CN104628919B - Method for preparing the rare-earth catalysis system and catalysis diene polymerization of high trans diene homopolymers and copolymer - Google Patents
Method for preparing the rare-earth catalysis system and catalysis diene polymerization of high trans diene homopolymers and copolymer Download PDFInfo
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Abstract
This application provides a kind of rare-earth catalysis system for preparing high trans diene polymer, comprising：The first helper component shown in rare earth compound, conjugated diolefin and Formula II shown in Formulas I；In Formulas I, Ln is rare earth；R is alkyl, substitution alkyl, aryl or substituted aryl；L is alcohols, sulfoxide type, amine or esters part；0≤x≤8,1≤y≤4；In Formula II, M is magnesium or zinc；R1And R2It independently is alkyl, aryl, substituted aryl or benzyl；The first helper component is (5~30) with the mol ratio of rare earth compound：1.The rare-earth catalysis system preferably also comprising alkyl aluminum compound etc., further improves catalysis activity.This application provides a kind of method for being catalyzed diene polymerization.The rare-earth catalysis system that the application is provided has preferable catalysis activity, can be catalyzed and high trans diene polymer is obtained.Ln(RSO3)3·xH2OyL Formulas I；R1MR2Formula II.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to a kind of rare earth for preparing high trans diene polymer
The method of catalyst system and catalyzing and catalysis diene polymerization.
Background technology
In recent years, with the progress and the development of social economy of science and technology, the requirement to elastomeric material kind and performance
Improve constantly.Wherein, the high trans-polybutadiene (TPBD) and high trans being polymerized by butadiene and isoprene monomer gather
Isoprene (TPI) rubber and high trans butadiene and isoprene copolymer rubber (TBIR) have unique performance, therefore
Cause the extensive attention of people.
High trans polymer refers to polymer of the transconfiguration molar content more than 65%, and the alkadienes of high trans structure
Polymer has good dynamic property, such as relatively low rolling resistance and compression heat generation, and excellent flexible resistance etc., it is
Develop the preferable sizing material of high-performance tire.Research about high trans polydiene just has started to early in late 1960s,
Mainly with titanium system, nickel system, chromium system and alcohol (sodium) alkene catalyst as catalyst system and catalyzing, high trans poly- two are synthesized using anion method
Alkene.
Wherein, due to there is big initiator amount, high cost and Polymer Processing poor-performing in alcohol (sodium) alkene catalyst system and catalyzing
The shortcomings of, and the visual field of people of gradually fading out.Nickel system, chromium system and vanadium system catalyst system and catalyzing are because catalytic efficiency is low and consumes energy high lacking
Point also limit its application.It is titanium system catalyst system and catalyzing to study now more, such as Chinese patent 95110352.0,
CN103387641A and CN103204973A are reported respectively：Anti-form-1 is prepared using carrying catalyst in titanium series, 4 structural contents are big
The anti-form-1 of polyisoprene, high trans butadiene isoprene copolymer and low-molecular-weight in 98%, 4 alkadienes are total to
Polymers.However, the reports on preparing high trans polydiene using rare-earth catalysis system few at present.
The content of the invention
In view of this, the application provides a kind of rare-earth catalysis system and catalysis for preparing high trans diene polymer
The method of diene polymerization, the rare-earth catalysis system that the application is provided has preferable catalysis activity.
The application provides a kind of rare-earth catalysis system for preparing high trans diene polymer, comprising：
Rare earth compound, conjugated diolefin and first helper component；
The rare earth compound has Formulas I formula：
Ln(RSO3)3·xH2OyL Formulas I；
Wherein, Ln is rare earth metal；R is selected from alkyl, substitution alkyl, aryl or substituted aryl；L is selected from alcohols part, Asia
Sulfone class part, amine part or esters part；0≤x≤8,1≤y≤4；
The molecular formula of the first helper component is as shown in Formula II：
R1MR2Formula II；
Wherein, M is selected from magnesium or zinc；R1And R2Independently selected from alkyl, aryl, substituted aryl or benzyl；
The first helper component is (5~30) with the mol ratio of rare earth compound：1.
Preferably, R1And R2Independently selected from phenyl, alkyl phenyl or C1~15 alkyl.
Preferably, the conjugated diolefin and the mol ratio of rare earth compound are (5~20)：1；
The conjugated diolefin is selected from butadiene or isoprene.
Preferably, Ln is selected from lanthanide series；R is selected from phenyl, alkyl phenyl, haloalkyl, C1~5 alkyl or nitrobenzene
Base.
Preferably, the alcohols part is selected from the fatty alcohol of phenmethylol or C2~15；The sulfoxide type part is selected from diformazan
Base sulfoxide or diphenyl sulfoxide；The amine part is selected from ethamine, diethylamine, triethylamine or N,N-dimethylformamide；It is described
Esters part is selected from TRI N BUTYL PHOSPHATE, triphenyl phosphate, diisobutyl phthalate or dioctyl phthalate.
Preferably, the system also includes second helper component, and the second helper component is selected from trialkylaluminium or hydrogenation
Alkyl aluminum；
The second helper component is (2~10) with the mol ratio of rare earth compound：1.
Preferably, the system also includes varsol.
The present invention also provides a kind of method for being catalyzed diene polymerization, comprises the following steps：
In the presence of rare-earth catalysis system, diolefinic monomer is carried out into polymerisation in varsol, obtain alkadienes
Polymer；The rare-earth catalysis system is included：
Rare earth compound, conjugated diolefin and first helper component；
The rare earth compound has Formulas I formula：
Ln(RSO3)3·xH2OyL Formulas I；
Wherein, Ln is rare earth metal；R is selected from alkyl, substitution alkyl, aryl or substituted aryl；L is selected from alcohols part, Asia
Sulfone class part, amine part or esters part；0≤x≤8,1≤y≤4；
The molecular formula of the first helper component is as shown in Formula II：
R1MR2Formula II；
Wherein, M is selected from magnesium or zinc；R1And R2Independently selected from alkyl, aryl, substituted aryl or benzyl；
The first helper component is (5~30) with the mol ratio of rare earth compound：1.
