CN106146707B - 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, conjugated diene shown in monoolefine shown in Formula II and formula III is contacted with each component in initiator system in alkane, after deviating from unreacted monomer, it is contacted with halogen-containing compound, carry out halogenation, the initiator system contains the compound for being capable of providing carbonium ion, lewis acid and activator, and the activator is selected from 2 compound represented of 1 compound represented of Formulas I and Formulas I.The method of the present invention can significantly improve polymerization efficiency, obtain higher polymer yield, moreover it is possible to obtain the polymer with higher molecular weight.The method of the present invention is omitted is redissolved process using solvent displacement and polymer necessary to slurry polymerization process, 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 solvent as polymer solvent using alkane solvent Displacement and the 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, by least one monoolefine and at least one conjugated diene and initiator body Each component in system contacts in polymer solvent, obtains the solution containing monoolefine-conjugated diene copolymer, and the polymerization is molten Agent is alkane；

The initiator system contain at least one compound for being capable of providing carbonium ion, at least one lewis acid and At least one activator, the activator 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 C of use⁺(that is, carbon just from Son)/lewis acid initiator system compares, and one side efficiency of initiation significantly improves, so as to be obtained with higher rate of polymerization Higher polymer yield；On the other hand the polymer with higher molecular weight, especially rubber high molecular weight can also be obtained Polymer.In addition, with simple C is used⁺/ lewis acid initiator system is compared, and method of the invention can be in higher temperature Lower implementation polymerization, so as to be effectively reduced the energy expenditure in polymerization process.

According to the method for the present invention, after the solution polymerizeing deviates from unreacted monomer, it is not necessarily to slurry polymerization legal system Solvent swap step and polymer redissolution process can be sent into halogenation step and carry out halogen necessary to standby polymer Change, effectively simplifies 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

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, by least one monoolefine and at least one conjugated diene and initiator body Each component in system contacts in polymer solvent, obtains the solution containing monoolefine-conjugated diene copolymer, and the polymerization is molten Agent is 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, "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 Compound, at least one lewis acid and at least one activator of carbonium ion are enough provided.

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-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).

The content of the activator, which is subject to, can obtain satisfactory polymerization effect.Usually, described to be capable of providing The compound of carbonium ion and the molar ratio of the activator can be 1: 0.01~5, preferably 1: 0.1~4, more preferably 1: 0.2~3, further preferably 1: 0.5~2.5.

The compound for being capable of providing carbonium ion, which can be various interacts with lewis acid, can be precipitated carbon just The compound of ion.Preferably, the compound for being capable of providing carbonium ion is selected from one or more hydrogen atom respectively QuiltThe respective quilt of one or more hydrogen atom on substituted alkane and arylSubstituted aromatic hydrocarbons, R₁₄、R₁₅、R₁₆And R₁₇Respectively hydrogen, C₁~C₈Alkyl, phenyl, C₇~C₁₀Phenylalkyl, C₇~C₁₀Alkyl phenyl or C₃ ~C₈Naphthenic base；X³And X⁴One kind respectively in halogen group, such as-F ,-Cl ,-Br or-I, preferably-Cl or-Br.

The C₁~C₈Alkyl include C₁~C₈Straight chained alkyl and C₃~C₈Branched alkyl, specific example can wrap It includes but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, 2- methyl Butyl, 3- methyl butyls, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methyl amyls, 4- methyl amyls, 2,3- bis- Methyl butyl, 2,2- dimethylbutyls, 3,3- dimethylbutyls, 2- ethyl-butyls, n-heptyl, 2- methylhexyls, 3- methyl oneself Base, 4- methylhexyls, 5- methylhexyls, 2,2- dimethyl amyl groups, 2,3- dimethyl amyl groups, 2,4- dimethyl amyl groups, 3,3- bis- Methyl amyl, 3,4- dimethyl amyl groups, 4,4- dimethyl amyl groups, 2- ethylpentyls, 3- ethylpentyls, n-octyl, 2- methyl heptan Base, 3- methylheptyls, 4- methylheptyls, 5- methylheptyls, 6- methylheptyls, 2,2- dimethylhexanyls, 2,3- dimethylhexanyls, 2,4- dimethylhexanyls, 2,5- dimethylhexanyls, 3,3- dimethylhexanyls, 3,4- dimethylhexanyls, 3,5- dimethylhexanyls, 4, 4- dimethylhexanyls, 4,5- dimethylhexanyls, 5,5- dimethylhexanyls, 2- ethylhexyls, 3- ethylhexyls, 4- ethylhexyls, 2- n-propyls amyl and 2- isopropyl amyls.

The C₇~C₁₀Phenylalkyl refer to C₁~C₄A hydrogen atom in alkyl is substituted by phenyl the group to be formed, Its specific example can include but is not limited to：(wherein, propylidene can be sub- n-propyl or Asia for benzyl, phenethyl, phenylpropyl Isopropyl) and benzene butyl (wherein, sub- normal-butyl can be sub- normal-butyl, sub- sec-butyl, isobutylidene or sub- tertiary butyl).

The C₇~C₁₀Alkyl phenyl refer to a hydrogen atom in phenyl by C₁~C₄Alkyl replaces the group to be formed, Its specific example can include but is not limited to：(wherein, propyl can be n-propyl or isopropyl for tolyl, ethylbenzene, propyl phenyl Base), butylbenzene base (wherein, butyl can be normal-butyl, sec-butyl, isobutyl group or tertiary butyl).

The C₃~C₈The specific example of naphthenic base can include but is not limited to：Cyclopropyl, cyclobutyl, cyclopenta, hexamethylene Base, suberyl and cyclooctyl.

The specific example of the compound for being capable of providing carbonium ion can include but is not limited to：2- chloro- 2,4,4- tri- Methylpentane (TMPC1), to dibenzyl chlorine (that is, Isosorbide-5-Nitrae-two (chloromethyl) benzene), to dibenzyl bromide (that is, Isosorbide-5-Nitrae-two (bromomethyl) Benzene), to dicumyl chlorine (that is, Isosorbide-5-Nitrae-two (2- chloro isopropyls) benzene), to dicumyl bromine (that is, Isosorbide-5-Nitrae-two (2- bromines isopropyl) benzene), Isosorbide-5-Nitrae-two (1- chloroethyls) benzene, Isosorbide-5-Nitrae-two (1- bromoethyls) benzene, three cumyl chlorine (that is, 1,3,5- tri- (2- chloro isopropyls) benzene) and three Cumyl bromine (that is, 1,3,5- tri- (2- bromines isopropyl) benzene).

