CN104974290A - Cationic polymerization method - Google Patents
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- CN104974290A CN104974290A CN201410136388.8A CN201410136388A CN104974290A CN 104974290 A CN104974290 A CN 104974290A CN 201410136388 A CN201410136388 A CN 201410136388A CN 104974290 A CN104974290 A CN 104974290A
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Abstract
The invention discloses a cationic polymerization method. The method comprises the step that under the condition of cationic polymerization, at least one kind of monoolefine and at least one kind of alkylstyrene are in contact with each component in an initiator system in at least a diluent, wherein the initiator system contains at least a compound, at least a Lewis acid and at least an activator; the compound can provide carbocations; the activator is selected from a compound shown in a formula I-1 and a compound shown in a formula I-2. When alkylstyrene and monoolefine are copolymerized in the low-polarity diluent through cationic polymerization, the copolymerization activity of alkylstyrene can be obviously improved by adopting the method, thus improving the polymerization efficiency of a polymerization system, achieving higher polymer yields and obtaining polymers with higher molecular weights. The formula I-1 and the formula I-2 are shown in the specification.
Description
Technical field
The present invention relates to a kind of cationic polymerization process.
Background technology
Iso-butylene-p-methylstyrene the multipolymer of bromination is generally that the multipolymer of iso-butylene and p-methylstyrene is carried out bromination, is that bromometllylstyrene group obtains by part p-methylstyrene group transformations.Because molecular backbone chain is full saturated structures, therefore iso-butylene-p-methylstyrene the multipolymer of bromination has the over-all properties more excellent than brominated butyl rubber, especially has better resistance toheat; Further, due to the existence of highly active bromotoluene functional group, sulfuration and covulcanization can be realized with various rubber in wider scope, also there is the modification advantage of more wide region in addition.This product is through making the air retaining wall of dynamic vulcanization alloy for the production of tire with nylon blending, can accomplish not only light but also thin, therefore, the iso-butylene of bromination and p-methylstyrene multipolymer can be used for production and have more high performance tire, and have quite wide market application foreground.
Therefore, researchist has carried out large quantity research for iso-butylene with to alkylstyrene copolymers and halogenide thereof.Such as: US5162445 and US5959049 individually discloses iso-butylene and to alkylstyrene copolymers and preparation method thereof.
Summary of the invention
The present inventor finds in research process, iso-butylene is when carrying out cationoid polymerisation, its polymerization efficiency (that is, polymer yield) is insensitive to Diluent Polarity, but when iso-butylene and ring-alkylated styrenes are carried out copolymerization by cationoid polymerisation mode, with the reduction of Diluent Polarity, polymerization efficiency decreases, to such an extent as to when system is Polymerization in Different Buffers, the Copolymerization activity of p-methylstyrene significantly reduces, cause polymerization efficiency extreme difference, polymer yield is very low.
The present inventor is studied for the problems referred to above, find: when monoolefine and ring-alkylated styrenes are carried out cationic copolymerization in the mode of solution polymerization, if introduce a kind of quinonoid compound polymerization efficiency can be significantly improved in initiator system, improve the yield of polymkeric substance and the molecular weight of polymkeric substance.Complete the present invention on this basis.
The invention provides a kind of cationic polymerization process, under the method is included in cationoid polymerisation condition, in at least one thinner, by each component contacts at least one monoolefine and at least one ring-alkylated styrenes and initiator system, described initiator system contains at least one can provide the compound of carbonium ion, at least one Lewis acid and at least one activator
Described activator is selected from the compound shown in the compound shown in formula I-1 and formula I-2,
In formula I-1 and formula I-2, R
1, R
2, R
3, R
4, R
5, R
6, R
7and R
8be-H ,-X separately
1,-NO
2,
with the one in-CN, X
1and X
2be the one in halogen group separately;
Described monoolefine is selected from the compound shown in formula II,
In formula II, R
9and R
10be C separately
1~ C
5straight or branched alkyl; Or R
9for hydrogen, R
10for C
3~ C
5branched-chain alkyl;
Described ring-alkylated styrenes is selected from the compound shown in formula III,
In formula III, R
11for C
1~ C
5straight or branched alkyl.
When ring-alkylated styrenes and monoolefine are carried out copolymerization by cationoid polymerisation in low Polar diluents, method of the present invention can significantly improve the Copolymerization activity of ring-alkylated styrenes, thus improve the polymerization efficiency of polymerization system, obtain higher polymer yield and the polymkeric substance with more high molecular.
Embodiment
The invention provides a kind of cationic polymerization process, under the method is included in cationoid polymerisation condition, in at least one thinner, by each component contacts at least one monoolefine and at least one ring-alkylated styrenes and initiator system, described initiator system contains at least one can provide the compound of carbonium ion, at least one Lewis acid and at least one activator.
Described activator for being selected from the compound shown in the compound shown in formula I-1 and formula I-2,
In formula I-1 and formula I-2, R
1, R
2, R
3, R
4, R
5, R
6, R
7and R
8be-H ,-X separately
1,-NO
2,
with the one in-CN, X
1and X
2be the one (such as :-F ,-Cl ,-Br or-I) in halogen group separately.
