CN104558342A - Cation polymerization method - Google Patents
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- CN104558342A CN104558342A CN201310491422.9A CN201310491422A CN104558342A CN 104558342 A CN104558342 A CN 104558342A CN 201310491422 A CN201310491422 A CN 201310491422A CN 104558342 A CN104558342 A CN 104558342A
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Abstract
The invention discloses a cation polymerization method which comprises the following steps: under the condition of cation polymerization, in one or more diluents, one or more types of monoolefine and one or more types of alkyl styrene are in contact with all components in an initiator system; the initiator system contains one or more compounds capable of providing protons, and one or more types of lewis acid and one or more activators; the activators are selected from a compound shown in a formula I-1 and a compound shown in a formula I-2; the diluents are one or more first diluents and one or more second diluents; the first diluents are selected from haloalkane; the second diluents are selected from aliphatic alkane and alicyclic alkane. According to the cation polymerization method, the satisfactory polymerization efficiency can be obtained.
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-p-methylstyrene multipolymer of bromination can be used for production and has more high performance tire, and has 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 (namely, polymer yield) 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.
The present inventor is studied for the problems referred to above, find: when being polymerized in low Polar diluents, if introduce quinonoid compound (particularly there is the quinonoid compound of electron-withdrawing substituent) in initiator system, can polymerization efficiency be improved, obtain high polymer yield.This completes the present invention.
The invention provides a kind of cationic polymerization process, the method comprises: under cationoid polymerisation condition, 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 carry protogenic compound, 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 in halogen group separately;
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;
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;
Described thinner is made up of at least one first thinner and at least one second thinner, and described first thinner is selected from halogenated alkane, and described second thinner is selected from aliphatic alkane and alicyclic alkanes.
Gratifying polymerization effect can be obtained according to polymerization process of the present invention.
Embodiment
The invention provides a kind of cationic polymerization process, the method comprises: under cationoid polymerisation condition, at least one thinner, by each component contacts at least one monoolefine and at least one ring-alkylated styrenes and initiator system.
According to method of the present invention, described initiator system (also can be called initiator composition) can carry protogenic compound, at least one Lewis acid and at least one activator containing at least one.
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 4--> 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.5 -->
Usually, described activator can be selected from tetrahydrochysene benzoquinones (comprising tetrahydrochysene para benzoquinone and the adjacent benzoquinones of tetrahydrochysene), tetrachlorobenzoquinone (comprising chloranil and monoethyl quinone), four cyano benzoquinones (comprising four cyano para benzoquinone and the adjacent benzoquinones of four cyano) and DDQ (comprising dichloro dicyano p-benzoquinone and the adjacent benzoquinones of dichloro dicyano).
According to method of the present invention, the content of described activator can carry out appropriate selection according to the embody rule occasion of this initiator system, is as the criterion can obtain gratifying polymerization efficiency.Usually, the described mol ratio can carrying protogenic compound and described activator can be 1:0.01 ~ 3, is preferably 1:0.1 ~ 2, is more preferably 1:0.2 ~ 1.8.
According to method of the present invention, described Lewis acid and describedly can carry protogenic compound and can select for the routine in cationoid polymerisation field, be not particularly limited, as long as described Lewis acid and protogenic compound can be carried can form cationic species, initiated polymerization.
Usually, described Lewis acid can be selected from but be not limited to: AlCl
3, BF
3, BCl
3, TiCl
4, SnCl
4, ZnCl
2, the Lewis acid shown in formula IV, the Lewis acid shown in formula V and R
15 3al,
In formula IV, X
31and X
32be the one (as-F ,-Cl ,-Br or-I) in halogen group separately, be preferably-Cl; R
12for C
1~ C
8straight or branched alkyl, be preferably C
1~ C
5straight or branched alkyl;
In formula V, X
4for the one (as-F ,-Cl ,-Br or-I) in halogen group, be preferably-Cl; R
13and R
14be C separately
1~ C
8straight or branched alkyl, be preferably C
1-C
5straight or branched alkyl.
In formula V, R
13and R
14can be identical, also can be different, preferably identical.