The lewis acid can be the conventional selection in cationic polymerization field, for example, the lewis acid can be selected from But it is not limited to：Formula IV compound represented, BF₃、BCl₃、TiCl₄、SnCl₄And ZnCl₂,

AlR¹⁸ _nX⁵ _(3-n)(formula IV)

In formula IV, n R¹⁸It is identical or different, respectively C₁~C₈Alkyl, preferably C₁~C₅Alkyl, more preferably Ethyl；3-n X⁵It is identical or different, one kind respectively in halogen group, such as-F ,-Cl ,-Br or-I, preferably-Cl；N is 0,1,2 or 3.

Preferably, the lewis acid is formula IV compound represented.

The specific example of formula IV compound represented can include but is not limited to：Dichloromethyl aluminium, ethyl aluminum dichloride, dichloro N-propyl aluminium, two chloro isopropyl aluminium, dichloro n-butylaluminum, dichloro aluminium isobutyl, dimethylaluminum chloride, diethyl aluminum chloride, two N-propyl aluminium chloride, diisopropyl aluminium chloride, di-n-butyl aluminium chloride, diisobutyl aluminum chloride and alchlor.

It is highly preferred that the lewis acid is formula IV compound represented.It, will be in formula IV compound represented in the present invention N be 1 when compound be known as dihalo alkyl aluminium, by n in formula IV compound represented be 2 when compound be known as dialkyl group halogen Change aluminium.It is further preferred that the lewis acid be dihalo alkyl aluminium and/or dialkylaluminum halides, as ethyl aluminum dichloride and/ Or diethyl aluminum chloride.

In a kind of preferred embodiment of the present invention, the lewis acid contains dihalo alkyl aluminium (preferably two Chloroethyl aluminium) and dialkylaluminum halides (preferably diethyl aluminum chloride), on the basis of lewis acidic total amount, dialkyl group halogenation The content of aluminium is 10~80 moles of %, and the content of dihalo alkyl aluminium is 20~90 moles of %, in this way can be in polymerisation speed Preferable balance is obtained between rate and polymer molecular weight.It is highly preferred that on the basis of lewis acidic total amount, dialkyl group halogenation The content of aluminium is 30~70 moles of %, and the content of dihalo alkyl aluminium is 30~70 moles of %.Higher polymerization speed can obtained Under the premise of rate, from the angle of the molecular weight for the monoolefine-conjugated diene copolymer for further increasing preparation, with Louis On the basis of the total amount of this acid, the content of dialkylaluminum halides is 50~70 moles of %, and the content of dihalo alkyl aluminium is 30~50 Mole %.It is highly preferred that the lewis acid is ethyl aluminum dichloride and diethyl aluminum chloride, using lewis acidic total amount as base The content of standard, diethyl aluminum chloride is 10~80 moles of %, preferably 30~70 moles of %, more preferably 50~70 moles of %.

The dosage of the compound for being capable of providing carbonium ion can be selected according to lewis acidic dosage.Generally Ground, the compound for being capable of providing carbonium ion and the lewis acidic molar ratio be 0.01~1: 1, preferably 0.02~ 0.5: 1, more preferably 0.03~0.4: 1, further preferably 0.03~0.3: 1.

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.It in one embodiment of the invention, can be with Each component in the initiator system is dissolved in solvent, and obtained mixture is aged, obtains initiator solution；It will The initiator solution is mixed with the monoolefine and the conjugated diene being dissolved in polymer solvent.

The purpose of the ageing is to make lewis acid in initiator system and is capable of providing the compound of carbonium ion Stable complexing is formed with activator and causes activated centre, can be carried out under normal conditions.Usually, the ageing can be with At -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 preferably -90 DEG C to -70 It is carried out within the temperature range of DEG C.The time of the ageing can be 15 minutes to 10 hours.Preferably, the time of the ageing is 30 minutes or more, such as 30 minutes to 5 hours.From the angle for further increasing polymerization efficiency, the time of the ageing is more Preferably 60 minutes or more, such as 60 minutes to 120 minutes.

The solvent can be it is various can dissolve the compound for being capable of providing carbonium ion, the lewis acid and The liquid substance of the activator.Usually, the solvent can be selected from alkane, halogenated alkane and aromatic hydrocarbons, be preferably selected from C₃~ C₁₀Alkane, C₁~C₁₀Halogenated alkane and C₆~C₁₂Aromatic hydrocarbons.

As solvent, the alkane includes aliphatic alkane and alicyclic alkanes, such as C₃~C₁₀Alkane include C₃~C₁₀ Aliphatic alkane and C₃~C₁₀Alicyclic alkanes.As solvent, the halogenated alkane includes halogenated aliphatic alkane and halogen For alicyclic alkanes, such as C₁~C₁₀Halogenated alkane include C₁~C₁₀Halogenated aliphatic alkane and C₃~C₁₀Halogenated cyclo Alkane.Halogen atom in the halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.The halogenated alkane is preferably C₁~C₄Halogenated aliphatic alkane.

The specific example of the solvent can include but is not limited to：Propane, normal butane, iso-butane, pentane, isopentane, Neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl cyclopentane, Normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- dimethyl Pentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2, 5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 2- Methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4- bis- Methyl heptane, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- trimethyls Hexane, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyl cyclohexanes, 2,4, 4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- methyl -4- Ethyl hexane, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- ethyls Hexamethylene, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane (include the various isomers of trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexane, 1,2,4- trimethyl-cyclohexanes, 1,2,5- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes), N-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl Octane, 3- ethyls octane, 4- ethyls octane, 2,3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethyl heptan Alkane, 2,4,5- trimethylheptanes, 2,4,6- trimethylheptanes, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- Trimethylheptane, 2,2,6- trimethylheptanes, 2,3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptan Alkane, 2- methyl -4- ethyl heptanes, 2- methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- Methyl -3- ethyl heptanes, 4- methyl -4- ethyl heptanes, 4- propyl heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- Methyl -3,3- diethylpentane, 1,2- diethyl cyclohexanes, 1,3- diethyl cyclohexanes, Isosorbide-5-Nitrae-diethyl cyclohexane, normal-butyl Hexamethylene, isobutyl butylcyclohexane, t-butylcyclohexane, tetramethyl-ring hexane (include the various isomers of tetramethyl-ring hexane, such as 1,2,3,4- tetramethyl-ring hexane, 1,2,4,5- tetramethyl-ring hexanes, 1,2,3,5- tetramethyl-ring hexanes), a fluoromethane, difluoro Methane, fluoroform, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane, Difluoroethane, Trifluoroethane, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethanes, tetrachloroethanes, pentachloro- Ethane, carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoro-propane, Octafluoropropane, a chloropropane, dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, eight chlorine Propane, a fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, octafluorobutane, Nine fluorine butane, ten fluorine butane, a chlorobutane, dichloroetane, three chlorobutanes, four chlorobutanes, pentachlorobutane, chlordene butane, heptachlor Butane, telodrine alkane, nine chlorobutanes, ten chlorobutanes, toluene, ethylbenzene and dimethylbenzene (including ortho-xylene, meta-xylene and to two Toluene).