The specific examples of described activator can include but not limited to: tetrahydrochysene para benzoquinone, the adjacent benzoquinones of tetrahydrochysene, one fluorine three hydrogen para benzoquinone, the adjacent benzoquinones of one fluorine three hydrogen, difluoro dihydro para benzoquinone, the adjacent benzoquinones of difluoro dihydro, trifluoro one hydrogen para benzoquinone, the adjacent benzoquinones of trifluoro one hydrogen, tetrafluoro para benzoquinone, the adjacent benzoquinones of tetrafluoro, one chlorine three hydrogen para benzoquinone, the adjacent benzoquinones of one chlorine three hydrogen, dichloro-dihydro para benzoquinone (comprises 2,3-dichloro para benzoquinone, 2,5-dichloro para benzoquinone, 2,6-dichloro para benzoquinone), the adjacent benzoquinones of dichloro-dihydro (comprises the adjacent benzoquinones of 3,4-dichloro, the adjacent benzoquinones of 3,5-dichloro, the adjacent benzoquinones of 3,6-dichloro), trichlorine one hydrogen para benzoquinone, the adjacent benzoquinones of trichlorine one hydrogen, chloranil, monoethyl quinone, monobromo three hydrogen para benzoquinone, the adjacent benzoquinones of monobromo three hydrogen, dibromo dihydro para benzoquinone (comprises 2,3-dibromo para benzoquinone, 2,5-dibromo para benzoquinone, 2,6-dibromo para benzoquinone), the adjacent benzoquinones of dibromo dihydro (comprises 3,4-dibromo-o benzoquinones, 3,5-dibromo-o benzoquinones, 3,6-dibromo-o benzoquinones), tribromo one hydrogen para benzoquinone, the adjacent benzoquinones of tribromo one hydrogen, tetrabromo para benzoquinone, tetrabromo-phthalic quinone, one fluorine trinitro-para benzoquinone, the adjacent benzoquinones of one fluorine trinitro-, difluoro dinitrobenzene para benzoquinone (comprises fluoro-5, the 6-dinitrobenzene para benzoquinone of 2,3-bis-, fluoro-3, the 6-dinitrobenzene para benzoquinone of 2,5-bis-, fluoro-3, the 5-dinitrobenzene para benzoquinone of 2,6-bis-), difluoro dinitro o benzoquinones (comprises fluoro-5, the 6-dinitro o benzoquinones of 3,4-bis-, fluoro-4, the 6-dinitro o benzoquinones of 3,5-bis-, fluoro-4, the 5-dinitro o benzoquinones of 3,6-bis-), trifluoro one nitro para benzoquinone, the adjacent benzoquinones of trifluoro one nitro, one chlorine trinitro-para benzoquinone, the adjacent benzoquinones of one chlorine trinitro-, dichloro dinitrobenzene para benzoquinone (comprises chloro-5, the 6-dinitrobenzene para benzoquinone of 2,3-bis-, chloro-3, the 6-dinitrobenzene para benzoquinone of 2,5-bis-, chloro-3, the 5-dinitrobenzene para benzoquinone of 2,6-bis-), dichloro dinitro o benzoquinones (comprises chloro-5, the 6-dinitro o benzoquinones of 3,4-bis-, chloro-4, the 6-dinitro o benzoquinones of 3,5-bis-, chloro-4, the 5-dinitro o benzoquinones of 3,6-bis-), trichlorine one nitro para benzoquinone, the adjacent benzoquinones of trichlorine one nitro, monobromo trinitro-para benzoquinone, the adjacent benzoquinones of monobromo trinitro-, dibromo dinitrobenzene para benzoquinone (comprises bromo-5, the 6-dinitrobenzene para benzoquinone of 2,3-bis-, bromo-3, the 6-dinitrobenzene para benzoquinone of 2,5-bis-, bromo-3, the 5-dinitrobenzene para benzoquinone of 2,6-bis-), dibromo dinitro o benzoquinones (comprises bromo-5, the 6-dinitro o benzoquinones of 3,4-bis-, bromo-4, the 6-dinitro o benzoquinones of 3,5-bis-, bromo-4, the 5-dinitro o benzoquinones of 3,6-bis-), tribromo one nitro para benzoquinone, the adjacent benzoquinones of tribromo one nitro, tetranitro para benzoquinone, the adjacent benzoquinones of tetranitro, one fluorine tricyano para benzoquinone, the adjacent benzoquinones of one fluorine tricyano, difluoro dicyano p-benzoquinone (comprises fluoro-5, the 6-dicyano p-benzoquinones of 2,3-bis-, fluoro-3, the 6-dicyano p-benzoquinones of 2,5-bis-, fluoro-3, the 5-dicyano p-benzoquinones of 2,6-bis-), the adjacent benzoquinones of difluoro dicyano (comprises the adjacent benzoquinones of fluoro-5, the 6-dicyanos of 3,4-bis-, the adjacent benzoquinones of fluoro-4, the 6-dicyanos of 3,5-bis-, the adjacent benzoquinones of fluoro-4, the 5-dicyanos of 3,6-bis-), trifluoro one cyano group para benzoquinone, the adjacent benzoquinones of trifluoro one cyano group, one chlorine tricyano para benzoquinone, the adjacent benzoquinones of one chlorine tricyano, dichloro dicyano p-benzoquinone (comprises chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-, chloro-3, the 6-dicyano p-benzoquinones of 2,5-bis-, chloro-3, the 5-dicyano p-benzoquinones of 2,6-bis-), the adjacent benzoquinones of dichloro dicyano (comprises the adjacent benzoquinones of chloro-5, the 6-dicyanos of 3,4-bis-, the adjacent benzoquinones of chloro-4, the 6-dicyanos of 3,5-bis-, the adjacent benzoquinones of chloro-4, the 5-dicyanos of 3,6-bis-), trichlorine one cyano group para benzoquinone, the adjacent benzoquinones of trichlorine one cyano group, monobromo tricyano para benzoquinone, the adjacent benzoquinones of monobromo tricyano, dibromo dicyano p-benzoquinone (comprises bromo-5, the 6-dicyano p-benzoquinones of 2,3-bis-, bromo-3, the 6-dicyano p-benzoquinones of 2,5-bis-, bromo-3, the 5-dicyano p-benzoquinones of 2,6-bis-), the adjacent benzoquinones of dibromo dicyano (comprises the adjacent benzoquinones of bromo-5, the 6-dicyanos of 3,4-bis-, the adjacent benzoquinones of bromo-4, the 6-dicyanos of 3,5-bis-, the adjacent benzoquinones of bromo-4, the 5-dicyanos of 3,6-bis-), tribromo one cyano group para benzoquinone, the adjacent benzoquinones of tribromo one cyano group, trinitro-one cyano group para benzoquinone, the adjacent benzoquinones of trinitro-one cyano group, dinitrobenzene dicyano p-benzoquinone (comprises 2,3-dinitrobenzene-5,6-dicyano p-benzoquinone, 2,5-dinitrobenzene-3,6-dicyano