CN104558342B - Cation polymerization method - Google Patents
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- CN104558342B CN104558342B CN201310491422.9A CN201310491422A CN104558342B CN 104558342 B CN104558342 B CN 104558342B CN 201310491422 A CN201310491422 A CN 201310491422A CN 104558342 B CN104558342 B CN 104558342B
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Abstract
The invention discloses a cation polymerization method which comprises the following steps: under the condition of cation polymerization, in one or more diluents, one or more types of monoolefine and one or more types of alkyl styrene are in contact with all components in an initiator system; the initiator system contains one or more compounds capable of providing protons, and one or more types of lewis acid and one or more activators; the activators are selected from a compound shown in a formula I-1 and a compound shown in a formula I-2; the diluents are one or more first diluents and one or more second diluents; the first diluents are selected from haloalkane; the second diluents are selected from aliphatic alkane and alicyclic alkane. According to the cation polymerization method, the satisfactory polymerization efficiency can be obtained.
Description
Technical field
The present invention relates to a kind of cationic polymerization process.
Background technology
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
(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.
The present inventor is studied for the problems referred to above, finds: when being polymerized in low Polar diluents,
If introducing quinonoid compound (particularly there is the quinonoid compound of electron-withdrawing substituent) in initiator system, it is possible to increase
Polymerization efficiency, obtains high polymer yield.This completes 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 made up of at least one first diluent and at least one second diluent, described first diluent
Selected from halogenated alkane, described second diluent is selected from aliphatic alkane and alicyclic alkanes.
Gratifying polymerization effect is obtained in that according to the polymerization of the present invention.
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 can be entered according to the concrete application occasion of this initiator system
The suitable selection of row, to be obtained in that gratifying polymerization efficiency is defined.Usually, described protogenic compound can be carried
Mol ratio with described activator 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 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.Halogen in described halogenated alkane is former
Son can be chlorine, bromine or fluorine, preferably chlorine or fluorine.Described halogenated alkane is preferably c1～c4Halogenated aliphatic alkane.
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.
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, Isosorbide-5-Nitrae-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, no longer describes in detail herein.
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 selected from the compound shown in 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 selected from the compound shown in 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 by least one first diluent and at least one second dilution
Agent forms, and described first diluent is selected from halogenated alkane, and described second diluent is selected from aliphatic alkane and alicyclic alkanes.Institute
State aliphatic alkane and be preferably c3～c10Aliphatic alkane, more preferably c3～c8Aliphatic alkane, more preferably c5
～c8Aliphatic alkane；Described alicyclic alkanes are preferably c3～c10Alicyclic alkanes, more preferably c5～c10's
Alicyclic alkanes.Described halogenated alkane is preferably c1～c10Halogenated alkane, more preferably c1～c4Halogenated alkane, described halogen
Can be chlorine, bromine or fluorine, preferably chlorine or fluorine for the halogen atom in alkane.
The method according to the invention, the ratio between described first diluent and described second diluent can be according to concrete
Condition selected.Usually, on the basis of the total amount of described diluent, the content of described second diluent can for 20～
99 volumes %；The content of described first diluent can be 1～80 volume %.The present invention one kind preferred embodiment in,
The amount of described first diluent is 30～70 volumes %, preferably 30～50 volumes %；The amount of described second diluent is 30～70
Volume %, preferably 50～70 volumes %, thus as the r in formula i-11、r2、r3And r4In at least one be-cn, the r in formula i-25、
r6、r7And r8In at least one be-cn when, if polyreaction is in the temperature of -120 DEG C to -60 DEG C (preferably -100 DEG C to -70 DEG C)
Carry out under degree, even if the lewis acid in initiator system does not contain the lewis acid shown in formula v, but be the Louis shown in formula iv
This acid, also can prepare molecular weight is 40 × 104Above polymer.This preferred embodiment in, described activator is preferred
For four cyano benzoquinone and/or DDQ.