The concentration of the initiator solution can be conventional selection, be not particularly limited.The dosage of the initiator solution It can be made appropriate choice according to specific polymerizing condition, polymerization can be caused by being subject to.Those skilled in the art can be Under the introduction of the prior art, the initiator amount for being adequate to bring about polymerization is determined by the experiment of limited number of time.

According to the method for the present invention, the monoolefine can be the monoene that can carry out cationic polymerization commonly used in the art Hydrocarbon.Usually, the monoolefine 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 alkane.The alkane includes aliphatic alkane and alicyclic alkane Hydrocarbon.The aliphatic alkane is preferably C₃~C₁₀Aliphatic alkane, more preferably C₃~C₈Aliphatic alkane, further it is excellent It is selected as C₅~C₈Aliphatic alkane；The alicyclic alkanes are preferably C₃~C₁₀Alicyclic alkanes, further preferably C₅~ C₁₀Alicyclic alkanes.

The specific example of the polymer solvent can include but is not limited to：Propane, normal butane, iso-butane, pentane, isoamyl Alkane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl ring penta Alkane, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- diformazans Base pentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4- Dimethyl heptane, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- front threes Base hexane, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyl cyclohexanes, 2, 4,4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- methyl - 4- ethyl hexanes, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- second Butylcyclohexane, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane, n-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyls octane, 4- ethyls octane, 2, 3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethylheptanes, 2,4,5- trimethylheptanes, 2,4,6- front threes Base heptane, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- trimethylheptanes, 2,2,6- trimethylheptanes, 2, 3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 2- methyl -4- ethyl heptanes, 2- methyl -5- Ethyl heptane, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyl heptanes, 4- methyl -4- ethyls Heptane, 4- propyl heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- diethylpentane, 1,2- diethyls Butylcyclohexane, 1,3- diethyl cyclohexanes, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, tertiary butyl ring Hexane and tetramethyl-ring hexane.

Preferably, the polymer solvent is selected from pentane, isopentane, n-hexane, hexamethylene and normal heptane.

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.

It is total that step (1) according to the method for the present invention can prepare monoolefine-conjugated diene with higher polymerization efficiency Polymers can especially prepare monoolefine-conjugated diene copolymer with higher molecular weight.Specifically, in the method for the present invention It is described to be capable of providing carbonium ion on the basis of step described previously (1) in a kind of preferred embodiment of step (1) Compound be 2- chloro- 2,4,4- trimethylpentanes, the lewis acid be dialkylaluminum halides and dihalo alkyl aluminium, with road On the basis of the total amount of Lewis acid, the content of dialkylaluminum halides (preferably diethyl aluminum chloride) is 30~70 moles of %, dihalo- The content of substituted alkyl aluminium (preferably ethyl aluminum dichloride) is 30~70 moles of %, and polymerisation is at -120 DEG C in -60 DEG C of temperature It is carried out in range.

According to the preferred embodiment weight average molecular weight can be prepared as 2 × 10 with higher polymerization efficiency⁵Above list Alkene-conjugated diene copolymer.Under the premise of can obtain monoolefine-conjugated diene copolymer with higher molecular weight, From the angle for further decreasing energy consumption, the temperature of polymerisation is preferably not lower than -90 DEG C, is more preferably not less than -85 ℃。

According to the preferred embodiment, it is preferable that the content of dialkylaluminum halides (preferably diethyl aluminum chloride) is The content of 50~70 moles of %, dihalo alkyl aluminium (preferably ethyl aluminum dichloride) are 30~50 moles of %, accordingly even when more It is polymerize in high temperature (such as -85 DEG C to -70 DEG C, even -70 DEG C to -60 DEG C) range, can be also prepared with higher molecular Monoolefine-conjugated diene copolymer of amount.

According to the preferred embodiment, the type of activator does not limit, and can be one in activator described previously Kind is two or more, preferably one or more of tetrachloroquinone, dichlorocyanobenzoquinone and four cyano benzoquinones.It is more excellent Selection of land, the activator are dichlorocyanobenzoquinone, under equal conditions, the monoolefine-conjugated diolefin copolymer so prepared Object has higher molecular weight, can reach 2.5 × 10⁵More than, or even 4.5 × 10 can be reached⁵More than, while can also obtain Higher polymerization efficiency.

In the preferred embodiment, the ratio in initiator system between each component is not particularly limited, Ke Yiwei Previously described ratio.Preferably, the compound for being capable of providing carbonium ion and the molar ratio of the activator are 1: 1.5 ~2.5, the compound for being capable of providing carbonium ion is 0.03~0.1: 1 with the lewis acidic molar ratio.More preferably The molar ratio of ground, the compound for being capable of providing carbonium ion and the activator is 1: 1.8~2.4, described to be capable of providing The compound of carbonium ion is 0.03~0.08: 1 with the lewis acidic molar ratio.

It is not particularly limited according to remaining condition in the preferred embodiment, 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, it is preferred that in removing unreacted Monomer in, monoolefine-conjugated diene copolymer will not be precipitated out from solution.

It is unreacted by stripping or flashing removing in step (2) in a kind of preferred embodiment of the present invention Monomer.Specifically, what can be obtained the steam of at least one polymer solvent feeding step (1) contains monoolefine-conjugated diene In the solution of hydrocarbon copolymer, to steam unreacted monomer, solution after removing monomer is obtained.The steam of the polymer solvent Feeding amount be enough will in the solution containing monoolefine-conjugated diene copolymer unreacted monomer it is whole or substantially all Subject to steaming.In this embodiment, depending on the boiling point 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 at 50 DEG C~90 DEG C In range；It can be 10~200kPa (absolute pressure) to carry out the pressure in the container of monomer removal, and preferably 50~120kPa is (absolutely Pressure), more preferably 80~120kPa (absolute pressure).In this embodiment, the steam of polymer solvent be passed through the time with can will Unreacted monomer in solution containing monoolefine-conjugated diene copolymer 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.In step (2), The type for forming the polymer solvent of steam can be identical or different with polymer solvent described in step (1)；It is being enough unreacted The precursor that steams of monomer under, it is preferably identical from the angle for being conducive to later separation and 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 %, more preferably 10~20 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 0.5~2 mole of %, preferably 1~1.5 in alkene-conjugated diene copolymer In the range 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 at a temperature of 0 DEG C to 80 DEG C, preferably at 20 DEG C to 60 DEG C It carries out in temperature range, is more preferably carried out within the temperature range of 30 DEG C to 50 DEG C.The time of the contact can be according to contact Temperature and expected halogenation degree selected, 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 for the mixture that halogenation obtains more preferably is neutralized to 8~10.It can be by adding in the mixture that is obtained to halogenation Add alkaline matter and neutralized, the alkaline matter for example can be NaOH and/or KOH, preferably NaOH.The basic species Choosing of fine quality 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 is condensed, to obtain halogenation monoolefine-conjugated diene copolymer.

