CN104558341B - 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
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- CN104558341B CN104558341B CN201310491408.9A CN201310491408A CN104558341B CN 104558341 B CN104558341 B CN 104558341B CN 201310491408 A CN201310491408 A CN 201310491408A CN 104558341 B CN104558341 B CN 104558341B
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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 its application, the invention still further relates to a kind of use described sun
The cationic polymerization process of cation polymerization initiator system.
Background technology
The isobutene. of bromination-p-methylstyrene copolymer, usually by the copolymer of isobutene. and p-methylstyrene
Carry out bromination, part p-methylstyrene group transformations are obtained from bromometllylstyrene group.Because molecular backbone is
Full saturated structures, therefore brominated isobutylene and p-methylstyrene copolymer have more excellent than brombutyl comprehensive
Can, especially there is more preferable heat resistance；And, the presence due to highly active benzyl bromo functional groups, can be with various rubbers
Glue realizes sulfuration and co-vulcanization in broader scope, in addition also has the modified advantage of wider range.This product passes through and Buddhist nun
Dragon blending makes dynamic vulcanization alloy for producing the inner liner of tire, can accomplish not only light but also thin, therefore, the isobutene. of bromination
Can be used for producing the tire with higher performance with p-methylstyrene copolymer, and before there is quite wide market application
Scape.
Therefore, research worker is directed to isobutene. and has carried out numerous studies to alkylstyrene copolymers and its halogenide.
For example: us5162445 and us5959049 individually discloses isobutene. and to alkylstyrene copolymers and preparation method thereof.
Content of the invention
The present inventor finds in research process, isobutene. when carrying out cationic polymerization, its polymerization efficiency
(that is, polymer yield) is to Diluent Polarity and insensitive, but isobutene. is being passed through cationic polymerization with ring-alkylated styrenes
When mode carries out combined polymerization, with the reduction of Diluent Polarity, polymerization efficiency decreases, so that system is Polymerization in Different Buffers
When (that is, using aliphatic alkane and/or alicyclic alkanes as diluent), polymerization efficiency extreme difference, not only rate of polymerization is excessively slow, and
And be difficult to the molecular size range of the polymer obtaining is regulated and controled.
The present inventor is studied for the problems referred to above, finds: if introducing quinoid in initiator system
Compound (particularly has the quinonoid compound of electron-withdrawing substituent), simultaneously will as lewis acidic dialkylaluminum halides with
Alkyl dihalides aluminum is applied in combination, and makes in lewis acid, and the content of dialkylaluminum halides is 20～90 moles of %, can not only
Significantly improve polymerization efficiency, obtain the polymer yield improving, and can obtain molecular weight is 40 × 104Above polymerization
Thing.This completes the present invention.
According to the first aspect of the invention, the invention provides a kind of cationic polymerization initiators system, this initiator body
System can carry protogenic compound, at least one lewis acid and at least one activator containing at least one,
Wherein, described activator is the compound shown in selected from formula i-1 and the compound shown in formula i-2,
In formula i-1 and formula i-2, r1、r2、r3、r4、r5、r6、r7And r8It is respectively-h ,-x1、-no2、In-cn
One kind, x1And x2It is respectively one of halogen group；
Described lewis acid contains the lewis acid shown in formula ii and the lewis acid shown in formula iii, with described Louis
On the basis of the total amount of acid, the lewis acidic content shown in formula ii is 20～90 moles of %, preferably 30～70 moles %；Formula iii
Shown lewis acidic content is 10～80 moles of %, preferably 30～70 moles %,
In formula ii, r9And r10It is respectively c1～c8Straight or branched alkyl, x3For one of halogen group,
In formula iii, r11For c1～c8Straight or branched alkyl, x41And x42Identical or different, respectively in halogen group
One kind.
According to the second aspect of the invention, the invention provides according to the initiator system of the present invention in cationic polymerization
Application.
According to the third aspect of the invention we, the invention provides a kind of cationic polymerization process, the method includes: sun from
Under sub- polymerizing condition, at least one diluent, by least one monoolefine and at least one ring-alkylated styrenes and the present invention
Each group tap in the initiator system providing is touched；
Described monoolefine is the compound shown in selected from formula iv,
In formula iv, r13And r14It is respectively c1～c5Straight or branched alkyl；Or r13For hydrogen, r14For c3～c5Side chain
Alkyl；
Described ring-alkylated styrenes is the compound shown in selected from formula v,
In formula v, r15For c1～c5Straight or branched alkyl.
Cationic polymerization can be obviously improved according to the cationic polymerization initiators system of the present invention, particularly with monoolefine
With ring-alkylated styrenes as the cationic polymerization of monomer polymerization efficiency.Using the initiator system according to the present invention, even if
Monoolefine is polymerized with ring-alkylated styrenes it is also possible to be obtained high polymer yield under Polymerization in Different Buffers, and is prepared
The molecular weight of polymer can reach 40 × 104More than.
Specific embodiment
The invention provides a kind of cationic polymerization initiators system, this initiator system contains at least one can be provided
The compound of proton, at least one lewis acid and at least one activator.
According to the initiator system of the present invention, described activator is shown in the compound shown in selected from formula i-1 and formula i-2
Compound,
In formula i-1 and formula i-2, r1、r2、r3、r4、r5、r6、r7And r8It is respectively-h ,-x1、-no2、In-cn
One kind, x1And x2It is respectively one of halogen group (for example :-f ,-cl ,-br or-i).Preferably, formula i-1 and formula i-2
In, r1、r2、r3、r4、r5、r6、r7And r8It is respectively-x1Or-cn.
