CN104974293B - A kind of cationic polymerization process - Google Patents
A kind of cationic polymerization process Download PDFInfo
- Publication number
- CN104974293B CN104974293B CN201410136466.4A CN201410136466A CN104974293B CN 104974293 B CN104974293 B CN 104974293B CN 201410136466 A CN201410136466 A CN 201410136466A CN 104974293 B CN104974293 B CN 104974293B
- Authority
- CN
- China
- Prior art keywords
- compound
- benzoquinones
- diluent
- monoolefine
- ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of cationic polymerization process, this method is included under the conditions of cationic polymerization, in at least one diluent, at least one monoolefine and at least one ring-alkylated styrenes are contacted with each component in initiator system, the initiator system contains at least one compound that can provide carbonium ion, at least one lewis acid and at least one activator, and the activator is selected from the compound shown in compound and Formulas I 2 shown in Formulas I 1.When being copolymerized with monoolefine by cationic polymerization in low Polar diluents, method of the invention can significantly improve the Copolymerization activity of ring-alkylated styrenes, so as to improve the polymerization efficiency of polymerization system, obtain higher polymer yield.In addition, the method according to the invention can prepare the polymer with different molecular weight size, to meet the requirement of different application occasion by adjusting the composition of initiator system under different polymerizing conditions.
Description
Technical field
The present invention relates to a kind of cationic polymerization process.
Background technology
The isobutene of bromination-p-methylstyrene copolymer, usually by isobutene and the copolymer of p-methylstyrene
Bromination is carried out, by part p-methylstyrene group transformations obtained from bromometllylstyrene group.Because molecular backbone is
Full saturated structures, therefore the isobutene of bromination-p-methylstyrene copolymer has the synthesis more excellent than brombutyl
Performance, especially with more preferable heat resistance；Also, the presence of the benzyl bromo functional groups due to high activity, can with it is various
Rubber realizes vulcanization and co-vulcanization in broader scope, also has the modification advantage of wider range in addition.The product pass through with
Nylon blending is made dynamic vulcanization alloy and is used to produce the inner liner of tire, can accomplish not only it is light but also thin, therefore, the isobutyl of bromination
Alkene and p-methylstyrene copolymer can be used for tire of the production with higher performance, and with quite wide market application before
Scape.
Therefore, researcher for isobutene and has carried out numerous studies to alkylstyrene copolymers and its halide.
Such as：US5162445 and US5959049 individually discloses isobutene and to alkylstyrene copolymers and preparation method thereof.
The content of the invention
The present inventor has found that isobutene is when carrying out cationic polymerization, its polymerization efficiency in research process
（That is, polymer yield）To Diluent Polarity and insensitive, but isobutene and ring-alkylated styrenes are being passed through into cationic polymerization
When mode carries out combined polymerization, with the reduction of Diluent Polarity, polymerization efficiency decreases, so that system is Polymerization in Different Buffers
When, the Copolymerization activity of p-methylstyrene significantly reduces, and causes polymerization efficiency extreme difference, and polymer yield is not high.
The present inventor is studied regarding to the issue above, is found：By monoolefine and ring-alkylated styrenes with solution
When the mode of polymerization carries out cationic copolymerization, if introduced in initiator system a kind of quinonoid compound can significantly improve it is poly-
Efficiency is closed, improves the yield of polymer.The present invention is completed on this basis.
The invention provides a kind of cationic polymerization process, this method is included under the conditions of cationic polymerization, at least one
In kind diluent, at least one monoolefine and at least one ring-alkylated styrenes are contacted with each component in initiator system, institute
State initiator system and contain at least one compound that carbonium ion can be provided, at least one lewis acid and at least one work
Agent,
The activator is selected from the compound shown in compound and Formulas I -2 shown in Formulas I -1,
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 contains the compound shown in Formula II and the compound shown in formula III,
In Formula II, R9And R10Respectively C1~C8Straight or branched alkyl, X3For one kind in halogen group；
In formula III, R11For C1~C8Straight or branched alkyl, X4And X5One kind respectively in halogen group；
The monoolefine is selected from the compound shown in formula IV,
In formula IV, R12And R13Respectively C1~C5Straight or branched alkyl；Or R12For hydrogen, R13For C3~C5Side chain
Alkyl；
The ring-alkylated styrenes is selected from the compound shown in Formula V,
In Formula V, R14For C1~C5Straight or branched alkyl.
When being copolymerized with monoolefine by cationic polymerization in low Polar diluents, method of the invention can be bright
The aobvious Copolymerization activity for improving ring-alkylated styrenes, so as to improve the polymerization efficiency of polymerization system, obtain higher polymer yield.
In addition, the method according to the invention is by adjusting the composition of initiator system, can under different polymerizing conditions
The polymer with different molecular weight size is prepared, to meet the requirement of different application occasion.
Embodiment
The invention provides a kind of cationic polymerization process, this method is included under the conditions of cationic polymerization, at least one
In kind diluent, at least one monoolefine and at least one ring-alkylated styrenes are contacted with each component in initiator system, institute
State initiator system and contain at least one compound that carbonium ion can be provided, at least one lewis acid and at least one work
Agent.
The activator be selected from the compound shown in the compound and Formulas I -2 shown in Formulas I -1,
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（Such as：- F ,-Cl ,-Br or-I）.