According to the method for the present invention, the efficiency of initiation of the initiator system of use is high, can be prepared with higher polymerization efficiency Monoolefine-conjugated diene copolymer with higher molecular weight, and then prepare the halogenation monoolefine-with higher molecular weight altogether Yoke diene copolymer.Particularly, method using the present invention can with higher polymerization efficiency, prepare weight average molecular weight be 10 × 10⁴Above, even 40 × 10⁴Above monoolefine-the conjugated diene copolymer, and then rubber halogenation monoolefine-can be prepared altogether Yoke diene copolymer.According to the method for the present invention particularly suitable for preparing halogenated isobutylene-isoprene copolymer, especially rubber Glue 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 8 deviate from the top of monomer removal device II.Obtained removing list Solution 9 is exported from the bottom of monomer removal device II after body, is subsequently entered in halogenation reactor III and is connect with halogen-containing compound 10 Reaction is touched, so that at least partly hydrogen atom in monoolefine-conjugated diene copolymer strand is replaced by halogen atom. When the content of halogen atom meets pre-provisioning request in monoolefine-conjugated diene copolymer strand, into halogenation reactor III It is sent into the aqueous solution 11 of alkaline matter, is neutralized.Finally, will neutralize obtain containing halogenation monoolefine-conjugated diene it is total The solution 12 of polymers exports, and is sent into subsequent handling and is detached and purified, to finally obtain halogenation monoolefine-conjugated diene Hydrocarbon 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 CDCl₃Make 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.

Preparation example 1~5 is used to prepare the compound for being capable of providing carbonium ion.

Preparation example 1：2- chloro- 2, the synthesis of 4,4- trimethylpentanes (TMPC1)

250mL flask with three necks,round bottom is placed in ice-water bath, then be added 2,4,4- trimethyl -1- amylenes of 30mL and 30mL dichloromethane.Under conditions of being continually fed into dry hydrogen chloride gas, 5h is reacted.Mixture carbonic acid obtained by the reaction Hydrogen sodium is neutralized, and after anhydrous magnesium sulfate then is added into solution, is filtered, and collects liquid mixture, and depressurized Distillation, (yield is 70 weight % to the fraction of collection 44 DEG C (2.1332kPa), determines that its purity is through gas chromatographic analysis 93%).Through characterization, confirm that the fraction is 2- chloro- 2,4,4- trimethylpentanes.Wherein,¹H-NMR (δ, ppm)：1.06(-C (CH₃)₃), 1.67 (- C (CH₃)₂Cl), 1.88 (- CH₂-)。

Preparation example 2：Synthesis to dicumyl chlorine

500mL is placed in ice-water bath equipped with three mouthfuls of round bottoms of slotting bottom air inlet pipe and an air outlet pipe and magnetic stirring apparatus burning In, 8g is then respectively adding to dicumyl alcohol, 10g CaCl₂And 100g dichloromethane.It is continually fed into three-necked flask dry Dry hydrogen chloride gas is stirred to react 10 hours.It is filtered after reaction, obtains clear solution, vacuum removal hydrogen chloride And dichloromethane, obtain 9.1g colourless acicular crystals (yield is 96 weight %).Gained acicular crystal is being dissolved in 50mL just In hexane, it is filtered to remove insoluble impurities, remaining liquid phase substance is cooled to -20 DEG C to -30 DEG C, is tied with stirring Crystalline substance is detached precipitating crystal with mother liquor, collects crystal.Determine that the crystal is to dicumyl chlorine through characterization.Wherein,¹H-NMR (δ, ppm)：2.00(), 7.56 (phenyl).

Preparation example 3：Synthesis to dicumyl bromine

It is prepared to dicumyl bromine using method similar with preparation example 2, unlike, hydrogen chloride gas bromination hydrogen Instead of.Wherein,¹H-NMR (δ, ppm)：2.11(), 7.06 (phenyl).

Preparation example 4：The synthesis of 1,3,5- tri- cumyl chlorine

(1) to 1000mL equipped with being added in two mouthfuls of round bottoms of magnetic stirring apparatus and condenser pipe and constant pressure funnel 1,3,5- benzenetricarboxylic acids of 18g (0.086mol) and 500mL absolute methanols.Then, the 20mL concentrated sulfuric acids, reflux are added dropwise at reflux After reaction 24 hours, reaction mixture is cooled to room temperature, and is placed 12 hours at a temperature of about -5 DEG C.Then, it carried out The solid matter being collected into is washed with distilled water for several times until anacidity washes out, to obtain colourless 1,3,5- benzene three by filter Sour methyl esters crystal.Wherein,¹H-NMR (δ, ppm)：3.98(-CH₃), 8.86 (phenyl).

(2) under the protection of dry nitrogen, in 500mL equipped with two mouthfuls of round bottoms of magnetic stirring apparatus and constant pressure funnel In flask, 1,3,5- benzenetricarboxylic acid methyl esters of 16g (0.063mol) is dissolved in 280mL anhydrous tetrahydro furans (THF), and is cooled to 0℃.Then, the diethyl ether solution (content of methyl-magnesium-bromide is 0.448mol) of methyl-magnesium-bromide is added dropwise, keeps 0 DEG C of reaction 12 small When.Then, mixture will be obtained and be added to 280g trash ices with the mixture of 18g ammonium chlorides with stirring, ether is used in combination to carry out Extraction, extract liquor are dried with anhydrous magnesium sulfate, and evaporation of solvent after extract liquor is filtered obtains 1,3,5- (2- hydroxyl isopropyls Base) benzene (that is, 1,3,5- tri- cumyl alcohol) crude product.1,3,5- tri- cumyl alcohol crude product is recrystallized in ethyl acetate, Obtain 1,3,5- tri- cumyl alcohol crystals.Wherein,¹H-NMR (δ, ppm)：1.61(In-CH₃)；7.52 (phenyl).

