CN104558341A - Cationic polymerization initiator system and application thereof and cationic polymerization method - Google Patents
Cationic polymerization initiator system and application thereof and cationic polymerization method Download PDFInfo
- Publication number
- CN104558341A CN104558341A CN201310491408.9A CN201310491408A CN104558341A CN 104558341 A CN104558341 A CN 104558341A CN 201310491408 A CN201310491408 A CN 201310491408A CN 104558341 A CN104558341 A CN 104558341A
- Authority
- CN
- China
- Prior art keywords
- formula
- initiator system
- cationic polymerization
- monoolefine
- lewis acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a cationic polymerization initiator system and application thereof. The cationic polymerization initiator system comprises a compound, a lewis acid and an activating agent, wherein the compound is capable of providing protons; the activating agent is a compound selected from a compound in the formula I-1 or the formula I-2 as shown in the description; the lewis acid contains dialkyl aluminum halide and alkyl aluminum dihalide; the content of dialkyl aluminum halide accounts for 20-90 mole percent of the total amount of lewis acid; the content of dialkyl aluminum halide accounts for 10-80 mole percent of the total amount of lewis acid. The invention further provides a cationic polymerization method which uses the cationic polymerization initiator system. By adoption of the cationic polymerization initiator system, the cationic polymerization efficiency, particularly the cationic polymerization efficiency of monoolefine and alkyl styrene as monomers, is remarkably improved, even when monoolefine and alkyl styrene are polymerized in a solution polymerization state, a high polymer yield can be achieved, and the molecular weight of a polymer can be equal to or greater than 40*10<4>.
Description
Technical field
The present invention relates to a kind of cationic polymerization initiators system and application thereof, the invention still further relates to a kind of cationic polymerization process using described cationic polymerization initiators system.
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 brominated isobutylene and p-methylstyrene multipolymer have the over-all properties more excellent than brominated butyl rubber, especially have 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 (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, to such an extent as to system be Polymerization in Different Buffers (namely, using aliphatic alkane and/or alicyclic alkanes as thinner) time, polymerization efficiency extreme difference, not only rate of polymerization is excessively slow, and be difficult to regulate and control the molecular size range of the polymkeric substance obtained.
The present inventor is studied for the problems referred to above, find: if introduce quinonoid compound (particularly there is the quinonoid compound of electron-withdrawing substituent) in initiator system, to combinationally use as lewis acidic dialkylaluminum halides and alkyl dihalides aluminium simultaneously, and make in Lewis acid, the content of dialkylaluminum halides is 20 ~ 90 % by mole, can not only polymerization efficiency be significantly improved, obtain the polymer yield improved, and can to obtain molecular weight be 40 × 10
4above polymkeric substance.This completes the present invention.
According to a first aspect of the invention, the invention provides a kind of cationic polymerization initiators system, this initiator system contains at least one can carry protogenic compound, at least one Lewis acid and at least one activator,
Wherein, 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 Lewis acid contains the Lewis acid shown in the Lewis acid shown in formula II and formula III, and with described lewis acidic total amount for benchmark, the lewis acidic content shown in formula II is 20 ~ 90 % by mole, is preferably 30 ~ 70 % by mole; Lewis acidic content shown in formula III is 10 ~ 80 % by mole, is preferably 30 ~ 70 % by mole,
In formula II, R
9and R
10be C separately
1~ C
8straight or branched alkyl, X
3for the one in halogen group,
In formula III, R
11for C
1~ C
8straight or branched alkyl, X
41and X
42identical or different, be the one in halogen group separately.
According to a second aspect of the invention, the invention provides the application of initiator system according to the present invention in cationoid polymerisation.
According to a third aspect of the invention we, 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 provided by the invention;
Described monoolefine for being selected from the compound shown in formula IV,
In formula IV, R
13and R
14be C separately
1~ C
5straight or branched alkyl; Or R
13for hydrogen, R
14for C
3~ C
5branched-chain alkyl;
Described ring-alkylated styrenes for being selected from the compound shown in formula V,
In formula V, R
15for C
1~ C
5straight or branched alkyl.