As diluent, the instantiation of described aliphatic alkane and alicyclic alkanes can include but is not limited to: propane,
Normal butane, iso-butane, pentane, isopentane, neopentane, Pentamethylene., normal hexane, 2- methylpentane, 3- methylpentane, 2,3- bis-
Methybutane, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- ethylpentane, 3- ethyl penta
Alkane, 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- tri-
Methylpentane, 2,4,4- trimethylpentane, 2- methyl -3- ethylpentane, n -nonane, 2- methyloctane, 3- methyloctane, 4- first
Base octane, 2,3- dimethyl heptane, 2,4- dimethyl heptane, 3- ethyl heptane, 4- ethyl heptane, 2,3,4- trimethyl cyclohexane,
2,3,5- trimethyl cyclohexane, 2,4,5- trimethyl cyclohexane, 2,2,3- trimethyl cyclohexane, 2,2,4- trimethyl cyclohexane, 2,2,5- tri-
Methyl hexane, 2,3,3- trimethyl cyclohexane, 2,4,4- trimethyl cyclohexane, 2- methyl -3- ethyl hexane, 2- methyl -4- ethyl hexyl
Alkane, 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 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- 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 and tetramethyl-ring hexane.
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, Difluoroethane, trifluoro
Ethane, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, dichloroethanes, trichloroethane, sym-tetrachloroethane, Pentalin.,
Carbon hexachloride, a fluoro-propane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoro
Propane, 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
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 first diluent is selected from monochloro methane, dichloromethane and monochlorethane, described second diluent choosing
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 is so that the temperature of diluent is -120 DEG C to 20 DEG C it is preferable that the temperature of diluent is -100
DEG C to 0 DEG C.The method according to the invention, the time of described 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 1～28 is used for the cationic polymerization process of the present invention is described.
Embodiment 1
(1) 0.133g chloranil is dissolved in 66.5g dichloromethane solution, obtains chloranil's solution.With weight
Gauge, in this solution, the concentration of chloranil is 2000ppm.
At -80 DEG C, sequentially add the 20ml being cooled to -80 DEG C in advance to contain hcl(concentration in 60ml Cornu Caprae seu Oviss bottle to be
Dichloromethane solution 0.0038mol/l), 1.8ml contain the hexane solution of ethyl aluminum dichloride (concentration be 0.9mol/l) with
And 0.5ml aforementioned chloranil solution, it is aged 15min at -80 DEG C after mix homogeneously, thus obtaining initiator solution.With weight
Gauge, in this initiator solution, the concentration of chloranil is 50ppm.
(2) be furnished with strength constant speed stirring 500ml glass reactor in sequentially add 100ml be cooled in advance -60 DEG C one
Chloromethanes, 80ml are cooled to -60 DEG C of normal hexane in advance, 32ml is cooled to -60 DEG C of isobutene. in advance and 1.3ml room temperature (25 DEG C) to first
Base styrene (content is 98 weight %), mix homogeneously.The initiator solution that in reactor prepared by Deca step (1).Wherein,
The addition of initiator solution is 16ml；Rate of addition is controlled to make the scope that the temperature in reactor is in -57 DEG C to -63 DEG C
Within.After being added dropwise to complete, keep the temperature in reactor to be within the scope of -57 DEG C to -63 DEG C, carry out with stirring
The polyreaction of 14min, then adds the methanol solution that 5ml contains 0.5 weight %naoh, to terminate gathering in reactant mixture
Close reaction.The mixed solution obtaining is placed in desolvation in hot bath, the product obtaining after washing, in vacuum drying oven in
60 DEG C of dryings to constant weight, thus obtaining 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
It is polymerized using method same as Example 1, except for the difference that, in initiator solution prepared by step (1) not
Containing chloranil.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 2
It is polymerized using method same as Example 1, except for the difference that, in the initiator solution that step (1) obtains, with
Weight meter, the concentration of chloranil is 100ppm；In step (2), the addition of initiator solution is 20ml, initiator solution