Preferably, the rare-earth catalysis system also includes second helper component, and the second helper component is selected from trialkyl
Aluminium or alkyl aluminium hydride；
The charging sequence of the polymerisation includes：
Sequentially add solution, first helper component, rare earth compound and conjugation that diolefinic monomer and varsol are formed
The mixture that diolefin and second helper component are formed；
Or, sequentially add solution, first helper component, rare earth compound that diolefinic monomer and varsol formed and
The mixture that conjugated diolefin and first helper component and second helper component are formed；
Or, sequentially add solution, second helper component, rare earth compound that diolefinic monomer and varsol formed and
The mixture that conjugated diolefin and first helper component are formed；
Or, sequentially add solution, first helper component and the second assisted group that diolefinic monomer and varsol are formed
Divide the mixture of mixture, rare earth compound and conjugated diolefin and the first helper component formation for being formed.
Preferably, the rare earth metal and the mol ratio of diolefinic monomer are 0.5 × 10-4~2 × 10-4mol/mol。
Compared with prior art, the rare-earth catalysis system that the application is provided belongs to sulfoacid rare earth catalyst system and catalyzing, for preparing
High trans diene polymer, is rare earth catalyst composition, and its composition is mainly：Rare earth compound, conjugated diene shown in Formulas I
First helper component shown in hydrocarbon and Formula II, wherein, the mol ratio of the first helper component and rare earth compound for (5~
30)：1.The rare earth catalyst composition that the application is provided has preferable catalysis activity, in diene polymerization, can prepare
High trans diene homopolymers or copolymer, beneficial to application.
Further, the rare earth catalyst composition that the application is provided is also comprising the second assisted group based on alkyl constructed of aluminium
Point, further improve catalysis activity.
Specific embodiment
The technical scheme in the embodiment of the present application is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the application, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model of the application protection
Enclose.
This application provides a kind of rare earth catalyst composition for preparing high trans diene polymer, comprising：
Rare earth compound, conjugated diolefin and first helper component；
The rare earth compound has Formulas I formula：
Ln(RSO3)3·xH2OyL Formulas I；
Wherein, Ln is rare earth metal；R is selected from alkyl, substitution alkyl, aryl or substituted aryl；L is selected from alcohols part, Asia
Sulfone class part, amine part or esters part；0≤x≤8,1≤y≤4；
The molecular formula of the first helper component is as shown in Formula II：
R1MR2Formula II；
Wherein, M is selected from magnesium or zinc；R1And R2Independently selected from alkyl, aryl, substituted aryl or benzyl；
The first helper component is (5~30) with the mol ratio of rare earth compound：1.
The rare earth catalyst composition that the application is provided is a kind of for preparing high trans diene homopolymers and copolymer
Sulfoacid rare earth catalyst system and catalyzing, the better catalytic activity in diene polymerization.
The rare earth catalyst composition that the application is provided includes rare earth compound, and the rare earth compound has Formulas I formula, has
Body is sulfoacid rare earth complex compound.In Formulas I, Ln is rare earth metal, as the positive Tricationic of rare earth metal；Ln preferably is selected from group of the lanthanides
Element, more preferably any one from lanthanum (La), neodymium (Nd), samarium (Sm), erbium (Er) and ytterbium (Yb).
In Formulas I, R is selected from alkyl, substitution alkyl, aryl or substituted aryl, preferably is selected from C1~5 alkyl, haloalkyl, benzene
Base, alkyl phenyl or nitrobenzophenone, more preferably from phenyl, dodecylphenyl, trifluoromethyl, methyl or m-nitro base；I.e.
RSO3It preferably is selected from benzene sulfonic acid base, DBSA base, trifluoromethane sulfonic acid base, methanesulfonic acid base or m-nitrobenzene sulfonic acid base.
In the present invention, the alkyl refers to minusing an alkyl for hydrogen atom in alkane molecule, and the alkyl is considered as
It is that corresponding hydrocarbon loses a hydrogen atom (H) remaining group afterwards；The substitution alkyl is referred in substitution alkyl after hydrogen atom
Group.Accordingly, the aryl refers to minusing an alkyl for hydrogen atom in aromatic hydrocarbon molecule；The substituted aryl refers to
Be group in substituted aryl after hydrogen atom.
In Formulas I, L is electron reagent part, such as alcohols part, sulfoxide type part, amine part and esters part.Its
In, the alcohols part preferably is selected from the fatty alcohol of phenmethylol or C2~15, more preferably from ethanol, propyl alcohol, isopropanol, butanol, penta
Alcohol, hexanol, enanthol, isooctanol, cyclohexanol or phenmethylol；The sulfoxide type part preferably is selected from dimethyl sulfoxide (DMSO) or diphenyl is sub-
Sulfone；The amine part preferably is selected from ethamine, diethylamine, triethylamine or N,N-dimethylformamide；The esters part preferably is selected from
TRI N BUTYL PHOSPHATE, triphenyl phosphate, diisobutyl phthalate or dioctyl phthalate.
In Formulas I, x is the integer or non-integer between 0~8, i.e. 0≤x≤8, and x is preferably 2,3 or 4；Y is between 1~4
Integer or non-integer, i.e. 1≤y≤4, y are preferably 2 or 3.In embodiments of the present invention, specifically, the rare earth compound can have
There is the formula of formula 1~4：
Sm(CH3SO3)3·3H2O·2CH3(CH2)2OH formulas 1；
Formula 2；
Yb(NO2C6H4SO3)3·3H2O·3CH3(CH2)2NH2Formula 3；
Er(C18H29SO3)3·2H2O3DOP formulas 4.
The present invention is not particularly limited to the source of the rare earth compound, preferably prepares in accordance with the following methods：
Reacted after rare earth oxide and sulfonic acid solutions are mixed, obtained sulfoacid rare earth compound solution；
The sulfoacid rare earth compound solution is concentrated, sulfoacid rare earth compound crystal is obtained；
The sulfoacid rare earth compound crystal and electron donor reagent are mixed, and with tetrahydrofuran as solvent, in boiling
Condensing reflux under state, obtains the rare earth compound Ln (RSO shown in Formulas I3)3·xH2O·yL。
Proportionally can be added to rare earth oxide in sulfonic acid solutions in the reactor by the above method, preferably in stirring bar
Reacted under part, removed unreacted rare earth oxide by filtering, it is concentrated, obtain sulfoacid rare earth compound solution.
Wherein, in the rare earth oxide rare earth element is as it was noted above, i.e. rare earth oxide such as lanthana, samarium oxide
Deng；It is molten that the sulfonic acid solutions are preferably benzene sulfonic acid solution, dodecylbenzenesulfonic acid solution, trifluoromethane sulfonic acid solution, methanesulfonic acid
Liquid or m-nitrobenzene sulfonic acid solution；In one embodiment of the invention, the mol ratio of the rare earth oxide and sulfonic acid solutions
It is 10:1.The temperature of the reaction is preferably 40 DEG C~80 DEG C, more preferably 50 DEG C~70 DEG C；The time of the reaction is preferably
2 hours~10 hours, more preferably 3 hours~8 hours, you can obtain sulfoacid rare earth compound water solution.
After obtaining sulfoacid rare earth compound solution, can be put in for this concentrate again and be concentrated at room temperature by the above method, from
Crystal is so separated out, this crystal is the sulfoacid rare earth compound with the crystallization water.The concentration is well known to those skilled in the art
Technological means, the present invention is not particularly limited to this process.
After obtaining sulfoacid rare earth compound crystal, the above method can in proportion respectively the sulfoacid rare earth compound crystal
In electron donor reagent addition reactor, tetrahydrofuran is added as solvent, the condensing reflux under solution fluidized state, one
Solvent is boiled off after fixing time, and is dried to constant weight, obtain sulfoacid rare earth complex compound, i.e., the rare earth compound shown in Formulas I.
Wherein, the electron donor reagent is ligand L mentioned above, will not be repeated here.In implementation of the invention
In example, the sulfoacid rare earth compound crystal rare earth elements can be 1 with the mol ratio of electron donor L：(3~10), preferably
1：(4~8).The above method can add the tetrahydrofuran of 0~40mL；Also, the preferably 10 hours time of the condensing reflux~
24 hours, more preferably 12 hours~22 hours.
Except above-mentioned rare earth compound, the rare earth catalyst composition that the present invention is provided includes conjugated diolefin.In the present invention
In, the conjugated diolefin preferably is selected from butadiene or isoprene.The conjugated diolefin is excellent with the mol ratio of rare earth compound
Elect as (5~20)：1, more preferably (6~18)：1.
The rare earth catalyst composition includes first helper component, the molecular formula such as Formula II institute of the first helper component
Show.In Formula II, M is selected from magnesium or zinc, i.e., described first helper component can be magnesium compound or zinc compound.R1And R2Independently select
From alkyl, aryl, substituted aryl or benzyl.Therefore, the first helper component is specially alkyl magnesium, zinc alkyl, aryl magnesium, virtue
Base zinc, substituted aryl magnesium, substituted aryl zinc, benzyl magnesium or benzyl zinc.R1And R2Independently it preferably is selected from phenyl, alkyl phenyl, benzyl
Or C1~15 (carbon number is 1~15) alkyl, more preferably from phenyl, benzyl, p-methylphenyl or C1~14 alkyl.
In Formula II, R1And R2Can be with identical, it is also possible to different.In a preferred embodiment of the invention, R1And R2Select
From phenyl, p-methylphenyl, benzyl or C1~15 alkyl；R1And R2It preferably is selected from phenyl, p-methylphenyl, benzyl, methyl, ethyl, just
Propyl group, normal-butyl, isopropyl, isobutyl group, amyl group, hexyl, cyclohexyl or octyl group, i.e., described first helper component are preferably diformazan
Base magnesium, magnesium ethide, diη-propyl magnesium, di-n-butyl magnesium, diisopropyl magnesium, diisobutyl magnesium, diamyl magnesium, dihexyl magnesium,
Dicyclohexyl magnesium, dioctyl magnesium, diphenyl magnesium, di-p-tolyl magnesium, dibenzyl magnesium, zinc methide, diethyl zinc, diη-propyl
Zinc, di-n-butyl zinc, diisopropyl zinc, diisobutyl zinc, diamyl zinc, dihexyl zinc, dicyclohexyl zinc, dioctyl zinc, two
Phenyl zinc, di-p-tolyl zinc or dibenzyl zinc.In another preferred embodiment of the invention, R1It is ethyl, R2Selected from benzyl
Or p-methylphenyl, i.e., described first helper component is preferably Ethylbenzyl magnesium, ethyl p-methylphenyl magnesium, Ethylbenzyl zinc or ethyl
P-methylphenyl zinc.
In the present invention, the first helper component includes at least in above-mentioned magnesium compound and above-mentioned zinc compound
Kind, preferably include the mixture of above-mentioned magnesium compound and above-mentioned zinc compound.The first helper component and rare earth compound
Mol ratio is (5~30)：1, preferably (6~20)：1, more preferably (8~15)：1.When first helper component is above-mentioned magnesium
During compound, it can be (5~20) with the mol ratio of rare earth compound：1；When first helper component is above-mentioned zinc compound, its
Can be (5~30) with the mol ratio of rare earth compound：1.
The rare earth catalyst composition preferably also includes second helper component, and the second helper component is selected from trialkylaluminium
Or alkyl aluminium hydride, it preferably is selected from triisobutyl aluminium (Al (i-Bu)3), triethyl aluminum (AlEt3), diisobutylaluminium hydride (Al (i-
Bu)2) or ADEH (AlEt H2H).The mol ratio of the second helper component and rare earth compound be preferably (2~
10)：1, more preferably (4~8)：1.
The present invention provide rare earth catalyst composition preferably also include varsol, the varsol be preferably just oneself
One or more in alkane, pentane, hexamethylene and normal heptane, more preferably n-hexane.The varsol can individually add
Enter in composition, it is also possible to and remixed after any component in composition forms solution；The present invention is to the varsol
Consumption be not particularly limited.
The present invention is not particularly limited to the preparation method of the rare earth catalyst composition, can be by rare earth compound, conjugation
Diolefin, first helper component and second helper component are added in organic solvent such as varsol, it is also possible to first mixed and added again
Enter organic solvent.For charging sequence, rare earth compound, conjugated diolefin and second helper component can be mixed successively, obtained
Lucium, first helper component is added in polymer fluid, adds the lucium of preparation, obtains rare earth catalyst group
Compound；Also rare earth compound, conjugated diolefin, second helper component and first helper component can be mixed successively, obtains rare earth
Mixture, first helper component is added in polymer fluid, is subsequently adding the lucium of preparation, obtains rare earth catalyst combination
Thing；Can also successively by rare earth compound, conjugated diolefin and first helper component mix, obtain lucium, by first and/
Or second helper component is added in polymer fluid, the lucium of preparation is added, obtain rare earth catalyst composition.Prepare institute
Stating rare earth catalyst composition can be aged under nitrogen protection, in dry hydrogen-catalyst reactor.Wherein, the ageing
Temperature is preferably 0 DEG C~80 DEG C.The time of the ageing is preferably 30 minutes~24 hours.
The rare earth catalyst composition that the embodiment of the present application is provided belongs to sulfoacid rare earth catalyst system and catalyzing, for preparing high trans two
Olefin polymer, its composition is mainly：The first helper component shown in rare earth compound, conjugated diolefin, Formula II shown in Formulas I
With the second helper component based on alkyl constructed of aluminium, wherein, the first helper component is with the mol ratio of rare earth compound
(5~30)：1.The rare earth catalyst composition that the application is provided has preferable catalysis activity, in diene polymerization, can prepare
High trans diene homopolymers or copolymer are obtained, beneficial to application.
Present invention also provides a kind of polymerization of alkadienes, comprise the following steps：
In the presence of rare earth catalyst composition, diolefinic monomer is carried out into polymerisation in varsol, obtain diene
Hydrocarbon polymer；The rare earth catalyst composition is included：
Rare earth compound, conjugated diolefin and first helper component；
The rare earth compound has Formulas I formula：
Ln(RSO3)3·xH2OyL Formulas I；
Wherein, Ln is rare earth metal；R is selected from alkyl, substitution alkyl, aryl or substituted aryl；L is selected from alcohols part, Asia
Sulfone class part, amine part or esters part；0≤x≤8,1≤y≤4；
The molecular formula of the first helper component is as shown in Formula II：
R1MR2Formula II；
Wherein, M is selected from magnesium or zinc；R1And R2Independently selected from alkyl, aryl, substituted aryl or benzyl；
The first helper component is (5~30) with the mol ratio of rare earth compound：1.
The polymerization of the alkadienes that the present invention is provided is the method for being catalyzed diene polymerization, is related to sulfoacid rare earth catalyst
The usage of system, the catalyst system and catalyzing has preferable catalysis activity, can prepare high trans diolefin homopolymers or copolymer.
The embodiment of the present invention preferably under nitrogen protection, in the polymerizer of anhydrous and oxygen-free add diolefinic monomer and hydro carbons
The solution that solvent is formed, then adds rare-earth catalysis system, carries out polymerisation, obtains diene polymer.
In the present invention, the diolefinic monomer is diolefin, preferably at least one in butadiene and isoprene.
The varsol is preferably one or more in n-hexane, pentane, hexamethylene and normal heptane, more preferably n-hexane.
The present invention is not particularly limited to the consumption of the varsol；In one embodiment of the invention, can add in polymerizer
Enter the diolefin hexane solution that 20mL monomer concentrations are 20g/100mL.
The rare-earth catalysis system or rare earth catalyst that the present invention is added are rare earth catalyst composition mentioned above, to it
Component will not be repeated here；And the rare earth metal is preferably 0.5 × 10 with the mol ratio of diolefinic monomer-4~2 × 10- 4mol/mol.In the present invention, the rare earth catalyst composition preferably also includes second helper component, the second helper component
Selected from trialkylaluminium or alkyl aluminium hydride；The rare earth catalyst composition preferably also includes varsol, second assisted group
Point and varsol content it is consistent with mentioned above, also repeat no more herein.
In embodiments of the present invention, the charging sequence of the polymerisation is preferably included：
Sequentially add solution, first helper component, rare earth compound and conjugation that diolefinic monomer and varsol are formed
The mixture that diolefin and second helper component are formed；
Or, sequentially add solution, first helper component, rare earth compound that diolefinic monomer and varsol formed and
The mixture that conjugated diolefin and first helper component and second helper component are formed；
Or, sequentially add solution, second helper component, rare earth compound that diolefinic monomer and varsol formed and
The mixture that conjugated diolefin and first helper component are formed；
Or, sequentially add solution, first helper component and the second assisted group that diolefinic monomer and varsol are formed
Divide the mixture of mixture, rare earth compound and conjugated diolefin and the first helper component formation for being formed.
Wherein, the mixture for being formed for rare earth compound and conjugated diolefin and second helper component, charging sequence can
For：Rare earth compound, conjugated diolefin, second helper component.For rare earth compound and conjugated diolefin and the first assisted group
Divide the mixture formed with second helper component, charging sequence can be：Rare earth compound, conjugated diolefin, second helper component,
First helper component.For the mixture that rare earth compound and conjugated diolefin and first helper component are formed, charging sequence can
For：Rare earth compound, conjugated diolefin, first helper component.
In another embodiment of the present invention, the charging sequence of the polymerisation can also be：Sequentially add diene
Solution, first helper component, rare earth compound and conjugated diolefin and first helper component that hydrocarbon monomer and varsol are formed
The mixture of formation；Wherein, the charging sequence of the mixture that rare earth compound and conjugated diolefin and first helper component are formed
For：Rare earth compound, conjugated diolefin, first helper component.
In the present invention, the temperature of the polymerisation is preferably 40 DEG C~80 DEG C.The time of the polymerisation is preferred
It is 1 hour~24 hours, can terminates anti-with the ethanol solution containing the BHT that mass fraction is 1%
Should, settle out polymer in ethanol, through ethanol washing extruding after, be dried under vacuum to constant weight, obtain trans diolefin homopolymers or
Copolymer.
The rare earth catalyst composition that the application is provided has preferable catalysis activity, in diene polymerization, obtained two
The trans content of olefin homo or copolymer is high, beneficial to application.
For a further understanding of the application, with reference to embodiment the application is provided for preparing high trans alkadienes
The rare earth catalyst composition of polymer and the polymerization of alkadienes are specifically described.
Embodiment 1
1.1 is in the reactor 10 according to the mol ratio of neodymia and TFMS：1 ratio, neodymia is added
To in TFMS solution, 70 DEG C are heated under agitation, react 8 hours, by filtering unreacted neodymia
Remove, it is concentrated, the TFMS neodymium compound aqueous solution is obtained, then the concentrate is put at room temperature precipitation crystal naturally,
This crystal is the TFMS neodymium compound with the crystallization water.
1.2 press rare earth：The mol ratio of electron donor L is 1:3 ratio, it is respectively that the TFMS neodymium compound is brilliant
Body and electron donor L are added in reactor, add 40mL tetrahydrofurans as solvent, the condensing reflux under solution fluidized state
16h, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I.The structure of the rare earth compound is specifically joined
1 is shown in Table, table 1 is the structural formula of the rare earth compound shown in Formulas I prepared by the embodiment of the present invention 1~5.
The structural formula of the rare earth compound shown in Formulas I prepared by 1 embodiment of the present invention of table 1~5
Embodiment 2
2.1 is in the reactor 10 according to the mol ratio of lanthana and benzene sulfonic acid：1 ratio, benzene is added to by lanthana
In sulfonic acid solutions, 80 DEG C are heated under agitation, reacted 5 hours, removed unreacted lanthana by filtering, through dense
Contracting, obtains the benzene sulfonic acid lanthanum compound aqueous solution, then the concentrate is put at room temperature into precipitation crystal naturally, and this crystal is band knot
The benzene sulfonic acid lanthanum compound of brilliant water.
2.2 press rare earth：The mol ratio of electron donor L is 1:3 ratio, respectively the benzene sulfonic acid lanthanum compound crystal and
Electron donor L is added in reactor, adds 40mL tetrahydrofurans as solvent, the condensing reflux 16h under solution fluidized state,
Solvent is boiled off, and is dried to constant weight, obtain the rare earth compound shown in Formulas I, the structure of the rare earth compound is referring specifically to table
1。
Embodiment 3
3.1 is in the reactor 10 according to the mol ratio of samarium oxide and methanesulfonic acid：1 ratio, first is added to by samarium oxide
In sulfonic acid solutions, 40 DEG C are heated under agitation, reacted 10 hours, removed unreacted samarium oxide by filtering, warp
Concentration, obtains the methanesulfonic acid samarium compound aqueous solution, then the concentrate is put at room temperature into precipitation crystal naturally, and this crystal is band
The methanesulfonic acid samarium compound of the crystallization water.
3.2 press rare earth：The mol ratio of electron donor L is 1:3 ratio, respectively the methanesulfonic acid samarium compound crystal and
Electron donor L is added in reactor, adds 40mL tetrahydrofurans as solvent, the condensing reflux 16h under solution fluidized state,
Solvent is boiled off, and is dried to constant weight, obtain the rare earth compound shown in Formulas I, the structure of the rare earth compound is referring specifically to table
1。
Embodiment 4
4.1 is in the reactor 10 according to the mol ratio of erbium oxide and DBSA：1 ratio, by erbium oxide
It is added in dodecylbenzenesulfonic acid solution, 80 DEG C is heated under agitation, reacts 2 hours, by filtering unreacted
Erbium oxide remove, it is concentrated, obtain the DBSA erbium compound aqueous solution, then by the concentrate be put at room temperature from
Crystal is so separated out, this crystal is the DBSA erbium compound with the crystallization water.
4.2 press rare earth：The mol ratio of electron donor L is 1:3 ratio, respectively the DBSA erbium chemical combination
Thing crystal and electron donor L are added in reactor, add 40mL tetrahydrofurans as solvent, are condensed under solution fluidized state
Backflow 16h, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I, the structure tool of the rare earth compound
Body is referring to table 1.
Embodiment 5
5.1 is in the reactor 10 according to the mol ratio of ytterbium oxide and m-nitrobenzene sulfonic acid：1 ratio, by ytterbium oxide plus
Enter in m-nitrobenzene sulfonic acid solution, 80 DEG C are heated under agitation, react 2 hours, by filtering unreacted oxygen
Change ytterbium to remove, it is concentrated, the m-nitrobenzene sulfonic acid ytterbium compound aqueous solution is obtained, then the concentrate is put at room temperature precipitation naturally
Crystal, this crystal is the m-nitrobenzene sulfonic acid ytterbium compound with the crystallization water.
5.2 press rare earth：The mol ratio of electron donor L is 1:3 ratio, respectively the m-nitrobenzene sulfonic acid ytterbium compound
Crystal and electron donor L are added in reactor, add 40mL tetrahydrofurans as solvent, are condensed back under solution fluidized state
Stream 16h, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I, and the structure of the rare earth compound is specific
Referring to table 1.
Embodiment 6
By rare earth：The mol ratio of electron donor L is 1:3 ratio, the benzene sulfonic acid lanthanum chemical combination for respectively being prepared by embodiment 2.1
Thing crystal and electron donor L are added in reactor, add 40mL tetrahydrofurans as solvent, are condensed under solution fluidized state
Backflow 10h, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I.The structure tool of the rare earth compound
Referring to table 2, table 2 is the structural formula of the rare earth compound shown in Formulas I prepared by the embodiment of the present invention 6 and 7 to body.
The structural formula of the rare earth compound shown in Formulas I prepared by 2 embodiment of the present invention of table 6 and 7
Embodiment 7
By rare earth：The mol ratio of electron donor L is 1:3 ratio, the m-nitrobenzene sulfonic acid for respectively being prepared by embodiment 5.1
Ytterbium compound crystal and electron donor L are added in reactor, 40mL tetrahydrofurans are added as solvent, in solution fluidized state
Lower condensing reflux 10h, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I, the rare earth compound
Structure is referring specifically to table 2.
Embodiment 8
By rare earth：The mol ratio of electron donor L is 1:5 ratio, the TFMS neodymium for respectively being prepared by embodiment 1.1
Compound crystal and electron donor L are added in reactor, the condensing reflux 15h under solution fluidized state, boil off solvent, and dry
To constant weight, the rare earth compound shown in Formulas I is obtained.The structure of the rare earth compound is referring specifically to table 3, and table 3 is real for the present invention
Apply the structural formula of the rare earth compound shown in the Formulas I of the preparation of example 8~12.
The structural formula of the rare earth compound shown in Formulas I prepared by 3 embodiment of the present invention of table 8~12
Embodiment 9
By rare earth：The mol ratio of electron donor L is 1:5 ratio, the benzene sulfonic acid lanthanum chemical combination for respectively being prepared by embodiment 2.1
Thing crystal and electron donor L are added in reactor, the condensing reflux 15h under solution fluidized state, boil off solvent, and dry to perseverance
Weight, obtains the rare earth compound shown in Formulas I, and the structure of the rare earth compound is referring specifically to table 3.
Embodiment 10
By rare earth：The mol ratio of electron donor L is 1:5 ratio, the methanesulfonic acid samarium chemical combination for respectively being prepared by embodiment 3.1
Thing crystal and electron donor L are added in reactor, the condensing reflux 15h under solution fluidized state, boil off solvent, and dry to perseverance
Weight, obtains the rare earth compound shown in Formulas I, and the structure of the rare earth compound is referring specifically to table 3.
Embodiment 11
By rare earth：The mol ratio of electron donor L is 1:5 ratio, the m-nitrobenzene sulfonic acid for respectively being prepared by embodiment 5.1
Ytterbium compound crystal and electron donor L are added in reactor, and the condensing reflux 15h under solution fluidized state boils off solvent, and do
Dry to obtain the rare earth compound shown in Formulas I to constant weight, the structure of the rare earth compound is referring specifically to table 3.
Embodiment 12
By rare earth：The mol ratio of electron donor L is 1:5 ratio, the detergent alkylate sulphur for respectively being prepared by embodiment 4.1
Sour erbium compound crystal and electron donor L are added in reactor, and the condensing reflux 15h under solution fluidized state boils off solvent, and
Dry to constant weight, obtain the rare earth compound shown in Formulas I, the structure of the rare earth compound is referring specifically to table 3.
Embodiment 13
By rare earth：The mol ratio of electron donor L is 1:3 ratio, the TFMS neodymium for respectively being prepared by embodiment 1.1
Compound crystal and electron donor L are added in reactor, 30mL tetrahydrofurans are added as solvent, under solution fluidized state
Condensing reflux 10h, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I.The knot of the rare earth compound
Referring specifically to table 4, table 4 is the structural formula of the rare earth compound shown in Formulas I prepared by the embodiment of the present invention 13~16 to structure.
The structural formula of the rare earth compound shown in Formulas I prepared by 4 embodiment of the present invention of table 13~16
Embodiment 14
By rare earth：The mol ratio of electron donor L is 1:3 ratio, the benzene sulfonic acid lanthanum chemical combination for respectively being prepared by embodiment 2.1
Thing crystal and electron donor L are added in reactor, add 30mL tetrahydrofurans as solvent, are condensed under solution fluidized state
Backflow 10h, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I, the structure tool of the rare earth compound
Body is referring to table 4.
Embodiment 15
By rare earth：The mol ratio of electron donor L is 1:3 ratio, the m-nitrobenzene sulfonic acid for respectively being prepared by embodiment 5.1
Ytterbium compound crystal and electron donor L are added in reactor, 30mL tetrahydrofurans are added as solvent, in solution fluidized state
Lower condensing reflux 10h, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I, the rare earth compound
Structure is referring specifically to table 4.
Embodiment 16
By rare earth：The mol ratio of electron donor L is 1:3 ratio, the detergent alkylate sulphur for respectively being prepared by embodiment 4.1
Sour erbium compound crystal and electron donor L are added in reactor, 30mL tetrahydrofurans are added as solvent, in solution boiling-like
Condensing reflux 10h under state, boils off solvent, and dries to constant weight, obtains the rare earth compound shown in Formulas I, the rare earth compound
Structure referring specifically to table 4.
Embodiment 17~20
Under nitrogen protection, in dry hydrogen-catalyst reactor, 1 × 10 is sequentially added-4Mol rare earth compounds, 0.5mL
2mol/L butadiene hexane solution and 0.25mL 2.0mol/L AlEt3Hexane solution, wherein, butadiene and rare earth
The mol ratio of compound rare earth elements is 10：1, the mol ratio 5 of triethyl aluminum and rare earth compound rare earth elements：1；Add again
4.25mL hexanes, it is 2 × 10 to be made into rare earth concentration-5The rare earth mixed liquor of mol/mL, in ageing 30 minutes at 80 DEG C.
Under nitrogen protection, it is 20g/100mL fourths two to 20mL monomer concentrations are sequentially added in the polymerizer of anhydrous and oxygen-free
Alkene hexane solution and concentration are 2 × 10-3The first helper component hexane solution of mol/mL, then adds the rare earth of preparation to mix
Liquid；The caltalyst series rare earth element (by taking Nd as an example) is 1 × 10 with the mol ratio of addition monomer-4Mol/mol, in anti-at 50 DEG C
Answer 8 hours, with the ethanol solution terminating reaction containing the BHT that mass fraction is 1%, in ethanol
Settle out polymer, after being extruded through ethanol washing, is dried under vacuum to constant weight, respectively obtains polybutadiene.Main experimental conditions and knot
Referring to table 5, table 5 is the main experimental conditions and result of embodiment 17~20 to fruit.
The main experimental conditions and result of the embodiment 17~20 of table 5
Embodiment 21~23
Under nitrogen protection, in dry hydrogen-catalyst reactor, 1 × 10 is sequentially added-4Mol rare earth compounds,
The isoprene hexane solution of the 2mol/L of 0.25mL, the Al (i-Bu) of the 2.0mol/L of 0.1mL2H hexane solutions and 0.5mL's
The dioctyl magnesium of 2.0mol/L, wherein, isoprene is 5 with the mol ratio of rare earth compound rare earth elements：1, hydrogenation two is different
The mol ratio 2 of butyl aluminium and rare earth compound rare earth elements：1, dioctyl magnesium and rare earth compound rare earth elements mole
Than being 10：1；4.15mL hexanes are added again, and it is 2 × 10 to be made into rare earth concentration-5The rare earth mixed liquor of mol/mL, in ageing at 0 DEG C
24 hours.
Under nitrogen protection, it is 20g/100mL isoamyls to 20mL monomer concentrations are sequentially added in the polymerizer of anhydrous and oxygen-free
Diene hexane solution and concentration are 2 × 10-3The first helper component hexane solution of mol/mL, then adds the rare earth of preparation to mix
Liquid；The caltalyst series rare earth element (by taking Nd as an example) is 1.5 × 10 with the mol ratio of addition monomer-4Mol/mol, in 40 DEG C of bars
Reacted 10 hours under part, with the ethanol solution terminating reaction containing the BHT that mass fraction is 1%, in
Settle out polymer in ethanol, after being extruded through ethanol washing, is dried under vacuum to constant weight, respectively obtains polyisoprene.Major experimental
, referring to table 6, table 6 is the main experimental conditions and result of embodiment 21~23 for condition and result.
The main experimental conditions and result of the embodiment 21~23 of table 6
Embodiment 24~26
Under nitrogen protection, in dry hydrogen-catalyst reactor, 1 × 10 is sequentially added-4Mol rare earth compounds, 0.5mL
2mol/L isoprene hexane solution, the Al (i-Bu) of the 2.0mol/L of 0.25mL3Hexane solution and 0.25mL's
The di-n-butyl zinc of 2.0mol/L, wherein, isoprene is 10 with the mol ratio of rare earth compound rare earth elements：1, three isobutyls
The mol ratio 5 of base aluminium and rare earth compound rare earth elements：1, di-n-butyl zinc and rare earth compound rare earth elements mole
Than being 5：1；4.0mL hexanes are added again, and it is 2 × 10 to be made into rare earth concentration-5The rare earth mixed liquor of mol/mL, in being aged 5 at 50 DEG C
Hour.
Under nitrogen protection, it is 20g/100mL butadiene-different to 20mL monomer concentrations are added in the polymerizer of anhydrous and oxygen-free
Pentadiene hexane solution, wherein butadiene are 80 with isoprene monomer mol ratio:20, it is 2 × 10 to add concentration-3mol/mL
First helper component hexane solution, then add the rare earth mixed liquor of preparation；The caltalyst series rare earth element (is with Nd
Example) with add monomer mol ratio be 0.5 × 10-4Mol/mol, reacts 1 hour under the conditions of 80 DEG C, is with containing mass fraction
The ethanol solution terminating reaction of 1% BHT, settle out polymer in ethanol, is squeezed through ethanol washing
After pressure, constant weight is dried under vacuum to, respectively obtains butadiene isoprene copolymer.Main experimental conditions and result referring to table 7,
Table 7 is the main experimental conditions and result of embodiment 24~26.
The main experimental conditions and result of the embodiment 24~26 of table 7
Embodiment 27~30
Under nitrogen protection, in dry hydrogen-catalyst reactor, 1 × 10 is sequentially added-4Mol rare earth compounds, 1.0mL
2mol/L butadiene hexane solution and 0.5mL 2.0mol/L diisopropyl magnesium, wherein, butadiene and rare earth compound
The mol ratio of rare earth elements is 20：1, diisopropyl magnesium is 10 with the mol ratio of rare earth compound rare earth elements：1；Mend again
Plus 3.5mL hexanes, it is 2 × 10 to be made into rare earth concentration-5The rare earth mixed liquor of mol/mL, in ageing 2 hours at 70 DEG C.
Under nitrogen protection, to added in the polymerizer of anhydrous and oxygen-free 20mL monomer concentrations be 20g/100mL butadiene oneself
Alkane solution, it is 2 × 10 to add concentration-3The first helper component and/or second helper component hexane solution of mol/mL, then add
Enter the rare earth mixed liquor of preparation；The caltalyst series rare earth element (by taking Nd as an example) is 2.0 × 10 with the mol ratio of addition monomer- 4Mol/mol, reacts 24 hours, with the second containing the BHT that mass fraction is 1% under the conditions of 60 DEG C
Alcoholic solution terminating reaction, settle out polymer in ethanol, after being extruded through ethanol washing, is dried under vacuum to constant weight, respectively obtains poly-
Butadiene.
, referring to table 8, table 8 is the main experimental conditions and result of embodiment 27~30 for main experimental conditions and result.
The main experimental conditions and result of the embodiment 27~30 of table 8
Embodiment 31~33
Under nitrogen protection, in dry hydrogen-catalyst reactor, 1 × 10 is sequentially added-4Mol rare earth compounds, 0.5mL
The butadiene hexane solution of 2mol/L, the first helper component magnesium compound of the 2.0mol/L of 0.25mL and 0.25mL
The AlEt of 2.0mol/L2H hexane solutions, wherein, butadiene is 10 with the mol ratio of rare earth compound rare earth elements：1, first
Helper component is 5 with the mol ratio of rare earth compound rare earth elements：1, ADEH and rare earth compound Rare Earth Elements
The mol ratio 5 of element：1；4.0mL hexanes are added again, and it is 2 × 10 to be made into rare earth concentration-5The rare earth mixed liquor of mol/mL, at 60 DEG C
Ageing 3 hours.
Under nitrogen protection, to added in the polymerizer of anhydrous and oxygen-free 20mL monomer concentrations be 20g/100mL butadiene oneself
Alkane solution, it is 2 × 10 to add concentration-3The first helper component zinc compound hexane solution of mol/mL, then adds what is prepared
Rare earth mixed liquor；The caltalyst series rare earth element (by taking Nd as an example) is 1.0 × 10 with the mol ratio of addition monomer-4Mol/mol,
Reacted 15 hours under the conditions of 70 DEG C, with the ethanol solution end containing the BHT that mass fraction is 1%
Only react, settle out polymer in ethanol, after being extruded through ethanol washing, be dried under vacuum to constant weight, respectively obtain polybutadiene.It is main
Want experiment condition and result referring to table 9, table 9 is the main experimental conditions and result of embodiment 31~33.
The main experimental conditions and result of the embodiment 31~33 of table 9
As seen from the above embodiment, in the embodiment of the present application, urged for preparing the rare earth of high trans diene polymer
Change composition and belong to sulfoacid rare earth catalyst system and catalyzing, shown in its rare earth compound main as shown in Formulas I, conjugated diolefin, Formula II
First helper component and based on alkyl constructed of aluminium second helper component composition.The rare earth catalyst composition that the application is provided
With preferable catalysis activity, in diene polymerization, high trans diene homopolymers or copolymer can be prepared, beneficial to should
With.
Claims (10)
1. a kind of rare-earth catalysis system for preparing high trans diene polymer, comprising：
Rare earth compound, conjugated diolefin and first helper component；
The rare earth compound has Formulas I formula：
Ln(RSO3)3·xH2OyL Formulas I；
Wherein, Ln is rare earth metal；R is selected from alkyl, substitution alkyl, aryl or substituted aryl；L is selected from alcohols part, sulfoxide type
Part, amine part or esters part；0≤x≤8,1≤y≤4；
The molecular formula of the first helper component is as shown in Formula II：
R1MR2Formula II；
Wherein, M is selected from magnesium or zinc；R1And R2Independently selected from alkyl, aryl, substituted aryl or benzyl；
The first helper component is (5~30) with the mol ratio of rare earth compound：1.
2. system according to claim 1, it is characterised in that R1And R2Independently selected from phenyl, alkyl phenyl or C1~15
Alkyl.
3. system according to claim 1, it is characterised in that the conjugated diolefin is with the mol ratio of rare earth compound
(5~20)：1；
The conjugated diolefin is selected from butadiene or isoprene.
4. system according to claim 1, it is characterised in that Ln is selected from lanthanide series；R is selected from phenyl, alkyl phenyl, halogen
Substituted alkyl, C1~5 alkyl or nitrobenzophenone.
5. system according to claim 1, it is characterised in that the alcohols part is selected from the fat of phenmethylol or C2~15
Alcohol；The sulfoxide type part is selected from dimethyl sulfoxide (DMSO) or diphenyl sulfoxide；The amine part is selected from ethamine, diethylamine, three second
Amine or N,N-dimethylformamide；The esters part is selected from TRI N BUTYL PHOSPHATE, triphenyl phosphate, the isobutyl of phthalic acid two
Ester or dioctyl phthalate.
6. the system according to any one of Claims 1 to 5, it is characterised in that the system also includes second helper component,
The second helper component is selected from trialkylaluminium or alkyl aluminium hydride；
The second helper component is (2~10) with the mol ratio of rare earth compound：1.
7. the system according to any one of Claims 1 to 5, it is characterised in that the system also includes varsol.
8. a kind of method for being catalyzed diene polymerization, comprises the following steps：
In the presence of rare-earth catalysis system, diolefinic monomer is carried out into polymerisation in varsol, obtain diene polymerization
Thing；The rare-earth catalysis system is included：
Rare earth compound, conjugated diolefin and first helper component；
The rare earth compound has Formulas I formula：
Ln(RSO3)3·xH2OyL Formulas I；
Wherein, Ln is rare earth metal；R is selected from alkyl, substitution alkyl, aryl or substituted aryl；L is selected from alcohols part, sulfoxide type
Part, amine part or esters part；0≤x≤8,1≤y≤4；
The molecular formula of the first helper component is as shown in Formula II：
R1MR2Formula II；
Wherein, M is selected from magnesium or zinc；R1And R2Independently selected from alkyl, aryl, substituted aryl or benzyl；
The first helper component is (5~30) with the mol ratio of rare earth compound：1.
9. method according to claim 8, it is characterised in that the rare-earth catalysis system also includes second helper component,
The second helper component is selected from trialkylaluminium or alkyl aluminium hydride；
The charging sequence of the polymerisation includes：
The solution for first adding diolefinic monomer and varsol to be formed；Add first helper component；It is subsequently adding rare earth chemical combination
The mixture that thing and conjugated diolefin and second helper component are formed；
Or, the solution for first adding diolefinic monomer and varsol to be formed；Add first helper component；It is subsequently adding rare earth
The mixture that compound and conjugated diolefin and first helper component and second helper component are formed；
Or, the solution for first adding diolefinic monomer and varsol to be formed；Add second helper component；It is subsequently adding rare earth
The mixture that compound and conjugated diolefin and first helper component are formed；
Or, the solution for first adding diolefinic monomer and varsol to be formed；Add first helper component and the second assisted group
Divide the mixture for being formed；It is subsequently adding the mixture that rare earth compound and conjugated diolefin and first helper component are formed.
10. method according to claim 8 or claim 9, it is characterised in that the mol ratio of the rare earth metal and diolefinic monomer
It is 0.5 × 10-4~2 × 10-4mol/mol。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0964008A1 (en) * | 1998-06-12 | 1999-12-15 | Bridgestone Corporation | Organo zinc and rare earth catalyst system in the polymerization of conjugated dienes |
| EP1939225A1 (en) * | 2006-12-28 | 2008-07-02 | The Goodyear Tire & Rubber Company | Catalyst system for synthesizing amine functionalized rubbery polymers having a high trans microstructure |
| CN101974023A (en) * | 2010-09-21 | 2011-02-16 | 中国科学院长春应用化学研究所 | Rare earth complex, catalyst, preparation method thereof and preparation method of polybutadiene |
| CN103059053A (en) * | 2013-01-28 | 2013-04-24 | 中国科学院长春应用化学研究所 | Rare earth complex and preparation method thereof, rare earth catalyst system and preparation method of butadiene-isoprene copolymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0964008A1 (en) * | 1998-06-12 | 1999-12-15 | Bridgestone Corporation | Organo zinc and rare earth catalyst system in the polymerization of conjugated dienes |
| EP1939225A1 (en) * | 2006-12-28 | 2008-07-02 | The Goodyear Tire & Rubber Company | Catalyst system for synthesizing amine functionalized rubbery polymers having a high trans microstructure |
| CN101974023A (en) * | 2010-09-21 | 2011-02-16 | 中国科学院长春应用化学研究所 | Rare earth complex, catalyst, preparation method thereof and preparation method of polybutadiene |
| CN103059053A (en) * | 2013-01-28 | 2013-04-24 | 中国科学院长春应用化学研究所 | Rare earth complex and preparation method thereof, rare earth catalyst system and preparation method of butadiene-isoprene copolymer |
Non-Patent Citations (1)
| Title |
|---|
| Rare Earths/Main Group Metal Alkyls Catalytic Systems for the 1,4-trans Stereoselective Coordinative Chain Transfer Polymerization of Isoprene;ANDREIA VALENTE 等;《Journal of Polymer Science:Part A: Polymer Chemistry》;20100908;第48卷;第4640-4647页 * |
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