R
15 3in Al, three R
15can be C separately
1~ C
8straight or branched alkyl, be preferably C
1~ C
5straight or branched alkyl.R
15 3in Al, three R
15can be identical, also can be different, preferably identical.
In the present invention, C
1~ C
8straight or branched alkyl 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.
In the present invention, the lewis acidic specific examples 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 and dichloro aluminium isobutyl.Preferably, the Lewis acid shown in formula IV is ethyl aluminum dichloride.
In the present invention, the lewis acidic specific examples shown in formula V can include but not limited to: dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminum chloride, di-isopropyl aluminum chloride, di-n-butyl aluminum chloride and diisobutyl aluminum chloride.Preferably, the Lewis acid shown in formula V is diethyl aluminum chloride.
In the present invention, R
15 3the specific examples of Al can include but not limited to: trimethyl aluminium and triethyl aluminum.
According to method of the present invention, described Lewis acid is preferably the Lewis acid shown in the Lewis acid shown in formula IV and/or formula V, is more preferably ethyl aluminum dichloride and/or diethyl aluminum chloride.
Containing two alkyl in lewis acidic molecular structure shown in formula V, the effect suppressing cation activity center that chain tra nsfer occurs can be played, thus the molecular weight of the polymkeric substance of preparation can be improved.But the lewis acidic too high levels shown in formula V, can reduce polymerization rate, extend polymerization time.Therefore, according to method of the present invention, the Lewis acid shown in formula V preferably combinationally uses with other Lewis acid, preferably combinationally uses with the Lewis acid shown in formula IV.That is, according to method of the present invention, described Lewis acid is preferably the Lewis acid shown in the Lewis acid shown in formula IV and formula V.
According to method of the present invention, when described Lewis acid is for Lewis acid shown in the Lewis acid shown in formula IV and formula V, with lewis acidic total amount for benchmark, lewis acidic content shown in formula V is preferably 10 ~ 90 % by mole, can obtain good balance like this between polymerization rate and polymericular weight.More preferably, with lewis acidic total amount for benchmark, the lewis acidic content shown in formula V is 20 ~ 80 % by mole.
Described lewis acidic content can be the conventional amount used in cationoid polymerisation field.Usually, describedly can carry protogenic compound and described lewis acidic mol ratio can be 0.01 ~ 1:1, be preferably 0.02 ~ 0.5:1, be more preferably 0.03 ~ 0.3:1.
Describedly can carry protogenic compound and variously can carry protogenic compound for conventional in cationoid polymerisation field.Usually, described can carry protogenic compound can for H
2o and/or protonic acid, its specific examples can include but not limited to: H
2o, HCl, HF, HBr, H
2sO
4, H
2cO
3, H
3pO
4and HNO
3.It is preferably, described that can to carry protogenic compound be HCl.
Conventional various methods can be adopted each component contacts in described monoolefine and ring-alkylated styrenes and described initiator system, to be polymerized, form monoolefine-alkylstyrene copolymers.
In one embodiment of the invention, can 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 to make the Lewis acid in initiator system and can carries protogenic compound and activator forms stable complexing initiating activity center, can carry out under normal conditions.Usually, the condition of described ageing comprises: temperature can be-100 DEG C to 20 DEG C, is preferably-100 DEG C to 0 DEG C.The time of described ageing can be 10 minutes to 10 hours.Preferably, the time of described ageing is more than 30 minutes, such as 30 minutes to 5 hours.More preferably, the time of described ageing is more than 60 minutes, such as 60 minutes to 2 hours.
Described solvent can be the various liquid substance that can dissolve described protonic acid, described Lewis acid and described activator.Usually, described solvent can be selected from alkane (can be aliphatic alkane and/or alicyclic alkanes), halogenated alkane and aromatic hydrocarbons, is preferably selected from C
3~ C
10alkane, C
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.Described halogenated alkane is preferably C
1~ C
4halogenated aliphatic alkane.
As solvent, described C
3~ C
10alkane comprise C
3~ C
10aliphatic alkane and C
3~ C
10alicyclic alkanes.
As solvent, described C
1~ C
10halogenated alkane comprise C
1~ C
10halogenated aliphatic alkane and C
3~ C
10halogenated cyclo alkane.