After being added dropwise to complete, the temperature in reactor is kept to be to be in the range of -60 DEG C to -65 DEG C, the time of polyreaction is
13min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 3
It is polymerized using method same as Example 1, except for the difference that, in the initiator solution that step (1) obtains, with
Weight meter, the concentration of chloranil is 300ppm；In step (2), the addition of initiator solution is 20ml, initiator solution
After being added dropwise to complete, the temperature in reactor is kept to be to be in the range of -60 DEG C to -65 DEG C, polymerization reaction time is 15min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 4
It is polymerized using method same as Example 1, except for the difference that, in step (1), digestion time is 25min, obtains
To initiator solution in, by weight, the concentration of chloranil is 800ppm；In step (2), the addition of initiator solution
Measure as 10ml, after initiator solution is added dropwise to complete, keep the temperature in reactor to be to be in the range of -85 DEG C to -90 DEG C, poly-
The time closing reaction is 15min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 5
(1) by 0.1596g chloranil be dissolved in 206g contain hcl(concentration be 0.0032mol/l) dichloromethane in,
Then above-mentioned solution is cooled to -80 DEG C in advance, and (concentration is 0.9mol/ to add the 11ml being cooled to -80 DEG C in advance to contain ethyl aluminum dichloride
L) hexane solution, after mix homogeneously, is aged 31min at -80 DEG C, thus obtaining initiator solution.Wherein, by weight,
In initiator solution, the concentration of tetrachloroquinone is 750ppm.
(2) sequentially add the chlorine that 60ml is cooled to -80 DEG C in advance in the 500ml glass reactor being furnished with the stirring of strength constant speed
Methane, 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 (25 DEG C) to first
Base styrene (content is 98 weight %), mix homogeneously.The initiator solution that in reactor prepared by Deca step (1).Wherein,
The addition of initiator solution is 20ml, controls rate of addition to make the scope that the temperature in reactor is in -80 DEG C to -85 DEG C
Within.After being added dropwise to complete, keep the temperature in reactor to be within the scope of -80 DEG C to -85 DEG C, carry out with stirring
The polyreaction of 10min, then adds the methanol solution that 5ml contains 0.5 weight %naoh, to terminate gathering in reactant mixture
Close reaction.The mixed solution obtaining is placed in desolvation in hot bath, the product 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 1.
Embodiment 6
It is polymerized using method same as Example 5, except for the difference that, in step (1), digestion time is 65min；Step
Suddenly in (2), the consumption of monochloro methane is 20ml, and the consumption of normal hexane is 180ml, and the addition of initiator solution is 20ml, gathers
The conjunction response time is 10min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 7
(1) be dissolved in 120g to contain hcl(concentration by chloro- for 0.072g2,3- bis- 5,6- dicyano p-benzoquinone is 0.0042mol/
L), in dichloromethane solution, then above-mentioned solution is cooled to -80 DEG C in advance, and add 5.6ml be cooled in advance -80 DEG C contain dichloro
The hexane solution of aluminium ethide (concentration is 0.9mol/l), after mix homogeneously, is aged 60min at -80 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 580ppm.
(2) 100ml is sequentially added to be cooled to -80 DEG C in advance in being furnished with the glass reactor of 500ml of strength constant speed stirring
Monochloro methane, 100ml 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 (25 DEG C)
P-methylstyrene (content is 98 weight %), mix homogeneously.The initiator solution that in reactor prepared by Deca step (1).Its
In, the addition of initiator solution is 25ml, controls rate of addition to make the temperature in reactor be in -85 DEG C to -90 DEG C
Within the scope of.After being added dropwise to complete, keep the temperature in reactor to be within the scope of -85 DEG C to -90 DEG C, carry out with stirring
The polyreaction of 17min, then adds the methanol solution that 5ml contains 0.5 weight %naoh, to terminate gathering in reactant mixture
Close reaction.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 1.