(3) 500mL is placed in equipped with the three neck round bottom flask of slotting bottom air inlet pipe and an air outlet pipe and magnetic stirring apparatus In ice-water bath, then, 8g1,3,5- tri- cumyl alcohols, 10g CaCl is added₂And 120g dichloromethane.Continue into three-necked flask It is passed through dry hydrogen chloride gas, is stirred to react 10 hours.It is filtered after reaction, obtains clear solution, vacuum removal HCl and dichloromethane obtain colourless acicular crystal (yield is 96 weight %).By gained dissolution of crystals in 50mL n-hexanes, It is filtered to remove insoluble impurities, remaining liquid substance is cooled to -20 DEG C to -30 DEG C, is crystallized, will be precipitated with stirring Crystal is detached with mother liquor, collects crystal.Confirm that the crystal is 1,3,5- tri- cumyl chlorine through characterization.Wherein,¹H-NMR (δ, ppm)： 2.01~2.03 ()；7.72 (phenyl).

Preparation example 5：The synthesis of 1,3,5- tri- cumyl bromine

1,3,5- tri- cumyl bromines are prepared using method identical with preparation example 4, unlike, in step (3), hydrogen chloride gas Body is replaced with bromination hydrogen.Wherein,¹H-NMR (δ, ppm)：2.12(), 6.83 (phenyl).

Experimental example 1~36 is used to illustrate the polymerization procedure in the method for the present invention.

Experimental example 1

(1) 0.0213g chloranils are dissolved in the dichloromethane that 26.4g contains TMPC1 (content 0.0137g), Obtained solution is cooled to -90 DEG C in advance, the ethyl aluminum dichloride of a concentration of 0.9mol/L of 1.5mL is then added into the solution (EADC) hexane solution, uniformly mixed be placed in -90 DEG C of cryostat is aged 60min, to obtain initiator solution.Its In, by weight, the content 800ppm of chloranil in initiator solution.

(2) 180mL is sequentially added in the 500mL glass reactors stirred equipped with strength constant speed and is being cooled to -60 DEG C in advance just Hexane, 32mL are cooled to -60 DEG C of isobutene in advance and 1mL is cooled to -20 DEG C of isoprene in advance, are uniformly mixed.It is dripped into reactor The initiator solution for adding step (1) to prepare.Wherein, the addition of initiator solution is 15mL；Control drop rate to react Temperature in device is within the scope of -85 DEG C to -90 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be in -85 DEG C Within the scope of to -90 DEG C, the polymerisation of 15min is carried out with stirring, 5mL is then added into reaction mixture contains The methanol solution of 0.5 weight %NaOH, to terminate polymerisation.Obtained mixed solution is placed in hot bath and removes solvent, Obtained product is after washing, dry to constant weight in 60 DEG C in vacuum drying oven, to obtain monoolefine-conjugated diolefin copolymer Object.The weight of obtained polymer is measured, calculates polymer yield, and measure the degree of unsaturation of the polymer of preparation, molecular weight And molecular weight distributing index, as a result listed in table 1.

Experimental example 2

It is polymerize using with 1 identical method of experimental example, unlike, in step (1), TMPC1 is with 0.0161g pairs two Benzyl chloride replaces.Experimental result is listed in table 1.

Experimental example 3

It is polymerize using with 1 identical method of experimental example, unlike, in step (1), TMPC1 is with 0.0243g pairs two Benzyl bromide replaces.Experimental result is listed in table 1.

Experimental example 4

It is polymerize using with 1 identical method of experimental example, unlike, in step (1), TMPC1 is with 0.0213g pairs two Cumyl chloro replaces.Experimental result is listed in table 1.

Experimental example 5

It is polymerize using with 1 identical method of experimental example, unlike, in step (1), TMPC1 is with 0.0295g pairs two Cumyl bromo replaces.Experimental result is listed in table 1.

Experimental example 6

It is polymerize using with 1 identical method of experimental example, unlike, in step (1), TMPC1 0.0277g1,3, Tri- cumyl chloros of 5- replace.Experimental result is listed in table 1.

Experimental example 7

It is polymerize using with 1 identical method of experimental example, unlike, in step (1), TMPC1 0.0397g1,3, Tri- cumyl bromos of 5- replace.Experimental result is listed in table 1.

Table 1

Experimental example 8

(1) by 0.0754g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- are dissolved in 150g and contain TMPC1 (content is In dichloromethane solution 0.0711g), above-mentioned solution is then cooled to -80 DEG C in advance, and 6mL is added is cooled to -80 DEG C in advance and contain The hexane solution of ethyl aluminum dichloride (a concentration of 0.9mol/L) is aged 60min at -80 DEG C, to be drawn after mixing Send out agent solution.Wherein, by weight, in initiator solution, a concentration of 500ppm of 2,3- bis- chloro- 5,6- dicyano p-benzoquinones.

(2) 200mL 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 N-hexane, 25mL are cooled to -80 DEG C of isobutene in advance and 0.8mL is cooled to -20 DEG C of isoprene in advance, are uniformly mixed.To reactor Initiator solution prepared by middle a dropping step (1).Wherein, the addition of initiator solution is 25mL, and control drop rate makes Temperature in reactor is within the scope of -85 DEG C to -90 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be in -85 DEG C within the scope of -90 DEG C, the polymerisation of 17min is carried out with stirring, 5mL is then added into reaction mixture contains The methanol solution of 0.5 weight %NaOH, to terminate polymerisation.Obtained mixed solution is placed in hot bath and removes solvent, Obtained solid is after washing, dry to constant weight in 60 DEG C in vacuum drying oven, to obtain monoolefine-conjugated diolefin copolymer Object.The weight of obtained polymer is measured, calculates polymer yield, and measure the degree of unsaturation of the polymer of preparation, molecular weight And molecular weight distributing index, as a result listed in table 2.

Experimental example 9

It is polymerize using with 8 identical method of experimental example, unlike, it is replaced with the four cyano 1,4-benzoquinone of equimolar amounts 2,3- bis- chloro- 5,6- dicyano p-benzoquinones.Experimental result is listed in table 2.

Experimental example 10

It is polymerize using with 8 identical method of experimental example, unlike, 2 are replaced with the chloranil of equimolar amounts, Bis- chloro- 5,6- dicyano p-benzoquinones of 3-.Experimental result is listed in table 2.

Experimental example 11

It is polymerize using with 8 identical method of experimental example, unlike, 2 are replaced with the tetrahydrochysene 1,4-benzoquinone of equimolar amounts, Bis- chloro- 5,6- dicyano p-benzoquinones of 3-.Experimental result is listed in table 2.