p-benzoquinone, 2,6-dinitrobenzene-3,5-dicyano p-benzoquinone), the adjacent benzoquinones of dinitrobenzene dicyano (comprises the adjacent benzoquinones of 3,4-dinitrobenzene-5,6-dicyano, the adjacent benzoquinones of 3,5-dinitrobenzene-4,6-dicyano, the adjacent benzoquinones of 3,6-dinitrobenzene-4,5-dicyano), one nitrotrimethylolmethane cyano group para benzoquinone, the adjacent benzoquinones of one nitrotrimethylolmethane cyano group, four cyano para benzoquinone, the adjacent benzoquinones of four cyano, one fluorine front three acid chloride group para benzoquinone, the adjacent benzoquinones of one fluorine front three acid chloride group, difluoro dimethyl chloride base para benzoquinone (comprises fluoro-5, the 6-dimethyl chloride base para benzoquinone of 2,3-bis-, fluoro-3, the 6-dimethyl chloride base para benzoquinone of 2,5-bis-, fluoro-3, the 5-dimethyl chloride base para benzoquinone of 2,6-bis-), the adjacent benzoquinones of difluoro dimethyl chloride base (comprises the adjacent benzoquinones of fluoro-5, the 6-dimethyl chloride bases of 3,4-bis-, the adjacent benzoquinones of fluoro-4, the 6-dimethyl chloride bases of 3,5-bis-, the adjacent benzoquinones of fluoro-4, the 5-dimethyl chloride bases of 3,6-bis-), trifluoro one formyl chloro para benzoquinone, the adjacent benzoquinones of trifluoro one formyl chloro, one chlorine front three acid chloride group para benzoquinone, the adjacent benzoquinones of one chlorine front three acid chloride group, dichloro dimethyl chloride base para benzoquinone (comprises chloro-5, the 6-dimethyl chloride base para benzoquinone of 2,3-bis-, chloro-3, the 6-dimethyl chloride base para benzoquinone of 2,5-bis-, chloro-3, the 5-dimethyl chloride base para benzoquinone of 2,6-bis-), the adjacent benzoquinones of dichloro dimethyl chloride base (comprises the adjacent benzoquinones of chloro-5, the 6-dimethyl chloride bases of 3,4-bis-, the adjacent benzoquinones of chloro-4, the 6-dimethyl chloride bases of 3,5-bis-, the adjacent benzoquinones of chloro-4, the 5-dimethyl chloride bases of 3,6-bis-), trichlorine one formyl chloro para benzoquinone, the adjacent benzoquinones of trichlorine one formyl chloro, monobromo front three acid chloride group para benzoquinone, the adjacent benzoquinones of monobromo front three acid chloride group, dibromo dimethyl chloride base para benzoquinone (comprises bromo-5, the 6-dimethyl chloride base para benzoquinone of 2,3-bis-, bromo-3, the 6-dimethyl chloride base para benzoquinone of 2,5-bis-, bromo-3, the 5-dimethyl chloride base para benzoquinone of 2,6-bis-), the adjacent benzoquinones of dibromo dimethyl chloride base (comprises the adjacent benzoquinones of bromo-5, the 6-dimethyl chloride bases of 3,4-bis-, the adjacent benzoquinones of bromo-4, the 6-dimethyl chloride bases of 3,5-bis-, the adjacent benzoquinones of bromo-4, the 5-dimethyl chloride bases of 3,6-bis-), tribromo one formyl chloro para benzoquinone, the adjacent benzoquinones of tribromo one formyl chloro, tetramethyl acid chloride group para benzoquinone and the adjacent benzoquinones of tetramethyl acid chloride group.
Preferably, described activator is selected from tetrachlorobenzoquinone (comprising chloranil and monoethyl quinone), DDQ (comprising dichloro dicyano p-benzoquinone and the adjacent benzoquinones of dichloro dicyano), tetrahydrochysene benzoquinones (comprising tetrahydrochysene para benzoquinone and the adjacent benzoquinones of tetrahydrochysene) and four cyano benzoquinones (comprising four cyano para benzoquinone and the adjacent benzoquinones of four cyano).
The described compound of carbonium ion that can provide can separate out the compound of carbonium ion for various interaction with Lewis acid.Particularly, the described compound of carbonium ion that can provide can be selected from by one or more
replace alkane and aryl in one or more hydrogen quilt
the aromatic hydrocarbons replaced, R
12, R
13, R
14and R
15be hydrogen, C separately
1~ C
8alkyl, phenyl, C
7~ C
10phenylalkyl, C
7~ C
10alkyl phenyl or C
3~ C
8cycloalkyl; X
3and X
4be the one in halogen group separately, as-F ,-Cl ,-Br or-I, be preferably-Cl or-Br.
Described C
1~ C
8alkyl comprise C
1~ C
8straight chained alkyl and C
3~ C
8branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethyl-butyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,2-dimethyl amyl group, 2,3-dimethyl amyl group, 2,4-dimethyl amyl group, 3,3-dimethyl amyl group, 3,4-dimethyl amyl group, 4,4-dimethyl amyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2,2-dimethylhexanyl, 2,3-dimethylhexanyl, 2,4-dimethylhexanyl, 2,5-dimethylhexanyl, 3,3-dimethylhexanyl, 3,4-dimethylhexanyl, 3,5-dimethylhexanyl, 4,4-dimethylhexanyl, 4,5-dimethylhexanyl, 5,5-dimethylhexanyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-n-propyl amyl group and 2-sec.-propyl amyl group.
Described C
7~ C
10phenylalkyl refer to C
1~ C
4a hydrogen atom in alkyl is substituted by phenyl the group of formation, its specific examples can include but not limited to: phenmethyl, styroyl, hydrocinnamyl are (wherein, propylidene can be sub-n-propyl or isopropylidene) and benzene butyl (wherein, sub-normal-butyl can be sub-normal-butyl, sub-sec-butyl, isobutylidene or the sub-tertiary butyl).
Described C
7~ C
10alkyl phenyl refer to that a hydrogen atom in phenyl is by C
1~ C
4alkyl replaces the group formed, its specific examples can include but not limited to: tolyl, ethylbenzene, propyl phenyl are (wherein, propyl group can be n-propyl or sec.-propyl), butylbenzene base (wherein, butyl can be normal-butyl, sec-butyl, isobutyl-or the tertiary butyl).
Described C
3~ C
8the specific examples of cycloalkyl can include but not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.