The instantiation of described activator can include but is not limited to: tetrahydrochysene 1,4-benzoquinone, tetrahydrochysene neighbour's benzoquinone, a fluorine three hydrogen pair
Benzoquinone, a fluorine three hydrogen neighbour's benzoquinone, difluoro dihydro 1,4-benzoquinone, difluoro dihydro neighbour's benzoquinone, trifluoro one hydrogen 1,4-benzoquinone, trifluoro one hydrogen neighbour's benzene
Quinone, tetrafluoro 1,4-benzoquinone, tetrafluoro neighbour benzoquinone, a chlorine three hydrogen 1,4-benzoquinone, a chlorine three hydrogen neighbour benzoquinone, dichloro-dihydro 1,4-benzoquinone (include 2,
3- dichloro 1,4-benzoquinone, 2,5- dichloro 1,4-benzoquinone, 2,6- dichloro 1,4-benzoquinone), dichloro-dihydro neighbour benzoquinone (include 3,4- dichloro neighbour benzene
Quinone, 3,5- dichloro neighbour benzoquinone, 3,6- dichloro neighbour benzoquinone), trichlorine one hydrogen 1,4-benzoquinone, trichlorine one hydrogen neighbour benzoquinone, chloranil, four
Chlorine neighbour's benzoquinone, monobromo three hydrogen 1,4-benzoquinone, monobromo three hydrogen neighbour's benzoquinone, dibromo dihydro 1,4-benzoquinone (include 2,3- dibromo 1,4-benzoquinone, 2,5-
Dibromo 1,4-benzoquinone, 2,6- dibromo 1,4-benzoquinone), dibromo dihydro neighbour benzoquinone (include 3,4- dibromo-o benzoquinone, 3,5- dibromo-o benzoquinone,
3,6- dibromo-o benzoquinone), tribromo one hydrogen 1,4-benzoquinone, tribromo one hydrogen neighbour benzoquinone, tetrabromo 1,4-benzoquinone, tetrabromo-phthalic quinone, a fluorine three nitre
Base 1,4-benzoquinone, fluorine trinitro- neighbour's benzoquinone, difluoro dinitro 1,4-benzoquinone (include the fluoro- 5,6- dinitro 1,4-benzoquinone of 2,3- bis-, 2,5-
Two fluoro- 3,6- dinitro 1,4-benzoquinone, the fluoro- 3,5- dinitro 1,4-benzoquinone of 2,6- bis-), difluoro dinitro o benzoquinone (include 3,4- bis-
Fluoro- 5,6- dinitro o benzoquinone, the fluoro- 4,6- dinitro o benzoquinone of 3,5- bis-, the fluoro- 4,5- dinitro o benzoquinone of 3,6- bis-), trifluoro
One nitro 1,4-benzoquinone, trifluoro one nitro neighbour's benzoquinone, a chlorine trinitro- 1,4-benzoquinone, chlorine trinitro- neighbour's benzoquinone, dichloro dinitro pair
Benzoquinone (includes the chloro- 5,6- dinitro 1,4-benzoquinone of 2,3- bis-, the chloro- 3,6- dinitro 1,4-benzoquinone of 2,5- bis-, the chloro- 3,5- bis- of 2,6- bis-
Nitro 1,4-benzoquinone), dichloro dinitro o benzoquinone (include the chloro- 5,6- dinitro o benzoquinone of 3,4- bis-, the chloro- 4,6- dinitro of 3,5- bis-
Base neighbour benzoquinone, the chloro- 4,5- dinitro o benzoquinone of 3,6- bis-), trichlorine one nitro 1,4-benzoquinone, trichlorine one nitro neighbour benzoquinone, monobromo three
Nitro 1,4-benzoquinone, monobromo trinitro- neighbour benzoquinone, dibromo dinitro 1,4-benzoquinone (include the bromo- 5,6- dinitro 1,4-benzoquinone of 2,3- bis-, 2,
The bromo- 3,6- dinitro 1,4-benzoquinone of 5- bis-, the bromo- 3,5- dinitro 1,4-benzoquinone of 2,6- bis-), dibromo dinitro o benzoquinone (include 3,4-
Two bromo- 5,6- dinitro o benzoquinone, the bromo- 4,6- dinitro o benzoquinone of 3,5- bis-, the bromo- 4,5- dinitro o benzoquinone of 3,6- bis-), three
Bromine one nitro 1,4-benzoquinone, tribromo one nitro neighbour benzoquinone, tetranitro 1,4-benzoquinone, tetranitro neighbour benzoquinone, a fluorine tricyano 1,4-benzoquinone, one
Fluorine tricyano neighbour's benzoquinone, difluoro dicyano p-benzoquinone (include the fluoro- 5,6- dicyano p-benzoquinone of 2,3- bis-, the fluoro- 3,6- bis- of 2,5- bis-
Cyano group 1,4-benzoquinone, the fluoro- 3,5- dicyano p-benzoquinone of 2,6- bis-), difluoro dicyano neighbour benzoquinone (include the fluoro- 5,6- dicyan of 3,4- bis-
Base neighbour's benzoquinone, 3,5- bis- fluoro- 4,6- dicyano neighbour's benzoquinone, 3,6- bis- fluoro- 4,5- dicyano neighbour's benzoquinone), trifluoro one cyano group is to benzene
Quinone, trifluoro one cyano group neighbour benzoquinone, a chlorine tricyano 1,4-benzoquinone, one chlorine tricyano neighbour benzoquinone, dichloro dicyano p-benzoquinone (include 2,
The chloro- 5,6- dicyano p-benzoquinone of 3- bis-, the chloro- 3,6- dicyano p-benzoquinone of 2,5- bis-, the chloro- 3,5- dicyano p-benzoquinone of 2,6- bis-),
Dichloro dicyano neighbour's benzoquinone (includes 3,4- bis- chloro- 5,6- dicyano neighbour's benzoquinone, 3,5- bis- chloro- 4,6- dicyano neighbour's benzoquinone, 3,6-
Two chloro- 4,5- dicyanos neighbour's benzoquinone), trichlorine one cyano group 1,4-benzoquinone, trichlorine one cyano group neighbour's benzoquinone, monobromo tricyano 1,4-benzoquinone, one
Bromine tricyano neighbour's benzoquinone, dibromo dicyano p-benzoquinone (include the bromo- 5,6- dicyano p-benzoquinone of 2,3- bis-, the bromo- 3,6- bis- of 2,5- bis-
Cyano group 1,4-benzoquinone, the bromo- 3,5- dicyano p-benzoquinone of 2,6- bis-), dibromo dicyano neighbour benzoquinone (include the bromo- 5,6- dicyan of 3,4- bis-
Base neighbour's benzoquinone, 3,5- bis- bromo- 4,6- dicyano neighbour's benzoquinone, 3,6- bis- bromo- 4,5- dicyano neighbour's benzoquinone), tribromo one cyano group is to benzene