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), one fluoromethane, methylene fluoride, trifluoromethane, tetrafluoro-methane, 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.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.
According to polymerization process of the present invention, the monoolefine that can carry out cationoid polymerisation that described monoolefine can be commonly used for this area.Usually, 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.
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.
According to method of the present invention, 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.
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 VI to ring-alkylated styrenes between shown in ring-alkylated styrenes and formula VII,
In formula VI, R
11for C
1~ C
5straight or branched alkyl;
In formula VII, 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.
According to method of the present invention, 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, described thinner is made up of at least one first thinner and at least one second thinner, and described first thinner is selected from halogenated alkane, and described second thinner is selected from aliphatic alkane and alicyclic alkanes.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.
According to method of the present invention, the ratio between described first thinner and described second thinner can be selected according to concrete condition.Usually, with the total amount of described thinner for benchmark, the content of described second thinner can be 20 ~ 99 volume %; The content of described first thinner can be 1 ~ 80 volume %.One of the present invention preferred embodiment in, the amount of described first thinner is 30 ~ 70 volume %, be preferably 30 ~ 50 volume %; The amount of described second thinner is 30 ~ 70 volume %, is preferably 50 ~ 70 volume %, thus as the R in formula I-1
1, R
2, R
3and R
4in at least one is-CN, the R in formula I-2
5, R
6, R
7and R
8in at least one be-CN time, if polyreaction is carried out at the temperature of-120 DEG C to-60 DEG C (preferably-100 DEG C to-70 DEG C), even if the Lewis acid in initiator system is not containing the Lewis acid shown in formula V, but is the Lewis acid shown in formula IV, also can prepare molecular weight is 40 × 10
4above polymkeric substance.This preferred embodiment in, described activator is preferably four cyano benzoquinones and/or DDQ.
As thinner, the specific examples of described aliphatic alkane and alicyclic alkanes 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.
As thinner, the specific examples of described halogenated alkane can include but not limited to: a fluoromethane, methylene fluoride, trifluoromethane, tetrafluoro-methane, 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 monochloro methane, methylene dichloride and monochlorethane, and described second thinner is selected from Skellysolve A, normal hexane and normal heptane.
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 can make the temperature of thinner be-120 DEG C to 20 DEG C, preferably makes the temperature of thinner be-100 DEG C to 0 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 (%)=(weight/total monomer weight of the polymkeric substance obtained) × 100%.
In following examples and comparative example, the molecular weight of polymkeric substance and molecular weight distributing index adopt Japanese Shimadzu Corporation to produce LC-20A type gel permeation chromatograph and measure, and 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.
The solvent used in following examples and comparative example and monomer before use, adopt the conventional method in this area to refine.
In following examples and comparative example, the preparation of polyreaction and initiator solution is all carried out in the operating under nitrogen case being furnished with low temperature cryostat.
Embodiment 1 ~ 28 is for illustration of cationic polymerization process of the present invention.
Embodiment 1
(1) 0.133g chloranil is dissolved in 66.5g dichloromethane solution, obtains chloranil's solution.By weight, in this solution, the concentration of chloranil is 2000ppm.
At-80 DEG C, in 60mL goat's horn bottle, order adds the 20mL being chilled to-80 DEG C in advance to contain HCl(concentration is 0.0038mol/L) dichloromethane solution, 1.8mL contain hexane solution and the aforementioned chloranil's solution of 0.5mL of ethyl aluminum dichloride (concentration is 0.9mol/L), at-80 DEG C of ageing 15min after mixing, thus obtain initiator solution.By weight, in this initiator solution, the concentration of chloranil is 50ppm.
(2) add normal hexane, the 32mL that monochloro methane, 80mL that 100mL is chilled to-60 DEG C be in advance chilled to-60 DEG C in advance and be chilled to the iso-butylene of-60 DEG C and the p-methylstyrene (content is 98 % by weight) of 1.3mL normal temperature (25 DEG C) in advance being furnished with order in the 500mL glass reactor that powerful constant speed stirs, mix.Initiator solution prepared by step (1) is dripped in reactor.Wherein, the add-on of initiator solution is 16mL; Controlling rate of addition makes the temperature in reactor be within the scope of-57 DEG C to-63 DEG C.After being added dropwise to complete, keeping the temperature in reactor to be within the scope of-57 DEG C to-63 DEG C, with stirring the polyreaction of carrying out 14min, in reaction mixture, then adding the methanol solution that 5mL contains 0.5 % by weight NaOH, to stop polyreaction.The mixing solutions obtained is placed in hot water bath desolvation, and the product obtained, after washing, is dried to constant weight in 60 DEG C, thus obtains subject polymer in vacuum drying oven.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in Table 1.
Comparative example 1
The method identical with embodiment 1 is adopted to be polymerized, unlike, not containing chloranil in initiator solution prepared by 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, in the initiator solution that step (1) obtains, by weight, the concentration of chloranil is 100ppm; In step (2), the add-on of initiator solution is 20mL, and after initiator solution is added dropwise to complete, keep the temperature in reactor to be in the scope of-60 DEG C to-65 DEG C, the time of polyreaction is 13min.
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, in the initiator solution that step (1) obtains, by weight, the concentration of chloranil is 300ppm; In step (2), the add-on of initiator solution is 20mL, and after initiator solution is added dropwise to complete, keep the temperature in reactor to be in the scope of-60 DEG C to-65 DEG C, polymerization reaction time is 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, in step (1), digestion time is 25min, and in the initiator solution obtained, by weight, the concentration of chloranil is 800ppm; In step (2), the add-on of initiator solution is 10mL, and after initiator solution is added dropwise to complete, keep the temperature in reactor to be in the scope of-85 DEG C to-90 DEG C, the time of polyreaction is 15min.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 5
(1) 0.1596g chloranil being dissolved in 206g, to contain HCl(concentration be 0.0032mol/L) methylene dichloride in, then above-mentioned solution is chilled to-80 DEG C in advance, and add the hexane solution that the 11mL being chilled to-80 DEG C in advance contains ethyl aluminum dichloride (concentration is 0.9mol/L), after mixing, at-80 DEG C of ageing 31min, thus obtain initiator solution.Wherein, by weight, in initiator solution, the concentration of tetrachlorobenzoquinone is 750ppm.
(2) add normal hexane, the 25mL that monochloro methane, 140mL that 60mL is chilled to-80 DEG C be in advance chilled to-80 DEG C in advance and be chilled to the iso-butylene of-80 DEG C and the p-methylstyrene (content is 98 % by weight) of 1.1mL normal temperature (25 DEG C) in advance being furnished with order in the 500mL glass reactor that powerful constant speed stirs, mix.Initiator solution prepared by step (1) is dripped in reactor.Wherein, the add-on of initiator solution is 20mL, controls rate of addition and the temperature in reactor is within the scope of-80 DEG C to-85 DEG C.After being added dropwise to complete, keeping the temperature in reactor to be within the scope of-80 DEG C to-85 DEG C, with stirring the polyreaction of carrying out 10min, in reaction mixture, then adding the methanol solution that 5mL contains 0.5 % by weight NaOH, to stop polyreaction.The mixing solutions obtained is placed in hot water bath desolvation, and the product obtained, after washing, is dried to constant weight in 60 DEG C, thus obtains subject polymer in vacuum drying oven.
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 5 is adopted to be polymerized, unlike, in step (1), digestion time is 65min; In step (2), the consumption of monochloro methane is 20mL, and the consumption of normal hexane is 180mL, and the add-on of initiator solution is 20mL, and polymerization reaction time is 10min.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 7
(1) by 0.072g2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 120g, and to contain HCl(concentration be 0.0042mol/L) dichloromethane solution in, then above-mentioned solution is chilled to-80 DEG C in advance, and add the hexane solution containing ethyl aluminum dichloride (concentration is 0.9mol/L) that 5.6mL is chilled to-80 DEG C in advance, after mixing, at-80 DEG C of ageing 60min, thus obtain initiator solution.Wherein, by weight, in initiator solution, the concentration of chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-is 580ppm.
(2) in the glass reactor being furnished with the 500mL that powerful constant speed stirs, order adds normal hexane, the 25mL that monochloro methane, 100mL that 100mL is chilled to-80 DEG C be in advance chilled to-80 DEG C in advance and is chilled to the iso-butylene of-80 DEG C and the p-methylstyrene (content is 98 % by weight) of 1.1mL normal temperature (25 DEG C) in advance, mixes.Initiator solution prepared by step (1) is dripped in reactor.Wherein, the add-on of initiator solution is 25mL, controls rate of addition and the temperature in reactor is within the scope of-85 DEG C to-90 DEG C.After being added dropwise to complete, keeping the temperature in reactor to be within the scope of-85 DEG C to-90 DEG C, with stirring the polyreaction of carrying out 17min, in reaction mixture, then adding the methanol solution that 5mL contains 0.5 % by weight NaOH, to stop polyreaction.The mixing solutions obtained is placed in hot water bath desolvation, and the solid obtained, after washing, is dried to constant weight in 60 DEG C, thus obtains subject polymer in vacuum drying oven.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 8
Adopt and be polymerized with the same procedure of embodiment 7, 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 9
The method identical with embodiment 7 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 10
Adopt and be polymerized with the identical method of embodiment 7, unlike, in the initiator solution that step (1) obtains, by weight, the concentration of chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-is 300ppm; In step (2), the consumption of monochloro methane is 80mL, and the consumption of normal hexane is 120mL, and the add-on of initiator solution is 24mL; After initiator solution is added dropwise to complete, the temperature in reactor is controlled within the scope for being in-65 DEG C to-70 DEG C, and carries out the polymerization of 12min.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 11
(1) by 0.0532g2,3-bis-chloro-5,6-dicyano p-benzoquinone be dissolved in 66.3g and containing HCl(concentration be 0.0027mol/L) methylene dichloride in, then above-mentioned solution is chilled to-85 DEG C in advance, and add the hexane solution containing ethyl aluminum dichloride (concentration is 0.9mol/L) that 4mL is chilled to-85 DEG C in advance, after mixing ,-85 DEG C of ageings 60 minutes, thus obtain initiator solution.Wherein, by weight, in initiator solution, the concentration of chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-is 770ppm.
(2) method identical with embodiment 7 is adopted to be polymerized, unlike, initiator solution is initiator solution prepared by embodiment 11 step (1); The consumption of monochloro methane is 40mL, and the consumption of normal hexane is 160mL; The add-on of initiator solution is 15mL, and polymerization time is 11min.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 12
The method identical with embodiment 7 is adopted to be polymerized, unlike, in step (1), digestion time is 10 minutes.
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 7 is adopted to be polymerized, unlike, in step (1), digestion time is 30 minutes.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 14
The method identical with embodiment 7 is adopted to be polymerized, unlike, replace chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-with the four cyano para benzoquinone of equivalent.
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 7 is adopted to be polymerized, unlike, replace chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-with the tetrahydrochysene para benzoquinone of equivalent.
Polymer yield, the molecular weight and molecualr weight distribution index of polymkeric substance obtained are listed in Table 1.
Embodiment 16
(1) by 0.0652g2,3-bis-chloro-5,6-dicyano p-benzoquinone be dissolved in 80g and containing HCl(concentration be 0.003mol/L) methylene dichloride in, the solution obtained is chilled to-85 DEG C in advance, then in this solution, order adds the toluene solution (molar ratio of EADC and DEAC is 7/3) that hexane solution that 2.8mL concentration is the EADC of 0.9mol/L and 1.2mL concentration are the DEAC of 0.9mol/L, after mixing, the mixed solution obtained is placed in the cryostat ageing 60min of-85 DEG C.Wherein, by weight, in initiator solution, the content of 2,3-bis-chloro-5,6-dicyano p-benzoquinones is 800ppm.
(2) 200mL two mouthfuls of flasks are placed in the low temperature cryostat that temperature control is-80 DEG C to-85 DEG C, in two mouthfuls of flasks, add 85mL be successively cooled to the normal hexane/monochloro methane mixing solutions of-85 DEG C (wherein, the volume ratio of normal hexane/monochloro methane is 9/1), 15mL is cooled to the iso-butylene of-85 DEG C and the p-methylstyrene of 0.62mL normal temperature (25 DEG C), mix, obtain monomer solution.In monomer solution, add initiator solution prepared by 10mL step (1), mix rear standing and reacting 40min, control in reaction process cryostat temperature be in-80 DEG C to-85 DEG C scope within.The methanol solution that 5mL contains 0.5 % by weight NaOH is added, to stop polyreaction in the backward reaction mixture of reaction end.Then mixing solutions is placed in hot water bath desolvation, after the solid obtained is washed, in vacuum drying oven, is dried to constant weight in 60 DEG C, obtains subject polymer.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 17
Adopt the method identical with embodiment 16 to prepare initiator solution, unlike under the condition that the total amount of, EADC and DEAC is constant, in adjustment initiator solution, the molar ratio of EADC and DEAC is 5/5.
The polymerization process identical with step (2) in embodiment 16 is adopted to carry out polyreaction.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 18
Adopt the method identical with embodiment 16 to prepare initiator solution, unlike under the condition that the total amount of, EADC and DEAC is constant, in adjustment initiator solution, the molar ratio of EADC and DEAC is 3/7.
The polymerization process identical with step (2) in embodiment 16 is adopted to carry out polyreaction.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 19
Adopt the method identical with embodiment 16 to prepare initiator solution, unlike under the condition that the total amount of, EADC and DEAC is constant, in adjustment initiator solution, the molar ratio of EADC and DEAC is 1/9.
The polymerization process identical with step (2) in embodiment 16 is adopted to carry out polyreaction.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 20
The method identical with embodiment 19 is adopted to prepare initiator solution and be polymerized, unlike, in step (2), under the condition that the total amount of normal hexane and monochloro methane is constant, the volume ratio of adjustment normal hexane and monochloro methane is 8/2.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 21
The method identical with embodiment 19 is adopted to prepare initiator solution and be polymerized, unlike, in step (2), under the condition that the total amount of normal hexane and monochloro methane is constant, the volume ratio of adjustment normal hexane and monochloro methane is 7/3.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 22
The method identical with embodiment 19 is adopted to prepare initiator solution and be polymerized, unlike, in step (2), under the condition that the total amount of normal hexane and monochloro methane is constant, the volume ratio of adjustment normal hexane and monochloro methane is 6/4.Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 23
Adopt and prepare initiator solution with embodiment 19 same procedure and be polymerized, unlike, in step (2), under the condition that the total amount of normal hexane and monochloro methane is constant, the volume ratio adjusting normal hexane and monochloro methane is 5/5.Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 24
(1) 0.0651 gram of chloranil is dissolved in 80g and containing HCl(concentration be 0.0042mol/L) dichloromethane solution in, the solution obtained is chilled to-85 DEG C in advance, then in this solution, order adds the n-heptane solution (EADC/DEAC molar ratio is 7/3) that hexane solution that 2.8mL concentration is the EADC of 0.9mol/L and 1.1mL concentration are the DEAC of 1.0mol/L, after mixing, the mixed solution obtained is placed in-85 DEG C of ageing 60min.Wherein, by weight, in initiator solution, the content of chloranil is 800ppm.
(2) method identical with embodiment 17 is adopted to be polymerized, unlike, under the condition that the total amount of normal hexane and monochloro methane is constant, the volume ratio adjusting normal hexane and monochloro methane is 6/4.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 25
The method identical with embodiment 24 is adopted to prepare initiator solution and be polymerized, unlike, in step (1), under the condition that the total amount of EADC and DEAC is constant, the mol ratio of adjustment EADC/DEAC is 5/5.
Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 26
The method identical with embodiment 24 is adopted to prepare initiator solution and be polymerized, unlike, in step (1), under the condition that the total amount of EADC and DEAC is constant, the mol ratio of adjustment EADC/DEAC is 3/7.Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 27
The method identical with embodiment 25 is adopted to prepare initiator solution and be polymerized, unlike, in step (2), under the condition that the total amount of normal hexane and monochloro methane is constant, the volume ratio of adjustment normal hexane and monochloro methane is 9/1.Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Embodiment 28
The method identical with embodiment 25 is adopted to prepare initiator solution and be polymerized, unlike, in step (2), under the condition that the total amount of normal hexane and monochloro methane is constant, the volume ratio of adjustment normal hexane and monochloro methane is 8/2.Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Comparative example 2
The method identical with embodiment 17 is adopted to prepare initiator solution and be polymerized, unlike, do not use chloro-5, the 6-dicyano p-benzoquinones of 2,3-bis-in step (1).Measure the weight of the polymkeric substance obtained, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymkeric substance, result is listed in table 2.
Table 2
Claims (17)
1. a cationic polymerization process, the method comprises: under cationoid polymerisation condition, 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 carry protogenic compound, 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 in halogen group separately;
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;
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;
Described thinner is made up of at least one first thinner and at least one second thinner, and described first thinner is selected from halogenated alkane, and described second thinner is selected from aliphatic alkane and alicyclic alkanes.
2. method according to claim 1, wherein, the described mol ratio can carrying protogenic compound and described activator is 1:0.01 ~ 3, is preferably 1:0.1 ~ 2, is more preferably 1:0.2 ~ 1.8.
3. method according to claim 1 and 2, wherein, described activator is selected from tetrahydrochysene benzoquinones, tetrachlorobenzoquinone, four cyano benzoquinones and DDQ.
4. method according to claim 1, wherein, describedly can carry protogenic compound and described lewis acidic mol ratio is 0.01 ~ 1:1, be preferably 0.02 ~ 0.5:1.
5. the method according to claim 1 or 4, wherein, described Lewis acid is the Lewis acid shown in the Lewis acid shown in formula IV and/or formula V,
In formula IV, X
31and X
32be the one in halogen group separately, be preferably-Cl; R
12for C
1~ C
8straight or branched alkyl, be preferably ethyl;
In formula V, X
4for the one in halogen group, be preferably-Cl; R
13and R
14be C separately
1~ C
8straight or branched alkyl, be preferably ethyl;
Preferably, described Lewis acid is the Lewis acid shown in the Lewis acid shown in formula IV and formula V, and in described Lewis acid, the Lewis acid of 10 ~ 90 % by mole is the Lewis acid shown in formula V.
It is 6. according to the method in claim 1,2 and 4 described in any one, wherein, described that can to carry protogenic compound be H
2o and/or protonic acid, be preferably HCl.
7. 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.
8. method according to claim 7, wherein, described solvent is selected from alkane, halogenated alkane and aromatic hydrocarbons.
9. method according to claim 7, wherein, the time of described ageing is 10 minutes to 10 hours, is preferably more than 30 minutes, is more preferably more than 60 minutes.
10. the method according to claim 7 or 9, wherein, the condition of described ageing comprises: temperature is-100 DEG C to 20 DEG C, is preferably-100 DEG C to 0 DEG C.
11. methods 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.
12. according to the method in claim 1,7 and 11 described in any one, and wherein, described ring-alkylated styrenes is p-methylstyrene and/or a vinyl toluene.
13. according to the method in claim 1,7 and 11 described in any one, and wherein, described monoolefine is iso-butylene.
14. methods according to claim 1, wherein, the condition of described contact comprises: temperature is-120 DEG C to 20 DEG C, is preferably-100 DEG C to 0 DEG C.
15. methods according to claim 5, wherein, described Lewis acid is the Lewis acid shown in formula IV, R
1, R
2, R
3and R
4in at least one is-CN, R
5, R
6, R
7and R
8in at least one is-CN, with the total amount of described thinner for benchmark, the content of described first thinner is 30 ~ 70 volume %, and the content of described second thinner is 30 ~ 70 volume %.
16. methods according to claim 15, wherein, the condition of described contact comprises: temperature is-120 DEG C to-60 DEG C, is preferably-100 DEG C to-70 DEG C.
17. methods according to claim 1 or 15, wherein, described first thinner is selected from C
1~ C
10halogenated alkane, described second thinner is selected from C
3~ C
10aliphatic alkane and C
3~ C
10alicyclic alkanes.
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| US5162445A (en) * | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
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