CN104558343B - Positive ion polymerization method - Google Patents
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- CN104558343B CN104558343B CN201310491442.6A CN201310491442A CN104558343B CN 104558343 B CN104558343 B CN 104558343B CN 201310491442 A CN201310491442 A CN 201310491442A CN 104558343 B CN104558343 B CN 104558343B
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Abstract
The invention discloses a positive ion polymerization method. The method comprises the following steps: making one or more monoolefines and one or more alkyl styrene to be in contact with all components in an initiator system under the condition of positive ion polymerization in one or more diluents, wherein the initiator system containing one or more compounds which can provide protons, one or more Lewis acids and one or more activating agents, the activating agents are selected from the compounds shown in formula I-1 and formula I-2, and the diluents are selected from C3-C10 aliphatic series alkane and C3-C10 alicyclic alkane. The polymerization method can improve polymerization efficiency; the prepared polymer has higher molecular weight; meanwhile, the polymerization method can adjust and control the molecular weight of the prepared polymer to acquire polymer with different molecular weight, so as to meet utilization requirements at different application occasions.
Description
Technical field
The present invention relates to a kind of cationic polymerization process.
Background technology
The isobutene. of bromination-p-methylstyrene copolymer, usually by 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, the therefore isobutene. of bromination-p-methylstyrene copolymer has the synthesis more excellent than brombutyl
Performance, especially has more preferable heat resistance；And, the presence due to highly active benzyl bromo functional groups, can with various
Rubber realizes sulfuration and co-vulcanization in broader scope, in addition also has the modified advantage of wider range.This product through with
Nylon blending makes dynamic vulcanization alloy for producing the inner liner of tire, can accomplish not only light but also thin, therefore, the isobutyl of bromination
Alkene-p-methylstyrene copolymer can be used for producing the tire with higher performance, 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 pair
Diluent Polarity is simultaneously insensitive, but when isobutene. is carried out combined polymerization with ring-alkylated styrenes by cationic polymerization mode,
With the reduction of Diluent Polarity, polymerization efficiency decreases, so that system is Polymerization in Different Buffers (that is, with aliphatic alkane
And/or alicyclic alkanes are as diluent) when, polymerization efficiency extreme difference, rate of polymerization is excessively slow, and is difficult to raising further and obtains
Polymer molecular weight.
The present inventor is studied for the problems referred to above, finds: with aliphatic alkane and/or alicyclic alkanes
As diluent, such as when the monoolefine of isobutene. and ring-alkylated styrenes are carried out combined polymerization by way of cationic polymerization,
Can be obvious if introducing quinonoid compound (particularly there is the quinonoid compound of electron-withdrawing substituent) in initiator system
Improve polymerization efficiency, obtain the yield compared with high polymer；Meanwhile, the polymer obtaining also has the molecular weight of raising.Thus complete
Become the present invention.
The invention provides a kind of cationic polymerization process, the method includes: under the conditions of cationic polymerization, at least one
In kind of diluent, at least one monoolefine and at least one ring-alkylated styrenes are touched with each group tap in initiator system；
Described initiator system contains at least one and can carry protogenic compound, at least one lewis acid and at least
A kind of activator, 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 monoolefine is the compound shown in selected from formula ii,
In formula ii, r9And r10It is respectively c1～c5Straight or branched alkyl；Or r9For hydrogen, r10For c3～c5Side chain
Alkyl；
Described ring-alkylated styrenes is the compound shown in selected from formula iii,
In formula iii, r11For c1～c5Straight or branched alkyl；
Described diluent is selected from c3～c10Aliphatic alkane and c3～c10Alicyclic alkanes.
The polymerization of the present invention can not only obtain the polymerization efficiency of raising, and the polymer prepared also have higher
Molecular weight.Meanwhile, the polymerization of the present invention can also regulate and control to the molecular weight of the polymer of preparation, obtain and have difference
The polymer of molecular size range is such that it is able to meet the use requirement of different application occasion.
Specific embodiment
The invention provides a kind of cationic polymerization process, the method includes: under the conditions of cationic polymerization, at least one
In kind of diluent, at least one monoolefine and at least one ring-alkylated styrenes are touched with each group tap in initiator system.