Quinone, tribromo one cyano group neighbour's benzoquinone, trinitro- one cyano group 1,4-benzoquinone, trinitro- one cyano group neighbour's benzoquinone, dinitro dicyano p-benzoquinone
(include 2,3- dinitro -5,6- dicyano p-benzoquinone, 2,5- dinitro -3,6- dicyano p-benzoquinone, 2,6- dinitro -3,5-
Dicyano p-benzoquinone), dinitro dicyano neighbour benzoquinone (include 3,4- dinitro -5,6- dicyano neighbour benzoquinone, 3,5- dinitro -
4,6- dicyano neighbour benzoquinone, 3,6- dinitro -4,5- dicyano neighbour benzoquinone), a nitro tricyano 1,4-benzoquinone, a nitro tricyano
Adjacent benzoquinone, four cyano 1,4-benzoquinone, four cyano neighbour benzoquinone, a fluorine front three acid chloride group 1,4-benzoquinone, one fluorine front three acid chloride group neighbour benzoquinone, two
Fluorine dimethyl chloride base 1,4-benzoquinone (includes the fluoro- 5,6- dimethyl chloride base 1,4-benzoquinone of 2,3- bis-, the fluoro- 3,6- dimethyl chloride base of 2,5- bis-
1,4-benzoquinone, the fluoro- 3,5- dimethyl chloride base 1,4-benzoquinone of 2,6- bis-), difluoro dimethyl chloride base neighbour benzoquinone (include the fluoro- 5,6- of 3,4- bis-
Dimethyl chloride base neighbour's benzoquinone, 3,5- bis- fluoro- 4,6- dimethyl chloride base neighbour's benzoquinone, 3,6- bis- fluoro- 4,5- dimethyl chloride base neighbour's benzene
Quinone), trifluoro one formyl chloro 1,4-benzoquinone, trifluoro one formyl chloro neighbour benzoquinone, a chlorine front three acid chloride group 1,4-benzoquinone, a chlorine three formyl
Chloro neighbour benzoquinone, dichloro dimethyl chloride base 1,4-benzoquinone (include the chloro- 5,6- dimethyl chloride base 1,4-benzoquinone of 2,3- bis-, 2,5- bis- chloro- 3,
6- dimethyl chloride base 1,4-benzoquinone, the chloro- 3,5- dimethyl chloride base 1,4-benzoquinone of 2,6- bis-), dichloro dimethyl chloride base neighbour benzoquinone (include 3,
4- bis- chloro- 5,6- dimethyl chloride base neighbour's benzoquinone, 3,5- bis- chloro- 4,6- dimethyl chloride base neighbour's benzoquinone, chloro- 4,5- bis- formyl of 3,6- bis-
Chloro neighbour benzoquinone), trichlorine one formyl chloro 1,4-benzoquinone, trichlorine one formyl chloro neighbour benzoquinone, monobromo front three acid chloride group 1,4-benzoquinone, one
Bromine front three acid chloride group neighbour benzoquinone, dibromo dimethyl chloride base 1,4-benzoquinone (include the bromo- 5,6- dimethyl chloride base 1,4-benzoquinone of 2,3- bis-, 2,
The bromo- 3,6- dimethyl chloride base 1,4-benzoquinone of 5- bis-, the bromo- 3,5- dimethyl chloride base 1,4-benzoquinone of 2,6- bis-), dibromo dimethyl chloride base neighbour benzene
(inclusion 3,4- bis- bromo- 5,6- dimethyl chloride base neighbour's benzoquinone, 3,5- bis- bromo- 4,6- dimethyl chloride base neighbour's benzoquinone, 3,6- bis- are bromo- for quinone
4,5- dimethyl chloride base neighbour benzoquinone), tribromo one formyl chloro 1,4-benzoquinone, tribromo one formyl chloro neighbour benzoquinone, tetramethyl acid chloride group pair
Benzoquinone and tetramethyl acid chloride group neighbour's benzoquinone.
Preferably, described activator be selected from four cyano benzoquinone (include four cyano 1,4-benzoquinone and four cyano neighbour benzoquinone) and/or
DDQ (includes dichloro dicyano p-benzoquinone and dichloro dicyano neighbour's benzoquinone).
According to the initiator system of the present invention, the content of described activator can be according to the concrete application of this initiator system
Occasion carries out suitable selection, to be obtained in that gratifying polymerization efficiency is defined.Usually, described can carry protogenic
Compound can be 1:0.01～3, preferably 1:0.1～2.5, more preferably 1:0.2～2 with the mol ratio of described activator.
According to the initiator system of the present invention, described lewis acid contains the lewis acid shown in formula ii,
In formula ii, r9And r10Can be identical or different, can be each c1～c8Straight or branched alkyl, preferably c1
～c5Straight or branched alkyl；Preferably, r9And r10For identical, it is c1～c5Straight or branched alkyl.
In formula ii, x3For one of halogen group, such as-f ,-cl ,-br or-i, preferably-cl.
In the present invention, c1～c8Straight or branched alkyl include c1～c8Straight chained alkyl and c3～c8Branched alkyl,
Its instantiation can include but is not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, 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 penta
Base, n-octyl, 2- methylheptyl, 3- methylheptyl, 4- methylheptyl, 5- methylheptyl, 6- methylheptyl, 2,2- dimethyl are own
Base, 2,3- dimethylhexanyl, 2,4- dimethylhexanyl, 2,5- dimethylhexanyl, 3,3- dimethylhexanyl, 3,4- dimethyl are own
Base, 3,5- dimethylhexanyl, 4,4- dimethylhexanyl, 4,5- dimethylhexanyl, 5,5- dimethylhexanyl, 2- ethylhexyl, 3-
Ethylhexyl, 4- ethylhexyl, 2- n-pro-pyl amyl group and 2- isopropyl amyl group.
In the present invention, the lewis acidic instantiation shown in formula ii can include but is not limited to: dimethylaluminum chloride, two
Ethylmercury chloride aluminum, diη-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl aluminum chloride and diisobutyl aluminum chloride.
Preferably, the lewis acid shown in formula ii is diethyl aluminum chloride.
