01~1 with the lewis acidic molar ratio：1, the compound for being capable of providing proton is H₂O and/ Or Bronsted acid, 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 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；R₁₄For C₁~C₈Linear or branched alkyl group；

In Formula V, X⁴For one kind in halogen group；R₁₅And R₁₆Respectively C₁~C₈Linear or branched alkyl 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~C₅Branched alkyl；

The conjugated diene is selected from formula III compound represented,

In formula III, R₁₁、R₁₂And R₁₃Respectively hydrogen or C₁~C₅Linear or branched alkyl group；

(2) unreacted monomer in the solution containing monoolefine-conjugated diene copolymer is removed, after obtaining removing monomer Solution；

(3) solution after the removing monomer is contacted with halogen-containing compound or halogen simple substance, so that the monoolefine-is altogether Part hydrogen atom in yoke diene copolymer strand is substituted with halogen atoms.

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 1：0.1~2.5.

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.

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 1：0.5~1.8.

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 0.05~0.15：1.

8. the method according to any one of claim 1~7, wherein the activator is selected from tetrahydrochysene benzoquinones, tetrachlorobenzene Quinone, four cyano benzoquinones and dichlorocyanobenzoquinone.

9. the method according to any one of claim 1~7, wherein in formula IV, X³¹And X³²Respectively-Cl；R₁₄For Ethyl.

10. the method according to any one of claim 1~7, wherein in Formula V, X⁴For-Cl；R₁₅And R₁₆Respectively second Base.

11. the method according to any one of claim 1~7, wherein the lewis acid is Louis shown in formula IV Lewis acid shown in this acid and Formula V, in the lewis acid, the lewis acid of 10~90 moles of % is Louis shown in Formula V This acid.

12. according to the method for claim 11, wherein the lewis acid is lewis acid shown in formula IV and Formula V institute The lewis acid shown, in the lewis acid, the lewis acid of 20~80 moles of % is lewis acid shown in Formula V.

13. according to the method for claim 12, wherein the lewis acid is lewis acid shown in formula IV and Formula V institute The lewis acid shown, in the lewis acid, the lewis acid of 30~70 moles of % is lewis acid shown in Formula V.

14. the method according to any one of claim 1~7, wherein the compound for being capable of providing proton is HCl。

15. 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.

16. according to the method for claim 15, wherein in step (1), temperature model of the contact at -100 DEG C to 0 DEG C Enclose interior progress.

17. according to the method for claim 16, wherein in step (1), temperature of the contact at -100 DEG C to -40 DEG C It is carried out in range.

18. according to the method for claim 17, wherein in step (1), temperature model of the contact at -90 DEG C to -60 DEG C Enclose interior progress.

19. according to the method described in any one of claim 1~7 and 15~18, wherein, will be at least one in step (1) The method that monoolefine and at least one conjugated diene 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 conjugated diene being dissolved in polymer solvent.

20. according to the method for claim 19, wherein the time of the ageing is 10 minutes to 10 hours.

21. according to the method for claim 20, wherein the time of the ageing is 30 minutes to 5 hours.

22. according to the method for claim 21, wherein the time of the ageing is 60 minutes to 120 minutes.

23. according to the method for claim 19, wherein the ageing carries out within the temperature range of -100 DEG C to 20 DEG C.

24. according to the method for claim 23, wherein the ageing carries out within the temperature range of -100 DEG C to 0 DEG C.

25. according to the method for claim 24, wherein the ageing carries out within the temperature range of -100 DEG C to -50 DEG C.

26. according to the method for claim 25, wherein the ageing carries out within the temperature range of -90 DEG C to -70 DEG C.

27. according to the method described in claim 1, wherein, on the basis of the total amount of the monoolefine and the conjugated diene, The content of the monoolefine is 80~99.5 weight %；The content of the conjugated diene is 0.5~20 weight %.

28. according to the method for claim 27, wherein using the total amount of the monoolefine and the conjugated diene as base The content of standard, the monoolefine is 90~98 weight %；The content of the conjugated diene is 2~10 weight %.

29. according to the method described in any one of claim 1~7,15~18,27 and 28, wherein the conjugated diene For isoprene；And/or

The monoolefine is isobutene.

30. according to the method described in claim 1, wherein, in step (3), the halogen simple substance is bromine and/or chlorine element.

31. the method according to claim 1 or 30, wherein in step (3), temperature model of the contact at 0 DEG C to 80 DEG C Interior progress is enclosed, the time of the contact is 1~30 minute.

32. according to the method for claim 31, wherein in step (3), temperature range of the contact at 10 DEG C to 60 DEG C The time of interior progress, the contact is 3~15 minutes.

33. according to the method described in any one of claim 1~7,15~18,27 and 28, wherein described in step (1) Polymer solvent is selected from C₃~C₁₀Aliphatic alkane.

34. according to the method for claim 33, wherein in step (1), the polymer solvent is selected from C₅~C₈Aliphatic Alkane.