The instantiation of the activator can include but is not limited to：Tetrahydrochysene 1,4-benzoquinone, tetrahydrochysene neighbour benzoquinones, the hydrogen pair of a fluorine three
Benzoquinones, the hydrogen neighbour benzoquinones of a fluorine three, difluoro dihydro 1,4-benzoquinone, difluoro dihydro neighbour benzoquinones, the hydrogen 1,4-benzoquinone of trifluoro one, the hydrogen neighbour's benzene of trifluoro one
Quinone, tetrafluoro 1,4-benzoquinone, tetrafluoro neighbour benzoquinones, the hydrogen 1,4-benzoquinone of a chlorine three, the hydrogen neighbour benzoquinones of a chlorine three, dichloro-dihydro 1,4-benzoquinone（Including 2,
3- dichloros 1,4-benzoquinone, 2,5- dichloros 1,4-benzoquinone, 2,6- dichloro 1,4-benzoquinone）, dichloro-dihydro neighbour's benzoquinones（Including 3,4- dichloro neighbour's benzene
Quinone, 3,5- dichloro neighbours benzoquinones, 3,6- dichloro neighbour's benzoquinones）, the hydrogen 1,4-benzoquinone of trichlorine one, the hydrogen neighbour benzoquinones of trichlorine one, chloranil, four
Chlorine neighbour benzoquinones, the hydrogen 1,4-benzoquinone of monobromo three, the hydrogen neighbour benzoquinones of monobromo three, dibromo dihydro 1,4-benzoquinone（Including 2,3- dibromos 1,4-benzoquinone, 2,5-
Dibromo 1,4-benzoquinone, 2,6- dibromo 1,4-benzoquinone）, dibromo dihydro neighbour's benzoquinones（Including 3,4- dibromo-os benzoquinones, 3,5- dibromo-os benzoquinones,
3,6- dibromo-o benzoquinones）, the hydrogen 1,4-benzoquinone of tribromo one, the hydrogen neighbour benzoquinones of tribromo one, tetrabromo 1,4-benzoquinone, tetrabromo-phthalic quinone, the nitre of a fluorine three
Base 1,4-benzoquinone, a fluorine trinitro- neighbour benzoquinones, difluoro dinitro 1,4-benzoquinone（Including the fluoro- 5,6- dinitros 1,4-benzoquinone of 2,3- bis-, 2,5-
Two fluoro- 3,6- dinitros 1,4-benzoquinone, the fluoro- 3,5- dinitros 1,4-benzoquinone of 2,6- bis-）, difluoro dinitro o benzoquinones（Including 3,4- bis-
Fluoro- 5,6- dinitro os benzoquinones, the fluoro- 4,6- dinitro os benzoquinones of 3,5- bis-, the fluoro- 4,5- dinitro os benzoquinones of 3,6- bis-）, trifluoro
One nitro 1,4-benzoquinone, the nitro neighbour benzoquinones of trifluoro one, a chlorine trinitro- 1,4-benzoquinone, a chlorine trinitro- neighbour benzoquinones, dichloro dinitro pair
Benzoquinones（Including the chloro- 5,6- dinitros 1,4-benzoquinone of 2,3- bis-, the chloro- 3,6- dinitros 1,4-benzoquinone of 2,5- bis-, the chloro- 3,5- bis- of 2,6- bis-
Nitro 1,4-benzoquinone）, dichloro dinitro o benzoquinones（Including the chloro- 5,6- dinitro os benzoquinones of 3,4- bis-, the chloro- 4,6- dinitros of 3,5- bis-
The chloro- 4,5- dinitro os benzoquinones of base neighbour benzoquinones, 3,6- bis-）, the nitro 1,4-benzoquinone of trichlorine one, the nitro neighbour benzoquinones of trichlorine one, monobromo three
Nitro 1,4-benzoquinone, monobromo trinitro- neighbour benzoquinones, dibromo dinitro 1,4-benzoquinone（Including the bromo- 5,6- dinitros 1,4-benzoquinone of 2,3- bis-, 2,
The bromo- 3,6- dinitros 1,4-benzoquinone of 5- bis-, the bromo- 3,5- dinitros 1,4-benzoquinone of 2,6- bis-）, dibromo dinitro o benzoquinones（Including 3,4-
Two bromo- 5,6- dinitro os benzoquinones, the bromo- 4,6- dinitro os benzoquinones of 3,5- bis-, the bromo- 4,5- dinitro os benzoquinones of 3,6- bis-）, three
The nitro 1,4-benzoquinone of bromine one, the nitro neighbour benzoquinones of tribromo one, tetranitro 1,4-benzoquinone, tetranitro neighbour benzoquinones, a fluorine tricyano 1,4-benzoquinone, one
Fluorine tricyano neighbour benzoquinones, difluoro dicyano p-benzoquinone（Including the fluoro- 5,6- dicyano p-benzoquinones of 2,3- bis-, the fluoro- 3,6- bis- of 2,5- bis-
The fluoro- 3,5- dicyano p-benzoquinones of cyano group 1,4-benzoquinone, 2,6- bis-）, difluoro dicyano neighbour's benzoquinones（Including the fluoro- 5,6- dicyan of 3,4- bis-
The fluoro- 4,5- dicyanos neighbour's benzoquinones of the fluoro- 4,6- dicyanos neighbour benzoquinones of base neighbour benzoquinones, 3,5- bis-, 3,6- bis-）, the cyano group of trifluoro one is to benzene
Quinone, the cyano group neighbour benzoquinones of trifluoro one, a chlorine tricyano 1,4-benzoquinone, a chlorine tricyano neighbour benzoquinones, dichloro dicyano p-benzoquinone（Including 2,
The chloro- 5,6- dicyano p-benzoquinones of 3- bis-, the chloro- 3,6- dicyano p-benzoquinones of 2,5- bis-, the chloro- 3,5- dicyano p-benzoquinones of 2,6- bis-）、
Dichloro dicyano neighbour's benzoquinones（Including the chloro- 5,6- dicyanos neighbour benzoquinones of 3,4- bis-, the chloro- 4,6- dicyanos neighbour benzoquinones of 3,5- bis-, 3,6-
Two chloro- 4,5- dicyanos neighbour's benzoquinones）, the cyano group 1,4-benzoquinone of trichlorine one, the cyano group neighbour benzoquinones of trichlorine one, monobromo tricyano 1,4-benzoquinone, one
Bromine tricyano neighbour benzoquinones, dibromo dicyano p-benzoquinone（Including the bromo- 5,6- dicyano p-benzoquinones of 2,3- bis-, the bromo- 3,6- bis- of 2,5- bis-
The bromo- 3,5- dicyano p-benzoquinones of cyano group 1,4-benzoquinone, 2,6- bis-）, dibromo dicyano neighbour's benzoquinones（Including the bromo- 5,6- dicyan of 3,4- bis-
The bromo- 4,5- dicyanos neighbour's benzoquinones of the bromo- 4,6- dicyanos neighbour benzoquinones of base neighbour benzoquinones, 3,5- bis-, 3,6- bis-）, the cyano group of tribromo one is to benzene
Quinone, the cyano group neighbour benzoquinones of tribromo one, the cyano group 1,4-benzoquinone of trinitro- one, the cyano group neighbour benzoquinones of trinitro- one, dinitro dicyano p-benzoquinone
（Including 2,3- dinitro -5,6- dicyano p-benzoquinones, 2,5- dinitro -3,6- dicyano p-benzoquinones, 2,6- dinitros -3,5-
Dicyano p-benzoquinone）, dinitro dicyano neighbour's benzoquinones（Including 3,4- dinitro -5,6- dicyano neighbours benzoquinones, 3,5- dinitros -
4,6- dicyano neighbours benzoquinones, 3,6- dinitro -4,5- dicyano neighbour's 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 the fluoro- 5,6- dimethyl chlorides base 1,4-benzoquinone of 2,3- bis-, the fluoro- 3,6- dimethyl chlorides bases of 2,5- bis-