Cationoid polymerisation obviously can be improved, particularly using monoolefine and ring-alkylated styrenes as the polymerization efficiency of the cationoid polymerisation of monomer according to cationic polymerization initiators system of the present invention.Use according to initiator system of the present invention, even if be polymerized with ring-alkylated styrenes by monoolefine under Polymerization in Different Buffers, also can obtain high polymer yield, and the molecular weight of the polymkeric substance of preparation can reach 40 × 10
4above.
Embodiment
The invention provides a kind of cationic polymerization initiators system, this initiator system contains at least one can carry protogenic compound, at least one Lewis acid and at least one activator.
According to initiator system of the present invention, 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.Preferably, in formula I-1 and formula I-2, R
1, R
2, R
3, R
4, R
5, R
6, R
7and R
8be-X separately
1or-CN.
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 1--> 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 four cyano benzoquinones (comprising four cyano para benzoquinone and the adjacent benzoquinones of four cyano) and/or DDQ (comprising dichloro dicyano p-benzoquinone and the adjacent benzoquinones of dichloro dicyano).
According to initiator system 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 ~ 2.5, is more preferably 1:0.2 ~ 2.
According to initiator system of the present invention, described Lewis acid contains the Lewis acid shown in formula II,
In formula II, R
9and R
10can be identical or different, can be C separately
1~ C
8straight or branched alkyl, be preferably C
1~ C
5straight or branched alkyl; Preferably, R
9and R
10for identical, be C
1~ C
5straight or branched alkyl.
In formula II, X
3for the one in halogen group, as-F ,-Cl ,-Br or-I, be preferably-Cl.
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 II 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 II is diethyl aluminum chloride.
According to initiator system of the present invention also containing the Lewis acid shown in formula III,
In formula III, R
11for C
1~ C
8straight or branched alkyl, be preferably C
1~ C
5straight or branched alkyl, X
41and X
42identical or different, be the one (as-F ,-Cl ,-Br or-I) in halogen group separately, be preferably-Cl.Lewis acidic specific examples shown in formula III 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 III is ethyl aluminum dichloride.
In a preferred embodiment of the invention, the Lewis acid shown in formula II is diethyl aluminum chloride, and the Lewis acid shown in formula III is ethyl aluminum dichloride.
Containing two alkyl in lewis acidic molecular structure shown in formula II, 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 II, can reduce polymerization rate, extend polymerization time.According to initiator system of the present invention, with lewis acidic total amount for benchmark, the lewis acidic content shown in formula II is 20 ~ 90 % by mole, is preferably 30 ~ 70 % by mole; Lewis acidic content shown in formula III is 10 ~ 80 % by mole, is preferably 30 ~ 70 % by mole, can obtain balance preferably like this between polymerization rate and polymericular weight.
According to initiator system of the present invention, except the Lewis acid shown in the Lewis acid shown in formula II and formula III, according to concrete use occasion, can also containing or other Lewis acid that cation polymerization field is conventional, such as: BCl
3, BF
3, AlCl
3, TiCl
4, SnCl
4, ZnCl
2and R
12 3al, R
12 3in Al, three R
12identical or different, can be C separately
1~ C
8straight or branched alkyl, be preferably C
1~ C
5straight or branched alkyl.R
12 3the specific examples of Al can include but not limited to: trimethyl aluminium and triethyl aluminum.
In initiator system of the present invention, 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 ~ 0.6:1.
According to initiator system of the present invention, 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.
According to a second aspect of the invention, the invention provides the application of initiator system according to the present invention in cationoid polymerisation.
Initiator system provided by the invention can be used as the initiator of various cationic polymerization.Initiator system provided by the invention is particularly suitable for Isobutylene Initiated and ring-alkylated styrenes carries out cationoid polymerisation, and preparation high molecular is (as 40 × 10
4iso-butylene-alkylstyrene copolymers above), and then preparation high molecular brominated isobutylene-alkylstyrene copolymers.