The described specific examples of the compound of carbonium ion that can provide can include but not limited to: to dibenzyl chlorine (namely, 1,4-bis-(chloromethyl) benzene), to dibenzyl bromine (namely, 1,4-bis-(brooethyl) benzene), to dicumyl chlorine (namely, 1,4-bis-(2-chloropropyl) benzene), to dicumyl bromine (namely, 1,4-bis-(2-bromopropyl) benzene), Isosorbide-5-Nitrae-two (1-chloroethyl) benzene, Isosorbide-5-Nitrae-two (1-bromotrifluoromethane) benzene, 1,4-bis-(2-chloropropyl) benzene and Isosorbide-5-Nitrae-two (2-bromopropyl) benzene.
Described Lewis acid can be that the routine in cationoid polymerisation field is selected, and such as, described Lewis acid can be selected from but be not limited to: the compound shown in formula IV, BF
3, BCl
3, TiCl
4, SnCl
4and ZnCl
2,
AlR
16 nx
5 (3-n)(formula IV)
In formula IV, n R
16be C separately
1~ C
8alkyl; 3-n X
5be the one in halogen group separately, as-F ,-Cl ,-Br or-I, be preferably-Cl; N is 0,1,2 or 3, is preferably 1.
Preferably, described Lewis acid is the compound shown in formula IV.
The specific examples of the compound shown in formula IV can include but not limited to: dichloromethyl aluminium, ethyl aluminum dichloride, dichloro n-propyl aluminium, two chloro isopropyl aluminium, dichloro n-butylaluminum, dichloro aluminium isobutyl, dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminum chloride, di-isopropyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride and aluminum chloride.
Describedly can provide the compound of carbonium ion, relative proportion between described Lewis acid and described activator can select according to concrete polymerizing condition.Particularly, the described mol ratio of the compound of carbonium ion and described activator that can provide can be 0.3 ~ 100:1, is preferably 0.4 ~ 10:1, is more preferably 0.5 ~ 5:1.The mol ratio of described Lewis acid and described activator can be 4 ~ 1000:1, is preferably 5 ~ 100:1, is more preferably 6 ~ 50:1.
Conventional various methods can be adopted each component contacts in described monoolefine and ring-alkylated styrenes and described initiator composition, to be polymerized, form monoolefine-alkylstyrene copolymers.
In one embodiment of the invention, the method of each component contacts at least one monoolefine and at least one ring-alkylated styrenes and described initiator system is comprised: by each components dissolved in described initiator system in solvent, and the mixture ageing that will obtain, obtain initiator solution; By described initiator solution and the mixing diluents being dissolved with described monoolefine and described ring-alkylated styrenes.
The object of described ageing is make the Lewis acid in initiator system and the compound of carbonium ion and activator can be provided to form stable complexing initiating activity center, can carry out under normal conditions, particularly, described ageing can be carried out in the temperature range of-100 DEG C to 20 DEG C, preferably carry out in the temperature range of-100 DEG C to 0 DEG C, more preferably carry out in the temperature range of-100 DEG C to-40 DEG C.
The time of described ageing can be more than 10 minutes, such as 15 minutes to 10 hours.Preferably, the time of described ageing is more than 30 minutes, such as 30 minutes to 5 hours, can improve the initiating activity of the initiator system of preparation so further, and improves the polymerization activity of polymerization system further.More preferably, the time of described ageing is more than 60 minutes, as 60 minutes to 120 minutes, can obtain more excellent initiating activity like this, and then obtains higher polymerization activity.
Described solvent can dissolve the described liquid substance that can provide the compound of carbonium ion, described Lewis acid and described activator for various.Usually, described solvent can be selected from alkane, halogenated alkane and aromatic hydrocarbons; Be preferably selected from C
3~ C
10alkane, C
1~ C
10halogenated alkane and C
6~ C
12aromatic hydrocarbons; More preferably C is selected from
1~ C
10halogenated alkane and C
6~ C
12aromatic hydrocarbons.Halogen atom in described halogenated alkane can be chlorine, bromine or fluorine, is preferably chlorine or fluorine.
The specific examples of described solvent can include but not limited to: propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, pentamethylene, normal hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, hexanaphthene, methylcyclopentane, normal heptane, 2-methyl hexane, 3-methyl hexane, 2-ethylpentane, 3-ethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3-ethyl hexane, 2，2，3-trimethyl-pentane, 2,3,3-trimethylpentane, 2,4,4-trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3-dimethyl heptane, 2,4-dimethyl heptane, 3-ethyl heptane, 4-ethyl heptane, 2,3,4-trimethyl cyclohexane, 2,3,5-trimethyl cyclohexane, 2,4,5-trimethyl cyclohexane, 2,2,3-trimethyl cyclohexane, 2,2,4-trimethyl cyclohexane, 2,2,5-trimethyl cyclohexane, 2,3,3-trimethyl cyclohexane, 2,4,4-trimethyl cyclohexane, 2-methyl-3-ethyl hexane, 2-methyl-4-ethyl hexane, 3-methyl-3-ethyl hexane, 3-methyl-4-ethyl hexane, 3,3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propyl hexanaphthene, normenthane, trimethyl-cyclohexane (comprises the various isomer of trimethyl-cyclohexane, as 1,2,3-trimethyl-cyclohexane, 1,2,4-trimethyl-cyclohexane, 1,2,5-trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexane), n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2,3-dimethyl octane, 2,4-dimethyl octane, 3-ethyl octane, 4-ethyl octane, 2,3,4-trimethylheptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane, 2,4,5-trimethylheptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6-trimethylheptane, 2,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethyl heptane, 2-methyl-4-ethyl heptane, 2-methyl-5-ethyl heptane, 3-methyl-3-ethyl heptane, 4-methyl-3-ethyl heptane, 5-methyl-3-ethyl heptane, 4-methyl-4-ethyl heptane, 4-propyl group heptane, 3,3-diethylhexane, 3,4-diethylhexane, 2-methyl-3,3-diethylpentane, 1,2-diethyl cyclohexane, 1,3-diethyl cyclohexane, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl-hexanaphthene, t-butylcyclohexane, tetramethyl-ring hexane (comprises the various isomer of tetramethyl-ring hexane, as 1,2,3,4-tetramethyl-ring hexane, 1,2,4,5-tetramethyl-ring hexane, 1,2,3,5-tetramethyl-ring hexane), monochloro methane, methylene dichloride, trichloromethane, tetracol phenixin, one fluoroethane, C2H4F2 C2H4F2, Halothane, Tetrafluoroethane, pentafluoride ethane, carbon hexa fluoride, monochlorethane, ethylene dichloride, trichloroethane, tetrachloroethane, pentaline, carbon hexachloride, one fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoropropane, one chloropropane, propylene dichloride, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, octachloropropane, one fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, Octafluorobutane, nine fluorine butane, ten fluorine butane, one chlorobutane, dichlorobutane, three chlorobutanes, four chlorobutanes, pentachlorobutane, chlordene butane, heptachlor butane, telodrine alkane, nine chlorobutanes, ten chlorobutanes, toluene, ethylbenzene and dimethylbenzene (comprise o-Xylol, m-xylene and p-Xylol).