The fluoro- 3,5- dimethyl chlorides base 1,4-benzoquinone of 1,4-benzoquinone, 2,6- bis-）, difluoro dimethyl chloride base neighbour's benzoquinones（Including bis- fluoro- 5,6- of 3,4-
Dimethyl chloride base neighbour benzoquinones, the fluoro- 4,6- dimethyl chlorides base neighbour benzoquinones of 3,5- bis-, the fluoro- 4,5- dimethyl chlorides base neighbour's benzene of 3,6- bis-
Quinone）, the formyl chloro 1,4-benzoquinone of trifluoro one, the formyl chloro neighbour benzoquinones of trifluoro one, a chlorine front three acid chloride group 1,4-benzoquinone, the formyl of a chlorine three
Chloro neighbour benzoquinones, dichloro dimethyl chloride base 1,4-benzoquinone（Including the chloro- 5,6- dimethyl chlorides base 1,4-benzoquinone of 2,3- bis-, 2,5- bis- chloro- 3,
The chloro- 3,5- dimethyl chlorides base 1,4-benzoquinone of 6- dimethyl chloride bases 1,4-benzoquinone, 2,6- bis-）, dichloro dimethyl chloride base neighbour's benzoquinones（Including 3,
The chloro- 5,6- dimethyl chlorides base neighbour benzoquinones of 4- bis-, the chloro- 4,6- dimethyl chlorides base neighbour benzoquinones of 3,5- bis-, the chloro- formyls of 4,5- bis- of 3,6- bis-
Chloro neighbour's benzoquinones）, the formyl chloro 1,4-benzoquinone of trichlorine one, the formyl chloro neighbour benzoquinones of trichlorine one, 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 the bromo- 5,6- dimethyl chlorides base 1,4-benzoquinone of 2,3- bis-, 2,
The bromo- 3,5- dimethyl chlorides base 1,4-benzoquinone of the bromo- 3,6- dimethyl chlorides base 1,4-benzoquinone of 5- bis-, 2,6- bis-）, dibromo dimethyl chloride base neighbour's benzene
Quinone（It is bromo- including the bromo- 5,6- dimethyl chlorides base neighbour benzoquinones of 3,4- bis-, the bromo- 4,6- dimethyl chlorides base neighbour benzoquinones of 3,5- bis-, 3,6- bis-
4,5- dimethyl chloride base neighbour's benzoquinones）, the formyl chloro 1,4-benzoquinone of tribromo one, the formyl chloro neighbour benzoquinones of tribromo one, tetramethyl acid chloride group pair
Benzoquinones and tetramethyl acid chloride group neighbour's benzoquinones.
Preferably, the activator is selected from tetrachloroquinone（Including chloranil and monoethyl quinone）, dichloro dicyano
Benzoquinones（Including dichloro dicyano p-benzoquinone and dichloro dicyano neighbour's benzoquinones）, tetrahydrochysene benzoquinones（It is adjacent including tetrahydrochysene 1,4-benzoquinone and tetrahydrochysene
Benzoquinones）With four cyano benzoquinones（Including four cyano 1,4-benzoquinone and four cyano neighbour's benzoquinones）.
The compound that carbonium ion can be provided can be that various interacted with lewis acid can separate out carbon just
The compound of ion.Specifically, the compound that can provide carbonium ion can be selected from by one or moreOne or more hydrogen quilt on substituted alkane and arylSubstituted aromatic hydrocarbons, R15、R16、R17With
R18Respectively hydrogen, C1~C8Alkyl, phenyl, C7~C10Phenylalkyl, C7~C10Alkyl phenyl or C3~C8Cycloalkanes
Base；X6And X7One kind respectively in halogen group, such as-F ,-Cl ,-Br or-I, it is preferably-Cl or-Br.
The C7~C10Phenylalkyl refer to C1~C4A hydrogen atom in alkyl is substituted by phenyl the group to be formed,
Its instantiation can include but is not limited to：Benzyl, phenethyl, phenylpropyl（Wherein, propylidene can be sub- n-propyl or Asia
Isopropyl）With benzene butyl（Wherein, sub- normal-butyl can be sub- normal-butyl, sub- sec-butyl, isobutylidene or the sub- tert-butyl group）.
The C7~C10Alkyl phenyl refer to a hydrogen atom in phenyl by C1~C4Alkyl substitutes the group to be formed,
Its instantiation can include but is not limited to：Tolyl, ethylbenzene, propyl phenyl（Wherein, propyl group can be n-propyl or isopropyl
Base）, butylbenzene base（Wherein, butyl can be normal-butyl, sec-butyl, isobutyl group or the tert-butyl group）.
The C3~C8The instantiation of cycloalkyl can include but is not limited to：Cyclopropyl, cyclobutyl, cyclopenta, hexamethylene
Base, suberyl and cyclooctyl.
In the present invention, C1~C8Alkyl include C1~C8Straight chained alkyl and C3~C8Branched alkyl, its instantiation
It can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl,
2- methyl butyls, 3- methyl butyls, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methyl amyls, 4- methyl amyls,
2,3- dimethylbutyls, 2,2- dimethylbutyls, 3,3- dimethylbutyls, 2- ethyl-butyls, n-heptyl, 2- methylhexyls, 3-
Methylhexyl, 4- methylhexyls, 5- methylhexyls, 2,2- dimethyl amyl groups, 2,3- dimethyl amyl groups, 2,4- dimethyl amyl groups,
3,3- dimethyl amyl groups, 3,4- dimethyl amyl groups, 4,4- dimethyl amyl groups, 2- ethyl pentyl groups, 3- ethyl pentyl groups, n-octyl, 2-
Methylheptyl, 3- methylheptyls, 4- methylheptyls, 5- methylheptyls, 6- methylheptyls, 2,2- dimethylhexanyls, 2,3- diformazans
Base hexyl, 2,4- dimethylhexanyls, 2,5- dimethylhexanyls, 3,3- dimethylhexanyls, 3,4- dimethylhexanyls, 3,5- dimethyl
Hexyl, 4,4- dimethylhexanyls, 4,5- dimethylhexanyls, 5,5- dimethylhexanyls, 2- ethylhexyls, 3- ethylhexyls, 4- second
Base hexyl, 2- n-propyls amyl group and 2- isopropyl amyl groups.
The instantiation of the compound that carbonium ion can be provided can include but is not limited to：To dibenzyl chlorine（That is,
1,4- bis- (chloromethyl) benzene）, to dibenzyl bromide（That is, Isosorbide-5-Nitrae-two (bromomethyl) benzene）, to dicumyl chlorine（That is, (the 2- chlorine third of Isosorbide-5-Nitrae-two
Base) benzene）, to dicumyl bromine（That is, Isosorbide-5-Nitrae-two (2- bromopropyls) benzene）, 1,4- bis- (1- chloroethyls) benzene, 1,4- bis- (1- bromoethyls)
Benzene, (2- chloropropyls) benzene of 1,4- bis- and 1,4- bis- (2- bromopropyls) benzene.
The lewis acid contains the compound shown in Formula II and the compound shown in formula III,
In Formula II, R9And R10Respectively C1~C8Straight or branched alkyl, respectively preferably C1~C4Straight or branched
Alkyl；X3It is preferably-Cl or-Br for one kind in halogen group, such as-F ,-Cl ,-Br or-I；
In formula III, R11For C1~C8Straight or branched alkyl, respectively preferably C1~C4Straight or branched alkyl；X4
And X5One kind respectively in halogen group, such as-F ,-Cl ,-Br or-I, it is preferably-Cl or-Br.