Initiator system of the present invention is not particularly limited for polymerizing condition, can carry out under the cationoid polymerisation condition of routine.
According to a third aspect of the invention we, the invention provides a kind of cationic polymerization process, the method comprises: under cationoid polymerisation condition, at least one thinner, by least one monoolefine and at least one ring-alkylated styrenes with according to each component contacts in initiator system of the present invention.
According to polymerization process of the present invention, kind and the content thereof of each component in initiator system are described in detail above, repeat no more herein.
According to polymerization process of the present 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 is preferably 30 minutes to 10 hours, and such as, the time of described ageing can be 30 minutes to 5 hours.More preferably, the time of described ageing is more than 60 minutes, as 60 minutes to 2 hours, can improve the initiating activity of the initiator system of preparation and the polymerization activity of polymerization system further like this.
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; More preferably C is selected from
1~ C
10halogenated alkane.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, the specific examples of described alkane 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 and tetramethyl-ring hexane (comprise 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).
As solvent, 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.
As solvent, the specific examples of described aromatic hydrocarbons can include but not limited to: toluene, ethylbenzene and dimethylbenzene (comprising 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.
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 for being selected from the compound shown in formula IV,
In formula IV, R
13and R
14be C separately
1~ C
5straight or branched alkyl; Or R
13for hydrogen, R
14for 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 polymerization process of the present invention, described ring-alkylated styrenes for being selected from the compound shown in formula V,
In formula V, R
15for 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,
R in formula VI
15with the R in formula VII
15be C separately
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 p-methylstyrene.
According to polymerization process 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, the various thinners that described thinner can be commonly used for cationoid polymerisation field, such as: described thinner can be the mixture of alkane, halogenated alkane or alkane and halogenated alkane.Described alkane can be aliphatic alkane and/or alicyclic alkanes, is preferably selected from C
3~ C
10alkane, described halogenated alkane can be halogenated aliphatic alkane and/or halogenated cyclo alkane, is preferably selected from C
1~ C
10halogenated alkane, be more preferably selected from C
1~ C
4halogenated alkane.Halogen atom in described halogenated alkane can be chlorine, bromine or fluorine, is preferably chlorine or fluorine.
Even if polymerization process according to the present invention is polymerized in low Polar diluents, also can improve polymer yield, and obtain the polymkeric substance with high molecular.The thinner of described low polarity can be such as described alkane, can also be the mixture of described alkane and described halogenated alkane.When described thinner is the mixture of described alkane and described halogenated alkane, with the total amount of described thinner for benchmark, the content of described alkane can be 20 ~ 99 volume %, is preferably 40 ~ 99 volume %, be more preferably 50 ~ 90 volume %, more preferably 50-70 % by weight; The content of described halogenated alkane can be 1 ~ 80 volume %, is preferably 1 ~ 60 volume %, is more preferably 10 ~ 50 volume %, more preferably 30-50 % by weight.
In the present invention, as thinner, the specific examples of described alkane 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 and tetramethyl-ring hexane (comprise 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).
In the present invention, 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 thinner is selected from Skellysolve A, normal hexane, normal heptane, monochloro methane, methylene dichloride 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 ~ 35 % by weight, is preferably 5 ~ 25 % by weight, is more 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 0 DEG C, is preferably-100 DEG C to-50 DEG C, is more preferably-100 DEG C to-70 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 polymerization process 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 ~ 14 is for illustration of initiator system according to the present invention and cationic polymerization process.
Embodiment 1
(1) 0.0532g dichloro dicyano p-benzoquinone is dissolved in 66.3g and containing HCl(concentration be 0.0037mol/L) methylene dichloride in, the solution obtained is chilled to-85 DEG C in advance, then in this solution, order adds the n-heptane solution (molar ratio of EADC and DEAC is 7/3) that ethyl aluminum dichloride (EADC) hexane solution that 3.2mL concentration is 0.9mol/L and 1.2mL concentration are the diethyl aluminum chloride (DEAC) of 1.0mol/L, after mixing, the mixed solution obtained is placed in the cryostat ageing 100min of-85 DEG C, thus obtains initiator solution.Wherein, by weight, in initiator solution, the content of dichloro dicyano p-benzoquinone is 770ppm.