Experimental comparison's example 1

It is polymerize using with 8 identical method of experimental example, unlike, 2,3- bis- chloro- 5,6- is not used in step (1) Dicyano p-benzoquinone, that is, the initiator solution prepared are free of 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones.Experimental result is in table 2 It lists.

Table 2

Experimental example 12

(1) 0.0201g chloranils 200g is dissolved in contain in the dichloromethane to TMPC1 (content 0.0858g), Obtained solution is cooled to -80 DEG C in advance, the ethyl aluminum dichloride of a concentration of 0.9mol/L of 10mL is then added into the solution (EADC) hexane solution, uniformly mixed be placed in -80 DEG C of cryostat is aged 60min, to obtain initiator solution.Its In, by weight, the content 100ppm of chloranil in initiator solution.

(2) 180mL is sequentially added in the 500mL glass reactors stirred equipped with strength constant speed and is being cooled to -60 DEG C in advance just Hexane, 32mL are cooled to -60 DEG C of isobutene in advance and 1mL is cooled to -20 DEG C of isoprene in advance, are uniformly mixed.It is dripped into reactor The initiator solution for adding step (1) to prepare.Wherein, the addition of initiator solution is 15mL；Control drop rate to react Temperature in device is within the scope of -80 DEG C to -85 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be in -80 DEG C Within the scope of to -85 DEG C, the polymerisation of 30min is carried out with stirring, 5mL is then added into reaction mixture contains The methanol solution of 0.5 weight %NaOH, to terminate polymerisation.Obtained mixed solution is placed in hot bath and removes solvent, Obtained product is after washing, dry to constant weight in 60 DEG C in vacuum drying oven, to obtain monoolefine-conjugated diolefin copolymer Object.The weight of obtained polymer is measured, calculates polymer yield, and measure degree of unsaturation, molecular weight and the molecule of polymer Profile exponent is measured, is as a result listed in table 3.

Experimental example 13

It is polymerize using with 12 identical method of experimental example, unlike, in step (1), the dosage of chloranil For 0.0805g.Experimental result is listed in table 3.

Experimental example 14

It is polymerize using with 12 identical method of experimental example, unlike, in step (1), the dosage of chloranil For 0.1611g.Experimental result is listed in table 3.

Experimental example 15

It is polymerize using with 12 identical method of experimental example, unlike, in step (1), the dosage of chloranil For 0.2013g.Experimental result is listed in table 3.

Experimental comparison's example 2

It is polymerize using with 12 identical method of experimental example, unlike, chloranil is not used in step (1), The initiator solution prepared is free of chloranil.Experimental result is listed in table 3.

Experimental example 16

It is polymerize using with 14 identical method of experimental example, unlike, in step (2), initiator solution is being added dropwise And in polymerization process, the temperature in reactor is made to be in the range of -60 DEG C to -70 DEG C.Experimental result arranges in table 3 Go out.

Table 3

*：By weight

Experimental example 17

(1) 0.0213g chloranils are dissolved in the dichloromethane that 26.4g contains 0.0213g TMPC1, by what is obtained Solution is cooled to -80 DEG C in advance, be then added into the solution ethyl aluminum dichloride (EADC) of 1.5mL a concentration of 0.9mol/L just oneself Alkane solution, uniformly mixed be placed in -80 DEG C of cryostat is aged 60min, to obtain initiator solution.Wherein, by weight, The content 800ppm of chloranil in initiator solution.

(2) 180mL is sequentially added in the 500mL glass reactors stirred equipped with strength constant speed and is being cooled to -60 DEG C in advance just Hexane, 32mL are cooled to -60 DEG C of isobutene in advance and 1mL is cooled to -20 DEG C of isoprene in advance, are uniformly mixed.It is dripped into reactor The initiator solution for adding step (1) to prepare.Wherein, the addition of initiator solution is 15mL；Control drop rate to react Temperature in device is within the scope of -85 DEG C to -90 DEG C.After being added dropwise to complete, the temperature in reactor is kept to be in -85 DEG C Within the scope of to -90 DEG C, the polymerisation of 15min is carried out with stirring, 5mL is then added into reaction mixture contains The methanol solution of 0.5 weight %NaOH, to terminate polymerisation.Obtained mixed solution is placed in hot bath and removes solvent, Obtained product is after washing, dry to constant weight in 60 DEG C in vacuum drying oven, to obtain monoolefine-conjugated diolefin copolymer Object.The weight of obtained polymer is measured, calculates polymer yield, and measure degree of unsaturation, molecular weight and the molecule of polymer Profile exponent is measured, is as a result listed in table 4.

Experimental example 18~21

It is polymerize using with 17 identical method of experimental example, unlike, in step (1), when the ageing of experimental example 18 Between be 180min, the digestion time of experimental example 19 is 120min, and the digestion time of experimental example 20 is 30min, experimental example 21 it is old The change time is 15min.Experimental result is listed in table 4.

Experimental comparison's example 3

It is polymerize using with 17 identical method of experimental example, unlike, chloranil is not used in step (1), The initiator solution prepared is free of chloranil.Experimental result is listed in table 4.

Table 4

*：By weight

Experimental example 22

(1) 0.0662g chloranils are dissolved in 80g and contain 2- chloro- 2, (content is 4,4- trimethylpentanes In dichloromethane solution 0.018g), obtained solution is cooled to -80 DEG C in advance, it is dense that 2.6mL is then sequentially added into the solution Degree is the diethyl aluminum chloride of the hexane solution and a concentration of 1.0mol/L of 1mL of the ethyl aluminum dichloride (EADC) of 0.9mol/L (DEAC) obtained mixed liquor is aged 80min at -80 DEG C by n-heptane solution after mixing, molten to obtain initiator Liquid.Wherein, by weight, the content of chloranil is 800ppm 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, polymer yield is calculated, measures the molecular weight and molecualr weight distribution of polymer As a result index is listed in table 5.

Experimental example 23

It is polymerize using with 22 identical method of experimental example, unlike, in step (2), initiator solution is being added dropwise The temperature of cryostat is controlled as within the scope of -40 DEG C to -50 DEG C in polymerization process.Experimental result is in table 5 It lists.

Experimental example 24

It is polymerize using with 22 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.It is real Result is tested to list in table 5.

Experimental example 25

It is polymerize using with 24 identical method of experimental example, unlike, in step (2), initiator solution is being added dropwise The temperature of cryostat is controlled as within the scope of -60 DEG C to -70 DEG C in polymerization process.Experimental result is in table 5 It lists.