Lewis acid shown in also containing formula iii for the initiator system according to the present invention,
In formula iii, r11For c1～c8Straight or branched alkyl, preferably c1～c5Straight or branched alkyl, x41With
x42Identical or different, respectively one of halogen group (as-f ,-cl ,-br or-i), preferably-cl.Road shown in formula iii
The instantiation of Lewis acid can include but is not limited to dichloromethyl aluminum, ethyl aluminum dichloride, dichloro n-pro-pyl aluminum, two chloro isopropyls
Aluminum, 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, shown in formula iii
Lewis acid is ethyl aluminum dichloride.
Contain two alkyl in lewis acidic molecular structure shown in formula ii, suppression cation activity center can be played
There is the effect of chain tra nsfer such that it is able to improve the molecular weight of the polymer of preparation.But, lewis acidic shown in formula ii contains
Amount is too high, can reduce polymerization rate, extends polymerization time.According to the initiator system of the present invention, with lewis acidic total
On the basis of amount, the lewis acidic content shown in formula ii is 20～90 moles of %, preferably 30～70 moles %；Shown in formula iii
Lewis acidic content is 10～80 moles of %, preferably 30～70 moles %, so can be in polymerization rate and polymer
Obtain between molecular weight and preferably balance.
According to the initiator system of the present invention, in addition to the lewis acid shown in except formula ii and the lewis acid shown in formula iii, root
According to specific use occasion, can also be with or without the conventional other lewis acids in cationic polymerization field, such as: bcl3、bf3、
alcl3、ticl4、sncl4、zncl2And r12 3Al, r12 3In al, three r12Identical or different, can be each c1～c8Straight chain
Or branched alkyl, preferably c1～c5Straight or branched alkyl.r12 3The instantiation of al can include but is not limited to: trimethyl
Aluminum and triethyl aluminum.
In the initiator system of the present invention, lewis acidic content can be the conventional amount used in cationic polymerization field.One
As, the described protogenic compound and described lewis acidic mol ratio of can carrying can be 0.01～1:1, preferably 0.02
～0.6:1.
According to the initiator system of the present invention, described can carry protogenic compound can be in cationic polymerization field
Conventional various can carry protogenic compound.It is usually, described that can to carry protogenic compound can be h2O and/or
Bronsted acid, its instantiation can include but is not limited to: h2o、hcl、hf、hbr、h2so4、h2co3、h3po4And hno3.Preferably,
Described can carry protogenic compound be hcl.
According to the second aspect of the invention, the invention provides according to the initiator system of the present invention in cationic polymerization
Application.
The initiator system that the present invention provides can be used as the initiator of various cationic polymerizations.The present invention provides
Initiator system be particularly suitable for Isobutylene Initiated and ring-alkylated styrenes and carry out cationic polymerization, preparation high molecular (as 40 ×
104More than) isobutene .-alkylstyrene copolymers, and then prepare high molecular brominated isobutylene-alkylstyrene copolymers.
The initiator system of the present invention is not particularly limited for polymerizing condition, can be in conventional cationic polymerization condition
Under carry out.
According to the third aspect of the invention we, the invention provides a kind of cationic polymerization process, the method includes: sun from
Under sub- polymerizing condition, at least one diluent, by least one monoolefine and at least one ring-alkylated styrenes with according to this
Each group tap in the initiator system of invention is touched.
According to the polymerization of the present invention, the species of each component in initiator system and its content have been carried out above
Detailed description, here is omitted.
According to the polymerization of the present invention, each component in described initiator system can be dissolved in solvent, and will
The mixture ageing obtaining, obtains initiator solution；By described initiator solution be dissolved with described monoolefine and described alkyl
Cinnamic diluent mixing.
The purpose of described ageing is to make lewis acid in initiator system and can propose protogenic compound and work
Agent forms stable complexation initiating activity center, can carry out under normal conditions.Usually, the condition bag of described ageing
Include: temperature can be -100 DEG C to 20 DEG C, preferably -100 DEG C to 0 DEG C.The preferably 30 minutes time of described ageing is little to 10
When, for example, the time of described ageing can be 30 minutes to 5 hours.It is highly preferred that the time of described ageing be 60 minutes with
On, such as 60 minutes to 2 hours, so can improve the initiating activity of initiator system of preparation and polymerization system further
Polymerization activity.
Described solvent can be the various liquids that can dissolve described Bronsted acid, described lewis acid and described activator
Matter.Usually, described solvent can be selected from alkane (can be aliphatic alkane and/or alicyclic alkanes), halogenated alkane and virtue
Hydrocarbon, is preferably selected from c3～c10Alkane, c1～c10Halogenated alkane and c6～c12Aromatic hydrocarbons；It is more preferably selected from c1～c10Halo
Alkane.Halogen atom in described halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.Described halogenated alkane is preferably
c1～c4Halogenated aliphatic alkane.
As solvent, the instantiation of described alkane can include but is not limited to: propane, normal butane, iso-butane, positive penta
Alkane, isopentane, neopentane, Pentamethylene., normal hexane, 2- methylpentane, 3- methylpentane, 2,3- dimethylbutane, hexamethylene, first
Cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- ethylpentane, 3- ethylpentane, 2,3- dimethyl pentane, 2,
4- dimethyl pentane, normal octane, 2- methyl heptane, 3- methyl heptane, 4- methyl heptane, 2,3- dimethylhexane, 2,4- diformazan
Base hexane, 2,5- dimethylhexane, 3- ethyl hexane, 2,2,3- trimethylpentane, 2,3,3- trimethylpentane, 2,4,4- front three
Base pentane, 2- methyl -3- ethylpentane, n -nonane, 2- methyloctane, 3- methyloctane, 4- methyloctane, 2,3- dimethyl-g
Alkane, 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- front three
Base hexane, 2,4,4- trimethyl cyclohexane, 2- methyl -3- ethyl hexane, 2- methyl -4- ethyl hexane, 3- methyl -3- ethyl hexyl
Alkane, 3- methyl -4- ethyl hexane, 3,3- diethylpentane, 1- methyl -2- ethyl cyclohexane, 1- methyl -3- ethyl cyclohexane,
1- methyl -4- ethyl cyclohexane, n-pro-pyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane (include trimethyl-cyclohexane
Various isomers, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- trimethyl-cyclohexanes, 1,2,5- trimethyl-cyclohexanes, 1,3,5-
Trimethyl-cyclohexane), n-decane, 2- methylnonane, 3- methylnonane, 4- methylnonane, 5- methylnonane, 2,3- dimethyl-octa
Alkane, 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- front three
Base heptane, 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, 1,4- diethyl
Hexamethylene, n-butyl cyclohexane, isobutyl butylcyclohexane, t-butylcyclohexane and tetramethyl-ring hexane (include tetramethyl-ring hexane
Various isomers, such as 1,2,3,4- tetramethyl-ring hexanes, 1,2,4,5- tetramethyl-ring hexanes, 1,2,3,5- tetramethyl hexamethylenes
Alkane).