(2) in the glass reactor being furnished with the 500mL that powerful constant speed stirs, order adds 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 is chilled to the iso-butylene of-80 DEG C and the p-methylstyrene (content 98 % by weight) of 1.1mL normal temperature 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, and carry out the polyreaction of 17min, in reaction mixture, then add 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.
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 prepare initiator solution and be polymerized, unlike, step does not use dichloro dicyano p-benzoquinone in (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 1.
Comparative example 2
The method identical with embodiment 1 is adopted to prepare initiator solution and be polymerized, unlike, step does not use dichloro dicyano p-benzoquinone in (1), and the ethyl aluminum dichloride of diethyl aluminum chloride equimolar amount replaces.
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.
Embodiment 2
(1) method identical with embodiment 1 step (1) is adopted to prepare initiator solution.
(2) 250mL there-necked flask is placed in the low temperature cryostat that temperature control is-80 DEG C to-85 DEG C, in there-necked flask, add normal hexane, the 15mL that 85mL is cooled to-80 DEG C be successively cooled to the iso-butylene of-80 DEG C and the p-methylstyrene (content 98% weight) of 0.62mL normal temperature, mix, obtain monomer solution.In monomer solution, add the initiator solution of 10mL, mix rear standing and reacting 50min, 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 1.
Comparative example 3
The method identical with embodiment 2 is adopted to prepare initiator solution and be polymerized, unlike, when preparing initiator solution, the ethyl aluminum dichloride of diethyl aluminum chloride equivalent replaces.
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.
Embodiment 3
(1) 0.0824g DDQ is dissolved in 99.0g and containing HCl(concentration be 0.0037mol/L) methylene dichloride in, the solution obtained is chilled to-85 DEG C in advance, then in this solution, order adds the n-heptane solution (molar ratio of EADC and DEAC is 5/5) that ethyl aluminum dichloride (EADC) hexane solution that 2.7mL concentration is 0.9mol/L and 2.4mL concentration are the diethyl aluminum chloride (DEAC) of 1.0mol/L, after mixing, the mixed solution obtained is placed in the cryostat ageing 60min of-85 DEG C, thus obtains initiator solution.Wherein, by weight, in initiator solution, the content of DDQ is 800ppm.
(2) method identical with step (2) in embodiment 1 is adopted to be polymerized, unlike, monochloro methane add-on is 80mL, and normal hexane add-on is 120mL.
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.
Embodiment 4
The method identical with step (2) with embodiment 3 step (1) is adopted to prepare initiator solution and be polymerized, unlike, in step (2), monochloro methane add-on is 40mL, and the add-on of normal hexane is 160mL.
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.
Embodiment 5
Adopt the method identical with embodiment 3 step (1) to prepare initiator solution, adopt the method identical with embodiment 2 step (2) to be polymerized.
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.
Embodiment 6
(1) 0.0652g DDQ is 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 3/7) that EADC hexane solution that 1.2mL concentration is 0.9mol/L and 2.8mL concentration are 0.9mol/LDEAC, 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 DDQ is 800ppm.
(2) method identical with embodiment 1 step (2) 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 1.
Embodiment 7
(1) method identical with embodiment 6 step (1) is adopted to prepare initiator solution.
(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 (content 98% weight) of 0.62mL normal temperature, 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 1.
Embodiment 8
(1) method identical with embodiment 6 step (1) is adopted to prepare initiator solution, unlike, under the condition that in initiator solution, the total amount of EADC and DEAC is constant, the molar ratio of adjustment EADC and DEAC is 1/9.
(2) method identical with embodiment 7 step (2) 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 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 1.
Embodiment 9
(1) method identical with embodiment 8 step (1) is adopted to prepare initiator solution.
(2) method identical with embodiment 7 step (2) 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 1.
Embodiment 10
(1) method identical with embodiment 8 step (1) is adopted to prepare initiator solution.