Experimental example 26

It is polymerize using with 22 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.It is real Result is tested to list in table 5.

Experimental example 27

(1) by 0.0602g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- are dissolved in 80g and contain 2- chloro- 2,4,4- trimethyls In the dichloromethane solution of pentane (content 0.018g), obtained solution is cooled to -85 DEG C in advance, then the sequence into the solution The diethyl 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 is added Obtained mixed liquor is placed in -85 DEG C of cryostat after mixing and is aged 100min by the n-heptane solution of aluminium chloride, to Obtain initiator solution.Wherein, by weight, the content of 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones is in initiator solution 730ppm。

(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, polymer yield is calculated, measures the molecular weight and molecualr weight distribution of polymer As a result index is listed in table 5.

Experimental comparison's example 4

It is polymerize using with 27 identical method of experimental example, unlike, in step (1), 2,3- bis- chloro- 5 is not used, 6- dicyano p-benzoquinones, that is, the initiator solution prepared do not contain 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones.Experimental result is in table It is listed in 5.

Experimental example 28

It is polymerize using with 27 identical method of experimental example, unlike, in step (1), always rub lewis acidic Under conditions of your amount is constant, diethyl aluminum chloride is not used, i.e., is replaced with the ethyl aluminum dichloride of equimolar amounts.Experimental result is in table It is listed in 5.

Experimental example 29

It is polymerize using with 27 identical method of experimental example, unlike, in step (2), initiator solution is being added dropwise The temperature of cryostat is controlled as within the scope of -60 DEG C to -70 DEG C in polymerization process.Experimental result is in table 5 It lists.

Experimental example 30

It is polymerize using with 27 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 2mL, DEAC, dosage 1.8mL.Experiment As a result it lists in table 5.

Experimental example 31

It is polymerize using with 30 identical method of experimental example, unlike, in step (2), initiator solution is being added dropwise The temperature of cryostat is controlled as within the scope of -60 DEG C to -70 DEG C in polymerization process.Experimental result is in table 5 It lists.

Experimental example 32

It is polymerize using with 30 identical method of experimental example, unlike, in step (2), initiator solution is being added dropwise The temperature of cryostat is controlled as within the scope of -40 DEG C to -50 DEG C in polymerization process.Experimental result is in table 5 It lists.

Experimental example 33

It is polymerize using with 27 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 1.2mL, DEAC, dosage 2.5mL.It is real Result is tested to list in table 5.

Experimental example 34~36

It is polymerize using with 27 identical method of experimental example, unlike, in step (1), when the ageing of experimental example 34 Between be 60min, the digestion time of experimental example 35 is 30min, and the digestion time of experimental example 36 is 15min.Experimental result is in table 5 It lists.

Table 5

The method that Examples 1 to 7 is used to illustrate the present invention.

Embodiment 1

(1) under conditions of -80 DEG C, the sequentially pre- 120mL for being cooled to -80 DEG C of addition contains TMPC1 in 150mL goat's horn bottles The dichloromethane solution of (content 0.0748g) and chloranil (content 0.1276g), that 5mL contains ethyl aluminum dichloride is (dense Degree is 0.9mol/L) hexane solution and 3mL contain the n-heptane solution of diethyl aluminum chloride (a concentration of 1mol/L), mix 60min is aged after closing uniformly at -80 DEG C, to obtain initiator solution.

(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 drop rate 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 6.

(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 the n-hexane steam that temperature is 80 DEG C, and to remove unreacted isobutene and isoprene, control is molten Operating pressure in agent displacer is 98kPa, and the duration that is passed through of n-hexane steam is 60min.

(4) obtained polymer solution (content of monoolefine-conjugated diene copolymer is 15.9 weight %) is used into nitrogen Air pressure enters in evacuated halogenation reactor, and the temperature controlled in halogenation reactor is 40 DEG C, is added into reactor 3.8g bromines, and it is stirred to react 5min at a temperature of 40 DEG C.Then, the aqueous solution for the NaOH that 7mL contains 2 weight % is added, Neutralization reaction is carried out, the duration of neutralization reaction is 5min.

(5) the glue water vapour after neutralization is removed into solvent and be condensed, obtained aqueous bromination glue is in open mill On at a temperature of 110 DEG C dry to constant weight, obtain bromination monoolefine-conjugated diene copolymer.Measure the bromination list prepared The content of bromine in alkene-conjugated diene copolymer, is as a result listed in table 6.

Embodiment 2

Bromination monoolefine-conjugated diene copolymer is prepared using method same as Example 1, unlike, step (1) in, TMPC1 is replaced with to dibenzyl chloro, in the dichloromethane solution for preparing initiator solution, to the dense of dibenzyl chlorine Degree is 0.0041mol/L, content 0.0861g.Experimental result is listed in table 6.

Embodiment 3

Bromination monoolefine-conjugated diene copolymer is prepared using method same as Example 1, unlike, step (1) in, TMPC1 is replaced with to dicumyl chloro, in the dichloromethane solution for preparing initiator solution, to the dense of dicumyl chlorine Degree is 0.0046mol/L, content 0.1275g.Experimental result is listed in table 6.

Embodiment 4

Bromination monoolefine-conjugated diene copolymer is prepared using method same as Example 1, unlike, step (1) in, TMPC1 is replaced with 1,3,5- tri- cumyl chloro, and in the dichloromethane solution for preparing initiator solution, 1,3,5- tri- is withered A concentration of 0.0044mol/L of base chlorine, content 0.1624g.Experimental result is listed in table 6.

Embodiment 5

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, the dichloromethane for preparing initiator solution The content of 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones is 0.0877g in solution.Experimental result is listed in table 6.

Embodiment 6

Bromination monoolefine-conjugated diene copolymer is prepared using method same as Example 1, unlike, step (1) it in, under the conditions of -80 DEG C, is sequentially added in 150mL goat's horn bottles and is cooled to -80 DEG C of 120mL in advance and contains TMPC1 (content is 0.064g) and dichloromethane solution, the 8mL of 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones (content 0.1116g) contain two chloroethenes The hexane solution of base aluminium (a concentration of 0.9mol/L) is aged 60min at -80 DEG C after mixing, molten to obtain initiator Liquid.Experimental result is listed in table 6.

Embodiment 7

Chlorination monoolefine-conjugated diene copolymer is prepared using method same as Example 1, unlike, cause Agent solution is using the initiator solution that with 3 step of embodiment (1) prepared by identical method；In step (4), bromine equivalent Chlorine replaces.Experimental result is listed in table 6.