The method according to the invention, described initiator system (being referred to as initiator composition) contains at least one energy
Enough carry protogenic compound, at least one lewis acid and at least one activator.
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 (for example :-f ,-cl ,-br or-i).
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.
Usually, described activator can be selected from tetrahydrochysene benzoquinone (including tetrahydrochysene 1,4-benzoquinone and tetrahydrochysene neighbour's benzoquinone), tetrachlorobenzene
Quinone (including chloranil and monoethyl quinone), four cyano benzoquinone (including four cyano 1,4-benzoquinone and four cyano neighbour's benzoquinone) and two
Chlorine dicyano benzoquinone (includes dichloro dicyano p-benzoquinone and dichloro dicyano neighbour's benzoquinone).
The method according to the invention, the content of described activator is defined by being obtained in that gratifying polymerization effect.One
As, the described protogenic compound and the mol ratio of described activator of can carrying can be 1:0.01～3, preferably 1:0.1
～2, more preferably 1:0.2～1.8.
The method according to the invention, described lewis acid and described can carry protogenic compound can for cation gather
The conventional selection in conjunction field, is not particularly limited, as long as described lewis acid and can carry protogenic compound and can be formed
Cationic species, cause and are polymerized.
Usually, described lewis acid can be selected from, but not limited to: alcl3、bf3、bcl3、ticl4、sncl4、zncl2, formula
Lewis acid shown in lewis acid shown in iv, formula v and r15 3Al,
In formula iv, x31And x32It is respectively one of halogen group (as-f ,-cl ,-br or-i), preferably-cl；r12For
c1～c8Straight or branched alkyl, preferably c1～c5Straight or branched alkyl；
In formula v, x4For one of halogen group (as-f ,-cl ,-br or-i), preferably-cl；r13And r14It is respectively c1
～c8Straight or branched alkyl, preferably c1～c5Straight or branched alkyl.
In formula v, r13And r14Can identical it is also possible to different, preferably identical.
r15 3In al, three r15Can be each c1～c8Straight or branched alkyl, preferably c1～c5Straight chain or
Alkyl group.r15 3In al, three r15Can be identical or different, preferably identical.
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 iv can include but is not limited to: dichloromethyl aluminum, dichloro
Aluminium ethide, dichloro n-pro-pyl aluminum, two chloro isopropyl aluminum, dichloro n-butylaluminum and dichloro aluminium isobutyl.Preferably, shown in formula iv
Lewis acid is ethyl aluminum dichloride.
In the present invention, the lewis acidic instantiation shown in formula v 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
Ground, the lewis acid shown in formula v is diethyl aluminum chloride.
In the present invention, r15 3The instantiation of al can include but is not limited to: trimethyl aluminium and triethyl aluminum.
The method according to the invention, described lewis acid is preferably the lewis acid shown in formula iv and/or the road shown in formula v
Lewis acid, more preferably ethyl aluminum dichloride and/or diethyl aluminum chloride.
Contain two alkyl in lewis acidic molecular structure shown in formula v, 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 v contains
Amount is too high, can reduce polymerization rate, extends polymerization time.Therefore, the method according to the invention, the Louis shown in formula v
Acid is preferably applied in combination with other lewis acids, is preferably applied in combination with the lewis acid shown in formula iv.That is, according to the present invention's
Method, described lewis acid is preferably the lewis acid shown in formula iv and the lewis acid shown in formula v.
The method according to the invention, is the lewis acid shown in formula iv and the Louis shown in formula v in described lewis acid
When sour, on the basis of lewis acidic total amount, the lewis acidic content shown in formula v is preferably 10～90 moles of %, so can
Good balance is obtained between polymerization rate and polymer molecular weight.It is highly preferred that with lewis acidic total amount as base
Standard, the lewis acidic content shown in formula v is 20～80 moles of %.
Described lewis acidic content can be the conventional amount used in cationic polymerization field.Usually, described can provide
The compound of proton and described lewis acidic mol ratio can be 0.01～1:1, preferably 0.02～0.5:1, more preferably
0.03～0.3:1.
Described can carry protogenic compound and various can provide proton for conventional in cationic polymerization field
Compound.It is usually, described that can to carry protogenic compound can be h2O and/or Bronsted acid, its instantiation can wrap
Include but be not limited to: h2o、hcl、hf、hbr、h2so4、h2co3、h3po4And hno3.Preferably, described protogenic chemical combination can be carried
Thing is hcl.
Can will be each in described monoolefine and ring-alkylated styrenes and described initiator system using conventional various methods
Component contacts, and to be polymerized, forms monoolefine-alkylstyrene copolymers.
In one embodiment of the invention, each component in described initiator system can be 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.
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 time of described ageing can be little to 10 for 10 minutes
When.Preferably, the time of described ageing is more than 30 minutes, such as 30 minutes to 5 hours.It is highly preferred that described ageing when
Between be more than 60 minutes, such as 60 minutes to 2 hours.
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 c3～c10Alkane, c1～c10Halogenated alkane and c6～c12Aromatic hydrocarbons.
As solvent, described c3～c10Alkane include c3～c10Aliphatic alkane and c3～c10Alicyclic alkanes.
As solvent, described c1～c10Halogenated alkane include c1～c10Halogenated aliphatic alkane and c3～c10Halo
Alicyclic alkanes.Halogen atom in described halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.Described halogenated alkane
It is preferably c1～c4Halogenated aliphatic alkane.
The instantiation of described solvent can include but is not limited to: propane, normal butane, iso-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- dimethyl 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- bis-
Methyl heptane, 3- ethyl heptane, 4- ethyl heptane, 2,3,4- trimethyl cyclohexane, 2,3,5- trimethyl cyclohexane, 2,4,5- trimethyl
Hexane, 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- ethyl cyclohexane, 1- methyl -3- ethyl cyclohexane, 1- methyl -4- ethyl
Hexamethylene, n-pro-pyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane (include the various isomers of trimethyl-cyclohexane, such 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- trimethyl heptan
Alkane, 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 heptan
Alkane, 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 cyclohexane, normal-butyl
Hexamethylene, isobutyl butylcyclohexane, t-butylcyclohexane, tetramethyl-ring hexane (include the various isomers of tetramethyl-ring hexane, such as
1,2,3,4- tetramethyl-ring hexane, 1,2,4,5- tetramethyl-ring hexane, 1,2,3,5- tetramethyl-ring hexane), a fluoromethane, difluoro
Methane, fluoroform, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane, Difluoroethane,
HFC-143a, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethane, sym-tetrachloroethane, pentachloro-
Ethane, carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane,
Octafluoropropane, a chloropropane, dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, eight chlorine
Propane, a fluorine butane, difluorobutane, trifluorobutane, tetrafluoro butane, 3-pentafluorobutane, hexafluoro butane, seven fluorine butane, Octafluorobutane.,
Nine fluorine butane, ten fluorine butane, a chlorobutane, dichloroetane, three chlorobutanes, four chlorobutanes, pentachlorobutane, chlordene butane, heptachlor
Butane, telodrine alkane, nine chlorobutanes, ten chlorobutanes, toluene, ethylbenzene and dimethylbenzene (include o-Dimethylbenzene, meta-xylene and to two
Toluene).
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 ii,
In formula ii, r9And r10It is respectively c1～c5Straight or branched alkyl；Or r9For hydrogen, r10For 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..
The method according to the invention, described ring-alkylated styrenes is the compound shown in selected from formula iii,
In formula iii, r11For 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,
In formula vi, r11For c1～c5Straight or branched alkyl；
In formula vii, r11For 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 preferably p-methylstyrene.
The relative usage of the method according to the invention, described monoolefine and described ring-alkylated styrenes can be prepared according to final
The concrete application occasion of polymer carry out suitable selection.Usually, with the total amount of described monoolefine and ring-alkylated styrenes it is
Benchmark, the content of described monoolefine can be 80～99 weight %, preferably 90～97 weight %；The content of described ring-alkylated styrenes
Can be 1～20 weight %, preferably 3～10 weight %.
According to the polymerization of the present invention, described diluent is selected from c3～c10Aliphatic alkane and/or c3～c10Fat
Ring race alkane.Described aliphatic alkane is preferably c3～c8Aliphatic alkane, more preferably c5～c8Aliphatic alkane.Institute
State alicyclic alkanes and be preferably c5～c10Alicyclic alkanes.
In the present invention, the instantiation of described diluent 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, 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- tri-
Methyl heptane, 2,3,3- trimethylheptane, 2,4,4- trimethylheptane, 2- methyl -3- ethyl heptane, 2- methyl -4- ethyl heptan
Alkane, 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- diethyl penta
Alkane, 1,2- diethyl cyclohexane, 1,3- diethyl cyclohexane, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene
Alkane, t-butylcyclohexane and tetramethyl-ring hexane.
Described diluent is preferably selected from pentane, normal hexane and normal heptane.
The consumption of described diluent can be the conventional selection of this area.Usually, the consumption of described diluent makes always
Monomer concentration is 2～25 weight %, 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 20 DEG C, preferably -100 DEG C to 0 DEG C.The method according to the invention, institute
The time stating contact can be the conventional selection of this area, repeats no more herein.
The method according to the invention, is additionally may included in polymerization and completes to be polymerized backward in the mixture obtaining and add polymerization eventually
Stop agent to make polyreaction terminate (such as alcohol).The present invention does not especially limit for the species of described polymerization terminator and consumption
Fixed, 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
Post is combined.Mobile phase is oxolane, and flow velocity is 0.7ml/min；Sample solution concentration is 2mg/ml, and sample size is 200 μ l；Survey
Examination 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 1～22 is used for the polymerization according to the present invention for the explanation.
Embodiment 1
(1) chloro- for 0.0532g 2,3- bis- 5,6- dicyano p-benzoquinone is dissolved in 66.3g and containing hcl(concentration is
In dichloromethane solution 0.0037mol/l), the solution obtaining is cooled to -85 DEG C in advance, then sequentially adds in this solution
The diethyl for 1.0mol/l for the hexane solution of ethyl aluminum dichloride (eadc) and 1.2ml concentration for 0.9mol/l for the 3.2ml concentration
The n-heptane solution of base aluminum chloride (deac), 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, chloro- 5, the 6- dicyano p-benzoquinone of 2,3- bis- in initiator solution
Content be 770ppm.
(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
In bottle, 85ml is cooled to -80 DEG C of normal hexane, 15ml is cooled to -80 DEG C of isobutene. and the right of 0.62ml room temperature (25 DEG C) for addition
Methyl styrene (content is 98 weight %), mix homogeneously, obtain monomer solution.10ml step (1) system is added in monomer solution
Standby initiator solution, standing and reacting 50min after mix homogeneously, control cryostat temperature to be to be in -80 DEG C extremely -85 in course of reaction
Within the scope of DEG C.Reaction terminates the methanol solution adding 5ml to contain 0.5 weight %naoh in backward reactant mixture, to terminate
Polyreaction.Then mixed solution is placed in desolvation in hot bath, after the solid obtaining is washed, in vacuum drying oven
In in 60 DEG C of dryings to constant weight, 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 the chloro- 5,6- dicyano p-benzoquinone of 2,3- bis-.
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 diethyl aluminum chloride.
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 1 and is polymerized, except for the difference that, in step (1) not
Using diethyl aluminum chloride and the chloro- 5,6- dicyano p-benzoquinone of 2,3- bis-.
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
Initiator solution is prepared using method same as Example 1 and is polymerized, except for the difference that, in step (2), will
Cryostat temperature control is to be within the scope of -60 DEG C to -70 DEG C, and the consumption of initiator solution is 15ml, and the response time is
110min.
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) method same as Example 1 is adopted to prepare initiator solution, except for the difference that, the normal hexane of ethyl aluminum dichloride
The concentration of solution is 0.9mol/l, and consumption is 1.7ml；The concentration of the n-heptane solution of diethyl aluminum chloride is 1.0mol/l, uses
Measure as 1.5ml.By weight, in the initiator solution obtaining, the content of 2,3- bis- chloro- 5,6- dicyano p-benzoquinones is
800ppm.
(2) it is polymerized using method same as Example 1, except for the difference that, prepared using embodiment 3 step (1)
Initiator solution.
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
Initiator solution is prepared using method same as Example 3 and is polymerized, except for the difference that, in step (2), will
The temperature control of cryostat is to be within the scope of -60 DEG C to -70 DEG C, and the response time is 90min.
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
Initiator solution is prepared using method same as Example 3 and is polymerized, except for the difference that, in step (2), will
The temperature control of cryostat is to be within the scope of -40 DEG C to -50 DEG C, and the response time is 90min.
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 0.0851g chloranil be dissolved in 103g and containing hcl(concentration be 0.0032mol/l) dichloromethane
In solution, the solution obtaining is cooled to -80 DEG C in advance, then sequentially adds 4.8ml concentration to be 0.9mol/l's in this solution
The n-heptane solution of the hexane solution of the eadc and 2ml concentration deac for 1.0mol/l, after mix homogeneously, by the mixing obtaining
Liquid is aged 100min at -80 DEG C, thus obtaining initiator solution.Wherein, by weight, chloranil in initiator solution
Content is 800ppm.
(2) it is polymerized using polymerization same as Example 1, except for the difference that, initiator solution is embodiment 6 step
Suddenly the initiator solution that prepared by (1).
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
Initiator solution is prepared using method same as Example 6 and is polymerized, except for the difference that, in step (1), will
The temperature control of cryostat is to be within the scope of -60 DEG C to -70 DEG C, and the consumption of initiator solution is 15ml, and the response time is
110min.
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) method same as Example 6 is adopted to prepare initiator solution, except for the difference that, the hexane solution of eadc
Concentration is 0.9mol/l, and consumption is 2.6ml, and the concentration of the n-heptane solution of deac is 1.0mol/l, and consumption is 2.3ml.
(2) it is polymerized using method same as Example 1, except for the difference that, initiator solution is embodiment 8 step
(1) initiator solution prepared.
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
Initiator solution is prepared using method same as Example 8 and is polymerized, except for the difference that, will in step (2)
The temperature control of cryostat is to be within the scope of -40 DEG C to -50 DEG C, and the response time is 90min.
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
Initiator solution is prepared using method same as Example 8 and is polymerized, except for the difference that, will in step (2)
The temperature control of cryostat is to be within the scope of -20 DEG C to -30 DEG C, and the response time is 120min.
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
Initiator solution is prepared using method same as Example 1 and is polymerized, except for the difference that, in step (1), old
The change time is 20min.Measure the weight of the polymer obtaining, calculate polymer yield, and measure the molecular weight of polymer and divide
Son amount profile exponent, result is listed in Table 1.
Table 1
Embodiment 12
(1) chloro- for 0.0532g 2,3- bis- 5,6- dicyano p-benzoquinone is dissolved in 66.3g and containing hcl(concentration is
In dichloromethane solution 0.0037mol/l), then above-mentioned solution is cooled to -85 DEG C in advance, adds the 4ml being cooled to -85 DEG C in advance to contain
The hexane solution of ethyl aluminum dichloride (concentration is 0.9mol/l), after mix homogeneously, is aged 100min at -85 DEG C, thus obtaining
Initiator solution.Wherein, by weight, in initiator solution, the concentration of 2,3- bis- chloro- 5,6- dicyano p-benzoquinones is
770ppm.
(2) two mouthfuls of glass reaction bottles of 250ml are placed in the low temperature cryostat that temperature control is -80 DEG C to -85 DEG C, to glass
Isobutene., the 0.62ml room temperature (25 that the normal hexane that 85ml is cooled to -80 DEG C in advance, 15ml are cooled to -80 DEG C in advance is sequentially added in reaction bulb
DEG C) p-methylstyrene (content 98 weight %), after mix homogeneously, initiator solution prepared by Deca 7ml step (1), then
Standing and reacting 50min, in Deca and course of reaction, controls cryostat temperature to be to be within the scope of -80 DEG C to -85 DEG C.Reaction
After end, add the methanol solution that 5ml contains 0.5 weight %naoh in reactant mixture, 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.Polymer yield, the polymer obtaining molecular weight and molecualr weight distribution index in table 2
List.
Embodiment 13
It is polymerized using with embodiment 12 identical method, except for the difference that, in step (2), the addition of initiator solution
Measure as 15ml, Deca initiator solution being reacted within -60 DEG C to -70 DEG C of temperature range, the response time is
110min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 14
It is polymerized using with embodiment 12 identical method, except for the difference that, in step (2), the addition of initiator solution
Measure as 15ml, within the temperature range of -40 DEG C to -50 DEG C, Deca initiator solution is simultaneously reacted, the response time is
180min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 15
(1) by 0.0532g tetrachloroquinone be dissolved in 66.3g and containing hcl(concentration be 0.0037mol/l) dichloromethane molten
In liquid, then above-mentioned solution is cooled to -85 DEG C in advance, adds and be cooled to -85 DEG C of 4ml in advance and contain ethyl aluminum dichloride (concentration is
Hexane solution 0.9mol/l), after mix homogeneously, is aged 100min at -85 DEG C, thus obtaining initiator solution.With weight
Meter, in the initiator solution obtaining, the concentration of tetrachloroquinone is 770ppm.
(2) two mouthfuls of glass reaction bottles of 250ml are placed in the low temperature cryostat that temperature control is -80 DEG C to -85 DEG C, to glass
Isobutene., the 0.62ml room temperature (25 that the normal hexane that 85ml is cooled to -80 DEG C in advance, 15ml are cooled to -80 DEG C in advance is sequentially added in reaction bulb
DEG C) p-methylstyrene (content be 98 weight %), after mix homogeneously, initiator solution prepared by Deca 15ml step (1),
Then standing and reacting 50min, in Deca and course of reaction, controls cryostat temperature to be to be within the scope of -80 DEG C to -85 DEG C.
After reaction terminates, add the methanol solution that 5ml contains 0.5 weight %naoh in reactant mixture, to terminate polyreaction.Will
The mixed solution obtaining is placed in desolvation in hot bath, the solid obtaining after washing, in 60 DEG C of dryings in vacuum drying oven
To constant weight, thus obtaining subject polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 16
It is polymerized, except for the difference that, Deca initiator solution and polyreaction mistake using with embodiment 15 identical method
Cheng Zhong, controls temperature to be to be within the scope of -60 DEG C to -70 DEG C, the response time is 110min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 17
It is polymerized, except for the difference that, Deca initiator solution and polyreaction mistake using with embodiment 15 identical method
Cheng Zhong, controls temperature to be to be within the scope of -40 DEG C to -50 DEG C, the response time is 180min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 18
(1) by 0.0442g chloranil be dissolved in 53g and containing hcl(concentration be 0.0037mol/l) dichloromethane molten
In liquid, then above-mentioned solution is cooled to -85 DEG C in advance, adds 2.7ml to be cooled to -85 DEG C in advance and contain ethyl aluminum dichloride (concentration is
Normal hexane 0.9mol/l), after mix homogeneously, is aged 85min at -85 DEG C, thus obtaining initiator solution.Wherein, with weight
Meter, in initiator solution, the concentration of tetrachloroquinone is 800ppm.
(2) 200ml is sequentially added just to be cooled to -85 DEG C in advance in the 500ml glass reactor being furnished with the stirring of strength constant speed
Hexane, 25ml are cooled to -85 DEG C of isobutene. and the p-methylstyrene (content is 98 weight %) of 1.1ml room temperature (25 DEG C) in advance, mix
After closing uniformly, initiator solution prepared by Deca 30ml step (1), then reacts 20min, in Deca and course of reaction, controls
Temperature is to be within the scope of -80 DEG C to -85 DEG C.After reaction terminates, 5ml is added to contain 0.5 weight % in reactant mixture
The methanol solution of naoh, to terminate polyreaction.The mixed solution obtaining is placed in desolvation in hot bath, the solid obtaining
After washing, in vacuum drying oven in 60 DEG C of dryings to constant weight, thus obtaining subject polymer.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 19
It is polymerized using with embodiment 18 identical method, except for the difference that, in step (1), the time of ageing is
15min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 20
It is polymerized using with embodiment 19 identical method, except for the difference that, the tetrahydrochysene 1,4-benzoquinone using equivalent replaces four
Chlorine 1,4-benzoquinone.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 21
It is polymerized using with embodiment 19 identical method, except for the difference that, using the four cyano 1,4-benzoquinone of equivalent, replaced
Chloranil.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Comparative example 4
It is polymerized using with embodiment 18 identical method, except for the difference that, initiator solution prepared by step (1) does not contain
Chloranil.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Embodiment 22
It is polymerized using with embodiment 15 identical method, except for the difference that, in initiator solution prepared by step (1),
With the toluene solution (concentration is as 0.9mol/l) of 4ml diethyl aluminum chloride, replace the hexane solution of ethyl aluminum dichloride；Step
(2) response time in is 40 minutes.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in table 2.
Table 2
Claims (25)
1. a kind of cationic polymerization process, the method includes: under the conditions of cationic polymerization, at least one diluent, will
At least one monoolefine and at least one ring-alkylated styrenes are touched with each group tap in initiator system；
Described initiator system contains at least one and can put forward protogenic compound, at least one lewis acid and at least one
Activator, 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 monoolefine is the compound shown in selected from formula ii,
In formula ii, r9And r10It is respectively c1～c5Straight or branched alkyl；Or r9For hydrogen, r10For c3～c5Branched alkyl；
Described ring-alkylated styrenes is the compound shown in selected from formula iii,
In formula iii, r11For c1～c5Straight or branched alkyl；
Described diluent is selected from c3～c10Aliphatic alkane and c3～c10Alicyclic alkanes.
2. method according to claim 1, wherein, described can carry protogenic compound and described activator mole
Than for 1:0.01～3.
3. method according to claim 2, wherein, described can carry protogenic compound and described activator mole
Than for 1:0.1～2.
4. method according to claim 3, wherein, described can carry protogenic compound and described activator mole
Than for 1:0.2～1.8.
5. the method according to any one in Claims 1 to 4, wherein, described activator is selected from tetrahydrochysene benzoquinone, tetrachlorobenzene
Quinone, four cyano benzoquinone and DDQ.
6. method according to claim 1, wherein, described can carry protogenic compound and lewis acidic rub with described
That ratio is 0.01～1:1.
7. method according to claim 6, wherein, described can carry protogenic compound and lewis acidic rub with described
That ratio is 0.02～0.5:1.
8. the method according to any one in claim 1,6 and 7, wherein, described lewis acid is the road shown in formula iv
Lewis acid shown in Lewis acid and/or formula v,
In formula iv, x31And x32It is respectively one of halogen group；r12For c1～c8Straight or branched alkyl；
In formula v, x4For one of halogen group；r13And r14It is respectively c1～c8Straight or branched alkyl.
9. method according to claim 8, wherein, in formula iv, x31And x32It is respectively-cl；r12For ethyl.
10. method according to claim 8, wherein, in formula v, x4For-cl；r13And r14It is respectively ethyl.
11. methods according to claim 8, wherein, described lewis acid is shown in the lewis acid shown in formula iv and formula v
Lewis acid, in described lewis acid, the lewis acid of 10～90 moles of % is the lewis acid shown in formula v.
12. methods according to any one in claim 1,2,6 and 7, wherein, described can carry protogenic compound
For h2O and/or Bronsted acid.
13. methods according to claim 12, wherein, described can carry protogenic compound be hcl.
14. methods according to claim 1, 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.
15. methods according to claim 14, wherein, the time of described ageing is 10 minutes to 10 hours.
16. methods according to claim 15, wherein, the time of described ageing is 30 minutes to 5 hours.
17. methods according to claim 16, wherein, the time of described ageing is 60 minutes to 2 hours.
18. methods according to any one in claim 14～17, wherein, the condition of described ageing includes: temperature be-
100 DEG C to 20 DEG C.
19. methods according to claim 18, wherein, the condition of described ageing includes: temperature is -100 DEG C to 0 DEG C.
20. methods according to claim 1, wherein, on the basis of the total amount of described monoolefine and described ring-alkylated styrenes,
The content of described monoolefine is 80～99 weight %；The content of described ring-alkylated styrenes is 1～20 weight %.
21. methods according to claim 20, 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 %.
22. methods according to any one in claim 1,14,20 and 21, wherein, described ring-alkylated styrenes is to first
Base styrene and/or a methyl styrene.
23. methods according to any one in claim 1,14,20 and 21, wherein, described monoolefine is isobutene..
24. methods according to claim 1, wherein, the condition of described contact includes: temperature is -120 DEG C to 20 DEG C.
25. methods according to claim 24, wherein, the condition of described contact includes: temperature is -100 DEG C to 0 DEG C.
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| 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 |
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| 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 |
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