CN106146708B

CN106146708B - A kind of cationic polymerization process

Info

Publication number: CN106146708B
Application number: CN201510195024.1A
Authority: CN
Inventors: 邱迎昕; 龚惠勤; 张月红; 张雷; 周新钦; 包巧云
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2015-04-22
Filing date: 2015-04-22
Publication date: 2018-08-17
Anticipated expiration: 2035-04-22
Also published as: CN106146708A

Abstract

The invention discloses a kind of cationic polymerization process, it is included under solution polymerization condition, conjugated diene shown in monoolefine shown in formula IV and Formula V is contacted with each component in initiator system in polymer solvent, the initiator system contains the compound for being capable of providing proton, lewis acid and activator, the activator is selected from compound shown in compound and Formulas I 2 shown in Formulas I 1, and the lewis acid of 10~90 moles of % is lewis acid shown in Formula II.With the simple H of use⁺/ lewis acid initiator system is compared, and this method efficiency of initiation significantly improves, and can obtain higher polymer yield with higher rate of polymerization；By adjusting the content and type of activator in initiator system, the polymer with different molecular weight can be obtained under different polymerizing conditions；It can also implement to polymerize at higher temperatures, reduce the energy expenditure in polymerization process.

Description

A kind of cationic polymerization process

Technical field

The present invention relates to a kind of cationic polymerization process.

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, then it is not necessarily to the polymer and is redissolved step, it is clear that polymerisation in solution Production of the method 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 high molecular weight products to improve efficiency of initiation and polymerization efficiency.

Invention content

The purpose of the present invention is to provide a kind of cationic polymerization process, this method prepares monoene using solution polymerization process It is total to prepare monoolefine-conjugated diene with higher molecular weight with higher polymerization efficiency for hydrocarbon-conjugated diene copolymer Polymers.

The present invention provides a kind of cationic polymerization process, this method is included under solution polymerization condition, will be at least one Monoolefine and at least one conjugated diene are contacted with each component in initiator system in polymer solvent,

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 lewis acid of 10~90 moles of % is lewis acid shown in Formula II,

In Formula II, R₉And R₁₀Respectively C₁~C₈Linear or branched alkyl group, X³For one kind in halogen group；

The monoolefine is selected from formula IV compound represented,

In formula IV, R₁₃And R₁₄Respectively C₁~C₅Linear or branched alkyl group；Or R₁₃For hydrogen, R₁₄For C₃~C₅Branch Alkyl；

The conjugated diene is selected from Formula V compound represented,

In Formula V, R₁₅、R₁₆And R₁₇Respectively hydrogen or C₁~C₅Linear or branched alkyl group.

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 it by adjusting the content and type of activator in initiator system, can be obtained under different polymerizing conditions Polymer with different molecular weight, so as to meet the requirement of different application occasion.In addition, with simple H is used⁺/ Lewis acid initiator system is compared, and method of the invention can be implemented to polymerize at higher temperatures, so as to be effectively reduced Energy expenditure in polymerization process.

Specific implementation mode

The present invention provides a kind of cationic polymerization process, this method is included under solution polymerization condition, will be at least one Monoolefine and at least one conjugated diene are contacted with each component in initiator system in polymer solvent.

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 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-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 proton and the molar ratio of the activator can be 1: 0.01~3, preferably 1: 0.1~2.8, more preferably 1: 0.2~2.5, further preferably 1: 0.8~1.5.

Polymerization according to the present invention, the lewis acid contain lewis acid shown in Formula II,

In Formula II, R₉And R₁₀Can be identical or different, can be respectively C₁~C₈Linear or branched alkyl group, preferably C₁ ~C₅Linear or branched alkyl group；Preferably, R₉And R₁₀It is identical, is C₁~C₅Linear or branched alkyl group, more preferably second Base.

In Formula II, X³For one kind in halogen group, such as-F ,-Cl ,-Br or-I, preferably-Cl.

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 II 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.