As solvent, the instantiation of described halogenated alkane can include but is not limited to: a fluoromethane, difluoromethane, three
Fluoromethane, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane, Difluoroethane, trifluoro second
Alkane, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethane, sym-tetrachloroethane, Pentalin., six
Chlorination carbon, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoro third
Alkane, a chloropropane, dichloropropane, 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 fourths
Alkane, ten fluorine butane, a chlorobutane, dichloroetane, three chlorobutanes, four chlorobutanes, pentachlorobutane, chlordene butane, heptachlor butane, eight
Chlorobutane, nine chlorobutanes and ten chlorobutanes.
As solvent, the instantiation of described aromatic hydrocarbons can include but is not limited to: toluene, ethylbenzene and dimethylbenzene (include adjacent
Dimethylbenzene, meta-xylene and xylol).
The concentration of described initiator solution can select for conventional, is not particularly limited.The consumption of described initiator solution
Suitable selection can be carried out according to specific polymerizing condition, so that polymerization can be caused to be defined.Those skilled in the art can be
Under the teaching of prior art, the initiator amount being adequate to bring about being polymerized is determined by the experiment of limited number of time.
According to the polymerization of the present invention, described monoolefine can carry out cationic polymerization for commonly used in the art
Monoolefine.Usually, described monoolefine is the compound shown in selected from formula iv,
In formula iv, r13And r14It is respectively c1～c5Straight or branched alkyl；Or r13For hydrogen, r14For c3～c5Side chain
Alkyl.
In the present invention, c1～c5Straight or branched alkyl include c1～c5Straight chained alkyl and c3～c5Branched alkyl,
Its instantiation can include but is not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
Specifically, described monoolefine can be selected from, but not limited to: 2- methyl-1-propylene (that is, isobutene .), 2- methyl isophthalic acid-
Butylene, 3-methyl-1-butene, 2,3- dimethyl -1-butylene, 2- Methyl-1-pentene, 3- Methyl-1-pentene, 4- methyl-1-pentene
Alkene, 2,3- dimethyl -1- amylene, 2,4- dimethyl -1- amylene, 2- methyl isophthalic acid-hexene, 2,3- dimethyl -1- hexene, 2,4- bis-
Methyl isophthalic acid-hexene, 2,5- dimethyl -1- hexene and 2,4,4- trimethyl -1- amylene.
Preferably, described monoolefine is isobutene..
According to the polymerization of the present invention, described ring-alkylated styrenes is the compound shown in selected from formula v,
In formula v, r15For c1～c5Straight or branched alkyl.
The example of described ring-alkylated styrenes can include but is not limited to: p-methylstyrene, a methyl styrene, to ethyl
Styrene and p-tert-butylstyrene.
Preferably, described ring-alkylated styrenes be selected from shown in formula vi to alkylbenzene between shown in ring-alkylated styrenes and formula vii
Ethylene,
R in formula vi15With the r in formula vii15It is respectively c1～c5Straight or branched alkyl.
It is highly preferred that described ring-alkylated styrenes is to ring-alkylated styrenes and/or a ring-alkylated styrenes, such as p-methylstyrene
And/or a methyl styrene.
It is further preferred that in described ring-alkylated styrenes, the content to ring-alkylated styrenes is more than 80 weight %, such as may be used
Think 80～100 weight %.It is highly preferred that in described ring-alkylated styrenes, the content to ring-alkylated styrenes is more than 90 weight %, example
As being 90～100 weight %.Most preferably, described ring-alkylated styrenes is p-methylstyrene.
According to the polymerization of the present invention, the relative usage of described monoolefine and described ring-alkylated styrenes can be according to final
The concrete application occasion of the polymer of preparation carries out suitable selection.Usually, total with described monoolefine and ring-alkylated styrenes
On the basis of amount, the content of described monoolefine can be 80～99 weight %, preferably 90～97 weight %；Described ring-alkylated styrenes
Content can be 1～20 weight %, preferably 3～10 weight %.
The various diluent that can be commonly used for cationic polymerization field according to the polymerization of the present invention, described diluent,
For example: described diluent can be the mixture of alkane, halogenated alkane or alkane and halogenated alkane.Described alkane can be
Aliphatic alkane and/or alicyclic alkanes, are preferably selected from c3～c10Alkane, described halogenated alkane can be halogenated aliphatic alkane
Hydrocarbon and/or halogenated cyclo alkane, are preferably selected from c1～c10Halogenated alkane, be more preferably selected from c1～c4Halogenated alkane.Described
Halogen atom in halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.
Even if the polymerization according to the present invention is polymerized in low Polar diluents, also polymer yield can be improved,
And obtain the polymer with high molecular.The diluent of described low polarity can be for example described alkane, can also be described
Alkane and the mixture of described halogenated alkane.In the mixture that described diluent is described alkane with described halogenated alkane, with
On the basis of the total amount of described diluent, the content of described alkane can be 20～99 volumes %, and preferably 40～99 volumes % are more excellent
Elect 50～90 volumes %, more preferably 50-70 weight % as；The content of described halogenated alkane can be 1～80 volume %, excellent
Elect 1～60 volume %, more preferably 10～50 volumes %, more preferably 30-50 weight % as.
In the present invention, as diluent, the instantiation of described alkane can include but is not limited to: propane, normal butane, different
Butane, pentane, isopentane, neopentane, Pentamethylene., normal hexane, 2- methylpentane, 3- methylpentane, 2,3- dimethylbutane,
Hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- ethylpentane, 3- ethylpentane, 2,3- diformazan
Base pentane, 2,4- dimethyl pentane, normal octane, 2- methyl heptane, 3- methyl heptane, 4- methyl heptane, 2,3- dimethylhexane,
2,4- dimethylhexane, 2,5- dimethylhexane, 3- ethyl hexane, 2,2,3- trimethylpentane, 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
Hexane, 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- second
Base hexane, 3- methyl -4- ethyl hexane, 3,3- diethylpentane, 1- methyl -2- ethyl cyclohexane, 1- methyl -3- cyclohexyl
Alkane, 1- methyl -4- ethyl cyclohexane, n-pro-pyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane (include 3-methyl cyclohexanol
The various isomers of alkane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- trimethyl-cyclohexanes, 1,2,5- trimethyl-cyclohexanes, 1,
3,5- trimethyl-cyclohexane), n-decane, 2- methylnonane, 3- methylnonane, 4- methylnonane, 5- methylnonane, 2,3- diformazan
Base octane, 2,4- dimethyl octane, 3- ethyl octane, 4- ethyl octane, 2,3,4- trimethylheptane, 2,3,5- trimethyl heptan
Alkane, 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- trimethyl heptan
Alkane, 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- diethyl are own
Alkane, 3,4- diethylhexane, 2- methyl -3,3- diethylpentane, 1,2- diethyl cyclohexane, 1,3- diethyl cyclohexane, 1,
4- diethyl cyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, t-butylcyclohexane and tetramethyl-ring hexane (include tetramethyl
The various isomers of butylcyclohexane, such as 1,2,3,4- tetramethyl-ring hexanes, 1,2,4,5- tetramethyl-ring hexanes, 1,2,3,5- tetramethyls
Butylcyclohexane).
In the present invention, as diluent, the instantiation of described halogenated alkane can include but is not limited to: a fluoromethane,
Difluoromethane, fluoroform, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane, difluoro
Ethane, HFC-143a, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethane, sym-tetrachloroethane,
Pentalin., carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, seven fluorine
Propane, octafluoropropane, a chloropropane, dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane,
Octachloropropane, a fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, octafluoro
Butane, nine fluorine butane, ten fluorine butane, a chlorobutane, dichloroetane, three chlorobutanes, four chlorobutanes, pentachlorobutane, chlordene butane,
Heptachlor butane, telodrine alkane, nine chlorobutanes and ten chlorobutanes.
Preferably, described diluent is selected from pentane, normal hexane, normal heptane, monochloro methane, dichloromethane and a chloroethene
Alkane.
The consumption of described diluent can be the conventional selection of this area.Usually, the consumption of described diluent makes always
Monomer concentration is 2～35 weight %, preferably 5～25 weight %, more preferably 5～15 weight %.
The method according to the invention, described cationic polymerization condition can be the conventional selection of this area.Usually, described
The condition of cationic polymerization includes: temperature is -120 DEG C to 0 DEG C, preferably -100 DEG C to -50 DEG C, more preferably -100 DEG C extremely -
70℃.The method according to the invention, the time of described contact can be the conventional selection of this area, repeats no more herein.
According to the polymerization of the present invention, it is additionally may included in polymerization and completes to be polymerized backward to add in the mixture obtaining and gather
Close terminator to make polyreaction terminate (such as alcohol).The present invention is not special for the species of described polymerization terminator and consumption
Limit, can be the conventional selection of this area, be defined so that polyreaction can be terminated, repeat no more herein.
The method according to the invention, for polymerization monomer and diluent before use preferably in condition commonly used in the art
Under refined, repeat no more herein.
Describe the present invention with reference to embodiments in detail.
In following examples and comparative example, polymer yield is measured using weight method,
Polymer yield (%)=(weight/total monomer weight of the polymer obtaining) × 100%.
In following examples and comparative example, the molecular weight of polymer and molecular weight distributing index are using the life of Japanese Shimadzu Corporation
Produce lc-20a type chromatograph of gel permeation to measure, using single aperture chromatographic column WithFour posts
Combination.Mobile phase is oxolane, and flow velocity is 0.7ml/min；Sample solution concentration is 2mg/ml, and sample size is 200 μ l；Test
Temperature is 35 DEG C；Using single distribution polystyrene as standard sample.
Solvent used in following examples and comparative example and monomer before use, are entered using method commonly used in the art
Row is refined.
In following examples and comparative example, the preparation of polyreaction and initiator solution is all in the nitrogen being furnished with low temperature cryostat
Carry out in gas control box.
Embodiment 1～14 is used for the initiator system according to the present invention and cationic polymerization process are described.
Embodiment 1
(1) by 0.0532g dichloro dicyano p-benzoquinone be dissolved in 66.3g and containing hcl(concentration be 0.0037mol/l) two
In chloromethanes, the solution obtaining is cooled to -85 DEG C in advance, then sequentially adds 3.2ml concentration to be 0.9mol/l's in this solution
The normal heptane of ethyl aluminum dichloride (eadc) the hexane solution and 1.2ml concentration diethyl aluminum chloride (deac) for 1.0mol/l is molten
Liquid (molar ratio of eadc and deac is 7/3), after mix homogeneously, the mixed liquor obtaining is placed in ageing in -85 DEG C of cryostat
100min, thus obtain initiator solution.Wherein, by weight, in initiator solution, the content of dichloro dicyano p-benzoquinone is
770ppm.
(2) be furnished with strength constant speed stirring 500ml glass reactor in sequentially add 60ml be cooled in advance -80 DEG C one
Chloromethanes, 140ml are cooled to -80 DEG C of normal hexane in advance, 25ml is cooled to -80 DEG C of isobutene. in advance and 1.1ml room temperature to methylbenzene
Ethylene (content 98 weight %), mix homogeneously.The initiator solution that in reactor prepared by Deca step (1).Wherein, initiator
The addition of solution is 25ml, controls rate of addition that the temperature in reactor is within the scope of -85 DEG C to -90 DEG C.
After being added dropwise to complete, keep the temperature in reactor to be within the scope of -85 DEG C to -90 DEG C, and it is anti-to carry out the polymerization of 17min
Should, in reactant mixture, then add the methanol solution that 5ml contains 0.5 weight %naoh, to terminate polyreaction.To obtain
Mixed solution be placed in desolvation in hot bath, the solid obtaining after washing, in 60 DEG C of dryings to permanent in vacuum drying oven
Weight, thus obtain subject polymer.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Comparative example 1
Initiator solution is prepared using method same as Example 1 and is polymerized, except for the difference that, in step (1) not
Using dichloro dicyano p-benzoquinone.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Comparative example 2
Initiator solution is prepared using method same as Example 1 and is polymerized, except for the difference that, in step (1) not
Using dichloro dicyano p-benzoquinone, diethyl aluminum chloride is replaced with the ethyl aluminum dichloride of equimolar amountss.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 2
(1) prepare initiator solution using with embodiment 1 step (1) identical method.
(2) 250ml there-necked flask is placed in the low temperature cryostat that temperature control is -80 DEG C to -85 DEG C, burns to three mouthfuls successively
Add in bottle that 85ml is cooled to -80 DEG C of normal hexane, 15ml is cooled to -80 DEG C of isobutene. and 0.62ml room temperature to methylbenzene
Ethylene (content 98% weight), mix homogeneously, obtain monomer solution.The initiator solution of 10ml, mixing is added in monomer solution
Standing and reacting 50min after uniformly, controls cryostat temperature to be to be within the scope of -80 DEG C to -85 DEG C in course of reaction.Reaction knot
The methanol solution that 5ml contains 0.5 weight %naoh is added, to terminate polyreaction in Shu Houxiang reactant mixture.Then will mix
Solution is placed in desolvation in hot bath, after the solid obtaining is washed, in 60 DEG C of dryings to constant weight in vacuum drying oven,
Obtain subject polymer.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Comparative example 3
Initiator solution is prepared using method same as Example 2 and is polymerized, except for the difference that, prepare initiator molten
During liquid, diethyl aluminum chloride is replaced with the ethyl aluminum dichloride of equivalent.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 3
(1) by 0.0824g DDQ be dissolved in 99.0g and containing hcl(concentration be 0.0037mol/l) dichloro
In methane, the solution obtaining is cooled to -85 DEG C in advance, in this solution, then sequentially adds 2.7ml concentration for 0.9mol/l two
The n-heptane solution of chloroethyl aluminum (eadc) the hexane solution and 2.4ml concentration diethyl aluminum chloride (deac) for 1.0mol/l
(molar ratio of eadc and deac is 5/5), after mix homogeneously, the mixed liquor obtaining is placed in ageing in -85 DEG C of cryostat
60min, thus obtain initiator solution.Wherein, by weight, in initiator solution, the content of DDQ is
800ppm.
(2) using being polymerized with step (2) identical method in embodiment 1, except for the difference that, monochloro methane addition is
80ml, normal hexane addition is 120ml.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 4
Prepare initiator solution and be polymerized using with embodiment 3 step (1) and step (2) identical method, different
, in step (2), monochloro methane addition is 40ml, and the addition of normal hexane is 160ml.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 5
Prepare initiator solution using with embodiment 3 step (1) identical method, using identical with embodiment 2 step (2)
Method be polymerized.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 6
(1) by 0.0652g DDQ be dissolved in 80g and containing hcl(concentration be 0.003mol/l) dichloromethane
In alkane, the solution obtaining is cooled to -85 DEG C in advance, in this solution, then sequentially adds the eadc that 1.2ml concentration is 0.9mol/l
Hexane solution and the toluene solution (molar ratio of eadc and deac is 3/7) that 2.8ml concentration is 0.9mol/ldeac, mixing
After uniformly, the mixed liquor obtaining is placed in ageing 60min in -85 DEG C of cryostat.Wherein, by weight, two in initiator solution
The content of chlorine dicyano benzoquinone is 800ppm.
(2) adopt and carry out polyreaction with embodiment 1 step (2) identical method.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 7
(1) prepare initiator solution using with embodiment 6 step (1) identical method.
(2) two mouthfuls of flasks of 200ml are placed in the low temperature cryostat that temperature control is -80 DEG C to -85 DEG C, burn to two mouthfuls successively
Normal hexane/monochloro methane mixed solution (wherein, volume ratio of normal hexane/monochloro methane that 85ml is cooled to -85 DEG C is added in bottle
For 9/1), 15ml be cooled to -85 DEG C of isobutene. and the p-methylstyrene (content 98% weight) of 0.62ml room temperature, mixing is all
Even, obtain monomer solution.Add initiator solution prepared by 10ml step (1) in monomer solution, stand anti-after mix homogeneously
Answer 40min, in course of reaction, control cryostat temperature to be to be within the scope of -80 DEG C to -85 DEG C.Reaction terminates backward reaction and mixes
The methanol solution that 5ml contains 0.5 weight %naoh is added, to terminate polyreaction in compound.Then mixed solution is placed in hot water
Desolvation in bath, after the solid obtaining is washed, in 60 DEG C of dryings to constant weight in vacuum drying oven, obtains target polymerization
Thing.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 8
(1) prepare initiator solution using with embodiment 6 step (1) identical method, except for the difference that, in initiator solution
Under conditions of the total amount of eadc and deac is constant, the molar ratio of adjustment eadc and deac is 1/9.
(2) using being polymerized with embodiment 7 step (2) identical method, except for the difference that, normal hexane and monochloro methane
Under conditions of total amount is constant, adjustment normal hexane is 5/5 with the volume ratio of monochloro methane.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 9
(1) prepare initiator solution using with embodiment 8 step (1) identical method.
(2) using being polymerized with embodiment 7 step (2) identical method, except for the difference that, normal hexane and monochloro methane
Under conditions of total amount is constant, adjustment normal hexane is 6/4 with the volume ratio of monochloro methane.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 10
(1) prepare initiator solution using with embodiment 8 step (1) identical method.
(2) using being polymerized with embodiment 7 step (2) identical method, except for the difference that, normal hexane and monochloro methane
Under conditions of total amount is constant, adjustment normal hexane is 7/3 with the volume ratio of monochloro methane.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 11
(1) prepare initiator solution using with embodiment 8 step (1) identical method.
(2) using being polymerized with embodiment 7 step (2) identical method, except for the difference that, normal hexane and monochloro methane
Under conditions of total amount is constant, adjustment normal hexane is 8/2 with the volume ratio of monochloro methane.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 12
(1) prepare initiator solution using with embodiment 8 step (1) identical method.