Claims (35)

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

It (1), will be at least one monoolefine and at least one conjugated diene and initiator system under the conditions of cationic polymerization Each component contacted in polymer solvent, obtain the solution containing monoolefine-conjugated diene copolymer, the polymer solvent is Alkane；

The initiator system contains at least one compound for being capable of providing carbonium ion, at least one lewis acid and at least The molar ratio of a kind of activator, the compound for being capable of providing carbonium ion and the activator is 1：0.01~5, the energy It is 0.01~1 enough to provide the compound of carbonium ion and the lewis acidic molar ratio：1, the activator is selected from -1 institute of Formulas I - 2 compound represented of compound and Formulas I shown,

In Formulas I -1 and Formulas I -2, R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Respectively-H ,-X¹、-NO₂、With one in-CN Kind, X¹And X²One kind respectively in halogen group；

The compound for being capable of providing carbonium ion is selected from quiltSubstituted alkane and bySubstituted virtue Hydrocarbon, R₁₄、R₁₅、R₁₆And R₁₇Respectively hydrogen, C₁~C₈Alkyl, phenyl, C₇~C₁₀Phenylalkyl, C₇~C₁₀Alkyl phenyl Or C₃~C₈Naphthenic base, X³And X⁴One kind respectively in halogen group；

The lewis acid is selected from formula IV compound represented,

AlR¹⁸ _nX⁵ _(3-n)(formula IV)

In formula IV, n R¹⁸Respectively C₁~C₈Alkyl；3-n X⁵One kind respectively in halogen group；N is 0,1,2 or 3；

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, the compound for being capable of providing carbonium ion and the activator Molar ratio is 1：0.1~4.

3. according to the method described in claim 2, wherein, the compound for being capable of providing carbonium ion and the activator Molar ratio is 1：0.2~3.

4. according to the method described in claim 3, wherein, the compound for being capable of providing carbonium ion and the activator Molar ratio is 1：0.5~2.5.

5. according to the method described in claim 1, wherein, the compound for being capable of providing carbonium ion and the lewis acid Molar ratio be 0.02~0.5：1.

6. according to the method described in claim 5, wherein, the compound for being capable of providing carbonium ion and the lewis acid Molar ratio be 0.03~0.4：1.

7. according to the method described in claim 6, wherein, the compound for being capable of providing carbonium ion and the lewis acid Molar ratio be 0.03~0.3：1.

8. according to the method described in claim 1, wherein, by least one monoolefine and at least one conjugated diene with it is described In initiator system each component contact method include：Each component in the initiator system is dissolved in solvent, and Obtained mixture is aged, initiator solution is obtained；By the initiator solution and the list being dissolved in polymer solvent Alkene and conjugated diene mixing.

9. according to the method described in claim 8, wherein, the time of the ageing is 15 minutes to 10 hours.

10. according to the method described in claim 9, wherein, the time of the ageing is 30 minutes to 5 hours.

11. according to the method described in claim 10, wherein, the time of the ageing is 60 minutes to 120 minutes.

12. the method according to any one of claim 8~11, wherein temperature of the ageing at -100 DEG C to 20 DEG C It spends in range and carries out.

13. according to the method for claim 12, wherein the ageing carries out within the temperature range of -100 DEG C to 0 DEG C.

14. according to the method for claim 13, wherein the ageing carries out within the temperature range of -100 DEG C to -50 DEG C.

15. according to the method for claim 14, wherein the ageing carries out within the temperature range of -90 DEG C to -70 DEG C.

16. according to the method described in claim 8, wherein, the solvent is one kind in alkane, halogenated alkane and aromatic hydrocarbons Or it is two or more.

17. according to the method described in any one of claim 1~11 and 16, wherein the activator be selected from tetrachloroquinone, Dichlorocyanobenzoquinone, tetrahydrochysene benzoquinones and four cyano benzoquinones.

18. according to the method described in any one of claim 1~11 and 16, wherein X³And X⁴Respectively-Cl or-Br.

19. according to the method described in any one of claim 1~11 and 16, wherein the carbonium ion that is capable of providing Compound is selected from the chloro- 2,4,4- trimethylpentanes of 2-, 1,4- bis- (chloromethyl) benzene, 1,4- bis- (bromomethyl) benzene, (the 2- chlorine of 1,4- bis- Isopropyl) benzene, 1,4- bis- (2- bromines isopropyl) benzene, (2- chloro isopropyls) benzene of 1,3,5- tri- and 1,3,5- tri- (2- bromines isopropyl) Benzene.

20. according to the method described in any one of claim 1~11 and 16, wherein in formula IV, 3-n X⁵Respectively-Cl.

21. according to the method described in any one of claim 1~11 and 16, wherein the lewis acid is preferably dichloro Aluminium ethide and/or diethyl aluminum chloride.

22. according to the method described in any one of claim 1~11 and 16, wherein the lewis acid is more preferably two Chloroethyl aluminium and diethyl aluminum chloride, on the basis of lewis acidic total amount, the content of diethyl aluminum chloride is rubbed for 10~80 You are %.

23. the method according to claim 11, wherein more, on the basis of lewis acidic total amount, diethyl aluminum chloride Content is 30~70 moles of %.

24. according to the method for claim 23, wherein on the basis of lewis acidic total amount, diethyl aluminum chloride contains Amount is 50~70 moles of %.

25. 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 %.

26. according to the method for claim 25, 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 %.

27. according to the method described in any one of claim 1~11,16,25 and 26, wherein the conjugated diene is Isoprene；And/or

The monoolefine is isobutene.

28. according to the method described in any one of claim 1~11,16,25 and 26, wherein described to connect in step (1) It touches and is carried out within the temperature range of -120 DEG C to 20 DEG C.

29. according to the method for claim 28, wherein in step (1), temperature model of the contact at -100 DEG C to 0 DEG C Enclose interior progress.

30. according to the method for claim 29, wherein in step (1), temperature of the contact at -100 DEG C to -40 DEG C It is carried out in range.

31. according to the method for claim 30, wherein in step (1), temperature model of the contact at -90 DEG C to -60 DEG C Enclose interior progress.

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

33. the method according to claim 1 or 32, wherein in step (3), the contact is at a temperature of 0 DEG C to 80 DEG C It carries out, the time of the contact is 1~30 minute.

34. according to the method for claim 33, wherein in step (3), it is described contact at a temperature of 20 DEG C to 60 DEG C into The time of row, the contact is 3~15 minutes.

35. according to the method described in any one of claim 1~11,16,25,26 and 32, wherein the polymer solvent is Selected from C₃~C₁₀One or more of aliphatic alkane.