Preferably, lewis acid shown in Formula II is diethyl aluminum chloride.

Containing there are two alkyl in lewis acidic molecular structure shown in Formula II, 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 II contain It measures excessively high, can reduce polymerization rate, extend polymerization time.Polymerization according to the present invention, with lewis acidic total amount On the basis of, lewis acidic content shown in Formula II is 10~90 moles of %, in this way can be in polymerization rate and polymer Preferable balance is obtained between molecular weight.Preferably, lewis acidic shown in Formula II to contain on the basis of lewis acidic total amount Amount is 20~80 moles of %.It is highly preferred that on the basis of lewis acidic total amount, lewis acidic content shown in Formula II is 30 ~70 moles of %.

Initiator system according to the present invention, 10~90 moles of % (preferably rub by 20~80 moles of %, more preferable 30~70 Your %) lewis acid be lewis acid shown in Formula II, remainder lewis acid can be cationic polymerization initiators body At least one of common lewis acid in system.Such as：Remainder lewis acid can be selected from BCl₃、BF₃、AlCl₃、 TiCl₄、SnCl₄、ZnCl₂, formula III compound represented and R¹² ₃Al,

In formula III, R₁₁For C₁~C₈Linear or branched alkyl group, preferably C₁~C₅Linear or branched alkyl group, more preferably For ethyl, X⁴¹And X⁴²It is identical or different, one kind (such as-F ,-Cl ,-Br or-I) respectively in halogen group, preferably-Cl；

R¹² ₃In Al, three R¹²It is identical or different, can be respectively C₁~C₈Linear or branched alkyl group, preferably C₁~C₅ Linear or branched alkyl group.

The specific example of formula III 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 and dichloro aluminium isobutyl.

R¹² ₃The specific example of Al can include but is not limited to：Trimethyl aluminium and triethyl aluminum.

Preferably, remainder lewis acid is formula III compound represented.That is, the lewis acid is preferably Formula II Shown in lewis acid and formula III compound represented, it is lewis acidic shown in Formula II on the basis of lewis acidic total amount Content is 10~90 moles of %, preferably 20~80 moles of %, more preferably 30~70 moles of %.

It is highly preferred that the lewis acid is diethyl aluminum chloride and ethyl aluminum dichloride, using lewis acidic total amount as base The content of standard, diethyl aluminum chloride is 10~90 moles of %, preferably 20~80 moles of %, more preferably 30~70 moles of %.

Polymerization according to the present invention, the lewis acidic content can be that the conventional of cationic polymerization field is used Amount.Usually, the compound for being capable of providing proton and the lewis acidic molar ratio can be 0.01~1: 1, preferably It is 0.02~0.5: 1, more preferably 0.04~0.3: 1, further preferably 0.05~0.1: 1.

The compound for being capable of providing proton can be capable of providing proton to be commonly various in cationic polymerization field Compound.Usually, the compound for being capable of providing proton can be H₂O and/or Bronsted acid, specific example can wrap It includes but is not limited to：H₂O、HCl、HF、HBr、H₂SO₄、H₂CO₃、H₃PO₄And HNO₃.Preferably, the chemical combination for being capable of providing proton Object is HCl.

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-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.

Polymerization according to the present invention, the monoolefine can carry out cationic polymerization for commonly used in the art Monoolefine.Usually, the monoolefine is selected from formula IV compound represented,

In formula IV, R₁₃And R₁₄Respectively C₁~C₅Linear or branched alkyl group；Or R₁₃For hydrogen, R₁₄For 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 Formula V compound represented,

In Formula V, R₁₅、R₁₆And R₁₇It 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 butadiene and/or isoprene.It is highly preferred that The conjugated diene is isoprene.

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 %.