Embodiment 8
It is polymerized using with the same procedure of embodiment 7, except for the difference that, in step (2), the consumption of monochloro methane is
60ml, the consumption of normal hexane is 140ml.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 9
It is polymerized using method same as Example 7, except for the difference that, in step (2), the consumption of monochloro methane is
20ml, the consumption of normal hexane is 180ml.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 10
It is polymerized using with the identical method of embodiment 7, except for the difference that, in the initiator solution that step (1) obtains,
By weight, the concentration of chloro- 5, the 6- dicyano p-benzoquinone of 2,3- bis- is 300ppm；In step (2), the consumption of monochloro methane is
80ml, the consumption of normal hexane is 120ml, and the addition of initiator solution is 24ml；After initiator solution is added dropwise to complete, will react
Temperature control in device is to be within the scope of -65 DEG C to -70 DEG C, and carries out the polymerization of 12min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 11
(1) chloro- for 0.0532g2,3- bis- 5,6- dicyano p-benzoquinone is dissolved in 66.3g and containing hcl(concentration is
In dichloromethane 0.0027mol/l), then above-mentioned solution is cooled to -85 DEG C in advance, and adds 4ml to be cooled to -85 DEG C contain in advance
The hexane solution of ethyl aluminum dichloride (concentration is 0.9mol/l), after mix homogeneously, is aged 60 minutes 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) it is polymerized using method same as Example 7, except for the difference that, initiator solution is embodiment 11 step
(1) initiator solution prepared；The consumption of monochloro methane is 40ml, and the consumption of normal hexane is 160ml；The addition of initiator solution
Measure as 15ml, polymerization time is 11min.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 12
It is polymerized using method same as Example 7, except for the difference that, in step (1), digestion time is 10 minutes.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 13
It is polymerized using method same as Example 7, except for the difference that, in step (1), digestion time is 30 minutes.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 14
It is polymerized using method same as Example 7, except for the difference that, replaced 2,3- with the four cyano 1,4-benzoquinone of equivalent
Two chloro- 5,6- dicyano p-benzoquinones.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 15
It is polymerized using method same as Example 7, except for the difference that, replaced 2,3- bis- with the tetrahydrochysene 1,4-benzoquinone of equivalent
Chloro- 5,6- dicyano p-benzoquinone.
Polymer yield, the molecular weight and molecualr weight distribution index of the polymer obtaining are listed in Table 1.
Embodiment 16
(1) chloro- for 0.0652g2,3- bis- 5,6- dicyano p-benzoquinone is dissolved in 80g and contains hcl(concentration for 0.003mol/
L) in dichloromethane, the solution obtaining is cooled to -85 DEG C in advance, then sequentially adds the 2.8ml concentration to be in this solution
The toluene solution of the hexane solution of the eadc of the 0.9mol/l and 1.2ml concentration deac for 0.9mol/l be (eadc and deac's
Molar ratio is 7/3), after mix homogeneously, the mixed liquor obtaining is placed in ageing 60min in -85 DEG C of cryostat.Wherein, with weight
Gauge, in initiator solution, the content of chloro- 5, the 6- dicyano p-benzoquinone of 2,3- bis- is 800ppm.
(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 of 0.62ml room temperature (25 DEG C), mix homogeneously, obtain
Monomer solution.The initiator solution that in monomer solution prepared by addition 10ml step (1), standing and reacting 40min after mix homogeneously,
Cryostat temperature is controlled to be to be within the scope of -80 DEG C to -85 DEG C in course of reaction.Reaction terminates to add in backward reactant mixture
Enter the methanol solution that 5ml contains 0.5 weight %naoh, to terminate polyreaction.Then mixed solution is placed in removing in hot bath
Solvent, after the solid obtaining is washed, in 60 DEG C of dryings to constant weight in vacuum drying oven, obtains 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 2.
Embodiment 17
Prepare initiator solution using with embodiment 16 identical method, except for the difference that, the total amount of eadc and deac is constant
Under conditions of, in adjustment initiator solution, the molar ratio of eadc and deac is 5/5.
Carry out polyreaction using with step (2) identical polymerization in embodiment 16.
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 2.
Embodiment 18
Prepare initiator solution using with embodiment 16 identical method, except for the difference that, the total amount of eadc and deac is constant
Under conditions of, in adjustment initiator solution, the molar ratio of eadc and deac is 3/7.
Carry out polyreaction using with step (2) identical polymerization in embodiment 16.
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 2.
Embodiment 19
Prepare initiator solution using with embodiment 16 identical method, except for the difference that, the total amount of eadc and deac is constant
Under conditions of, in adjustment initiator solution, the molar ratio of eadc and deac is 1/9.
Carry out polyreaction using with step (2) identical polymerization in embodiment 16.
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 2.
Embodiment 20
Prepare initiator solution being polymerized using with embodiment 19 identical method, except for the difference that, 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 2.
Embodiment 21
Prepare initiator solution being polymerized using with embodiment 19 identical method, except for the difference that, in step (2),
Under conditions of the total amount of normal hexane and monochloro methane 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 2.
Embodiment 22
Prepare initiator solution being polymerized using with embodiment 19 identical method, except for the difference that, in step (2),
Under conditions of the total amount of normal hexane and monochloro methane is constant, adjustment normal hexane is 6/4 with the volume ratio of monochloro methane.Mensure obtains
Polymer weight, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymer, result is in table 2
In list.
Embodiment 23
Using preparing initiator solution with embodiment 19 same procedure and being polymerized, except for the difference that, in step (2), just
Under conditions of the total amount of hexane and monochloro methane is constant, adjustment normal hexane is 5/5 with the volume ratio of monochloro methane.Mensure obtains
The weight of polymer, calculating polymer yield, and measure the molecular weight and molecualr weight distribution index of polymer, result is in table 2
List.
Embodiment 24
(1) by 0.0651 gram of chloranil be dissolved in 80g and containing hcl(concentration be 0.0042mol/l) dichloromethane
In solution, the solution obtaining is cooled to -85 DEG C in advance, then sequentially adds 2.8ml concentration to be 0.9mol/l's in this solution
(eadc/deac molar ratio is 7/ to the n-heptane solution of the hexane solution of the eadc and 1.1ml concentration deac for 1.0mol/l
3), after mix homogeneously, the mixed liquor obtaining is placed in -85 DEG C of ageing 60min.Wherein, by weight, tetrachloro in initiator solution
The content of 1,4-benzoquinone is 800ppm.
(2) it is polymerized using with embodiment 17 identical method, except for the difference that, the total amount of normal hexane and monochloro methane is not
Under conditions of change, 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 2.
Embodiment 25
Prepare initiator solution being polymerized using with embodiment 24 identical method, except for the difference that, in step (1),
Under conditions of the total amount of eadc and deac is constant, the mol ratio of adjustment eadc/deac is 5/5.
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 2.
Embodiment 26
Prepare initiator solution being polymerized using with embodiment 24 identical method, except for the difference that, in step (1),
Under conditions of the total amount of eadc and deac is constant, the mol ratio of adjustment eadc/deac is 3/7.Measure the weight of the polymer obtaining
Amount, calculating polymer yield, and measure the molecular weight and molecualr weight distribution index of polymer, result is listed in table 2.
Embodiment 27
Prepare initiator solution being polymerized using with embodiment 25 identical method, except for the difference that, in step (2),
Under conditions of the total amount of normal hexane and monochloro methane is constant, adjustment normal hexane is 9/1 with the volume ratio of monochloro methane.Mensure obtains
Polymer weight, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymer, result is in table 2
In list.
Embodiment 28
Prepare initiator solution being polymerized using with embodiment 25 identical method, except for the difference that, 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.Mensure obtains
Polymer weight, calculate polymer yield, and measure the molecular weight and molecualr weight distribution index of polymer, result is in table 2
In list.
Comparative example 2
Using preparing initiator solution with embodiment 17 identical method and being 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 the polymer obtaining, calculate polymer yield, and measure poly-
The molecular weight and molecualr weight distribution index of compound, result is listed in table 2.
Table 2
Claims (30)
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 made up of at least one first diluent and at least one second diluent, and described first diluent is selected from
Halogenated alkane, described second diluent is selected from aliphatic alkane and alicyclic 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, described solvent is selected from alkane, halogenated alkane and aromatic hydrocarbons.
16. methods according to claim 14, wherein, the time of described ageing is 10 minutes to 10 hours.
17. methods according to claim 16, wherein, the time of described ageing is 30 minutes to 5 hours.
18. methods according to claim 17, wherein, the time of described ageing is 60 minutes to 2 hours.
19. methods according to any one in claim 14 and 16～18, wherein, the condition of described ageing includes: temperature
Spend for -100 DEG C to 20 DEG C.
20. methods according to claim 19, wherein, the condition of described ageing includes: temperature is -100 DEG C to 0 DEG C.
21. 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 %.
22. methods according to claim 21, 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 %.
23. methods according to any one in claim 1,14,21 and 22, wherein, described ring-alkylated styrenes is to first
Base styrene and/or a methyl styrene.
24. methods according to any one in claim 1,14,21 and 22, wherein, described monoolefine is isobutene..
25. methods according to claim 1, wherein, the condition of described contact includes: temperature is -120 DEG C to 20 DEG C.
26. methods according to claim 25, wherein, the condition of described contact includes: temperature is -100 DEG C to 0 DEG C.
27. methods according to claim 8, wherein, described lewis acid is the lewis acid shown in formula iv, r1、r2、r3
And r4In at least one be-cn, r5、r6、r7And r8In at least one is-cn, on the basis of the total amount of described diluent, described the
The content of one diluent is 30～70 volumes %, and the content of described second diluent is 30～70 volumes %.
28. methods according to claim 27, wherein, the condition of described contact includes: temperature is -120 DEG C to -60 DEG C.
29. methods according to claim 28, wherein, the condition of described contact includes: temperature is -100 DEG C to -70 DEG C.
30. methods according to claim 1 or 27, wherein, described first diluent is selected from c1～c10Halogenated alkane, institute
State the second diluent and be selected from c3～c10Aliphatic alkane and c3～c10Alicyclic alkanes.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162445A (en) * | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
| CN1212000A (en) * | 1996-02-29 | 1999-03-24 | 国际壳牌研究有限公司 | Process for preparation of copolymers |
| US6028144A (en) * | 1990-07-24 | 2000-02-22 | Exxon Chemical Patents, Inc. | Composition for the carcass |
| CN102399311A (en) * | 2010-08-19 | 2012-04-04 | 中国石油化工股份有限公司 | Cationic polymerization initiation system and cationic polymerization method |
| CN103122052A (en) * | 2011-11-18 | 2013-05-29 | 北京化工大学 | Segmented copolymer with fully-saturated soft segment and crystallizable hard segment and preparation method of segmented copolymer |
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| FR2846660B1 (en) * | 2002-11-05 | 2006-07-07 | Atofina | CATIONIC CATALYSIS SYSTEM COMPRISING AN INITIATOR, CATALYST AND CO-CATALYST |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162445A (en) * | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
| US6028144A (en) * | 1990-07-24 | 2000-02-22 | Exxon Chemical Patents, Inc. | Composition for the carcass |
| CN1212000A (en) * | 1996-02-29 | 1999-03-24 | 国际壳牌研究有限公司 | Process for preparation of copolymers |
| CN102399311A (en) * | 2010-08-19 | 2012-04-04 | 中国石油化工股份有限公司 | Cationic polymerization initiation system and cationic polymerization method |
| CN103122052A (en) * | 2011-11-18 | 2013-05-29 | 北京化工大学 | Segmented copolymer with fully-saturated soft segment and crystallizable hard segment and preparation method of segmented copolymer |
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