The concentration of described initiator solution can be conventional selection, is not particularly limited.Usually, by weight, in described initiator solution, the concentration of described activator can be 10 ~ 3000ppm, is preferably 100 ~ 2000ppm, is more preferably 200 ~ 1500ppm.The consumption of described initiator solution can carry out appropriate selection according to concrete polymerizing condition, being as the criterion by initiated polymerization.Those skilled in the art under the instruction of prior art, can determine by the experiment of limited number of time the initiator amount being enough to initiated polymerization, no longer describe in detail herein.
The monoolefine that can carry out cationoid polymerisation that described monoolefine can be commonly used for this area.Usually, described monoolefine for being selected from the compound shown in formula II,
In formula II, R
9and R
10be C separately
1~ C
5straight or branched alkyl; Or R
9for hydrogen, R
10for C
3~ C
5branched-chain alkyl.
In the present invention, C
1~ C
5straight or branched alkyl comprise C
1~ C
5straight chained alkyl and C
3~ C
5branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
Particularly, described monoolefine can be selected from but be not limited to: 2-methyl-1-propylene (namely, iso-butylene), 2-methyl-1-butene alkene, 3-methyl-1-butene, 2,3-dimethyl-1-butylene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2,3-dimethyl-1-amylenes, 2,4-dimethyl-1-amylene, 2-methyl isophthalic acid-hexene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexenes, 2,5-dimethyl-1-hexenes and 2,4,4-trimethylammonium-1-amylene.
Preferably, described monoolefine is iso-butylene.
Described ring-alkylated styrenes for being selected from the compound shown in formula III,
In formula III, R
11for C
1~ C
5straight or branched alkyl.
The example of described ring-alkylated styrenes can include but not limited to: p-methylstyrene, a vinyl toluene, p-ethyl-styrene and p-tert-butylstyrene.
Preferably, described ring-alkylated styrenes be selected from shown in formula V to ring-alkylated styrenes between shown in ring-alkylated styrenes and formula VI,
In formula V, R
11for C
1~ C
5straight or branched alkyl;
In formula VI, R
11for C
1~ C
5straight or branched alkyl.
More preferably, described ring-alkylated styrenes is to ring-alkylated styrenes and/or a ring-alkylated styrenes, as p-methylstyrene and/or a vinyl toluene.
Further preferably, in described ring-alkylated styrenes, being more than 80 % by weight to the content of ring-alkylated styrenes, such as, can be 80 ~ 100 % by weight.More preferably, in described ring-alkylated styrenes, being more than 90 % by weight to the content of ring-alkylated styrenes, such as, can be 90 ~ 100 % by weight.Most preferably, described ring-alkylated styrenes is preferably p-methylstyrene.
The relative usage of described monoolefine and described ring-alkylated styrenes can carry out appropriate selection according to the embody rule occasion of the polymkeric substance finally prepared.Usually, with the total amount of described monoolefine and ring-alkylated styrenes for benchmark, the content of described monoolefine can be 80 ~ 99 % by weight, is preferably 90 ~ 97 % by weight; The content of described ring-alkylated styrenes can be 1 ~ 20 % by weight, is preferably 3 ~ 10 % by weight.
According to polymerization process of the present invention, the thinner that described thinner can be commonly used for cationoid polymerisation field, such as alkane and/or halogenated alkane.
Preferably, described thinner contains the first thinner and the second thinner, described first thinner be aliphatic alkane (namely, paraffinic hydrocarbons) and/or alicyclic alkanes is (namely, naphthenic hydrocarbon), described second thinner is halogenated alkane, can obtain the polymkeric substance with more high molecular like this.Relative proportion between described first thinner and the second thinner can be selected according to specific requirement.Usually, with the total amount of described thinner for benchmark, the content of described second thinner can be 1 ~ 80 volume %, is preferably 10 ~ 50 volume %; The content of described first thinner can be 20 ~ 99 volume %, is preferably 50 ~ 90 volume %.
Described aliphatic alkane is preferably C
3~ C
10aliphatic alkane, be more preferably C
3~ C
8aliphatic alkane, more preferably C
5~ C
8aliphatic alkane; Described alicyclic alkanes is preferably C
3~ C
10alicyclic alkanes, more preferably C
5~ C
10alicyclic alkanes.Described halogenated alkane is preferably C
1~ C
10halogenated alkane, be more preferably C
1~ C
4halogenated alkane, the halogen atom in described halogenated alkane can be chlorine, bromine or fluorine, be preferably chlorine or fluorine.
The specific examples of described first thinner can include but not limited to: propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, pentamethylene, normal hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, hexanaphthene, methylcyclopentane, normal heptane, 2-methyl hexane, 3-methyl hexane, 2-ethylpentane, 3-ethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3-ethyl hexane, 2，2，3-trimethyl-pentane, 2,3,3-trimethylpentane, 2,4,4-trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3-dimethyl heptane, 2,4-dimethyl heptane, 3-ethyl heptane, 4-ethyl heptane, 2,3,4-trimethyl cyclohexane, 2,3,5-trimethyl cyclohexane, 2,4,5-trimethyl cyclohexane, 2,2,3-trimethyl cyclohexane, 2,2,4-trimethyl cyclohexane, 2,2,5-trimethyl cyclohexane, 2,3,3-trimethyl cyclohexane, 2,4,4-trimethyl cyclohexane, 2-methyl-3-ethyl hexane, 2-methyl-4-ethyl hexane, 3-methyl-3-ethyl hexane, 3-methyl-4-ethyl hexane, 3,3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propyl hexanaphthene, normenthane, trimethyl-cyclohexane, n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2,3-dimethyl octane, 2,4-dimethyl octane, 3-ethyl octane, 4-ethyl octane, 2,3,4-trimethylheptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane, 2,4,5-trimethylheptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6-trimethylheptane, 2,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethyl heptane, 2-methyl-4-ethyl heptane, 2-methyl-5-ethyl heptane, 3-methyl-3-ethyl heptane, 4-methyl-3-ethyl heptane, 5-methyl-3-ethyl heptane, 4-methyl-4-ethyl heptane, 4-propyl group heptane, 3,3-diethylhexane, 3,4-diethylhexane, 2-methyl-3,3-diethylpentane, 1,2-diethyl cyclohexane, 1,3-diethyl cyclohexane, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl-hexanaphthene, t-butylcyclohexane and tetramethyl-ring hexane.
The specific examples of described second thinner can include but not limited to: monochloro methane, methylene dichloride, trichloromethane, tetracol phenixin, one fluoroethane, C2H4F2 C2H4F2, Halothane, Tetrafluoroethane, pentafluoride ethane, carbon hexa fluoride, monochlorethane, ethylene dichloride, trichloroethane, tetrachloroethane, pentaline, carbon hexachloride, one fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoropropane, one chloropropane, propylene dichloride, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, octachloropropane, one fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, Octafluorobutane, nine fluorine butane, ten fluorine butane, one chlorobutane, dichlorobutane, three chlorobutanes, four chlorobutanes, pentachlorobutane, chlordene butane, heptachlor butane, telodrine alkane, nine chlorobutanes and ten chlorobutanes.
Preferably, described first thinner is selected from Skellysolve A, normal hexane and normal heptane, and described second thinner is selected from methylene dichloride, monochloro methane and monochlorethane.
The consumption of described thinner can be the routine selection of this area.Usually, the consumption of described thinner makes total monomer concentration be 2 ~ 25 % by weight, is preferably 5 ~ 15 % by weight.
According to method of the present invention, described cationoid polymerisation condition can be that the routine of this area is selected.Usually, the condition of described cationoid polymerisation comprises: temperature is-120 DEG C to 20 DEG C, is preferably-100 DEG C to 0 DEG C, is more preferably-100 DEG C to-40 DEG C.According to method of the present invention, the time of described contact can be the routine selection of this area, repeats no more herein.
According to method of the present invention, can also be included in be polymerized and add polymerization terminator in mixture that backward polymerization obtains and stop (such as alcohol) to make polyreaction.The present invention is not particularly limited for the kind of described polymerization terminator and consumption, can be that the routine of this area is selected, be as the criterion, repeat no more herein can stop polyreaction.
According to method of the present invention, for refining under the monomer that is polymerized and the thinner before use preferred condition conventional in this area, repeat no more herein.
The present invention is described in detail below in conjunction with embodiment.
In following examples and comparative example, weighting method is adopted to measure polymer yield,
Polymer yield (%)=(gross weight of the monomer of the weight of the polymkeric substance obtained/add) × 100%.
In following examples and comparative example, the molecular weight of polymkeric substance and molecular weight distributing index (M
w/ M
n) adopt Japanese Shimadzu Corporation to produce LC-20A type liquid phase gel permeation chromatograph mensuration, adopt single aperture chromatographic column
with
four post couplings.Moving phase is tetrahydrofuran (THF), and flow velocity is 0.7mL/min; Sample solution concentration is 2mg/mL, and sample size is 200 μ L; Probe temperature is 35 DEG C; Using single distribution polystyrene as standard model.
In following examples and comparative example, proton nmr spectra test adopts the AVANCE400 nuclear magnetic resonance analyser be purchased from Bruker company of Switzerland, using deuterochloroform as solvent, with tetramethylsilane (TMS) for interior mark.
The solvent used in following examples and comparative example and monomer before use, adopt the conventional method in this area to refine, and the preparation of polyreaction and initiator solution is all carried out being furnished with being purchased of low temperature cryostat in the loft drier of German MBRAUN company.
Embodiment 1 ~ 16 is for illustration of the present invention.
Embodiment 1
(1) by 0.021g2,3-bis-chloro-5,6-dicyano p-benzoquinone and 0.035g are dissolved in 53.0g methylene dichloride to dibenzyl chlorine, the solution obtained is chilled to-85 DEG C in advance, then the hexane solution adding the ethyl aluminum dichloride (EADC) that 3.6mL concentration is 0.9mol/L in this solution is made into initiator solution, mixes in the cryostat being placed on-85 DEG C and carries out ageing.By weight, in initiator solution, the content of 2,3-bis-chloro-5,6-dicyano p-benzoquinones is 400ppm.
(2) add to being furnished with in powerful constant speed churned mechanically 500mL glass polymerization reactor the monochloro methane that 100mL is cooled to-80 DEG C successively, 100mL is cooled to the normal hexane of-80 DEG C, 22mL is cooled to the iso-butylene of-80 DEG C and the p-methylstyrene (content is 98 % by weight) of 0.93mL normal temperature, start and be uniformly mixed rear formation monomer solution, adopt liquid nitrogen control temperature, 15mL step (1) preparation is slowly dripped and at the initiator solution of-85 DEG C of ageing 60min in monomer solution, then stirring reaction 10min, control temperature of reaction in reaction process to be in the scope of-80 DEG C to-85 DEG C.
After reaction terminates, in reaction mixture, add 5mL contain the methanol solution of 0.5 % by weight NaOH to stop polyreaction.Then, mixing solutions is placed in hot water bath desolvation, in vacuum drying oven, is dried to constant weight in 60 DEG C after washing, obtains polymkeric substance.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Comparative example 1
The method identical with embodiment 1 is adopted to be polymerized, unlike, do not use chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-in step (1).
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to be polymerized, unlike the initiator solution used in, step (2) for step (1) is prepared and at the initiator solution of-85 DEG C of ageing 30min.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 3
The method identical with embodiment 1 is adopted to be polymerized, unlike the initiator solution used in, step (2) for step (1) is prepared and at the initiator solution of-85 DEG C of ageing 15min.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 4
The method identical with embodiment 1 is adopted to be polymerized, unlike the initiator solution used in, step (2) for step (1) is prepared and at the initiator solution of-85 DEG C of ageing 120min.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 5
The method identical with embodiment 1 is adopted to be polymerized, unlike, the chloranil of the quality such as the middle use of step (1) replaces 2,3-bis-chloro-5,6-dicyano p-benzoquinones.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 6
The method identical with embodiment 1 is adopted to be polymerized, unlike, the tetrahydrochysene para benzoquinone of the quality such as the middle use of step (1) replaces 2,3-bis-chloro-5,6-dicyano p-benzoquinones.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 7
The method identical with embodiment 1 is adopted to be polymerized, unlike, the four cyano para benzoquinone of the quality such as the middle use of step (1) replaces 2,3-bis-chloro-5,6-dicyano p-benzoquinones.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 8
The method identical with embodiment 1 is adopted to be polymerized, unlike, in step (1) 2, the consumption of chloro-5, the 6-dicyano p-benzoquinones of 3-bis-makes in the initiator solution of final preparation, by weight, the concentration of chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-is 800ppm.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 9
(1) by 0.1274g2,3-bis-chloro-5,6-dicyano p-benzoquinone and 0.105g are dissolved in 159.1g methylene dichloride to dibenzyl chlorine, the solution obtained is chilled to-85 DEG C in advance, then in this solution, add the hexane solution of the ethyl aluminum dichloride (EADC) that 5.6mL concentration is 0.9mol/L and 2.4mL concentration is that the toluene solution of 0.9mol/L diethyl aluminum chloride (DEAC) is made into initiator solution, mixes in the cryostat being placed on-85 DEG C and carries out ageing.By weight, in initiator solution, the content of 2,3-bis-chloro-5,6-dicyano p-benzoquinones is 800ppm.
(2) add normal hexane, the 22mL that monochloro methane, 100mL that 100mL is cooled to-80 DEG C be cooled to-80 DEG C be cooled to the iso-butylene of-80 DEG C and the p-methylstyrene (content is 98 % by weight) of 0.93mL normal temperature to being furnished with in powerful constant speed churned mechanically 500mL glass polymerization reactor successively, start and be uniformly mixed rear formation monomer solution.Liquid nitrogen is adopted to control polymeric reaction temperature, in monomer solution, slowly drip 15mL step (1) preparation and at the initiator solution of-85 DEG C of ageing 60min, then stirring reaction 7min, controls temperature of reaction and be in the scope of-80 DEG C to-85 DEG C in reaction process.
After reaction terminates, in reaction mixture, add 5mL contain the methanol solution of 0.5 % by weight NaOH to stop polyreaction.Then, mixing solutions is placed in hot water bath desolvation, in vacuum drying oven, is dried to constant weight in 60 DEG C after washing, obtains polymkeric substance.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 10
The method identical with embodiment 9 is adopted to be polymerized, unlike, in step (2), the consumption of monochloro methane is 60mL, and the consumption of normal hexane is 140mL.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 11
The method identical with embodiment 9 is adopted to be polymerized, unlike, in step (2), the consumption of monochloro methane is 20mL, and the consumption of normal hexane is 180mL.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 12
(1) 0.0853g chloranil and 0.070g are dissolved in 106.1g methylene dichloride to dibenzyl chlorine, the solution obtained is chilled to-85 DEG C in advance, then the hexane solution adding the ethyl aluminum dichloride (EADC) that 8mL concentration is 0.9mol/L in this solution is made into initiator solution, mixes in the cryostat being placed on-85 DEG C and carries out ageing.By weight, the content 800ppm of chloranil in initiator solution.
(2) add normal hexane, the 22mL that monochloro methane, 120mL that 80mL is cooled to-80 DEG C be cooled to-80 DEG C be cooled to the iso-butylene of-80 DEG C and the p-methylstyrene (content is 98 % by weight) of 0.93mL normal temperature to being furnished with in powerful constant speed churned mechanically 500mL glass polymerization still successively, start and be uniformly mixed rear formation monomer solution.Adopt liquid nitrogen control temperature, in monomer solution, slowly drip 15mL step (1) preparation and at the initiator solution of-85 DEG C of ageing 140min, then stirring reaction 10min, controls temperature of reaction and be in the scope of-80 DEG C to-85 DEG C in reaction process.
After reaction terminates, in reaction mixture, add 5mL contain the methanol solution of 0.5 % by weight NaOH to stop polyreaction.Then, mixing solutions is placed in hot water bath desolvation, in vacuum drying oven, is dried to constant weight in 60 DEG C after washing, obtains polymkeric substance.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 13
The method identical with embodiment 12 is adopted to be polymerized, unlike, step does not use dibenzyl chlorine in (1), but uses 0.1056g dibenzyl bromine; The digestion time of the initiator solution used in step (2) is 200min.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 14
(1) 0.0853g chloranil and 0.035g are dissolved in 53.0g methylene dichloride to dibenzyl chlorine, the solution obtained is chilled to-85 DEG C in advance, then in this solution, add the hexane solution of the ethyl aluminum dichloride (EADC) that 1.3mL concentration is 0.9mol/L and 1.3mL concentration is that the toluene solution of the diethyl aluminum chloride (DEAC) of 0.9mol/L is made into initiator solution, mixes in the cryostat being placed on-85 DEG C and carries out ageing.By weight, the content 800ppm of chloranil in initiator solution.
(2) in the polymerization bottle of 150mL, add normal hexane, the 11mL that monochloro methane, 80mL that 20mL is cooled to-80 DEG C be cooled to-80 DEG C be successively cooled to the iso-butylene of-80 DEG C and the p-methylstyrene (content is 98 % by weight) of 0.46mL normal temperature, after mixing, form monomer solution.Polymerization bottle is placed in the low temperature cryostat of-85 DEG C, 10mL step (1) preparation is added and at the initiator solution of-85 DEG C of ageing 60min in monomer solution, then stirring reaction 60min, controls cryostat temperature and is in the scope of-80 DEG C to-85 DEG C in reaction process.
After reaction terminates, in reaction mixture, add 5mL contain the methanol solution of 0.5 % by weight NaOH to stop polyreaction.Then, mixing solutions is placed in hot water bath desolvation, in vacuum drying oven, is dried to constant weight in 60 DEG C after washing, obtains polymkeric substance.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 15
The method identical with embodiment 14 is adopted to be polymerized, unlike, step does not use dibenzyl chlorine in (1), but uses 0.0528g dibenzyl bromine.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 16
(1) by 0.048g2,3-bis-chloro-5,6-dicyano p-benzoquinone and 0.053g are dissolved in 79.5g methylene dichloride to dibenzyl chlorine, the solution obtained is chilled to-80 DEG C in advance, then the hexane solution adding the ethyl aluminum dichloride (EADC) that 4.3mL concentration is 0.9mol/L in this solution is made into initiator solution, mixes in the cryostat being placed on-85 DEG C and carries out ageing.By weight, the content 600ppm of 2,3-bis-chloro-5,6-dicyano p-benzoquinones in initiator solution.
(2) in the polymerization bottle of 150mL, add normal hexane, the 10mL that monochloro methane, 50mL that 50mL is cooled to-80 DEG C be cooled to-80 DEG C be successively cooled to the iso-butylene of-80 DEG C and the p-methylstyrene (content is 98 % by weight) of 0.42mL normal temperature, after mixing, form monomer solution.Polymerization bottle is placed in the low temperature cryostat of-80 DEG C, 10mL step (1) preparation is added and at the initiator solution of-80 DEG C of ageing 90min in monomer solution, then stirring reaction 60min, controls cryostat temperature and is in the scope of-70 DEG C to-75 DEG C in reaction process.
After reaction terminates, in reaction mixture, add 5mL contain the methanol solution of 0.5 % by weight NaOH to stop polyreaction.Then, mixing solutions is placed in hot water bath desolvation, in vacuum drying oven, is dried to constant weight in 60 DEG C after washing, obtains polymkeric substance.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Claims (15)
1. a cationic polymerization process, under the method is included in cationoid polymerisation condition, in at least one thinner, by each component contacts at least one monoolefine and at least one ring-alkylated styrenes and initiator system, described initiator system contains at least one can provide the compound of carbonium ion, at least one Lewis acid and at least one activator
Described activator is selected from the compound shown in the compound shown in formula I-1 and formula I-2,
In formula I-1 and formula I-2, R
1, R
2, R
3, R
4, R
5, R
6, R
7and R
8be-H ,-X separately
1,-NO
2,
with the one in-CN, X
1and X
2be the one in halogen group separately;
Described monoolefine is selected from the compound shown in formula II,
In formula II, R
9and R
10be C separately
1~ C
5straight or branched alkyl; Or R
9for hydrogen, R
10for C
3~ C
5branched-chain alkyl;
Described ring-alkylated styrenes is selected from the compound shown in formula III,
In formula III, R
11for C
1~ C
5straight or branched alkyl.
2. method according to claim 1, wherein, the described mol ratio of the compound of carbonium ion, described Lewis acid and described activator that can provide is 0.3 ~ 100:4 ~ 1000:1, is preferably 0.4 ~ 10:5 ~ 100:1, is more preferably 0.5 ~ 5:6 ~ 50:1.
3. method according to claim 1, wherein, the method of each component contacts at least one monoolefine and at least one ring-alkylated styrenes and described initiator system is comprised: by each components dissolved in described initiator system in solvent, and the mixture ageing that will obtain, obtain initiator solution; By described initiator solution and the mixing diluents being dissolved with described monoolefine and described ring-alkylated styrenes.
4. method according to claim 3, wherein, the time of described ageing is 15 minutes to 10 hours, is preferably more than 30 minutes, is more preferably more than 60 minutes.
5. the method according to claim 3 or 4, wherein, described ageing is carried out in the temperature range of-100 DEG C to 20 DEG C, preferably carries out in the temperature range of-100 DEG C to 0 DEG C.
6. method according to claim 3, wherein, described solvent be selected from alkane, halogenated alkane and aromatic hydrocarbons one or more.
7. according to the method in claims 1 to 3 described in any one, wherein, described activator is selected from tetrachlorobenzoquinone, DDQ, tetrahydrochysene benzoquinones and four cyano benzoquinones.
8. according to the method in claims 1 to 3 described in any one, wherein, described can provide the compound of carbonium ion be selected from by
the alkane replaced and quilt
the aromatic hydrocarbons replaced, R
12, R
13, R
14and R
15be hydrogen, C separately
1~ C
8alkyl, phenyl, C
7~ C
10phenylalkyl, C
7~ C
10alkyl phenyl or C
3~ C
8cycloalkyl, X
3and X
4be the one in halogen group separately, be preferably-Cl or-Br;
Preferably, the described compound of carbonium ion that can provide is to dibenzyl chlorine and/or to dibenzyl bromine.
9. according to the method in claims 1 to 3 described in any one, wherein, described Lewis acid is selected from the compound shown in formula IV,
AlR
16 nx
5 (3-n)(formula IV)
In formula IV, n R
16be C separately
1~ C
8alkyl; 3-n X
5be the one in halogen group separately, be preferably-Cl; N is 0,1,2 or 3.
10. method according to claim 1, wherein, with the total amount of described monoolefine and described ring-alkylated styrenes for benchmark, the content of described monoolefine is 80 ~ 99 % by weight, is preferably 90 ~ 97 % by weight; The content of described ring-alkylated styrenes is 1 ~ 20 % by weight, is preferably 3 ~ 10 % by weight.
11. according to the method in claim 1,3 and 10 described in any one, and wherein, described monoolefine is iso-butylene.
12. according to the method in claim 1,3 and 10 described in any one, and wherein, described ring-alkylated styrenes is p-methylstyrene and/or a vinyl toluene.
13. methods according to claim 1, wherein, described thinner contains the first thinner and the second thinner, and described first thinner is selected from aliphatic alkane and alicyclic alkanes, and described second thinner is selected from halogenated alkane.
14. methods according to claim 13, wherein, the content of described first thinner is 20 ~ 99 volume %, and the content of described second thinner is 1 ~ 80 volume %.
15. methods according to claim 1, wherein, the condition of described contact comprises: temperature is-100 DEG C to 20 DEG C, is preferably-100 DEG C to 0 DEG C.
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