(2) method identical with embodiment 7 step (2) 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 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 1.
Embodiment 11
(1) method identical with embodiment 8 step (1) is adopted to prepare initiator solution.
(2) method identical with embodiment 7 step (2) 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 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 1.
Embodiment 12
(1) method identical with embodiment 8 step (1) is adopted to prepare initiator solution.
(2) method identical with embodiment 7 step (2) 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 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 1.
Embodiment 13
The method identical with embodiment 1 is adopted to prepare initiator solution and be polymerized, unlike, under the condition that in step (1), in initiator solution, EADC and DEAC total amount is constant, the molar ratio of adjustment EADC and DEAC is 8/2; Under the condition that in step (2), 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 1.
Embodiment 14
The method identical with embodiment 1 is adopted to prepare initiator solution and be polymerized, unlike, the digestion time in step (1) is 30min.
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.
Table 1
Claims (16)
1. a cationic polymerization initiators system, this initiator system contains at least one can carry protogenic compound, at least one Lewis acid and at least one activator,
Wherein, 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 Lewis acid contains the Lewis acid shown in the Lewis acid shown in formula II and formula III, and with described lewis acidic total amount for benchmark, the lewis acidic content shown in formula II is 20 ~ 90 % by mole, is preferably 30 ~ 70 % by mole; Lewis acidic content shown in formula III is 10 ~ 80 % by mole, is preferably 30 ~ 70 % by mole,
In formula II, R
9and R
10be C separately
1~ C
8straight or branched alkyl, X
3for the one in halogen group,
In formula III, R
11for C
1~ C
8straight or branched alkyl, X
41and X
42identical or different, be the one in halogen group separately.
2. initiator system 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 ~ 2.5, is more preferably 1:0.2 ~ 2.
3. initiator system according to claim 1 and 2, wherein, described activator is four cyano benzoquinones and/or DDQ.
4. initiator system 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 ~ 0.6:1.
5. the initiator system according to claim 1 or 4, wherein, in formula II, X
3for-Cl, in formula III, X
41and X
42be-Cl; Preferably, the Lewis acid shown in formula II is diethyl aluminum chloride, and the Lewis acid shown in formula III is ethyl aluminum dichloride.
It is 6. according to the initiator system 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. the application of the initiator system in claim 1 ~ 6 described in any one in cationoid polymerisation.
8. a cationic polymerization process, the method comprises: under cationoid polymerisation condition, in at least one thinner, by each component contacts in the initiator system at least one monoolefine and at least one ring-alkylated styrenes and claim 1 ~ 6 described in any one;
Described monoolefine for being selected from the compound shown in formula IV,
In formula IV, R
13and R
14be C separately
1~ C
5straight or branched alkyl; Or R
13for hydrogen, R
14for C
3~ C
5branched-chain alkyl;
Described ring-alkylated styrenes for being selected from the compound shown in formula V,
In formula V, R
15for C
1~ C
5straight or branched alkyl.
9. method according to claim 8, 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.
10. method according to claim 9, wherein, described solvent be selected from alkane, halogenated alkane and aromatic hydrocarbons one or more.
11. methods according to claim 9, wherein, the time of described ageing is 30 minutes to 10 hours, is preferably more than 60 minutes, is more preferably 60 minutes to 2 hours.
12. methods according to claim 9 or 11, 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.
13. methods according to claim 8 or claim 9, wherein, described monoolefine is iso-butylene, and described ring-alkylated styrenes is p-methylstyrene and/or a vinyl toluene.
14. methods according to claim 8 or claim 9, 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.
15. methods according to claim 8 or claim 9, wherein, described thinner is the mixture of alkane, halogenated alkane or alkane and halogenated alkane.
16. methods according to claim 8, wherein, the condition of described contact comprises: temperature is-120 DEG C to 0 DEG C, is preferably-100 DEG C to-50 DEG C, is more preferably-100 DEG C to-70 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310491408.9A CN104558341B (en) | 2013-10-18 | 2013-10-18 | cationic polymerization initiator system and application thereof and cationic polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310491408.9A CN104558341B (en) | 2013-10-18 | 2013-10-18 | cationic polymerization initiator system and application thereof and cationic polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558341A true CN104558341A (en) | 2015-04-29 |
| CN104558341B CN104558341B (en) | 2017-02-01 |
Family
ID=53075486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310491408.9A Active CN104558341B (en) | 2013-10-18 | 2013-10-18 | cationic polymerization initiator system and application thereof and cationic polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558341B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146691A (en) * | 2015-05-13 | 2016-11-23 | 马萨诸塞州大学 | Produce polymerization initiation system and the method for high response alkene functional polymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162445A (en) * | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
| CN1212000A (en) * | 1996-02-29 | 1999-03-24 | 国际壳牌研究有限公司 | Process for preparation of copolymers |
| US6028144A (en) * | 1990-07-24 | 2000-02-22 | Exxon Chemical Patents, Inc. | Composition for the carcass |
| CN102399311A (en) * | 2010-08-19 | 2012-04-04 | 中国石油化工股份有限公司 | Cationic polymerization initiation system and cationic polymerization method |
| CN103122052A (en) * | 2011-11-18 | 2013-05-29 | 北京化工大学 | Segmented copolymer with fully-saturated soft segment and crystallizable hard segment and preparation method of segmented copolymer |
-
2013
- 2013-10-18 CN CN201310491408.9A patent/CN104558341B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162445A (en) * | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
| US6028144A (en) * | 1990-07-24 | 2000-02-22 | Exxon Chemical Patents, Inc. | Composition for the carcass |
| CN1212000A (en) * | 1996-02-29 | 1999-03-24 | 国际壳牌研究有限公司 | Process for preparation of copolymers |
| CN102399311A (en) * | 2010-08-19 | 2012-04-04 | 中国石油化工股份有限公司 | Cationic polymerization initiation system and cationic polymerization method |
| CN103122052A (en) * | 2011-11-18 | 2013-05-29 | 北京化工大学 | Segmented copolymer with fully-saturated soft segment and crystallizable hard segment and preparation method of segmented copolymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146691A (en) * | 2015-05-13 | 2016-11-23 | 马萨诸塞州大学 | Produce polymerization initiation system and the method for high response alkene functional polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558341B (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104558341A (en) | Cationic polymerization initiator system and application thereof and cationic polymerization method | |
| CN104558343B (en) | Positive ion polymerization method | |
| CN104974291B (en) | Cationic polymerization method | |
| CN104558357A (en) | Positive ion polymerization method | |
| CN104558344A (en) | Cationic polymerization initiator system, application thereof and cationic polymerization method | |
| CN104558342A (en) | Cation polymerization method | |
| CN106146700A (en) | A kind of preparation method of halogen polymer | |
| CN106146711B (en) | A kind of cationic polymerization process | |
| CN106317349B (en) | A kind of styrene-isomonoolefin-styrene triblock copolymer and preparation method thereof | |
| CN104974292B (en) | Cationic polymerization method | |
| CN106146697A (en) | A kind of cationic polymerization process | |
| CN106146704A (en) | A kind of preparation method of halogen polymer | |
| CN104974290A (en) | Cationic polymerization method | |
| CN104974293A (en) | Cationic polymerization method | |
| CN106146696B (en) | A kind of cationic polymerization process | |
| CN106146706B (en) | A kind of cationic polymerization process | |
| CN106146705B (en) | A kind of preparation method of halogen polymer | |
| CN106146710B (en) | A kind of cationic polymerization process | |
| CN106146699A (en) | A kind of preparation method of halogen polymer | |
| CN106032399B (en) | A kind of star block copolymer and preparation method thereof | |
| CN106146703A (en) | A kind of cationic polymerization process | |
| CN106146708A (en) | A kind of cationic polymerization process | |
| CN106146701B (en) | A kind of preparation method of halogen polymer | |
| CN103724508B (en) | A kind of branched polymer and preparation method thereof | |
| CN105440231A (en) | Block copolymer preparation method and block copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |