CN106146708A - A kind of cationic polymerization process - Google Patents
A kind of cationic polymerization process Download PDFInfo
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- CN106146708A CN106146708A CN201510195024.1A CN201510195024A CN106146708A CN 106146708 A CN106146708 A CN 106146708A CN 201510195024 A CN201510195024 A CN 201510195024A CN 106146708 A CN106146708 A CN 106146708A
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Abstract
The invention discloses a kind of cationic polymerization process, it is included under solution polymerization condition, monoolefine shown in formula IV is contacted with each component in initiator system with conjugated diene shown in Formula V in polymer solvent, described initiator system contains can carry protogenic compound, lewis acid and activator, described activator is selected from compound shown in compound shown in Formulas I-1 and Formulas I-2, and the lewis acid of 10～90 moles of % is lewis acid shown in Formula II.The H simple with employing+/ lewis acid initiator system is compared, and the method efficiency of initiation significantly improves, and can obtain higher polymer yield with higher rate of polymerization；By regulating content and the kind of activator in initiator system, the polymer with different molecular weight can be obtained under different polymerizing conditions；Polymerization can also be implemented at higher temperatures, reduce the energy expenditure in polymerization process.
Description
Technical field
The present invention relates to a kind of cationic polymerization process.
Background technology
At present, the most commonly used slurry polymerization process with monochloro methane as diluent produces fourth
Base rubber, its reason essentially consists in: the production efficiency of slurry polymerization process is high, and the molecular weight of product is high,
Good processability.
Compared with slurry polymerization process, polymerisation in solution rule does not has obvious advantage in these areas, especially
The molecular weight product that solution polymerization process obtains is low, processing characteristics is poor, is the most commercially difficult to and slurry
The product that polymerization obtains is competed mutually.But, the development space ratio of solution polymerization process is broader, such as:
Solution polymerization process more meets environmental requirement than slurry polymerization process, and wider to the subject range of polymerization temperature
General, especially there is more preferable DEVELOPMENT PROSPECT to realizing high temperature polymerization aspect.Additionally, halogenated butyl rubber
Generally use solwution method to prepare, namely the butyl rubber being dissolved in alkane is connect with halogen-containing compound
Touch and carry out halogenation, when using slurry polymerization process to prepare butyl rubber, need in polymerization procedure
With setting is intended to replace the halogen in the mixture that slurry polymerization process obtains with alkane between halogenation step
For solvent swap step and the polymer re-dissolved step of alkane, and in solution polymerization process, then without institute
State polymer re-dissolved step, it is clear that solution polymerization process is more suitable for the life of solwution method halogenated butyl rubber
Produce.
But, for producing butyl rubber in the solution, main problems faced is drawing of initiator system
Send out efficiency low, cause polymerization efficiency poor, be difficult to obtain the product of high molecular.
It is the effective initiator preparing butyl rubber in the solution that US3361725 proposes aluminum alkyl halide,
The product of higher molecular weight can be obtained at a higher temperature, but require dialkyl group in aluminum alkyl halide
The molar ratio of aluminum halide reaches more than 80%, and the molar ratio of monoalkyl dihalide aluminum is then less than
20%, thus by the self-initiating effect of alkyl aluminum in the solution (such as hexane) in prepare butyl rubber.But
It is that it practice, the efficiency of initiation of this initiator system is the lowest, and rate of polymerization is the slowest, it is impossible to full
The needs of full border application.To this end, this initiator system is improved by US6403747, i.e. exist
Above-mentioned dialkylaluminum halides/monoalkyl dihalide aluminum mixed system introduces water or the aikyiaiurnirsoxan beta of trace, makes to draw
Send out agent system activity to improve, such that it is able to prepare weight average molecular weight at-60 DEG C to-80 DEG C to reach 400,000
Above butyl rubber.Although the efficiency of initiation of initiator system disclosed in US6403747 and rate of polymerization
It is improved to some extent, but the most unsatisfactory in actual mechanical process, and initiator body
System's preparation is relatively difficult, especially requires the highest to the technology of preparing of aikyiaiurnirsoxan beta.
Therefore, for the cationic solution polymerization technique of butyl rubber, need exploitation badly and be adapted to solution
The high activity initiator system of polymerization, to improve efficiency of initiation and polymerization efficiency, it is thus achieved that high molecular weight products.
Summary of the invention
It is an object of the invention to provide a kind of cationic polymerization process, the method uses polymerisation in solution legal system
Standby monoolefine-conjugated diene copolymer, can have higher molecular weight with higher polymerization efficiency preparation
Monoolefine-conjugated diene copolymer.
The invention provides a kind of cationic polymerization process, the method is included under solution polymerization condition, will
At least one monoolefine and at least one conjugated diene and each component in initiator system be polymerized molten
Agent contacts,
Described initiator system contains at least one can carry protogenic compound, at least one Louis
Acid and at least one activator, described activator is selected from shown in the compound shown in Formulas I-1 and Formulas I-2
Compound,
In Formulas I-1 and Formulas I-2, R1、R2、R3、R4、R5、R6、R7And R8It is respectively-H ,-X1、
-NO2、With the one in-CN, X1And X2It is respectively the one in halogen group；
The lewis acid of 10～90 moles of % is the lewis acid shown in Formula II,
In Formula II, R9And R10It is respectively C1～C8Straight or branched alkyl, X3For in halogen group
One；
Described monoolefine is selected from the compound shown in formula IV,
In formula IV, R13And R14It is respectively C1～C5Straight or branched alkyl；Or R13For hydrogen,
R14For C3～C5Branched alkyl；
Described conjugated diene is selected from the compound shown in Formula V,
In Formula V, R15、R16And R17It is respectively hydrogen or C1～C5Straight or branched alkyl.
The method using the present invention prepares monoolefine-conjugated diene copolymer, the H simple with employing+/
Lewis acid initiator system is compared, and on the one hand efficiency of initiation significantly improves, it is thus possible to higher polymerization
Speed obtains higher polymer yield；On the other hand by the content of activator in regulation initiator system
And kind, under different polymerizing conditions, it is obtained in that the polymer with different molecular weight, it is thus possible to full
The use requirement of foot different application occasion.It addition, the H simple with employing+/ lewis acid initiator system
Comparing, the method for the present invention can implement polymerization at higher temperatures, it is thus possible to it is anti-to be effectively reduced polymerization
Energy expenditure during Ying.
Detailed description of the invention
The invention provides a kind of cationic polymerization process, the method is included under solution polymerization condition, will
At least one monoolefine and at least one conjugated diene and each component in initiator system be polymerized molten
Agent contacts.
In the present invention, " at least one " represents one or more.
The method according to the invention, described initiator system (being referred to as initiator composition) contains
At least one can carry protogenic compound, at least one lewis acid and at least one activator.
Described activator is selected from the compound shown in Formulas I-1 and the compound shown in Formulas I-2,
In Formulas I-1 and Formulas I-2, R1、R2、R3、R4、R5、R6、R7And R8It is respectively-H ,-X1、
-NO2、With the one in-CN, X1And X2The one that is respectively in halogen group (such as:
-F ,-Cl ,-Br or-I).
The instantiation of described activator can include but not limited to: tetrahydrochysene 1,4-benzoquinone, tetrahydrochysene neighbour's benzoquinone,
One fluorine three hydrogen 1,4-benzoquinone, fluorine three hydrogen neighbour's benzoquinone, difluoro dihydro 1,4-benzoquinone, difluoro dihydro neighbour's benzoquinone, three
Fluorine one hydrogen 1,4-benzoquinone, trifluoro one hydrogen neighbour's benzoquinone, tetrafluoro 1,4-benzoquinone, tetrafluoro neighbour's benzoquinone, chlorine three hydrogen are to benzene
Quinone, chlorine three hydrogen neighbour's benzoquinone, dichloro-dihydro 1,4-benzoquinone (include 2,3-dichloro 1,4-benzoquinone, 2,5-dichloro pair
Benzoquinone, 2,6-dichloro 1,4-benzoquinone), dichloro-dihydro neighbour's benzoquinone (include 3,4-dichloro neighbour's benzoquinone, 3,5-dichloro
Adjacent benzoquinone, 3,6-dichloro neighbour's benzoquinone), trichlorine one hydrogen 1,4-benzoquinone, trichlorine one hydrogen neighbour's benzoquinone, chloranil,
Monoethyl quinone, 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's 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's benzoquinone, tetrabromo 1,4-benzoquinone, tetrabromo-phthalic quinone, a fluorine trinitro-1,4-benzoquinone, fluorine trinitro-neighbour's benzene
Quinone, difluoro dinitro 1,4-benzoquinone (include 2,3-bis-fluoro-5,6-dinitro 1,4-benzoquinone, 2,5-bis-fluoro-3,6-dinitro
Base 1,4-benzoquinone, 2,6-bis-fluoro-3,5-dinitro 1,4-benzoquinone), difluoro dinitro o benzoquinone (include 3,4-difluoro
-5,6-dinitro o benzoquinone, 3,5-bis-fluoro-4,6-dinitro o benzoquinone, 3,6-bis-fluoro-4,5-dinitro o benzene
Quinone), trifluoro one nitro 1,4-benzoquinone, trifluoro one nitro neighbour's benzoquinone, a chlorine trinitro-1,4-benzoquinone, a chlorine three
Nitro neighbour's benzoquinone, dichloro dinitro 1,4-benzoquinone (include 2,3-bis-chloro-5,6-dinitro 1,4-benzoquinone, 2,5-bis-
Chloro-3,6-dinitro 1,4-benzoquinone, 2,6-bis-chloro-3,5-dinitro 1,4-benzoquinone), dichloro dinitro o benzoquinone (bag
Include 3,4-bis-chloro-5,6-dinitro o benzoquinone, 3,5-bis-chloro-4,6-dinitro o benzoquinone, 3,6-bis-chloro-4,5-bis-
Nitro neighbour's benzoquinone), trichlorine one nitro 1,4-benzoquinone, trichlorine one nitro neighbour's benzoquinone, monobromo trinitro-1,4-benzoquinone,
Monobromo trinitro-neighbour's benzoquinone, dibromo dinitro 1,4-benzoquinone (include 2,3-bis-bromo-5,6-dinitro 1,4-benzoquinone,
2,5-bis-bromo-3,6-dinitro 1,4-benzoquinone, 2,6-bis-bromo-3,5-dinitro 1,4-benzoquinone), dibromo dinitro o benzene
Quinone (include 3,4-bis-bromo-5,6-dinitro o benzoquinone, 3,5-bis-bromo-4,6-dinitro o benzoquinone, 3,6-dibromo
-4,5-dinitro o benzoquinone), tribromo one nitro 1,4-benzoquinone, tribromo one nitro neighbour's benzoquinone, tetranitro is to benzene
Quinone, tetranitro neighbour's benzoquinone, a fluorine tricyano 1,4-benzoquinone, fluorine tricyano neighbour's benzoquinone, difluoro dicyano pair
Benzoquinone (include 2,3-bis-fluoro-5,6-dicyano p-benzoquinone, 2,5-bis-fluoro-3,6-dicyano p-benzoquinone, 2,6-bis-
Fluoro-3,5-dicyano p-benzoquinone), difluoro dicyano neighbour's benzoquinone (include 3,4-bis-fluoro-5,6-dicyano 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's benzoquinone, a chlorine tricyano 1,4-benzoquinone, chlorine tricyano neighbour's benzoquinone, dichloro dicyan
Base 1,4-benzoquinone (include 2,3-bis-chloro-5,6-dicyano p-benzoquinone, 2,5-bis-chloro-3,6-dicyano p-benzoquinone, 2,6-
Two chloro-3,5-dicyano p-benzoquinone), dichloro dicyano neighbour's benzoquinone (include 3,4-bis-chloro-5,6-dicyano neighbour's benzene
Quinone, 3,5-bis-chloro-4,6-dicyano neighbour's benzoquinone, 3,6-bis-chloro-4,5-dicyano neighbour's benzoquinone), trichlorine one cyano group
1,4-benzoquinone, trichlorine one cyano group neighbour's benzoquinone, monobromo tricyano 1,4-benzoquinone, monobromo tricyano neighbour's benzoquinone, dibromo
Dicyano p-benzoquinone (include 2,3-bis-bromo-5,6-dicyano p-benzoquinone, 2,5-bis-bromo-3,6-dicyano p-benzoquinone,
2,6-bis-bromo-3,5-dicyano p-benzoquinone), dibromo dicyano neighbour's benzoquinone (include 3,4-bis-bromo-5,6-dicyano
Adjacent 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 1,4-benzoquinone, tribromo one cyano group neighbour's benzoquinone, trinitro-one cyano group 1,4-benzoquinone, trinitro-one cyano group neighbour's benzene
Quinone, 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's benzoquinone (includes
3,4-dinitro-5,6-dicyano neighbour's benzoquinone, 3,5-dinitro-4,6-dicyano neighbour's benzoquinone, 3,6-dinitro-4,5-
Dicyano neighbour's benzoquinone), a nitrotrimethylolmethane cyano group 1,4-benzoquinone, nitrotrimethylolmethane cyano group neighbour's benzoquinone, four cyano is to benzene
Quinone, four cyano neighbour's benzoquinone, a fluorine front three acid chloride group 1,4-benzoquinone, fluorine front three acid chloride group neighbour's benzoquinone, difluoro
Dimethyl chloride base 1,4-benzoquinone (include 2,3-bis-fluoro-5,6-dimethyl chloride base 1,4-benzoquinone, 2,5-bis-fluoro-3,6-diformazan
Acid chloride group 1,4-benzoquinone, 2,6-bis-fluoro-3,5-dimethyl chloride base 1,4-benzoquinone), difluoro dimethyl chloride base neighbour's benzoquinone (bag
Include 3,4-bis-fluoro-5,6-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 benzoquinone), trifluoro one formyl chloro 1,4-benzoquinone, trifluoro one formyl chloro neighbour's benzene
Quinone, a chlorine front three acid chloride group 1,4-benzoquinone, chlorine front three acid chloride group neighbour's benzoquinone, dichloro dimethyl chloride base are to benzene
Quinone (include 2,3-bis-chloro-5,6-dimethyl chloride base 1,4-benzoquinone, 2,5-bis-chloro-3,6-dimethyl chloride base 1,4-benzoquinone,
2,6-bis-chloro-3,5-dimethyl chloride base 1,4-benzoquinone), dichloro dimethyl chloride base neighbour's 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, 3,6-bis-chloro-4,5-dimethyl chloride
Base neighbour's benzoquinone), trichlorine one formyl chloro 1,4-benzoquinone, trichlorine one formyl chloro neighbour's benzoquinone, monobromo three formyl
Chloro 1,4-benzoquinone, monobromo front three acid chloride group neighbour's benzoquinone, dibromo dimethyl chloride base 1,4-benzoquinone (include 2,3-bis-
Bromo-5,6-dimethyl chloride base 1,4-benzoquinone, 2,5-bis-bromo-3,6-dimethyl chloride base 1,4-benzoquinone, 2,6-bis-bromo-3,5-bis-
Formyl chloro 1,4-benzoquinone), (including 3,4-bis-bromo-5,6-dimethyl chloride base is adjacent for dibromo dimethyl chloride base neighbour's benzoquinone
Benzoquinone, 3,5-bis-bromo-4,6-dimethyl chloride base neighbour's benzoquinone, 3,6-bis-bromo-4,5-dimethyl chloride base neighbour's benzoquinone),
Tribromo one formyl chloro 1,4-benzoquinone, tribromo one formyl chloro neighbour's benzoquinone, tetramethyl acid chloride group 1,4-benzoquinone and tetramethyl
Acid chloride group neighbour's benzoquinone.
Described activator is preferably selected from tetrahydrochysene benzoquinone (including tetrahydrochysene 1,4-benzoquinone and tetrahydrochysene neighbour's benzoquinone), tetrachloro
Benzoquinone (including chloranil and monoethyl quinone), four cyano benzoquinone (include four cyano 1,4-benzoquinone and
Four cyano neighbour's benzoquinone) and DDQ (include that dichloro dicyano p-benzoquinone and dichloro dicyano are adjacent
Benzoquinone).
The content of described activator is to be obtained in that gratifying polymerization effect is as the criterion.Usually, described
The mol ratio that can carry protogenic compound and described activator can be 1: 0.01～3, preferably 1:
0.1～2.8, more preferably 1: 0.2～2.5, more preferably 1: 0.8～1.5.
According to the polymerization of the present invention, described lewis acid contains the lewis acid shown in Formula II,
In Formula II, R9And R10Can be identical or different, can be each C1～C8Straight or branched
Alkyl, preferably C1～C5Straight or branched alkyl；Preferably, R9And R10For identical, for C1~
C5Straight or branched alkyl, more preferably ethyl.
In Formula II, X3For the one in halogen group, such as-F ,-Cl ,-Br or-I, it is preferably-Cl.
In the present invention, C1～C8Straight or branched alkyl include C1～C8Straight chained alkyl and C3～C8
Branched alkyl, its instantiation can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 2-methyl butyl, 3-methyl butyl, 2,2-bis-
Methyl-propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 2,3-dimethylbutyl,
2,2-dimethylbutyls, 3,3-dimethylbutyl, 2-ethyl-butyl, n-heptyl, 2-methylhexyl, 3-first
Base hexyl, 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 penta
Base, 3-ethyl pentyl group, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methyl heptan
Base, 6-methylheptyl, 2,2-dimethylhexanyl, 2,3-dimethylhexanyl, 2,4-dimethylhexanyl, 2,5-
Dimethylhexanyl, 3,3-dimethylhexanyl, 3,4-dimethylhexanyl, 3,5-dimethylhexanyl, 4,4-diformazan
Base hexyl, 4,5-dimethylhexanyl, 5,5-dimethylhexanyl, 2-ethylhexyl, 3-ethylhexyl, 4-second
Base hexyl, 2-n-pro-pyl amyl group and 2-isopropyl amyl group.
In the present invention, the lewis acidic instantiation shown in Formula II can include but not limited to: dimethyl
Aluminum chloride, diethyl aluminum chloride, diη-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl chlorination
Aluminum and diisobutyl aluminum chloride.
Preferably, the lewis acid shown in Formula II is diethyl aluminum chloride.
Containing two alkyl in lewis acidic molecular structure shown in Formula II, it is possible to play suppression cation
There is the effect of chain tra nsfer in active center such that it is able to improves the molecular weight of the polymer of preparation.But,
Lewis acidic too high levels shown in Formula II, can reduce polymerization rate, extends polymerization time.Root
According to the polymerization of the present invention, on the basis of lewis acidic total amount, lewis acidic shown in Formula II contains
Amount is 10～90 moles of %, so can obtain relatively between polymerization rate and polymer molecular weight
Good balance.Preferably, on the basis of lewis acidic total amount, the lewis acidic content shown in Formula II
It is 20～80 moles of %.It is highly preferred that on the basis of lewis acidic total amount, the Louis shown in Formula II
The content of this acid is 30～70 moles of %.
According to the initiator system of the present invention, 10～90 moles of % are (preferably 20～80 moles %, more excellent
Select 30～70 moles of %) lewis acid be the lewis acid shown in Formula II, remainder lewis acid
Can be at least one in lewis acid conventional in cationic polymerization initiators system.Such as: residue
Part lewis acid can be selected from BCl3、BF3、AlCl3、TiCl4、SnCl4、ZnCl2, formula III institute
The compound shown and R12 3Al,
In formula III, R11For C1～C8Straight or branched alkyl, preferably C1～C5Straight chain or
Alkyl group, more preferably ethyl, X41And X42Identical or different, the respectively one in halogen group
(such as-F ,-Cl ,-Br or-I), is preferably-Cl；
R12 3In Al, three R12Identical or different, can be each C1～C8Straight or branched alkyl,
It is preferably C1～C5Straight or branched alkyl.
The instantiation of the compound shown in formula III can include but not limited to dichloromethyl aluminum, two chloroethenes
Base aluminum, dichloro n-pro-pyl aluminum, two chloro isopropyl aluminum, dichloro n-butylaluminum and dichloro aluminium isobutyl.
R12 3The instantiation of Al can include but not limited to: trimethyl aluminium and triethyl aluminum.
Preferably, remainder lewis acid is the compound shown in formula III.That is, described lewis acid
It is preferably the lewis acid shown in Formula II and the compound shown in formula III, with lewis acidic total amount as base
Standard, the lewis acidic content shown in Formula II is 10～90 moles of %, preferably 20～80 moles %,
More preferably 30～70 moles of %.
It is highly preferred that described lewis acid is diethyl aluminum chloride and ethyl aluminum dichloride, with lewis acidic
On the basis of total amount, the content of diethyl aluminum chloride is 10～90 moles of %, preferably 20～80 moles %,
More preferably 30～70 moles of %.
According to the polymerization of the present invention, described lewis acidic content can be cationic polymerization field
Conventional amount used.Usually, described protogenic compound and the described lewis acidic mol ratio of can carrying can
Think 0.01～1: 1, preferably 0.02～0.5: 1, more preferably 0.04～0.3: 1, the most excellent
Elect 0.05～0.1: 1 as.
Described can carry protogenic compound can be in cationic polymerization field conventional various can
Carry protogenic compound.It is usually, described that can to carry protogenic compound can be H2O and/or
Bronsted acid, its instantiation can include but not limited to: H2O、HCl、HF、HBr、H2SO4、H2CO3、
H3PO4And HNO3.It is preferably, described that can to carry protogenic compound be HCl.
Conventional various methods can be used described monoolefine and conjugated diene and described initiator body
Each component contact in system, to be polymerized, forms monoolefine-conjugated diene copolymer.
In one embodiment of the invention, each component in described initiator system can be dissolved in
In solvent, and the mixture ageing that will obtain, obtain initiator solution；By described initiator solution with molten
The solution described monoolefine in polymer solvent and the mixing of described conjugated diene.
The lewis acid that the purpose of described ageing is to make in initiator system with can put forward protogenicization
Compound and activator form stable complexation initiating activity center, can carry out under normal conditions.Typically
Ground, described ageing can be at-100 DEG C to 20 DEG C, preferably-100 DEG C to 0 DEG C, more preferably-100 DEG C to-50
DEG C, carry out within the temperature range of further preferably-90 DEG C to-70 DEG C.The time of described ageing can be 10
Minute to 10 hours.Preferably, the time of described ageing is more than 30 minutes, and such as 30 minutes to 5
Hour.It is highly preferred that the time of described ageing is more than 60 minutes, such as 60 minutes to 120 minutes.
Described solvent can be various can to dissolve described Bronsted acid, described lewis acid and described activator
Liquid substance.Usually, described solvent can be selected from alkane, halogenated alkane and aromatic hydrocarbons, is preferably selected from
C3～C10Alkane, C1～C10Halogenated alkane and C6～C12Aromatic hydrocarbons.
As solvent, described alkane includes aliphatic alkane and alicyclic alkanes, such as C3～C10Alkane
Including C3～C10Aliphatic alkane and C3～C10Alicyclic alkanes.
As solvent, described halogenated alkane includes halogenated aliphatic alkane and halogenated cyclo alkane, as
C1～C10Halogenated alkane include C1～C10Halogenated aliphatic alkane and C3～C10Halogenated cyclo
Alkane.Halogen atom in described halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine or fluorine.Described
Halogenated alkane is preferably C1～C4Halogenated aliphatic alkane.
The instantiation of described solvent can include but not limited to: propane, normal butane, iso-butane, positive penta
Alkane, isopentane, neopentane, Pentamethylene., normal hexane, 2-methylpentane, 3-methylpentane, 2,3-diformazan
Base butane, hexamethylene, methyl cyclopentane, normal heptane, 2-methyl hexane, 3-methyl hexane, 2-ethyl
Pentane, 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-dimethyl oneself
Alkane, 3-ethyl hexane, 2，2，3-trimethyl-pentane, 2,3,3-trimethylpentanes, 2,4,4-trimethylpentanes,
2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3-
Dimethyl heptane, 2,4-dimethyl heptane, 3-ethyl heptane, 4-ethyl heptane, 2,3,4-trimethyl cyclohexanes,
2,3,5-trimethyl cyclohexanes, 2,4,5-trimethyl cyclohexanes, 2,2,3-trimethyl cyclohexanes, 2,2,4-trimethyl cyclohexanes,
2,2,5-trimethyl cyclohexanes, 2,3,3-trimethyl cyclohexanes, 2,4,4-trimethyl cyclohexanes, 2-methyl-3-ethyl hexane,
2-methyl-4-ethyl hexane, 3-methyl-3-ethyl hexane, 3-methyl-4-ethyl hexane, 3,3-diethyl penta
Alkane, 1-methyl-2-ethyl cyclohexane, 1-methyl-3-ethyl cyclohexane, 1-methyl-4-ethyl cyclohexane, just
Propyl cyclohexane, isopropyl cyclohexane, trimethyl-cyclohexane (include the various isomeries of trimethyl-cyclohexane
Body, such as 1,2,3-trimethyl-cyclohexanes, 1,2,4-trimethyl-cyclohexanes, 1,2,5-trimethyl-cyclohexanes, 1,3,5-
Trimethyl-cyclohexane), n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methyl nonyl
Alkane, 2,3-dimethyl octane, 2,4-dimethyl octane, 3-ethyl octane, 4-ethyl octane, 2,3,4-front threes
Base heptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane, 2,4,5-trimethylheptane, 2,4,6-tri-
Methyl heptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6-
Trimethylheptane, 2,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethyl heptane, 2-
Methyl-4-ethyl heptane, 2-methyl-5-ethyl heptane, 3-methyl-3-ethyl heptane, 4-methyl-3-ethyl heptan
Alkane, 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 basic ring
Hexane, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, t-butylcyclohexane,
Tetramethyl-ring hexane (include the various isomers of tetramethyl-ring hexane, such as 1,2,3,4-tetramethyl-ring hexanes,
1,2,4,5-tetramethyl-ring hexane, 1,2,3,5-tetramethyl-ring hexanes), a fluoromethane, difluoromethane, trifluoro
Methane, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluoroethane,
Difluoroethane, HFC-143a, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, two chloroethenes
Alkane, trichloroethane, sym-tetrachloroethane, Pentalin., carbon hexachloride, a fluoro-propane, difluoropropane, three
Fluoro-propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoropropane, a chloropropane,
Dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, eight chlorine third
Alkane, 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 neoprenes
Alkane, toluene, ethylbenzene and dimethylbenzene (including o-Dimethylbenzene, meta-xylene and xylol).
The concentration of described initiator solution can be conventional selection, is not particularly limited.Described initiator is molten
The consumption of liquid can carry out suitable selection according to concrete polymerizing condition, so that polymerization can be caused to be as the criterion.
Those skilled in the art can be determined by the experiment of limited number of time and be adequate to bring about under the teaching of prior art
The initiator amount of polymerization.
According to the polymerization of the present invention, described monoolefine can be commonly used in the art can carry out sun from
The monoolefine of son polymerization.Usually, described monoolefine is selected from the compound shown in formula IV,
In formula IV, R13And R14It is respectively C1～C5Straight or branched alkyl；Or R13For hydrogen,
R14For C3～C5Branched alkyl.
In the present invention, C1～C5Straight or branched alkyl include C1～C5Straight chained alkyl and C3～C5
Branched alkyl, its instantiation can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, 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-1-butene alkene, 3-methyl-1-butene, 2,3-dimethyl-1-butylene, 2-Methyl-1-pentene, 3-methyl
-1-amylene, 4-methyl-1-pentene, 2,3-dimethyl-1-amylene, 2,4-dimethyl-1-amylene, 2-methyl isophthalic acid-
Hexene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2,5-dimethyl-1-hexene and 2,4,4-tri-
Methyl-1-pentene.
Preferably, described monoolefine is isobutene..
The method according to the invention, described conjugated diene refers to the change in molecular structure containing conjugated double bond
Compound.Preferably, described conjugated diene is selected from the compound shown in Formula V,
In Formula V, R15、R16And R17Identical or different, respectively hydrogen or C1～C5Straight chain or
Alkyl group.
The instantiation of described conjugated diene can include but not limited to butadiene and/or isoprene.
It is highly preferred that described conjugated diene is isoprene.
The relative usage of the method according to the invention, described monoolefine and described conjugated diene can basis
The concrete application scenario of the polymer of final preparation carries out suitable selection.Usually, with described monoolefine
On the basis of the total amount of conjugated diene, the content of described monoolefine can be 80～99.5 weight %, excellent
Elect 90～98 weight % as；The content of described conjugated diene can be 0.5～20 weight %, is preferably
2～10 weight %.
According to the polymerization of the present invention, described polymer solvent can be that various being enough to makes polyreaction molten
The solvent carried out under liquid status, the most described polymer solvent can not only dissolve monoolefine and conjugated diene, and
And the polymer that polymerization is formed can be dissolved.Usually, described polymer solvent can be selected from alkane and (can be
Aliphatic alkane and/or alicyclic alkanes) and halogenated alkane, it is preferably selected from C3～C10Alkane and C1~
C10Halogenated alkane.Halogen atom in described halogenated alkane can be chlorine, bromine or fluorine, preferably chlorine
Or fluorine.Described halogenated alkane is preferably C1～C4Halogenated alkane.
According to the polymerization of the present invention, even if being polymerized in low polar polymeric solvent, also can be with height
Polymerization efficiency prepare the polymer of high molecular.Described low polar polymeric solvent can be such as described alkane
Hydrocarbon, it is also possible to for the mixture of described alkane Yu described halogenated alkane.It is described alkane at described polymer solvent
During the mixture of hydrocarbon and described halogenated alkane, on the basis of the total amount of described polymer solvent, described alkane
Content can be 20～99 volume %, preferably 40～99 volume %, more preferably 50～90 volume %；
The content of described halogenated alkane can be 1～80 volume %, preferably 1～60 volume %, more preferably
10～50 volume %.
The instantiation of described polymer solvent can include but 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-bis-
Methyl hexane, 3-ethyl hexane, 2，2，3-trimethyl-pentane, 2,3,3-trimethylpentanes, 2,4,4-trimethyls
Pentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane,
2,3-dimethyl heptanes, 2,4-dimethyl heptane, 3-ethyl heptane, 4-ethyl heptane, 2,3,4-trimethyls oneself
Alkane, 2,3,5-trimethyl cyclohexanes, 2,4,5-trimethyl cyclohexanes, 2,2,3-trimethyl cyclohexanes, 2,2,4-trimethyls
Hexane, 2,2,5-trimethyl cyclohexanes, 2,3,3-trimethyl cyclohexanes, 2,4,4-trimethyl cyclohexanes, 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 ring
Hexane, n-pro-pyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane (include trimethyl-cyclohexane
Various isomers, such as 1,2,3-trimethyl-cyclohexanes, 1,2,4-trimethyl-cyclohexanes, 1,2,5-3-methyl cyclohexanols
Alkane, 1,3,5-trimethyl-cyclohexanes), n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane,
5-methylnonane, 2,3-dimethyl octane, 2,4-dimethyl octane, 3-ethyl octane, 4-ethyl octane,
2,3,4-trimethylheptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane, 2,4,5-trimethylheptane,
2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane,
2,2,6-trimethylheptane, 2,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethyl heptane,
2-methyl-4-ethyl heptane, 2-methyl-5-ethyl heptane, 3-methyl-3-ethyl heptane, 4-methyl-3-ethyl
Heptane, 5-methyl-3-ethyl heptane, 4-methyl-4-ethyl heptane, 4-propyl group heptane, 3,3-diethyl oneself
Alkane, 3,4-diethylhexane, 2-methyl-3,3-diethylpentane, 1,2-diethyl cyclohexane, 1,3-diethyl
Butylcyclohexane, Isosorbide-5-Nitrae-diethyl cyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, t-butylcyclohexyl
Alkane, tetramethyl-ring hexane (include the various isomers of tetramethyl-ring hexane, such as 1,2,3,4-tetramethyl-rings
Hexane, 1,2,4,5-tetramethyl-ring hexanes, 1,2,3,5-tetramethyl-ring hexanes), a fluoromethane, difluoromethane,
Fluoroform, carbon tetrafluoride, monochloro methane, dichloromethane, chloroform, carbon tetrachloride, a fluorine second
Alkane, Difluoroethane, HFC-143a, tetrafluoroethane, pentafluoroethane, carbon hexa fluoride, monochlorethane, two
Ethyl chloride, trichloroethane, sym-tetrachloroethane, Pentalin., carbon hexachloride, a fluoro-propane, difluoropropane,
Trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, heptafluoro-propane, octafluoropropane, a chlorine third
Alkane, dichloropropane, trichloropropane, four chloropropanes, pentachloropropane, chlordene propane, heptachloropropane, eight
Chloropropane, 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 neoprenes
Alkane, four chlorobutanes, pentachlorobutane, chlordene butane, heptachlor butane, telodrine alkane, nine chlorobutanes and ten
Chlorobutane.
Described polymer solvent is preferably selected from pentane, normal hexane, normal heptane, monochloro methane, dichloromethane
And monochlorethane.
The consumption of described polymer solvent can be the conventional selection of this area.Usually, described polymer solvent
Consumption make total monomer concentration be 2～50 weight %, preferably 5～30 weight %, more preferably 5～
20 weight %.
According to the polymerization of the present invention, described cationic polymerization condition can be the conventional choosing of this area
Select.Usually, contacting of monoolefine and conjugated diene and each component in initiator system can be
-120 DEG C to 20 DEG C, preferably-100 DEG C to 0 DEG C, more preferably-100 DEG C to-40 DEG C, further preferably-90
DEG C to carrying out within the temperature range of-60 DEG C.According to the polymerization of the present invention, during described contact lasting
Between can be the conventional selection of this area, can be typically 10～180 minutes, preferably 30～120 points
Clock.
The method according to the invention, in a preferred embodiment, described activator is dichloro dicyan
Base benzoquinone (includes dichloro dicyano p-benzoquinone and dichloro dicyano neighbour's benzoquinone), and described lewis acid is formula
Lewis acid (preferably ethyl aluminum dichloride) shown in III and the lewis acid shown in Formula II are (preferably
Diethyl aluminum chloride), on the basis of described lewis acidic total amount, lewis acidic shown in formula III contains
Amount is 10～50 moles of %, and the lewis acidic content shown in Formula II is 50～90 moles of %, described poly-
Bonding solvent contains halogenated alkane and alkane, on the basis of the total amount of described polymer solvent, and described halogenated alkane
Content be 10～50 volume %, preferably 20～50 volume %, the content of described alkane is 50～90
Volume %, preferably 50～80 volume %.According to this preferred embodiment, can be with higher polymerization effect
Rate preparation has higher molecular weight (if weight average molecular weight is 3 × 105Monoolefine-conjugated diene above)
Hydrocarbon copolymer.This preferred embodiment in, on the basis of described lewis acidic total amount, formula III
Shown lewis acidic content is preferably 10～30 moles of %, the lewis acidic content shown in Formula II
It is preferably 70～90 moles of %, so can prepare and there is higher molecular weight (if weight average molecular weight is 5
×105Monoolefine-conjugated diene copolymer above).According to this preferred embodiment, polymerization is anti-
Should preferably carry out at a temperature of-70 DEG C to-120 DEG C, more preferably-80 DEG C extremely-100 DEG C.Preferred at this
In embodiment, in initiator system, the ratio between each component is not particularly limited, can be for institute above
The ratio stated, but, the described mol ratio that can carry protogenic compound and described activator is preferably
1: 0.5～1.5；Described protogenic compound and the described lewis acidic mol ratio of can carrying is preferably
0.04～0.1: 1.This preferred embodiment in, remaining reaction condition can be previously described bar
Part.
According to the polymerization of the present invention, another preferred embodiment in, described activator is four
Cyano group benzoquinone (including four cyano 1,4-benzoquinone and four cyano neighbour's benzoquinone) and/or DDQ (include
Dichloro dicyano p-benzoquinone and dichloro dicyano neighbour's benzoquinone), described lewis acid is the Louis shown in formula III
Lewis acid (preferably diethyl aluminum chloride) shown in this acid (preferably ethyl aluminum dichloride) and Formula II,
On the basis of described lewis acidic total amount, the lewis acidic content shown in formula III is 30～70 moles
%, the lewis acidic content shown in Formula II is 30～70 moles of %, old when preparing initiator solution
The change time is more than 30 minutes, and described polymer solvent is alkane.According to this preferred embodiment, i.e.
Make to be polymerized in higher temperature (such as not higher than-60 DEG C to-70 DEG C), also can be with higher polymerization effect
Rate preparation has higher molecular weight (if weight average molecular weight is 2.5 × 105Monoolefine-conjugation two above)
Olefin copolymer.It is highly preferred that described activator is DDQ (includes dichloro dicyano pair
Benzoquinone and dichloro dicyano neighbour's benzoquinone), so it is obtained in that higher polymerization efficiency.Preferred according to this
Embodiment, polyreaction is carried out at a temperature of-60 DEG C to-120 DEG C, preferably-80 DEG C to-90 DEG C.?
This preferred embodiment in, in initiator system, the ratio between each component is not particularly limited, permissible
For previously described ratio, but, described can carry protogenic compound and described activator mole
Ratio preferably 1: 0.8～1.5；Described protogenic compound and the described lewis acidic mol ratio of can carrying
It is preferably 0.04～0.1: 1.This preferred embodiment in, remaining reaction condition can be for institute above
The condition stated.
Polymerization according to the present invention, it is also possible to be included in and be polymerized the mixture that backward polymerization obtains
Middle interpolation polymerization terminator makes polyreaction terminate (such as alcohol).The present invention is for described polymerization
Kind and the consumption of agent are not particularly limited, and can be the conventional selection of this area, can terminate polymerization
Reaction is as the criterion, and repeats no more herein.
The present invention is described in detail below in conjunction with embodiment.
In following example and comparative example, weight method is used to measure polymer yield,
Polymer yield (%)=(gross weight of the monomer of the weight/addition of the polymer obtained) × 100%.
In following example and comparative example, the molecular weight of polymer and molecular weight distributing index use the day island proper
The LC-20A type liquid phase chromatograph of gel permeation that Tianjin company produces measures, and uses single aperture chromatographic columnWithFour post combinations.Flowing is oxolane mutually, and flow velocity is
0.7mL/min；Sample solution concentration is 2mg/mL, and sample size is 200 μ L；Test temperature is 35 DEG C；
Using single distribution polystyrene as standard sample.
In following example and comparative example, use the AVANCE400 commercially available from Bruker company of Switzerland
Nuclear magnetic resonance analyser, with CDC13Making solvent, TMS is internal standard, measures the monoolefine-conjugated diene of preparation
The degree of unsaturation of hydrocarbon copolymer is (that is, by isoprene in the monoolefine-conjugated diene copolymer of preparation
The content of the construction unit formed).
Solvent used in following example and comparative example and monomer before use, use commonly used in the art
Method refine, the preparation of polyreaction and initiator solution is all at the nitrogen being furnished with low temperature cryostat
Control box is carried out.
Embodiment 1～31 is for the method that the present invention is described.
Embodiment 1
(1) 0.0662g chloranil is dissolved in 80g and containing HCl (concentration is 0.0036mol/L)
Dichloromethane solution in, the solution obtained is cooled to-80 DEG C in advance, then in this solution order add
2.6mL concentration is the hexane solution of the ethyl aluminum dichloride (EADC) of 0.9mol/L and 1mL concentration is
The n-heptane solution of the diethyl aluminum chloride (DEAC) of 1.0mol/L, after mix homogeneously, by obtain
Mixed liquor is aged 80min at-80 DEG C, thus obtains initiator solution.Wherein, by weight, initiator
In solution, the content of chloranil is 800ppm.
(2) 250mL there-necked flask is placed in the low temperature cryostat that temperature control is-80 DEG C to-85 DEG C,
Add in there-necked flask successively 85mL be cooled to-80 DEG C normal hexane, 15mL be cooled to-80 DEG C different
Butylene and 0.5mL are cooled to the isoprene of-20 DEG C, mix homogeneously in advance, obtain monomer solution.To monomer
The initiator solution that in solution prepared by addition 10mL step (1), standing and reacting 30min after mix homogeneously,
Dropping initiator solution and course of reaction in control cryostat temperature be in-80 DEG C to-85 DEG C scope it
In.Reaction terminates to add in backward reactant mixture the methanol solution that 5mL contains 0.5 weight %NaOH,
To terminate polyreaction.Then mixed solution is placed in desolvation in hot bath, the solid obtained is entered
After row washing, it is dried to constant weight in 60 DEG C in vacuum drying oven, obtains monoolefine-conjugated diolefin copolymer
Thing.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Embodiment 2
Using side same as in Example 1 to be polymerized, except for the difference that, in step (2), dropping is drawn
Send out in agent solution and polymerization process, the temperature of cryostat is controlled the scope for being in-40 DEG C to-50 DEG C
Within, the consumption of initiator solution is 15mL, and polymerization reaction time is 50min.Polymer yield with
And the molecular weight of polymer, molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Embodiment 3
Method same as in Example 1 is used to be polymerized, except for the difference that, in step (1), EADC
The concentration of hexane solution be 0.9mol/L, consumption is the dense of the n-heptane solution of 1.9mL, DEAC
Degree is 1.0mol/L, and consumption is 1.7mL.Polymer yield and the molecular weight of polymer, molecular weight divide
Cloth index and degree of unsaturation, result is listed in Table 1.
Embodiment 4
Method same as in Example 3 is used to be polymerized, except for the difference that, in step (2), dropping
In initiator solution and polymerization process, the temperature of cryostat is controlled the model for being in-60 DEG C to-70 DEG C
Within enclosing, polymerization reaction time is 40min.Polymer yield and the molecular weight of polymer, molecular weight
Profile exponent and degree of unsaturation, result is listed in Table 1.
Embodiment 5
Method same as in Example 1 is used to be polymerized, except for the difference that, in step (1), EADC
The concentration of hexane solution be 0.9mol/L, consumption is the dense of the n-heptane solution of 1.1mL, DEAC
Degree is 1.0mol/L, and consumption is 2.3mL.Polymer yield and the molecular weight of polymer, molecular weight divide
Cloth index and degree of unsaturation, result is listed in Table 1.
Embodiment 6
(1) by 0.0602g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 80g and containing HCl (concentration
For 0.0040mol/L) dichloromethane solution in, the solution obtained is cooled to-85 DEG C in advance, then to this
The normal hexane sequentially adding the ethyl aluminum dichloride (EADC) that 2.8mL concentration is 0.9mol/L in solution is molten
Liquid and the n-heptane solution of diethyl aluminum chloride (DEAC) that 1.1mL concentration is 1.0mol/L, mixing
After Jun Yun, the mixed liquor obtained is placed in the cryostat of-85 DEG C ageing 100min, thus obtains initiator
Solution.Wherein, by weight, 2,3-bis-chloro-5 in initiator solution, the content of 6-dicyano p-benzoquinone is
730ppm。
(2) 250mL there-necked flask is placed in the low temperature cryostat that temperature control is-80 DEG C to-85 DEG C,
Add in there-necked flask successively 85mL be cooled to-80 DEG C normal hexane, 15mL be cooled to-80 DEG C different
Butylene and 0.5mL are cooled to the isoprene of-20 DEG C, mix homogeneously in advance, obtain monomer solution.To monomer
The initiator solution that in solution prepared by addition 10mL step (1), standing and reacting 30min after mix homogeneously,
Dropping initiator solution and course of reaction in control cryostat temperature be in-80 DEG C to-85 DEG C scope it
In.Reaction terminates to add in backward reactant mixture the methanol solution that 5mL contains 0.5 weight %NaOH,
To terminate polyreaction.Then mixed solution is placed in desolvation in hot bath, the solid obtained is entered
After row washing, it is dried to constant weight in 60 DEG C in vacuum drying oven, obtains monoolefine-conjugated diolefin copolymer
Thing.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Comparative example 1
Use method preparation initiator solution same as in Example 6 and be polymerized, except for the difference that, step
(1) do not use 2 suddenly, 3-bis-chloro-5,6-dicyano p-benzoquinone.Polymer yield and the molecule of polymer
Amount, molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Comparative example 2
Use method preparation initiator solution same as in Example 6 and be polymerized, except for the difference that, step
(1) does not use diethyl aluminum chloride, the i.e. ethyl aluminum dichloride of diethyl aluminum chloride equimolar amounts suddenly
Replace.Polymer yield and the molecular weight of polymer, molecular weight distributing index and degree of unsaturation, result
List in Table 1.
Embodiment 7
Method same as in Example 6 is used to be polymerized, except for the difference that, in step (2), dropping
In initiator solution and polymerization process, cryostat temperature is controlled the scope for being in-60 DEG C to-70 DEG C
Within, the consumption of initiator solution is 15mL, and polymerization reaction time is 40min.Polymer yield with
And the molecular weight of polymer, molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Embodiment 8
Method same as in Example 6 is used to be polymerized, except for the difference that, in step (1), dichloro
The concentration of the hexane solution of aluminium ethide is 0.9mol/L, and consumption is 2mL；The positive heptan of diethyl aluminum chloride
The concentration of alkane solution is 1.0mol/L, and consumption is 1.8mL.Polymer yield and the molecular weight of polymer,
Molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Embodiment 9
Method the same as in Example 8 is used to be polymerized, except for the difference that, in step (2), dropping
In initiator solution and polymerization process, the temperature of cryostat is controlled the model for being in-60 DEG C to-70 DEG C
Within enclosing, polymerization reaction time is 40min.Polymer yield and the molecular weight of polymer, molecular weight
Profile exponent and degree of unsaturation, result is listed in Table 1.
Embodiment 10
Method the same as in Example 8 is used to be polymerized, except for the difference that, in step (2), dropping
In initiator solution and polymerization process, the temperature of cryostat is controlled the model for being in-40 DEG C to-50 DEG C
Within enclosing, polymerization reaction time is 50min.Polymer yield and the molecular weight of polymer, molecular weight
Profile exponent and degree of unsaturation, result is listed in Table 1.
Embodiment 11
Method same as in Example 6 is used to be polymerized, except for the difference that, in step (1), dichloro
The concentration of the hexane solution of aluminium ethide is 0.9mol/L, and consumption is 1.2mL；Diethyl aluminum chloride is just
The concentration of n-heptane solution is 1.0mol/L, and consumption is 2.5mL.Polymer yield and the molecule of polymer
Amount, molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Embodiment 12
Using the method identical with 6 to be polymerized, except for the difference that, in step (1), digestion time is
60min.Polymer yield and the molecular weight of polymer, molecular weight distributing index and degree of unsaturation, knot
Fruit is listed in Table 1.
Embodiment 13
Method same as in Example 6 is used to be polymerized, except for the difference that, in step (1), ageing
Time is 30min.Polymer yield and the molecular weight of polymer, molecular weight distributing index and unsaturation
Degree, result is listed in Table 1.
Embodiment 14
Method same as in Example 6 is used to be polymerized, except for the difference that, in step (1), ageing
Time be 10min.Polymer yield and the molecular weight of polymer, molecular weight distributing index and insatiable hunger
And degree, result is listed in Table 1.
Embodiment 15
Method same as in Example 6 is used to be polymerized, except for the difference that, except for the difference that, step (1)
In, 2,3-bis-chloro-5, the tetrahydrochysene 1,4-benzoquinone of the weight such as 6-dicyano use replaces.Polymer yield and polymerization
The molecular weight of thing, molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Embodiment 16
Method same as in Example 6 is used to be polymerized, except for the difference that, except for the difference that, step (1)
In, 2,3-bis-chloro-5, the four cyano 1,4-benzoquinone of the weight such as 6-dicyano use replaces.Polymer yield and poly-
The molecular weight of compound, molecular weight distributing index and degree of unsaturation, result is listed in Table 1.
Embodiment 17
(1) by 0.0576g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 80g and containing HCl (concentration
For 0.0044mol/L) dichloromethane in, the solution obtained is cooled to-85 DEG C in advance, then to this solution
Middle order adds the hexane solution of EADC that 0.4mL concentration is 0.9mol/L and 3.2mL concentration is
The n-heptane solution (molar ratio of EADC Yu DEAC is 1/9) of the DEAC of 1.0mol/L, mixed
After closing uniformly, the mixed liquor obtained is placed in the cryostat of-85 DEG C ageing 60min.Wherein, by weight,
2,3-bis-chloro-5 in initiator solution, the content of 6-dicyano p-benzoquinone is 700ppm.
(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,
In two mouthfuls of flasks, add 85mL be successively cooled to normal hexane/monochloro methane mixed solution (its of-85 DEG C
In, the volume ratio of normal hexane/monochloro methane is 9/1), 15mL be cooled to isobutene. and the 0.5mL of-85 DEG C
It is cooled to the isoprene of-20 DEG C, mix homogeneously in advance, obtains monomer solution.10mL is added in monomer solution
Initiator solution prepared by step (1), standing and reacting 30min after mix homogeneously, dropping initiator is molten
Liquid and course of reaction control cryostat temperature for being within the scope of-80 DEG C to-85 DEG C.After reaction terminates
The methanol solution that 5mL contains 0.5 weight %NaOH is added in reactant mixture, anti-to terminate polymerization
Should.Then mixed solution is placed in desolvation in hot bath, after the solid obtained is washed,
Vacuum drying oven is dried to constant weight in 60 DEG C, obtains monoolefine-conjugated diene copolymer.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Comparative example 3
Use the method identical with embodiment 17 to be polymerized, except for the difference that, in step (1), do not make
With 2,3-bis-chloro-5,6-dicyano p-benzoquinone.Measure the weight of the polymer obtained, calculate polymer yield,
And measuring the molecular weight of polymer, molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 18
Use the method identical with embodiment 17 to be polymerized, except for the difference that, in step (2), keep
The total amount of normal hexane and monochloro methane is constant, and the volume ratio adjusting normal hexane and monochloro methane is 8/2.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 19
Use the method identical with embodiment 17 to be polymerized, except for the difference that, in step (2), keep
The total amount of normal hexane and monochloro methane is constant, and the volume ratio adjusting normal hexane and monochloro methane is 7/3.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 20
Use the method identical with embodiment 17 to be polymerized, except for the difference that, in step (2), keep
The total amount of normal hexane and monochloro methane is constant, and the volume ratio adjusting normal hexane and monochloro methane is 6/4.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 21
Use and be polymerized with embodiment 17 same procedure, except for the difference that, in step (2), just keeping
The total amount of hexane and monochloro methane is constant, and the volume ratio adjusting normal hexane and monochloro methane is 5/5.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight and
Molecular weight distributing index, result is listed in table 2.
Embodiment 22
(1) by 0.0652g 2,3-bis-chloro-5,6-dicyano p-benzoquinone is dissolved in 80g and containing HCl (concentration
For 0.0044mol/L) dichloromethane in, the solution obtained is cooled to-85 DEG C in advance, then to this solution
Middle order adds the hexane solution of EADC that 2.8mL concentration is 0.9mol/L and 1.2mL concentration is
The toluene solution (molar ratio of EADC Yu DEAC is 7/3) of the DEAC of 0.9mol/L, mixing
After Jun Yun, the mixed liquor obtained is placed in the cryostat of-85 DEG C ageing 60min.Wherein, by weight,
2,3-bis-chloro-5 in initiator solution, the content of 6-dicyano p-benzoquinone 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,
In two mouthfuls of flasks, add 85mL be successively cooled to normal hexane/monochloro methane mixed solution (its of-85 DEG C
In, the volume ratio of normal hexane/monochloro methane is 9/1), 15mL be cooled to isobutene. and the 0.5mL of-85 DEG C
It is cooled to the isoprene of-20 DEG C, mix homogeneously in advance, obtains monomer solution.10mL is added in monomer solution
Initiator solution prepared by step (1), standing and reacting 40min after mix homogeneously, dropping initiator is molten
Liquid and course of reaction control cryostat temperature for being within the scope of-80 DEG C to-85 DEG C.After reaction terminates
The methanol solution that 5mL contains 0.5 weight %NaOH is added in reactant mixture, anti-to terminate polymerization
Should.Then mixed solution is placed in desolvation in hot bath, after the solid obtained is washed,
Vacuum drying oven is dried to constant weight in 60 DEG C, obtains monoolefine-conjugated diene copolymer.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 23
Use the method identical with embodiment 22 to be polymerized, except for the difference that, in step (1), keep
The total amount of EADC with DEAC is constant, adjusts the mol ratio of EADC Yu DEAC in initiator solution
Example is 5/5.Measure the weight of the polymer obtained, calculate polymer yield, and measure dividing of polymer
Son amount, molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 24
Use the method identical with embodiment 22 to be polymerized, except for the difference that, in step (1), keep
The total amount of EADC with DEAC is constant, adjusts the mol ratio of EADC Yu DEAC in initiator solution
Example is 3/7.Measure the weight of the polymer obtained, calculate polymer yield, and measure dividing of polymer
Son amount, molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 25
(1) 0.0651g chloranil is dissolved in 80g and containing HCl (concentration is 0.0042mol/L)
Dichloromethane solution in, the solution obtained is cooled to-85 DEG C in advance, then in this solution order add
2.8mL concentration is the hexane solution of the EADC of 0.9mol/L and 1.1mL concentration is 1.0mol/L's
The n-heptane solution (EADC/DEAC molar ratio is 7/3) of DEAC, after mix homogeneously, will obtain
Mixed liquor be placed in-85 DEG C ageing 60min.Wherein, by weight, chloranil in initiator solution
Content be 800ppm.
(2) use the method identical with embodiment 22 be polymerized, except for the difference that, keep normal hexane with
The total amount of monochloro methane is constant, and the volume ratio adjusting normal hexane and monochloro methane is 6/4.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 26
Use the method identical with embodiment 25 to be polymerized, except for the difference that, in step (1), keep
The total amount of EADC with DEAC is constant, and the mol ratio adjusting EADC/DEAC is 5/5.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 27
Use the method identical with embodiment 25 to be polymerized, except for the difference that, in step (1), keep
The total amount of EADC with DEAC is constant, and the mol ratio adjusting EADC/DEAC is 3/7.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Comparative example 4
Use the method identical with embodiment 27 to be polymerized, except for the difference that, in step (1), cause
Agent solution does not contains chloranil.Measure the weight of the polymer obtained, calculate polymer yield, and survey
Determining the molecular weight of polymer, molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 28
Using the method identical with embodiment 25 to be polymerized, except for the difference that, digestion time is 30min.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 29
Using the method identical with embodiment 25 to be polymerized, except for the difference that, digestion time is 10min.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 30
The method identical with embodiment 25 is used to be polymerized, except for the difference that, in step (1), tetrachloro
The tetrahydrochysene 1,4-benzoquinone of the weight such as 1,4-benzoquinone use replaces.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
Embodiment 31
The method identical with embodiment 25 is used to be polymerized, except for the difference that, in step (1), tetrachloro
The four cyano 1,4-benzoquinone of the weight such as 1,4-benzoquinone use replaces.
Measure the weight of polymer obtained, calculate polymer yield, and measure polymer molecular weight,
Molecular weight distributing index and degree of unsaturation, result is listed in table 2.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a cationic polymerization process, the method is included under solution polymerization condition, by least one
Monoolefine contacts with each component in initiator system with at least one conjugated diene in polymer solvent,
Described initiator system contains at least one can carry protogenic compound, at least one Louis
Acid and at least one activator, described activator is selected from shown in the compound shown in Formulas I-1 and Formulas I-2
Compound,
In Formulas I-1 and Formulas I-2, R1、R2、R3、R4、R5、R6、R7And R8It is respectively-H ,-X1、
-NO2、With the one in-CN, X1And X2It is respectively the one in halogen group；
The lewis acid of 10～90 moles of % is the lewis acid shown in Formula II,
In Formula II, R9And R10It is respectively C1～C8Straight or branched alkyl, X3For in halogen group
One；
Described monoolefine is selected from the compound shown in formula IV,
In formula IV, R13And R14It is respectively C1～C5Straight or branched alkyl；Or R13For hydrogen,
R14For C3～C5Branched alkyl；
Described conjugated diene is selected from the compound shown in Formula V,
In Formula V, R15、R16And R17It is respectively hydrogen or C1～C5Straight or branched alkyl.
Method the most according to claim 1, wherein, described can carry protogenic compound with
The mol ratio of described activator is 1:0.01～3, preferably 1:0.1～2.8, more preferably 1:0.2～
2.5, more preferably 1:0.8～1.5.
Method the most according to claim 1 and 2, wherein, described activator selected from tetrahydrochysene benzoquinone,
Tetrachloroquinone, four cyano benzoquinone and DDQ.
Method the most according to claim 1, wherein, in Formula II, X3For-Cl；Preferably, formula
Lewis acid shown in II is diethyl aluminum chloride.
5. according to the method described in claim 1 or 4, wherein, remainder lewis acid is formula III
Shown compound,
In formula III, R11For C1～C8Straight or branched alkyl, X41And X42It is respectively halogen group
In one；
Preferably, remainder lewis acid is ethyl aluminum dichloride.
6. according to the method described in any one in claim 1,4 and 5, wherein, 20～80 moles
The lewis acid of % is the lewis acid shown in Formula II, and the preferably lewis acid of 30～70 moles of % is formula
Lewis acid shown in II.
7. according to the method described in any one in claim 1 and 4～6, wherein, described can carry
Protogenic compound and described lewis acidic mol ratio are 0.01～1:1, preferably 0.02～0.5:
1, more preferably 0.04～0.3:1, more preferably 0.05～0.1:1.
8. according to the method described in any one in claim 1,2 and 7, wherein, described can carry
Protogenic compound is H2O and/or Bronsted acid, preferably HCl.
Method the most according to claim 1, wherein, described contact-120 DEG C to 20 DEG C, excellent
Select-100 DEG C of temperature models to 0 DEG C, more preferably-100 DEG C to-40 DEG C, further preferably-90 DEG C to-60 DEG C
Carry out in enclosing.
10. according to the method described in any one in claim 1～9, wherein, that at least one is single
The method that alkene contacts with each component in described initiator system with at least one conjugated diene includes:
Each component in described initiator system is dissolved in solvent, and the mixture ageing that will obtain, obtain
Initiator solution；By described initiator solution and the described monoolefine being dissolved in polymer solvent and described common
Yoke alkadienes mixes.
11. methods according to claim 10, wherein, the time of described ageing be 10 minutes extremely
10 hours, preferably more than 30 minutes, more preferably more than 60 minutes, more preferably 60 points
Clock was to 120 minutes.
12. methods according to claim 10, wherein, described ageing-100 DEG C to 20 DEG C,
Preferably-100 DEG C temperature to 0 DEG C, more preferably-100 DEG C to-50 DEG C, further preferably-90 DEG C to-70 DEG C
In the range of carry out.
13. methods according to claim 1, wherein, with described monoolefine and described conjugated diene
On the basis of the total amount of hydrocarbon, the content of described monoolefine is 80～99.5 weight %, preferably 90～98 weights
Amount %；The content of described conjugated diene is 0.5～20 weight %, preferably 2～10 weight %.
14. according to the method described in any one in claim 1～13, wherein, described conjugated diene
Hydrocarbon is isoprene；And/or
Described monoolefine is isobutene..
15. methods according to claim 1, wherein, described polymer solvent selects alkane and alkyl halide
Hydrocarbon, is preferably selected from C1～C10Halogenated alkane and C3～C10Alkane.
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| US6028144A (en) * | 1990-07-24 | 2000-02-22 | Exxon Chemical Patents, Inc. | Composition for the carcass |
| CN102702409A (en) * | 2012-06-07 | 2012-10-03 | 北京石油化工学院 | Technology for directly producing halogenated butyl rubber using butyl glue prepared by solution 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6028144A (en) * | 1990-07-24 | 2000-02-22 | Exxon Chemical Patents, Inc. | Composition for the carcass |
| 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 |
| CN102702409A (en) * | 2012-06-07 | 2012-10-03 | 北京石油化工学院 | Technology for directly producing halogenated butyl rubber using butyl glue prepared by solution method |
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