(2) using being polymerized with embodiment 7 step (2) identical method, except for the difference that, normal hexane and monochloro methane
Under conditions of total amount is constant, adjustment normal hexane is 9/1 with the volume ratio of monochloro methane.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 13
Initiator solution is prepared using method same as Example 1 and is polymerized, except for the difference that, step is drawn in (1)
Send out under conditions of in agent solution, eadc and deac total amount is constant, the molar ratio of adjustment eadc and deac is 8/2；In step (2)
Under conditions of the total amount of normal hexane and monochloro methane is constant, adjustment normal hexane is 8/2 with the volume ratio of monochloro methane.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Embodiment 14
Initiator solution is prepared using method same as Example 1 and is polymerized, except for the difference that, in step (1)
Digestion time is 30min.
Measure the weight of polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and molecular weight divides
Cloth index, result is listed in Table 1.
Table 1
Claims (31)
1. a kind of cationic polymerization initiators system, this initiator system contain at least one can carry protogenic compound,
At least one lewis acid and at least one activator,
Wherein, described activator is the compound shown in selected from formula i-1 and the compound shown in formula i-2,
In formula i-1 and formula i-2, r1、r2、r3、r4、r5、r6、r7And r8It is respectively-h ,-x1、-no2、With in-cn
Kind, x1And x2It is respectively one of halogen group；
Described lewis acid contains the lewis acid shown in formula ii and the lewis acid shown in formula iii, with described lewis acidic
On the basis of total amount, the lewis acidic content shown in formula ii is 20～90 moles of %；Lewis acidic content shown in formula iii is
10～80 moles of %,
In formula ii, r9And r10It is respectively c1～c8Straight or branched alkyl, x3For one of halogen group,
In formula iii, r11For c1～c8Straight or branched alkyl, x41And x42Identical or different, respectively in halogen group one
Kind.
2. initiator system according to claim 1, wherein, on the basis of described lewis acidic total amount, shown in formula ii
Lewis acidic content be 30～70 moles of %；Lewis acidic content shown in formula iii is 30～70 moles of %.
3. initiator system according to claim 1, wherein, described protogenic compound and the described activator of can carrying
Mol ratio be 1:0.01～3.
4. initiator system according to claim 3, wherein, described protogenic compound and the described activator of can carrying
Mol ratio be 1:0.1～2.5.
5. initiator system according to claim 4, wherein, described protogenic compound and the described activator of can carrying
Mol ratio be 1:0.2～2.
6. initiator system according to claim 2, wherein, described protogenic compound and the described activator of can carrying
Mol ratio be 1:0.01～3.
7. initiator system according to claim 6, wherein, described protogenic compound and the described activator of can carrying
Mol ratio be 1:0.1～2.5.
8. initiator system according to claim 7, wherein, described protogenic compound and the described activator of can carrying
Mol ratio be 1:0.2～2.
9. the initiator system according to any one in claim 1～8, wherein, described activator is four cyano benzoquinone
And/or DDQ.
10. initiator system according to claim 1, wherein, described protogenic compound and the described Louis of can carrying
This sour mol ratio is 0.01～1:1.
11. initiator systems according to claim 10, wherein, described protogenic compound and the described Louis of can carrying
This sour mol ratio is 0.02～0.6:1.
12. initiator systems according to any one in claim 1,10 and 11, wherein, in formula ii, x3For-cl, formula
In iii, x41And x42It is-cl.
13. initiator systems according to claim 12, wherein, the lewis acid shown in formula ii is diethyl aluminum chloride,
Lewis acid shown in formula iii is ethyl aluminum dichloride.
14. initiator systems according to any one in claim 1～8,10 and 11, wherein, described can provide matter
The compound of son is h2O and/or Bronsted acid.
15. initiator systems according to claim 14, wherein, described can carry protogenic compound be hcl.
Application in cationic polymerization for the initiator system described in any one in 16. claim 1～15.
A kind of 17. cationic polymerization process, the method includes: under the conditions of cationic polymerization, at least one diluent, will
In initiator system described in any one at least one monoolefine and at least one ring-alkylated styrenes and claim 1～15
Each group tap touch；
Described monoolefine is the compound shown in selected from formula iv,
In formula iv, r13And r14It is respectively c1～c5Straight or branched alkyl；Or r13For hydrogen, r14For c3～c5Branched alkane
Base；
Described ring-alkylated styrenes is the compound shown in selected from formula v,
In formula v, r15For c1～c5Straight or branched alkyl.
18. methods according to claim 17, wherein, by least one monoolefine and at least one ring-alkylated styrenes and institute
State the tactile method of the tap of each group in initiator system to include: each component in described initiator system is dissolved in solvent,
And the mixture obtaining is aged, obtain initiator solution；By described initiator solution be dissolved with described monoolefine and described
The diluent mixing of ring-alkylated styrenes.
19. methods according to claim 18, wherein, described solvent is in alkane, halogenated alkane and aromatic hydrocarbons
Plant or multiple.
20. methods according to claim 18, wherein, the time of described ageing is 30 minutes to 10 hours.
21. methods according to claim 20, wherein, the time of described ageing is 60 minutes to 10 hours.
22. methods according to claim 21, wherein, the time of described ageing is 60 minutes to 2 hours.
23. methods according to any one in claim 18 and 20～22, wherein, the condition of described ageing includes: temperature
Spend for -100 DEG C to 20 DEG C.
24. methods according to claim 23, wherein, the condition of described ageing includes: temperature is -100 DEG C to 0 DEG C.
25. methods according to claim 17 or 18, wherein, described monoolefine is isobutene., and described ring-alkylated styrenes is
P-methylstyrene and/or a methyl styrene.
26. methods according to claim 17 or 18, wherein, the total amount with described monoolefine and described ring-alkylated styrenes is
Benchmark, the content of described monoolefine is 80～99 weight %；The content of described ring-alkylated styrenes is 1～20 weight %.
27. methods according to claim 26, wherein, with the total amount of described monoolefine and described ring-alkylated styrenes as base
Standard, the content of described monoolefine is 90～97 weight %；The content of described ring-alkylated styrenes is 3～10 weight %.
28. methods according to claim 17 or 18, wherein, described diluent is alkane, halogenated alkane or alkane and
The mixture of halogenated alkane.
29. methods according to claim 17, wherein, the condition of described contact includes: temperature is -120 DEG C to 0 DEG C.
30. methods according to claim 29, wherein, the condition of described contact includes: temperature is -100 DEG C to -50 DEG C.
31. methods according to claim 30, wherein, the condition of described contact includes: temperature is -100 DEG C to -70 DEG C.
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