The instantiation of compound shown in Formula II can include but is not limited to：Dimethylaluminum chloride, diethyl aluminum chloride,
Diη-propyl aluminium chloride, diisopropyl aluminium chloride, di-n-butyl aluminium chloride and diisobutyl aluminum chloride.Preferably, shown in Formula II
Compound be diethyl aluminum chloride.
The instantiation of compound shown in formula III can include but is not limited to：Dichloromethyl aluminium, ethyl aluminum dichloride, two
Chlorine n-propyl aluminium, two chloro isopropyl aluminium, dichloro n-butylaluminum and dichloro aluminium isobutyl.Preferably, the compound shown in formula III is
Ethyl aluminum dichloride.
In the lewis acid, the content of the compound shown in compound and formula III shown in Formula II can be according to specific
Polymerizing condition and expected polymer property carry out appropriate selection.
Contain two alkyl in lewis acidic molecular structure shown in Formula II, can play and suppress cation activity center
The effect of chain tra nsfer occurs, so as to improve the molecular weight of the polymer of preparation.But lewis acidic shown in Formula II contains
Measure too high, can reduce polymerization rate, extend polymerization time.It is therefore preferred that on the basis of lewis acidic total amount, formula
The content of compound shown in II is 10~95 moles of %, and the content of the compound shown in formula III is 5~90 moles of %, such energy
It is enough that preferably balance is obtained between polymerization rate and polymer molecular weight.It is highly preferred that using lewis acidic total amount as
Benchmark, the content of the compound shown in Formula II is 30~70 moles of %（Such as 40~60 moles of %）, compound shown in formula III contains
Measure as 30~70 moles of %（Such as 40~60 moles of %）.
Relative scale between the compound that carbonium ion can be provided, the lewis acid and the activator can
To be selected according to specific polymerizing condition.Specifically, the compound that carbonium ion can be provided and the activator
Mol ratio can be 0.3~100：1, preferably 0.4~10：1, more preferably 0.5~5：1, more preferably 0.5~
2.5：1.The mol ratio of the lewis acid and the activator can be 4~1000：1, preferably 6~100：1, more preferably
8~50：1.
Conventional various methods can be used by the monoolefine and ring-alkylated styrenes and the initiator composition
Each component contacts, and to be polymerize, forms monoolefine-alkylstyrene copolymers.
In one embodiment of the invention, at least one monoolefine and at least one ring-alkylated styrenes are drawn with described
The method of each component contact in hair agent system includes：Each component in the initiator system is dissolved in solvent, and will
Obtained mixture ageing, obtains initiator solution；By the initiator solution and it is dissolved with the monoolefine and the alkyl
The diluent mixing of styrene.
The purpose of the ageing is in the lewis acid in initiator system is made and the compound that can provide carbonium ion
Stable complexing is formed with activator and triggers activated centre, can be carried out under normal conditions, and specifically, the ageing can be with
Carry out, preferably carried out within the temperature range of -100 DEG C to 0 DEG C, more preferably -100 within the temperature range of -100 DEG C to 20 DEG C
DEG C to carrying out within the temperature range of -40 DEG C.
The time of the ageing can be more than 10 minutes, such as 15 minutes to 10 hours.Preferably, the ageing when
Between be more than 30 minutes, such as 30 minutes to 5 hours, the initiation that so can further improve the initiator system of preparation was lived
Property, and further improve the polymerization activity of polymerization system.It is highly preferred that the time of the ageing is more than 60 minutes, such as 60 points
Clock can so obtain more excellent initiation activity, and then obtain higher polymerization activity to 120 minutes.
The solvent can be it is various can dissolve the compound that carbonium ion can be provided, the lewis acid and
The liquid substance of the activator.Usually, the solvent can be selected from alkane, halogenated alkane and aromatic hydrocarbons；It is preferably selected from C3~
C10Alkane, C1~C10Halogenated alkane and C6~C12Aromatic hydrocarbons；It is more preferably selected from C1~C10Halogenated alkane and C6~C12's
Aromatic hydrocarbons.Halogen atom in the halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.
The instantiation 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（Various isomers including trimethyl-cyclohexane, such as
1,2,3- trimethyl-cyclohexanes, 1,2,4- trimethyl-cyclohexanes, 1,2,5- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes）、
N-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl
Octane, 3- ethyls octane, 4- ethyls octane, 2,3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethyls heptan
Alkane, 2,4,5- trimethylheptanes, 2,4,6- trimethylheptanes, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5-
Trimethylheptane, 2,2,6- trimethylheptanes, 2,3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptan
Alkane, 2- methyl -4- ethyl heptanes, 2- methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5-
Methyl -3- ethyl heptanes, 4- methyl -4- ethyl heptanes, 4- propyl group heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2-
Methyl -3,3- diethylpentane, 1,2- diethyl cyclohexane, 1,3- diethyl cyclohexanes, Isosorbide-5-Nitrae-diethyl cyclohexane, normal-butyl
Hexamethylene, isobutyl butylcyclohexane, t-butylcyclohexane, tetramethyl-ring hexane（Various isomers including tetramethyl-ring hexane, such as
1,2,3,4- tetramethyl-rings hexane, 1,2,4,5- tetramethyl-rings hexane, 1,2,3,5- tetramethyl-ring hexanes）, monochloro methane, dichloro
Methane, chloroform, carbon tetrachloride, a fluoroethane, Difluoroethane, HFC-143a, HFC-134a, pentafluoroethane, carbon hexa fluoride,
Monochlorethane, dichloroethanes, trichloroethanes, tetrachloroethanes, pentachloroethane, carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro
Propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoropropane, a chloropropane, dichloropropane, trichloropropane,
Four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, octachloropropane, 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 paraxylene）.
The concentration of the initiator solution can be conventional selection, be not particularly limited.Usually, by weight, it is described
In initiator solution, the concentration of the activator can be 10~3000ppm, preferably 100~2000ppm, more preferably 200
~1500ppm.The dosage of the initiator solution can carry out appropriate selection according to specific polymerizing condition, that can trigger
Polymerization is defined.Those skilled in the art can determine to be adequate to bring about gathering under the teaching of prior art by the experiment of limited number of time
The initiator amount of conjunction, is no longer described in detail herein.
The monoolefine can be the monoolefine that can carry out cationic polymerization commonly used in the art.Usually, the list
Alkene be selected from the compound shown in formula IV,
In formula IV, R12And R13Respectively C1~C5Straight or branched alkyl；Or R12For hydrogen, R13For C3~C5Side chain
Alkyl.
In the present invention, C1~C5Straight or branched alkyl include C1~C5Straight chained alkyl and C3~C5Branched alkyl,
Its instantiation 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 isophthalic acids-
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 isophthalic acids-hexene, 2,3- dimethyl -1- hexenes, 2,4- bis-
Methyl isophthalic acid-hexene, 2,5- dimethyl -1- hexenes and 2,4,4- trimethyl -1- amylenes.
Preferably, the monoolefine is isobutene.
The ring-alkylated styrenes be selected from the compound shown in Formula V,
In Formula V, R14For C1~C5Straight or branched alkyl.
The example of the ring-alkylated styrenes can include but is not limited to：P-methylstyrene, a methyl styrene, to ethyl
Styrene and p-tert-butylstyrene.
Preferably, the ring-alkylated styrenes be selected from shown in Formula IV to alkylbenzene between shown in ring-alkylated styrenes and Formula VII
Ethene,
In Formula IV, R14For C1~C5Straight or branched alkyl；
In Formula VII, R14For C1~C5Straight or branched alkyl.
It is highly preferred that the ring-alkylated styrenes is to ring-alkylated styrenes and/or a ring-alkylated styrenes, such as p-methylstyrene
An and/or methyl styrene.
It is further preferred that in the ring-alkylated styrenes, the content to ring-alkylated styrenes is more than 80 weight %, such as can
Think 80~100 weight %.It is highly preferred that in the ring-alkylated styrenes, the content to ring-alkylated styrenes is more than 90 weight %, example
Such as can be 90~100 weight %.Most preferably, the ring-alkylated styrenes is preferably p-methylstyrene.
The relative usage of the monoolefine and the ring-alkylated styrenes can specifically should according to the polymer finally prepared
Appropriate selection is carried out with occasion.Usually, on the basis of the total amount of the monoolefine and ring-alkylated styrenes, the monoolefine
Content can be 80~99 weight %, preferably 90~97 weight %；The content of the ring-alkylated styrenes can be 1~20 weight %,
Preferably 3~10 weight %.
The diluent is selected from the polymerization according to the present invention, and the diluent can be that cationic polymerization field is commonly used
Diluent, such as alkane and/or halogenated alkane.
Preferably, the diluent contains the first diluent and the second diluent, and first diluent is aliphatic alkane
Hydrocarbon（That is, alkane）And/or alicyclic alkanes（That is, cycloalkane）, second diluent is halogenated alkane, can so be obtained
Polymer with higher molecular weight.Relative scale between first diluent and the second diluent can be wanted according to specific
Ask and selected.Usually, on the basis of the total amount of the diluent, the content of second diluent can be 1~80 body
Product %, preferably 20~50 volume %；The content of first diluent can be 20~99 volume %, preferably 50~80 bodies
Product %.
The aliphatic alkane is preferably C3~C10Aliphatic alkane, more preferably C3~C8Aliphatic alkane, enter one
Step is preferably C5~C8Aliphatic alkane；The alicyclic alkanes are preferably C3~C10Alicyclic alkanes, more preferably
C5~C10Alicyclic alkanes.The halogenated alkane is preferably C1~C10Halogenated alkane, more preferably C1~C4Alkyl halide
Hydrocarbon, the halogen atom in the halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.
The instantiation of first diluent can include but is not limited to：It is propane, normal butane, iso-butane, pentane, different
Pentane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl ring
Pentane, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- bis-
Methylpentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethyl oneself
Alkane, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethyls penta
Alkane, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes,
2,4- dimethyl heptanes, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5-
Trimethyl cyclohexane, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyls oneself
Alkane, 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- first
Base -4- ethyl cyclohexanes, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane, n-decane, 2- methylnonanes, 3- first
Base nonane, 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- trimethylheptanes, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- trimethylheptanes, 2,2,6- trimethyls
Heptane, 2,3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 2- methyl -4- ethyl heptanes, 2-
Methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyl heptanes, 4- methyl -
4- ethyl heptanes, 4- propyl group heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- diethylpentanes, 1,
2- diethyl cyclohexanes, 1,3- diethyl cyclohexanes, 1,4- diethyl cyclohexanes, n-butyl cyclohexane, isobutyl butylcyclohexane, uncle
Butyl cyclohexane and tetramethyl-ring hexane.
The instantiation of second diluent can include but is not limited to：Monochloro methane, dichloromethane, chloroform,
Carbon tetrachloride, a fluoroethane, Difluoroethane, HFC-143a, HFC-134a, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloro
Ethane, trichloroethanes, tetrachloroethanes, pentachloroethane, carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane,
Pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoropropane, a chloropropane, dichloropropane, trichloropropane, four chloropropanes, pentachloro-
Propane, chlordene propane, heptachloropropane, octachloropropane, 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, tetrachloro
Butane, pentachlorobutane, chlordene butane, heptachlor butane, telodrine alkane, nine chlorobutanes and ten chlorobutanes.
Preferably, first diluent is selected from pentane, n-hexane and normal heptane, and second diluent is dichloromethane
Alkane and/or monochlorethane.
The dosage of the diluent can be the conventional selection of this area.Usually, the dosage of the diluent causes always
Monomer concentration is 2~25 weight %, preferably 5~20 weight %.
The method according to the invention, the cationic polymerization condition can be the conventional selection of this area.Usually, it is described
The condition of cationic polymerization can make it that the temperature of diluent is -120 DEG C to 20 DEG C, it is preferable that the temperature of diluent is -100
DEG C to 0 DEG C, the temperature for more preferably causing diluent is -100 DEG C to -40 DEG C.The method according to the invention, the time of the contact
It can be the conventional selection of this area, repeat no more herein.
The method according to the invention, it is additionally may included in polymerize to complete to polymerize backward in obtained mixture and adds polymerization eventually
Only agent terminates polymerisation（Such as alcohol）.The present invention does not limit especially for the species and dosage of the polymerization terminator
It is fixed, it can be the conventional selection of this area, be defined so that polymerisation can be terminated, repeated no more herein.
Describe the present invention in detail with reference to embodiments.
In following examples and comparative example, polymer yield is determined using weight method,
Polymer yield（%）=（The gross weight of the monomer of weight/addition of obtained polymer）×100%.
In following examples and comparative example, the molecular weight and molecular weight distributing index of polymer（Mw/Mn）Using Japanese Shimadzu
Company's production LC-20A type liquid phases gel permeation chromatograph measure, using single aperture chromatographic column
WithFour posts are combined.Mobile phase is tetrahydrofuran, flow velocity 0.7mL/min；Sample solution concentration is 2mg/mL, sample size
For 200 μ L；Test temperature is 35 DEG C；Standard sample is used as using single distribution polystyrene.
In following examples and comparative example, proton nmr spectra test is using commercially available from Bruker companies of Switzerland
AVANCE400 NMRs, with CDCl3As solvent, with tetramethylsilane（TMS）For internal standard.
Solvent and monomer used in following examples and comparative example using method commonly used in the art before use, entered
Row is refined, and the preparation of polymerisation and initiator solution is in the doing commercially available from German MBRAUN companies equipped with low temperature cryostat
Carried out in dry case.
Embodiment 1~20 is used to illustrate the present invention.
Embodiment 1
（1）The chloro- 5,6- dicyano p-benzoquinones of 0.0497g2,3- bis- and 0.0422g are dissolved in 62.1g dichloros to dibenzyl chlorine
In methane, obtained solution is cooled to -85 DEG C in advance, two chloroethenes that 4.0mL concentration is 0.9mol/L are then added into the solution
Base aluminium（EADC）Hexane solution and 0.44mL concentration be 0.9mol/L diethyl aluminum chloride（DEAC）Toluene solution match somebody with somebody
Into initiator solution, it is placed in -80 DEG C of cryostat and is aged after well mixed.By weight, 2,3- bis- in initiator solution
The content 800ppm of chloro- 5,6- dicyano p-benzoquinones, the content to dibenzyl chlorine are 680ppm.
（2）Successively to equipped with the churned mechanically 500mL glass polymerizations reactor of strength constant speed add 100mL be cooled to-
80 DEG C of n-hexane, 100mL be cooled to -80 DEG C of monochloro methane, 22mL is cooled to -80 DEG C of isobutene and 0.92mL normal temperature
P-methylstyrene（Content is 98 weight %）, start and form monomer solution after being stirred.Temperature, Xiang Dan are controlled using liquid nitrogen
16mL steps are slowly added dropwise in liquid solution（1）Prepare and 100min initiator solution is aged at -80 DEG C, then stirring reaction
12min, controlling reaction temperature is in the range of -80 DEG C to -85 DEG C in course of reaction.
After reaction terminates, the methanol solution that 5mL contains 0.5 weight %NaOH is added into reactant mixture and is polymerize with terminating
Reaction.Then, mixed solution is placed in desolvation in hot bath, dried after washing in vacuum drying oven in 60 DEG C to constant weight,
Obtain polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 2
It is polymerize using method same as Example 1, unlike, step（1）In the initiator solution of preparation, with
Weight meter, the content 50ppm. of 2,3- bis- chloro- 5,6- dicyano p-benzoquinones
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Comparative example 1
It is polymerize using method same as Example 2, unlike, step（1）In without using bis- chloro- 5,6- of 2,3-
Dicyano p-benzoquinone.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 3
It is polymerize using method same as Example 1, unlike, step（1）In, with etc. quality tetrachloro-p-phenylene
Quinone replaces the chloro- 5,6- dicyano p-benzoquinones of 2,3- bis-.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 4
It is polymerize using method same as Example 1, unlike, step（1）In, with etc. quality tetrahydrochysene to benzene
Quinone replaces the chloro- 5,6- dicyano p-benzoquinones of 2,3- bis-.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 5
It is polymerize using method same as Example 1, unlike, step（1）In, with etc. quality four cyano pair
Benzoquinones replaces the chloro- 5,6- dicyano p-benzoquinones of 2,3- bis-.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 6
It is polymerize using method same as Example 1, unlike, step（2）The middle initiator solution that uses is
Step（1）Prepare and 60min initiator solution is aged at -80 DEG C.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 7
It is polymerize using method same as Example 1, unlike, step（2）The middle initiator solution that uses is
Step（1）Prepare and 30min initiator solution is aged at -80 DEG C.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 8
It is polymerize using method same as Example 1, unlike, step（2）The middle initiator solution that uses is
Step（1）Prepare and 15min initiator solution is aged at -80 DEG C.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 9
It is polymerize using method same as Example 1, unlike, step（2）In, cryostat is controlled in course of reaction
Temperature is in the range of -60 DEG C to -70 DEG C.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 10
It is polymerize using method same as Example 1, unlike, step（2）In, cryostat is controlled in course of reaction
Temperature is in the range of -40 DEG C to -50 DEG C.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 11
（1）The chloro- 5,6- dicyano p-benzoquinones of 0.0497g2,3- bis- and 0.0422g are dissolved in 62.1g dichloros to dibenzyl chlorine
In methane, obtained solution is cooled to -85 DEG C in advance, two chloroethenes that 2.3mL concentration is 0.9mol/L are then added into the solution
The hexane solution and 1.0mL concentration of base aluminium are that the toluene solution of 0.9mol/L diethyl aluminum chloride is made into initiator solution,
It is placed in -80 DEG C of cryostat and is aged after well mixed.By weight, chloro- 5, the 6- dicyanos of 2,3- bis- in initiator solution
The content 800ppm of 1,4-benzoquinone, the content to dibenzyl chlorine are 680ppm.
（2）Successively to equipped with the churned mechanically 500mL glass polymerizations reactor of strength constant speed add 100mL be cooled to-
80 DEG C of n-hexane, 100mL be cooled to -80 DEG C of monochloro methane, 22mL is cooled to -80 DEG C of isobutene and 0.92mL normal temperature
P-methylstyrene（Content is 98 weight %）, start and form monomer solution after being stirred.Temperature, Xiang Dan are controlled using liquid nitrogen
15mL steps are slowly added dropwise in liquid solution（1）Prepare and 100min initiator solution is aged at -80 DEG C, then stirring reaction
10min, controlling reaction temperature is in the range of -80 DEG C to -85 DEG C in course of reaction.
After reaction terminates, the methanol solution that 5mL contains 0.5 weight %NaOH is added into reactant mixture and is polymerize with terminating
Reaction.Then, mixed solution is placed in desolvation in hot bath, dried after washing in vacuum drying oven in 60 DEG C to constant weight,
Obtain polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 12
It is polymerize using with the identical method of embodiment 11, unlike, step（2）In, the dosage of n-hexane is
140mL, the dosage of monochloro methane is 60mL.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 13
It is polymerize using with the identical method of embodiment 11, unlike, step（2）In, the dosage of n-hexane is
160mL, the dosage of monochloro methane is 40mL.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 14
（1）The chloro- 5,6- dicyano p-benzoquinones of 0.0497g2,3- bis- and 0.0422g are dissolved in 62.1g dichloros to dibenzyl chlorine
In methane, obtained solution is cooled to -85 DEG C in advance, two chloroethenes that 1.7mL concentration is 0.9mol/L are then added into the solution
The hexane solution and 1.7mL concentration of base aluminium are that the toluene solution of 0.9mol/L diethyl aluminum chloride is made into initiator solution,
It is placed in -80 DEG C of cryostat and is aged after well mixed.By weight, chloro- 5, the 6- dicyanos of 2,3- bis- in initiator solution
The content 800ppm of 1,4-benzoquinone, the content to dibenzyl chlorine are 680ppm.
（2）Into 250mL polymerization bottle, 60mL is cooled to -80 DEG C of n-hexane, 40mL is cooled to -80 DEG C for addition successively
Monochloro methane, 11mL are cooled to -80 DEG C of isobutene and the p-methylstyrene of 0.46mL normal temperature（Content is 98 weight %）, mix
Monomer solution is formed after conjunction.Polymerization bottle is placed in -80 DEG C of low temperature cryostat, 10mL steps are added into monomer solution（1）Match somebody with somebody
Make and 60min initiator solution is aged at -80 DEG C, then stand reaction 60min, controlled in course of reaction at cryostat temperature
In the range of -80 DEG C to -85 DEG C.
After reaction terminates, the methanol solution that 5mL contains 0.5 weight %NaOH is added into reactant mixture and is polymerize with terminating
Reaction.Then, mixed solution is placed in desolvation in hot bath, dried after washing in vacuum drying oven in 60 DEG C to constant weight,
Obtain polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 15
It is polymerize using with the identical method of embodiment 14, unlike, step（2）In, the dosage of n-hexane is
80mL, the dosage of monochloro methane is 20mL.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 16
（1）0.0497g chloranils and 0.0422g are dissolved in 62.1g dichloromethane to dibenzyl chlorine, by what is obtained
Solution is cooled to -85 DEG C in advance, and the hexane solution for the ethyl aluminum dichloride that 1.7mL concentration is 0.9mol/L is then added into the solution
Initiator solution is made into the toluene solution for the diethyl aluminum chloride that 1.7mL concentration is 0.9mol/L, -80 are placed in after well mixed
DEG C cryostat in be aged.By weight, in initiator solution chloranil content 800ppm, dibenzyl chlorine is contained
Measure as 680ppm.
（2）Into 250mL polymerization bottle, 60mL is cooled to -80 DEG C of n-hexane, 40mL is cooled to -80 DEG C for addition successively
Monochloro methane, 11mL are cooled to -80 DEG C of isobutene and the p-methylstyrene of 0.46mL normal temperature（Content is 98 weight %）, mix
Monomer solution is formed after conjunction.Polymerization bottle is placed in -80 DEG C of low temperature cryostat, 10mL steps are added into monomer solution（1）Match somebody with somebody
Make and 100min initiator solution is aged at -80 DEG C, then stand reaction 60min, controlled in course of reaction at cryostat temperature
In the range of -80 DEG C to -85 DEG C.
After reaction terminates, the methanol solution that 5mL contains 0.5 weight %NaOH is added into reactant mixture and is polymerize with terminating
Reaction.Then, mixed solution is placed in desolvation in hot bath, dried after washing in vacuum drying oven in 60 DEG C to constant weight,
Obtain polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 17
It is polymerize using with the identical method of embodiment 16, unlike, step（2）In, the dosage of n-hexane is
80mL, the dosage of monochloro methane is 20mL.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 18
It is polymerize using with the identical method of embodiment 16, unlike, step（1）In, by 0.0497g tetrachloro-p-phenylenes
Quinone and 0.0621g are dissolved in 62.1g dichloromethane to dibenzyl chlorine, and obtained solution is cooled into -85 DEG C in advance, then to the solution
The diethyl that the hexane solution and 1.7mL concentration for the ethyl aluminum dichloride that middle addition 1.7mL concentration is 0.9mol/L are 0.9mol/L
The toluene solution of base aluminium chloride is made into initiator solution, is placed in -80 DEG C of cryostat and is aged after well mixed.With weight
Count, the content 800ppm of chloranil in initiator solution, the content to dibenzyl chlorine is 1000ppm.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 19
It is polymerize using with the identical method of embodiment 16, unlike, step（1）In, with etc. quality to dibenzyl
Bromide is replaced to dibenzyl chlorine.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Embodiment 20
（1）The chloro- 5,6- dicyano p-benzoquinones of 0.0186g2,3- bis- and 0.0422g are dissolved in 62.1g dichloros to dibenzyl chlorine
In methane, obtained solution is cooled to -85 DEG C in advance, two chloroethenes that 4.0mL concentration is 0.9mol/L are then added into the solution
The hexane solution and 0.44mL concentration of base aluminium are that the toluene solution of 0.9mol/L diethyl aluminum chloride is made into initiator solution,
It is placed in -80 DEG C of cryostat and is aged after well mixed.By weight, chloro- 5, the 6- dicyanos of 2,3- bis- in initiator solution
The content 300ppm of 1,4-benzoquinone, the content to dibenzyl chlorine are 680ppm.
（2）Successively to equipped with the churned mechanically 500mL glass polymerizations reactor of strength constant speed add 140mL be cooled to-
80 DEG C of n-hexane, 60mL be cooled to -80 DEG C of monochloro methane, 22mL is cooled to -80 DEG C of isobutene and 1.26mL normal temperature
P-methylstyrene（Content is 98 weight %）, start and form monomer solution after being stirred.Temperature, Xiang Dan are controlled using liquid nitrogen
15mL steps are slowly added dropwise in liquid solution（1）Prepare and 100min initiator solution is aged at -80 DEG C, then stirring reaction
12min, controlling reaction temperature is in the range of -80 DEG C to -85 DEG C in course of reaction.
After reaction terminates, the methanol solution that 5mL contains 0.5 weight %NaOH is added into reactant mixture and is polymerize with terminating
Reaction.Then, mixed solution is placed in desolvation in hot bath, dried after washing in vacuum drying oven in 60 DEG C to constant weight,
Obtain polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of obtained polymer are listed in table 1.
Claims (22)
1. a kind of cationic polymerization process, this method are included under the conditions of cationic polymerization, near at least one diluent
A kind of few monoolefine and at least one ring-alkylated styrenes contact with each component in initiator system, and the initiator system is by extremely
A kind of few compound that carbonium ion can be provided, at least one lewis acid and at least one activator composition, it is described can
The mol ratio for providing the compound of carbonium ion, the lewis acid and the activator is 0.3~100：4~1000：1,
The activator is selected from the compound shown in compound and Formulas I -2 shown in Formulas I -1,
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 contains the compound shown in Formula II and the compound shown in formula III,
In Formula II, R9And R10Respectively C1~C8Straight or branched alkyl, X3For one kind in halogen group；
In formula III, R11For C1~C8Straight or branched alkyl, X4And X5One kind respectively in halogen group；
The compound that carbonium ion can be provided is selected from quiltSubstituted aromatic hydrocarbons, R17And R18Respectively hydrogen, C1~
C8Alkyl, phenyl, C7~C10Phenylalkyl, C7~C10Alkyl phenyl or C3~C8Cycloalkyl, X7For in halogen group
One kind；
The monoolefine is selected from the compound shown in formula IV,
In formula IV, R12And R13Respectively C1~C5Straight or branched alkyl；Or R12For hydrogen, R13For C3~C5Branched alkane
Base；
The ring-alkylated styrenes is selected from the compound shown in Formula V,
In Formula V, R14For C1~C5Straight or branched alkyl；
The diluent contains the first diluent and the second diluent, and first diluent is aliphatic alkane and/or alicyclic ring
Race's alkane, second diluent are halogenated alkane.