Polymerization according to the present invention, the polymer solvent can be enough to make polymerisation under solution state to be various The solvent of progress, i.e., the described polymer solvent can not only dissolve monoolefine and conjugated diene, and can dissolve the poly- of polymerization formation Close object.Usually, the polymer solvent can be selected from alkane (can be aliphatic alkane and/or alicyclic alkanes) and alkyl halide Hydrocarbon is preferably selected from C₃~C₁₀Alkane and C₁~C₁₀Halogenated alkane.Halogen atom in the halogenated alkane can be chlorine, bromine Or fluorine, preferably chlorine or fluorine.The halogenated alkane is preferably C₁~C₄Halogenated alkane.

Polymerization according to the present invention, even if can be imitated with high polymerization if polymerization in low polar polymeric solvent Rate prepares the polymer of high molecular weight.The low polar polymeric solvent can be for example the alkane, can also be the alkane With the mixture of the halogenated alkane.When the polymer solvent is the mixture of the alkane and the halogenated alkane, with institute On the basis of the total amount for stating polymer solvent, the content of the alkane can be 20~99 volume %, preferably 40~99 volume %, more Preferably 50~90 volume %；The content of the halogenated alkane can be 1~80 volume %, preferably 1~60 volume %, more excellent It is selected as 10~50 volume %.

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 (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- 3-methyl cyclohexanols Alkane), n-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- bis- Methyloctane, 3- ethyls octane, 4- ethyls octane, 2,3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethyls Heptane, 2,4,5- trimethylheptanes, 2,4,6- trimethylheptanes, 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- ethyls Heptane, 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, positive fourth Butylcyclohexane, isobutyl butylcyclohexane, t-butylcyclohexane, tetramethyl-ring hexane (include the various isomers of tetramethyl-ring hexane, Such as 1,2,3,4- tetramethyl-ring hexanes, 1,2,4,5- tetramethyl-ring hexanes, 1,2,3,5- tetramethyl-ring hexanes), a fluoromethane, two Fluoromethane, fluoroform, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane, difluoro second Alkane, trifluoroethane, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethanes, tetrachloroethanes, five Chloroethanes, carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, seven fluorine third Alkane, octafluoropropane, a chloropropane, dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, eight Chloropropane, a fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, octafluoro fourth Alkane, nine fluorine butane, ten fluorine butane, a chlorobutane, dichloroetane, three chlorobutanes, four chlorobutanes, pentachlorobutane, chlordene butane, seven Chlorobutane, telodrine alkane, nine chlorobutanes and ten chlorobutanes.

The polymer solvent is preferably selected from pentane, n-hexane, normal heptane, monochloro methane, dichloromethane and monochlorethane.

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.

Polymerization according to the present invention, the cationic polymerization condition can be the conventional selection of this field.Usually, Monoolefine and conjugated diene can be at -120 DEG C to 20 DEG C, preferably -100 DEG C extremely with the contact of each component in initiator system It is carried out within the temperature range of 0 DEG C, more preferably -100 DEG C to -40 DEG C, further preferably -90 DEG C to -60 DEG C.It is according to the present invention poly- Conjunction method, the duration of the contact can be the conventional selection of this field, can be generally 10~180 minutes, preferably 30~120 minutes.

According to the method for the present invention, in a preferred embodiment, the activator is dichlorocyanobenzoquinone (packet Include dichloro dicyano p-benzoquinone and dichloro dicyano neighbour benzoquinones), the lewis acid be formula III shown in lewis acid (preferably For ethyl aluminum dichloride) and Formula II shown in lewis acid (preferably diethyl aluminum chloride), be with the lewis acidic total amount Benchmark, lewis acidic content shown in formula III are 10~50 moles of %, and lewis acidic content is 50~90 shown in Formula II Mole %, the polymer solvent contains halogenated alkane and alkane, on the basis of the total amount of the polymer solvent, the halogenated alkane Content be 10~50 volume %, preferably 20~50 volume %, the content of the alkane is 50~90 volume %, preferably 50 ~80 volume %.According to the preferred embodiment, can be prepared with higher polymerization efficiency has higher molecular weight (as divided equally again Son amount is 3 × 10⁵More than) monoolefine-conjugated diene copolymer.In the preferred embodiment, with the Louis On the basis of the total amount of acid, lewis acidic content shown in formula III is preferably 10~30 moles of %, lewis acid shown in Formula II Content be preferably 70~90 moles of %, can prepare in this way with higher molecular weight (such as weight average molecular weight be 5 × 10⁵More than) Monoolefine-conjugated diene copolymer.According to the preferred embodiment, polymerisation preferably -70 DEG C to -120 DEG C, more It is preferred that being carried out at a temperature of -80 DEG C to -100 DEG C.In the preferred embodiment, the ratio in initiator system between each component Example is not particularly limited, and can be previously described ratio, still, the compound for being capable of providing proton and the activator Molar ratio be preferably 1: 0.5~1.5；The compound for being capable of providing proton is preferably with the lewis acidic molar ratio 0.04~0.1: 1.In the preferred embodiment, remaining reaction condition can be previously described condition.

Polymerization according to the present invention, in another preferred embodiment, the activator is four cyano benzoquinones (including four cyano 1,4-benzoquinone and four cyano neighbour benzoquinones) and/or dichlorocyanobenzoquinone (including dichloro dicyano p-benzoquinone and two Chlorine dicyano neighbour benzoquinones), the lewis acid is shown in lewis acid shown in formula III (preferably ethyl aluminum dichloride) and Formula II Lewis acid (preferably diethyl aluminum chloride), on the basis of the lewis acidic total amount, lewis acid shown in formula III Content be 30~70 moles of %, lewis acidic content shown in Formula II is 30~70 moles of %, when preparing initiator solution Digestion time be 30 minutes or more, the polymer solvent be alkane.According to the preferred embodiment, even if in higher temperature Degree is polymerize (as being not higher than -60 DEG C to -70 DEG C), and can also be prepared with higher polymerization efficiency has higher molecular weight (such as weight Average molecular weight is 2.5 × 10⁵More than) monoolefine-conjugated diene copolymer.It is highly preferred that the activator is dichloro two Cyano benzoquinones (including dichloro dicyano p-benzoquinone and dichloro dicyano neighbour benzoquinones), can obtain higher polymerization efficiency in this way. According to the preferred embodiment, polymerisation carries out at a temperature of -60 DEG C to -120 DEG C, preferably -80 DEG C to -90 DEG C. In the preferred embodiment, the ratio in initiator system between each component is not particularly limited, and can be previously described Ratio, still, the compound for being capable of providing proton and the molar ratio of the activator are preferably 1: 0.8~1.5；The energy It is preferably 0.04~0.1: 1 that protogenic compound, which is enough put forward, with the lewis acidic molar ratio.In the preferred embodiment In, remaining reaction condition can be previously described condition.

Polymerization according to the present invention can also include adding to gather in the mixture obtained to polymerization after completion of polymerization Terminator is closed to make polymerisation terminate (such as alcohol).The present invention is not special for the type and dosage of the polymerization terminator It limits, can be the conventional selection of this field, polymerisation can be terminated by being subject to, and repeats no more herein.

The present invention will be described in detail with reference to embodiments.

In following embodiment and comparative example, polymer yield is measured using weight method,

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

In following embodiment and comparative example, the molecular weight and molecular weight distributing index of polymer are given birth to using Japanese Shimadzu Corporation The LC-20A type liquid phase gel permeation chromatographs of production measure, using single aperture chromatographic columnWithFour columns are combined.Mobile phase is tetrahydrofuran, flow velocity 0.7mL/min；A concentration of 2mg/mL of sample solution, sample size are 200μL；Test temperature is 35 DEG C；Using single distribution polystyrene as standard sample.

In following embodiment and comparative example, using the AVANCE400 Nuclear Magnetic Resonance commercially available from Bruker companies of Switzerland, with CDC1₃Make solvent, TMS is internal standard, measures the degree of unsaturation of monoolefine-conjugated diene copolymer of preparation (that is, the list prepared The content of the structural unit formed by isoprene in alkene-conjugated diene copolymer).

Solvent and monomer used in following embodiment and comparative example before use, using method commonly used in the art into Row is refined, and the preparation of polymerisation and initiator solution carries out in the operating under nitrogen case equipped with low temperature cryostat.

The method that Examples 1 to 31 is used to illustrate the present invention.

Embodiment 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, 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.

Embodiment 2

It is polymerize using side same as Example 1, 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 molecular weight of polymer yield and polymer, molecular weight distributing index and unsaturation Degree, is as a result listed in table 1.

Embodiment 3

It is polymerize using method same as Example 1, 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.Polymerization The molecular weight of produce rate and polymer, molecular weight distributing index and degree of unsaturation, are as a result listed in table 1.

Embodiment 4

It is polymerize using method same as Example 3, 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 molecular weight of polymer yield and polymer, molecular weight distributing index and degree of unsaturation, are as a result listed in table 1.

Embodiment 5

It is polymerize using method same as Example 1, 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.Polymerization The molecular weight of produce rate and polymer, molecular weight distributing index and degree of unsaturation, are as a result listed in table 1.

Embodiment 6

(1) by 0.0602g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 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 of the hexane solution and a concentration of 1.0mol/L of 1.1mL of the ethyl aluminum dichloride (EADC) of a concentration of 0.9mol/L of 2.8mL Obtained mixed liquor is placed in -85 DEG C of cryostat and is aged after mixing by the n-heptane solution of base aluminium chloride (DEAC) 100min, to obtain initiator solution.Wherein, by weight, 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones in initiator solution Content be 730ppm.

Comparative example 1

Initiator solution is prepared using method same as Example 6 and is polymerize, unlike, in step (1) not Use 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones.The molecular weight of polymer yield and polymer, molecular weight distributing index and not As a result saturation degree is listed in table 1.

Comparative example 2

Initiator solution is prepared using method same as Example 6 and is polymerize, unlike, in step (1) not It is replaced using the ethyl aluminum dichloride of diethyl aluminum chloride, i.e. diethyl aluminum chloride equimolar amounts.Polymer yield and polymerization Molecular weight, molecular weight distributing index and the degree of unsaturation of object, are as a result listed in table 1.

Embodiment 7

It is polymerize using method same as Example 6, 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 molecular weight of polymer yield and polymer, molecular weight distributing index and unsaturation Degree, is as a result listed in table 1.

Embodiment 8

It is polymerize using method same as Example 6, 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 molecular weight of polymer yield and polymer, molecular weight distributing index and degree of unsaturation, as a result arrange in table 1 Go out.

Embodiment 9

It is polymerize using method same as Example 8, 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 molecular weight of polymer yield and polymer, molecular weight distributing index and degree of unsaturation, are as a result listed in table 1.

Embodiment 10

It is polymerize using method same as Example 8, 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 molecular weight of polymer yield and polymer, molecular weight distributing index and degree of unsaturation, are as a result listed in table 1.

Embodiment 11

It is polymerize using method same as Example 6, 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 molecular weight of polymer yield and polymer, molecular weight distributing index and degree of unsaturation, as a result arrange in table 1 Go out.

Embodiment 12

It is polymerize using method identical with 6, unlike, in step (1), digestion time 60min.It polymerize produce The molecular weight of rate and polymer, molecular weight distributing index and degree of unsaturation, are as a result listed in table 1.

Embodiment 13

It is polymerize using method same as Example 6, unlike, in step (1), digestion time 30min.It is poly- Produce rate and molecular weight, molecular weight distributing index and the degree of unsaturation of polymer are closed, is as a result listed in table 1.

Embodiment 14

It is polymerize using method same as Example 6, unlike, in step (1), the time of ageing is 10min. The molecular weight of polymer yield and polymer, molecular weight distributing index and degree of unsaturation, are as a result listed in table 1.

Embodiment 15

It is polymerize using method same as Example 6, unlike, unlike, in step (1), 2,3- bis- is chloro- 5,6- dicyanos with etc. the tetrahydrochysene 1,4-benzoquinone of weight replace.The molecular weight of polymer yield and polymer, molecular weight distribution refer to Number and degree of unsaturation, are as a result listed in table 1.

Embodiment 16

It is polymerize using method same as Example 6, 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 molecular weight of polymer yield and polymer, molecular weight distribution As a result index and degree of unsaturation are listed in table 1.

Embodiment 17

(1) by 0.0576g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- be dissolved in 80g and containing HCl it is (a concentration of In dichloromethane 0.0044mol/L), obtained solution is cooled to -85 DEG C in advance, 0.4mL is sequentially then added into the solution N-heptane solution (the EADC of the DEAC of a concentration of 1.0mol/L of hexane solution and 3.2mL of the EADC of a concentration of 0.9mol/L Molar ratio with DEAC is 1/9), after mixing, obtained mixed liquor to be placed in -85 DEG C of cryostat and is aged 60min.Its In, by weight, the content of 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones is 700ppm in initiator solution.

(2) 200mL two mouth flasks are placed in temperature control in -80 DEG C to -85 DEG C of low temperature cryostat, to be burnt successively to two mouthfuls N-hexane/monochloro methane mixed solution (wherein, volume ratio of n-hexane/monochloro methane that 85mL is cooled to -85 DEG C is added in bottle For 9/1), 15mL is cooled to -85 DEG C of isobutene and 0.5mL is cooled to -20 DEG C of isoprene in advance, be uniformly mixed, obtain monomer Solution.Initiator solution prepared by 10mL steps (1) is added into monomer solution, stands reaction 30min after mixing, is added dropwise It is within the scope of -80 DEG C to -85 DEG C that cryostat temperature is controlled in initiator solution and reaction process.After reaction to anti- It answers and the methanol solution that 5mL contains 0.5 weight %NaOH is added in mixture, to terminate polymerisation.Then mixed solution is set Solvent is removed in hot bath, it is dry to constant weight in 60 DEG C in vacuum drying oven after obtained solid is washed, obtain list Alkene-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 2.

Comparative example 3

It is polymerize using with 17 identical method of embodiment, unlike, in step (1), 2,3- bis- chloro- 5 is not used, 6- dicyano p-benzoquinones.The weight of obtained polymer is measured, polymer yield is calculated, and measures the molecular weight of polymer, divide Son amount profile exponent and degree of unsaturation, are as a result listed in table 2.

Embodiment 18

It is polymerize using with 17 identical method of embodiment, unlike, in step (2), keep n-hexane and a chlorine The total amount of methane is constant, and the volume ratio for adjusting n-hexane and monochloro methane is 8/2.

Embodiment 19

It is polymerize using with 17 identical method of embodiment, unlike, in step (2), keep n-hexane and a chlorine The total amount of methane is constant, and the volume ratio for adjusting n-hexane and monochloro methane is 7/3.

Embodiment 20

It is polymerize using with 17 identical method of embodiment, unlike, in step (2), keep n-hexane and a chlorine The total amount of methane is constant, and the volume ratio for adjusting n-hexane and monochloro methane is 6/4.

Embodiment 21

It is polymerize using with 17 same procedure of embodiment, unlike, in step (2), keep n-hexane and a chloromethane The total amount of alkane is constant, and the volume ratio for adjusting n-hexane and monochloro methane is 5/5.

The weight of obtained polymer is measured, polymer yield is calculated, and measures the molecular weight and molecular weight point of polymer As a result cloth index is listed in table 2.

Embodiment 22

(1) by 0.0652g 2, bis- chloro- 5,6- dicyano p-benzoquinones of 3- be dissolved in 80g and containing HCl it is (a concentration of In dichloromethane 0.0044mol/L), obtained solution is cooled to -85 DEG C in advance, 2.8mL is sequentially then added into the solution The DEAC of a concentration of 0.9mol/L of hexane solution and 1.2mL of the EADC of a concentration of 0.9mol/L toluene solution (EADC with The molar ratio of DEAC is 7/3), after mixing, obtained mixed liquor to be placed in -85 DEG C of cryostat and is aged 60min.Its In, by weight, the content of 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones is 800ppm in initiator solution.

(2) 200mL two mouth flasks are placed in temperature control in -80 DEG C to -85 DEG C of low temperature cryostat, to be burnt successively to two mouthfuls N-hexane/monochloro methane mixed solution (wherein, volume ratio of n-hexane/monochloro methane that 85mL is cooled to -85 DEG C is added in bottle For 9/1), 15mL is cooled to -85 DEG C of isobutene and 0.5mL is cooled to -20 DEG C of isoprene in advance, be uniformly mixed, obtain monomer Solution.Initiator solution prepared by 10mL steps (1) is added into monomer solution, stands reaction 40min after mixing, is added dropwise It is within the scope of -80 DEG C to -85 DEG C that cryostat temperature is controlled in initiator solution and reaction process.After reaction to anti- It answers and the methanol solution that 5mL contains 0.5 weight %NaOH is added in mixture, to terminate polymerisation.Then mixed solution is set Solvent is removed in hot bath, it is dry to constant weight in 60 DEG C in vacuum drying oven after obtained solid is washed, obtain list Alkene-conjugated diene copolymer.

Embodiment 23

It is polymerize using with 22 identical method of embodiment, unlike, in step (1), keep EADC's and DEAC Total amount is constant, and the molar ratio for adjusting EADC and DEAC in initiator solution is 5/5.Measure the weight of obtained polymer, meter Polymer yield is calculated, and measures the molecular weight, molecular weight distributing index and degree of unsaturation of polymer, is as a result listed in table 2.

Embodiment 24

It is polymerize using with 22 identical method of embodiment, unlike, in step (1), keep EADC's and DEAC Total amount is constant, and the molar ratio for adjusting EADC and DEAC in initiator solution is 3/7.Measure the weight of obtained polymer, meter Polymer yield is calculated, and measures the molecular weight, molecular weight distributing index and degree of unsaturation of polymer, is as a result listed in table 2.

Embodiment 25

(1) 0.0651g chloranils are dissolved in 80g and the dichloromethane for containing HCl (a concentration of 0.0042mol/L) is molten In liquid, obtained solution is cooled to -85 DEG C in advance, the EADC of a concentration of 0.9mol/L of 2.8mL is then sequentially added into the solution Hexane solution and a concentration of 1.0mol/L of 1.1mL DEAC n-heptane solution (EADC/DEAC molar ratios be 7/3), After mixing, obtained mixed liquor is placed in -85 DEG C of ageing 60min.Wherein, by weight, tetrachloro pair in initiator solution The content of benzoquinones is 800ppm.

(2) using being polymerize with 22 identical method of embodiment, unlike, keep the total of n-hexane and monochloro methane Measure constant, the volume ratio for adjusting n-hexane and monochloro methane is 6/4.

Embodiment 26

It is polymerize using with 25 identical method of embodiment, unlike, in step (1), keep EADC's and DEAC Total amount is constant, and the molar ratio for adjusting EADC/DEAC is 5/5.

Embodiment 27

It is polymerize using with 25 identical method of embodiment, unlike, in step (1), keep EADC's and DEAC Total amount is constant, and the molar ratio for adjusting EADC/DEAC is 3/7.

Comparative example 4

It is polymerize using with 27 identical method of embodiment, unlike, in step (1), initiator solution is free of four Chlorine 1,4-benzoquinone.The weight of obtained polymer is measured, polymer yield is calculated, and measures the molecular weight of polymer, molecular weight point As a result cloth index and degree of unsaturation are listed in table 2.

Embodiment 28

It is polymerize using with 25 identical method of embodiment, unlike, digestion time 30min.

Embodiment 29

It is polymerize using with 25 identical method of embodiment, unlike, digestion time 10min.

Embodiment 30

It is polymerize using with 25 identical method of embodiment, unlike, in step (1), the weights such as chloranil uses The tetrahydrochysene 1,4-benzoquinone of amount replaces.

Embodiment 31

It is polymerize using with 25 identical method of embodiment, unlike, in step (1), the weights such as chloranil uses The four cyano 1,4-benzoquinone of amount replaces.

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

1. a kind of cationic polymerization process, this method are included under solution polymerization condition, by least one monoolefine and at least one Kind conjugated diene is contacted with each component in initiator system in polymer solvent,

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 of 10~90 moles of % is lewis acid shown in Formula II,

Remainder lewis acid is formula III compound represented,

In formula III, R₁₁For C₁~C₈Linear or branched alkyl group, X⁴¹And X⁴²One kind respectively in halogen group；

The monoolefine is selected from formula IV compound represented,

In formula IV, R₁₃And R₁₄Respectively C₁~C₅Linear or branched alkyl group；Or R₁₃For hydrogen, R₁₄For C₃~C₅Branched alkane Base；

The conjugated diene is selected from Formula V compound represented,

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 1：0.1~2.8.

3. according to the method described in claim 2, wherein, mole of the compound for being capable of providing proton and the activator Than being 1：0.2~2.5.

4. according to the method described in claim 3, wherein, mole of the compound for being capable of providing proton and the activator Than being 1：0.8~1.5.

5. the method according to any one of Claims 1 to 4, wherein the activator is selected from tetrahydrochysene benzoquinones, tetrachlorobenzene Quinone, four cyano benzoquinones and dichlorocyanobenzoquinone.

6. according to the method described in claim 1, wherein, in Formula II, X³For-Cl.

7. according to the method described in claim 6, wherein, lewis acid shown in Formula II is diethyl aluminum chloride.

8. according to the method described in any one of claim 1,6 and 7, wherein remainder lewis acid is Dichloroethyl Aluminium.

9. according to the method described in any one of claim 1,6 and 7, wherein the lewis acid of 20~80 moles of % is formula Lewis acid shown in II.

10. according to the method described in claim 9, wherein, the lewis acid of 30~70 moles of % is Louis shown in Formula II Acid.

11. according to the method described in any one of claim 1,6 and 7, wherein the compound for being capable of providing proton with The lewis acidic molar ratio is 0.02~0.5：1.

12. according to the method for claim 11, wherein the compound for being capable of providing proton with it is described lewis acidic Molar ratio is 0.04~0.3：1.

13. according to the method for claim 12, wherein the compound for being capable of providing proton with it is described lewis acidic Molar ratio is 0.05~0.1：1.

14. the method according to any one of Claims 1 to 4, wherein the compound for being capable of providing proton is HCl。

15. according to the method described in claim 1, wherein, the contact carries out within the temperature range of -120 DEG C to 20 DEG C.

16. according to the method for claim 15, wherein the contact carries out within the temperature range of -100 DEG C to 0 DEG C.

17. according to the method for claim 16, wherein the contact carries out within the temperature range of -100 DEG C to -40 DEG C.

18. according to the method for claim 17, wherein the contact carries out within the temperature range of -90 DEG C to -60 DEG C.

19. according to the method described in any one of Claims 1 to 4 and 15~18, wherein by least one monoolefine and extremely A kind of method that conjugated diene is contacted with each component in the initiator system includes less：It will be in the initiator system Each component is dissolved in solvent, and obtained mixture is aged, and obtains initiator solution；By the initiator solution and dissolving The monoolefine in polymer solvent and conjugated diene mixing.

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 Claims 1 to 4,15~18,27 and 28, wherein the conjugated diene For isoprene；And/or

The monoolefine is isobutene.

30. according to the method described in claim 1, wherein, the polymer solvent is selected from alkane and halogenated alkane.

31. according to the method for claim 30, wherein the polymer solvent is selected from C₁~C₁₀Halogenated alkane and C₃~C₁₀ Alkane.