2. the method according to claim 11, wherein, the compound that carbonium ion can be provided, the lewis acid
Mol ratio with the activator is 0.4~10：6~100：1.
3. the method according to claim 11, wherein, the compound that carbonium ion can be provided, the lewis acid
Mol ratio with the activator is 0.5~5：8~50：1.
4. according to the method for claim 1, wherein, by least one monoolefine and at least one ring-alkylated styrenes with it is described
The method of each component contact in initiator system includes：Each component in the initiator system is dissolved in solvent, and
Obtained mixture is aged, obtains initiator solution；By the initiator solution and it is dissolved with the monoolefine and the alkane
The diluent mixing of base styrene.
5. according to the method for claim 4, wherein, the time of the ageing is 15 minutes to 10 hours.
6. according to the method for claim 5, wherein, the time of the ageing is 30 minutes to 5 hours.
7. according to the method for claim 6, wherein, the time of the ageing is 60 minutes to 120 minutes.
8. the method according to any one in claim 4~7, wherein, temperature of the ageing at -100 DEG C to 20 DEG C
In the range of carry out.
9. according to the method for claim 8, wherein, the ageing is carried out within the temperature range of -100 DEG C to 0 DEG C.
10. according to the method for claim 4, wherein, the solvent is one kind in alkane, halogenated alkane and aromatic hydrocarbons
It is or a variety of.
11. the method according to any one in Claims 1 to 4, wherein, the activator is selected from tetrachloroquinone, dichloro
Dicyano benzoquinone, tetrahydrochysene benzoquinones and four cyano benzoquinones.
12. the method according to claim 11, wherein, X7Respectively-Cl or-Br.
13. according to the method for claim 1, wherein, the compound that can provide carbonium ion is to dibenzyl chlorine
And/or to dibenzyl bromide.
14. according to the method for claim 1, wherein, the compound shown in Formula II is diethyl aluminum chloride, shown in formula III
Compound be ethyl aluminum dichloride.
15. according to the method described in any one in Claims 1 to 4 and 14, wherein, using the lewis acidic total amount as base
Standard, the content of the compound shown in Formula II is 10~95 weight %, and the content of the compound shown in formula III is 5~90 weight %.
16. the method according to claim 11, wherein, on the basis of the total amount of the monoolefine and the ring-alkylated styrenes,
The content of the monoolefine is 80~99 weight %；The content of the ring-alkylated styrenes is 1~20 weight %.
17. the method according to claim 11, wherein, using the total amount of the monoolefine and the ring-alkylated styrenes as base
Standard, the content of the monoolefine is 90~97 weight %；The content of the ring-alkylated styrenes is 3~10 weight %.
18. according to the method described in any one in claim 1,4,16 and 17, wherein, the monoolefine is isobutene.
19. according to the method described in any one in claim 1,4,16 and 17, wherein, the ring-alkylated styrenes is to methyl
Styrene and/or a methyl styrene.
20. the method according to claim 11, wherein, on the basis of the total amount of the diluent, first diluent
Content is 20~99 volume %, and the content of second diluent is 1~80 volume %.
21. according to the method for claim 1, wherein, the condition of the contact includes：Temperature is -100 DEG C to 20 DEG C.
22. according to the method for claim 21, wherein, the condition of the contact includes：Temperature is -100 DEG C to 0 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410136466.4A CN104974293B (en) | 2014-04-04 | 2014-04-04 | A kind of cationic polymerization process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410136466.4A CN104974293B (en) | 2014-04-04 | 2014-04-04 | A kind of cationic polymerization process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104974293A CN104974293A (en) | 2015-10-14 |
| CN104974293B true CN104974293B (en) | 2018-04-10 |
Family
ID=54271291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410136466.4A Active CN104974293B (en) | 2014-04-04 | 2014-04-04 | A kind of cationic polymerization process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104974293B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735643A (en) * | 2002-11-05 | 2006-02-15 | 阿肯马公司 | Synthesis method for polydimethylketene by friedel - craft cationic polymerization of dimethylketene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162445A (en) * | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
| CA2086098C (en) * | 1990-07-24 | 2001-09-18 | Vi N. Schmidt | Composition for tire carcass |
| CN102399311B (en) * | 2010-08-19 | 2013-12-04 | 中国石油化工股份有限公司 | Cationic polymerization initiation system and cationic polymerization method |
| CN103122052B (en) * | 2011-11-18 | 2015-12-09 | 北京化工大学 | A kind of soft section of crystallizable segmented copolymer of complete saturated hard section and preparation method thereof |
-
2014
- 2014-04-04 CN CN201410136466.4A patent/CN104974293B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735643A (en) * | 2002-11-05 | 2006-02-15 | 阿肯马公司 | Synthesis method for polydimethylketene by friedel - craft cationic polymerization of dimethylketene |
Non-Patent Citations (1)
| Title |
|---|
| "异丁烯与对甲基苯乙烯共聚合反应竞聚率的测定";任苹等;《弹性体》;20120225;第22卷(第1期);第25-28页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104974293A (en) | 2015-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104974293B (en) | A kind of cationic polymerization process | |
| CN104974291B (en) | Cationic polymerization method | |
| CN104558357B (en) | A kind of cationic polymerization process | |
| CN106146700B (en) | A kind of preparation method of halogen polymer | |
| CN104558341B (en) | cationic polymerization initiator system and application thereof and cationic polymerization method | |
| CN106317349B (en) | A kind of styrene-isomonoolefin-styrene triblock copolymer and preparation method thereof | |
| CN104558343B (en) | Positive ion polymerization method | |
| CN104974290B (en) | Cationic polymerization method | |
| CN104974292B (en) | Cationic polymerization method | |
| CN106146697B (en) | A kind of cationic polymerization process | |
| CN106032399B (en) | A kind of star block copolymer and preparation method thereof | |
| CN106146711B (en) | A kind of cationic polymerization process | |
| CN104558342B (en) | Cation polymerization method | |
| CN104558344B (en) | Cationic polymerization initiator system, application thereof and cationic polymerization method | |
| CN106146699B (en) | A kind of preparation method of halogen polymer | |
| CN106146703B (en) | A kind of cationic polymerization process | |
| CN106146708B (en) | A kind of cationic polymerization process | |
| CN105440231B (en) | The preparation method and block copolymer of a kind of block copolymer | |
| CN106146705B (en) | A kind of preparation method of halogen polymer | |
| CN106146701B (en) | A kind of preparation method of halogen polymer | |
| CN106146704A (en) | A kind of preparation method of halogen polymer | |
| CN106146709B (en) | A kind of cationic polymerization process | |
| CN106146706B (en) | A kind of cationic polymerization process | |
| CN106146702B (en) | A kind of preparation method of halogen polymer | |
| CN106146710B (en) | A kind of cationic polymerization process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |