CN100448898C - Rare-earth catalyst and conjugated diene polymerization process - Google Patents
Rare-earth catalyst and conjugated diene polymerization process Download PDFInfo
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- CN100448898C CN100448898C CNB2005100588315A CN200510058831A CN100448898C CN 100448898 C CN100448898 C CN 100448898C CN B2005100588315 A CNB2005100588315 A CN B2005100588315A CN 200510058831 A CN200510058831 A CN 200510058831A CN 100448898 C CN100448898 C CN 100448898C
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Abstract
The present invention relates to a rare earth catalyst, particularly to a rare earth catalyst used for polymerizing conjugated dialkene and a polymerization method of conjugated dialkene. The rare earth catalyst of the present invention has high catalytic activity; the rare earth catalyst can start the polymerization reaction of conjugated dialkene even at very low temperature and can obtain polymerization products with high conversion rate, high molecular weight, narrow molecular weight distribution and high cis-structures; the catalyst is a homogeneous phase and has the advantages of convenient use, stable catalytic performance, correspondingly small temperature fluctuation in the polymerization process and easily controlled reaction. The conjugated dialkene polymerization method of the present invention can still perfectly control polymerization reaction, when the concentration of butadiene monomers in polymerization systems reaches about 30%.
Description
Technical field:
The present invention relates to a kind of rare earth catalyst especially for the rare earth catalyst of conjugate diene polymerization and a kind of polymerization process of conjugated diene.
Background technology:
Conjugated diene carries out tactic polymerization and can synthesize and have Gao Shun-1 under titanium system, cobalt system, nickel system and rare earth catalyst effect, 4 structural unit content (suitable-1,4 content＞95%) polyhutadiene or polyisoprene, this material are specially adapted to make tire and other resilient materials.
The polybutadiene rubber that rare earth catalyst makes is that the polybutadiene rubber that catalysis obtains is compared with traditional titanium system, cobalt system, nickel, better green strength and cured properties are arranged, as performances such as green strength, tear strength, autohension, hysteresis loss, abrasion performance, warping strength be full of cracks, heat-resisting air aging and antifatigues.Therefore, the polybutadiene rubber that rare earth catalyst makes adapts to the performance of running at high speed of automobile, can be used for making high-performance tire.
In the conjugated diene liquid polymerization that rare earth catalyst exists, catalyzer is made up of Primary Catalysts rare-earth salts, co-catalyst organo-aluminium compound and the 3rd component composition that can discharge halogen atom usually.Disclose a kind of rare earth catalyst system that is used for conjugate diene polymerization as US5428119, it consists of rare earth carboxylate, alkyl-al hydride compound, chlorination alkylaluminium cpd; The process of the rare earth catalyst conjugate diene polymerization described in the WO9305083, the 3rd component halide-containing is selected silicon halide or organic halogenation silicon for use in the catalyzer.This class rare earth catalyst mostly is heterogeneous catalysis system, the less stable of catalyzer, in addition, and owing to may there be many active centre, the difficult control of catalytic process and polymerization process, so the molecular weight of controlling polymers and distribution thereof are difficult problems.In adopting solution method polymerization technique production polybutadiene rubber process, if the molecular weight distribution of polymkeric substance is wide, then the polymerization system kinetic viscosity is very big, bring difficulty for production processes such as heat transfer, conveying, spray glue, cohesion, thereby increased energy consumption, limited the raising (being generally 10%～15%) of monomer concentration, reduced throughput and efficient as divinylic monomer concentration.
People attempt by change and adjusting co-catalyst organoaluminum and prepare the homogeneous phase rare earth catalyst and solve the problems referred to above, disclose a kind of catalyzer that in the presence of a small amount of conjugated diene, carries out " prefabricated " among the US3794604, can be converted into homogeneous system by nonhomogeneous system.US5686371 adds few butadiene and prepares homogeneous catalyst in rare earth carboxylate/aluminum alkyls/halogenated silanes system, can reduce polyhutadiene molecular weight and molecular weight distributing index simultaneously, and the narrowest dispersion index is 2.20.CN1342719 provides a kind of mixture by carboxylic acid neodymium compound, aluminum alkyls and alkyl aluminium hydride, halide-containing (tertiary butyl chloride, sesquialter aluminium Al
2R
3Cl
3, dialkylaluminum chloride AlR
2Cl or chloro methyl-monosilane Me
4-nSiCl
n) and the homogeneous phase rare-earth catalysis system formed of divinyl or isoprene, and reach the purpose of regulation and control polymericular weight and molecular weight distribution by the ratio of regulating two kinds of aluminum alkylss, can make molecular weight distribution at 2.0～3.5 high-cis rare earth polybutadiene rubber.CN1296982 and CN1347923 disclose a kind of mixture by rare-earth salts (neodymium naphthenate or neodecanoic acid neodymium), aluminum alkyls (triethyl aluminum or triisobutyl aluminium) and hydrogenation aluminium isobutyl, have the homogeneous phase rare-earth catalysis system that organic hydrochloric ether (tertiary butyl chloride, benzyl chloride or chlorallylene) of active chlorine atom is formed, and also comes the molecular weight of telomerized polymer by the ratio of regulating two kinds of aluminum alkylss.Flat 3-185008 adopts R
1-CO-N (OH)-C
6H
2(R)
3Part for rare earth element, can improve the catalyzer phase and make the polybutadiene rubber of narrow molecular weight distributions (dispersion index is 1.5～1.8), but cause molecular weight to reduce (Mooney viscosity value is lower than 35) simultaneously, do not reach when using requirement (Mooney viscosity value is generally about 45) molecular weight as tire material.
Summary of the invention:
The purpose of this invention is to provide a kind of homogeneous phase rare earth catalyst of conjugate diene polymerization and a kind of polymerization process of conjugated diene of can be used for.When the catalytic activity height that guarantees catalyzer and catalytic performance are stable, make steadily control easily of polymerization process, and can prepare suitable-1,4 structural unit content greater than 95%, molecular weight ranges broad (2.0 * 10
4～2.5 * 10
6), the conjugated diene polymer of narrow molecular weight distribution (the I of dispersion index reaches 1.4).
The invention provides a kind of rare earth catalyst, it mainly consists of:
A. rare earth carboxylate compound; Be preferably C
6-C
10The carboxylic acid neodymium, can be neodymium naphthenate or branched alkyl carboxylic acid's neodymium (as neodymium octoate, n-nonanoic acid neodymium, capric acid neodymium).
B. organo-aluminium compound is AlR
3Or AlHR
2Or both mixtures, wherein R is C
1-C
6Alkyl; Can be any in the following material group or their mixture: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride, hydrogenation dibutyl aluminium.Be preferably tri-butyl aluminum, hydrogenation dibutyl aluminium and composition thereof.
C. activator, be any in the following material group or their mixture: 2-phenyl-2 cbloropropane isopropyl chloride, 1,4-two (2-chloro-propyl) benzene, methylene dichloride, ethylene dichloride, propylene dichloride, dichlorobutane, trichloromethane, trichloroethane, three chlorobutanes, three chloropentanes, methyl chloroacetate, ethyl chloroacetate, the Mono Chloro Acetic Acid propyl ester, methyl dichloroacetate, ethyl dichloroacetate, the dichloro acetic acid propyl ester, the dichloro acetic acid butyl ester, the Tripon ethyl ester, the dichloro-butyric acid ethyl ester, methyl trichloroacetate, ethyl trichloroacetate, the trichoroacetic acid(TCA) propyl ester, butyl trichloroacetate, the chloropon ethyl ester, the trichlorobutyric acid ethyl ester.Be preferably: ethylene dichloride, propylene dichloride, dichlorobutane, 2-phenyl-2 cbloropropane isopropyl chloride, 1,4-two (2-chloro-propyl) benzene, trichloromethane, trichloroethane, three chlorobutanes, three chloropentanes, methyl trichloroacetate, ethyl trichloroacetate, trichoroacetic acid(TCA) propyl ester, butyl trichloroacetate, chloropon ethyl ester, trichlorobutyric acid ethyl ester.
D. be conjugated alkene or C
6-C
10Carboxylic acid, said conjugated alkene is preferably any in divinyl, isoprene, the vinylbenzene or their mixture; C
6-C
10Carboxylic acid be caproic acid, enanthic acid, n-nonanoic acid, sad, capric acid or their mixture.
The mol ratio of each component is A: B: C: D=1: 1～30: 1～50: 0～17/6.
Catalyzer of the present invention is the catalyst system of being made up of Primary Catalysts carboxylic acid neodymium, co-catalyst aluminum alkyls and chloro activator, can present homogeneous state usually, after the adding D component, can make the stable more and/or raising catalytic activity of catalyst system phase.
The Preparation of catalysts method is fairly simple, under-30～60 ℃, the ageing behind thorough mixing of each component of ABCD can be made catalyst solution.
The present invention also provides a kind of polymerization process of conjugated diene, in the presence of above-mentioned catalyzer, is polymer solvent with the hydrocarbon compound, starts polyreaction under-70～70 ℃ of temperature, and catalyst consumption is 0.08～5mmol/mol monomer.
Said polymer solvent is that conjugate diene polymerization is commonly used in the above-mentioned polymerization process, is preferably any in the following material group or their mixture: hexane, hexanaphthene, heptane, octane, methylcyclohexane.
Polymerization process of the present invention is applicable to the polymerization or the copolymerization of conjugated diene, comprising 1,3-butadiene, 1, and 3-isoprene, 2,3-dimethylbutadiene, 2,4-hexadiene, 1,3-pentadiene or 2-methyl isophthalic acid, 3-pentadiene etc.
The polymerization process of conjugated diene of the present invention can carry out under normal pressure or middle pressure (below the 10atm), is applicable to that single polyreaction apparatus or poly close the continuous or batchwise polymerization mode of reactor assembly.
Rare earth catalyst provided by the invention has high catalytic activity, even also can start conjugated diene (as divinyl) polyreaction under the low temperature very much, and obtains the polymerisate of high conversion, high molecular, narrow molecular weight distributions and high-cis structure.Catalyzer is homogeneous phase, and is easy to use, and catalytic performance is stable, in the polymerization process temperature fluctuation relatively little, reaction is control easily.
The polymerization process of conjugated diene of the present invention, especially for the butadiene solution polymerization, monomer concentration was at nearly 30% o'clock in the system, polyreaction is well controlled, can make and not contain gel, suitable-1 substantially, 4 structural unit content can reach more than 97%, molecular weight can be regulated in wide region, molecular weight distribution can be regulated the high-cis polybutadiene product of (dispersion index 1.4～4.0), particularly can prepare the high cis-polybutadiene product of high molecular and narrow molecular weight distributions.
Embodiment:
The present invention describes with following embodiment, does not constitute the restriction to the scope of the invention or implementation method.The molecular weight of polymkeric substance is represented with limiting viscosity and viscosity-average molecular weight, number-average molecular weight and the weight-average molecular weight of dilute solution in the following example.Under 30 ℃, 0.1 measure the limiting viscosity and the viscosity-average molecular weight of dilute solution in the toluene solution of～0.5% (quality), adopt gel permeation chromatograph (GPC) to measure number-average molecular weight, weight-average molecular weight and the molecular weight distributing index of polymkeric substance (is solvent and moving phase with the tetrahydrofuran (THF)).Adopt infrared spectra or
13The microtexture content of C-NMR spectrum quantitative assay polymkeric substance.
Embodiment 1
At 50 ℃ and N
2Under the protection, with neodymium octoate (0.05mmol), triisobutyl aluminium (Al (i-Bu)
3) (0.78mmol), trichloromethane (1.7mmol), dichlorobutane (0.05mmol) and vinylbenzene (0.049mmol) adds in the exsiccant catalyst preparation bottle, mixes, and behind the ageing 26h, obtains the transparent homogeneous catalyst solution of light green.
At N
2Protection down; divinyl/the cyclohexane solution (wherein monomer mass concentration is 12%) and the above-mentioned catalyst solution (catalyzer/monomer=1.0mmol/mol) startup polymerization that under 10 ℃, in polymerization reactor, add 30ml; behind the reaction 4h; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate.The weight-average molecular weight of product is 1.05 * 10
6, molecular weight distributing index is 1.49.
Embodiment 2
At 50 ℃ and N
2Under the protection, with neodymium octoate (0.09mmol), triisobutyl aluminium Al (i-Bu)
3(1.44mmol), trichloromethane (3.15mmol) and ethyl dichloroacetate (0.002mmol) add in the exsiccant catalyst preparation bottle, mixes, and behind the ageing 2h, obtains the transparent homogeneous catalyst solution of shallow grey blue.
At N
2Protection down, adding the divinyl of 40ml and hexanaphthene/raffinate oil under-62 ℃ in polymerization reactor (is C
6～C
8The alkane mixing solutions) (wherein monomer mass concentration is 20%, hexanaphthene/raffinate oil=1/1) and above-mentioned catalyst solution (catalyzer/monomer=0.9mmol/mol) starts polymerization, behind the adiabatic reaction 4h, adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate.Monomer conversion is 100%, and the weight-average molecular weight of product is 7.89 * 10
5, molecular weight distributing index is 2.06.
Embodiment 3
At 40 ℃ and N
2Protection adds neodymium octoate (0.08mmol), triisobutyl aluminium (1.2mmol), trichloroethane (0.38mmol) in the exsiccant catalyst preparation bottle down, mix ageing 1.5h after, obtain the transparent homogeneous catalyst solution of shallow grey blue.
At N
2Protection down; (wherein monomer mass concentration is 20% to add the divinyl of 30ml and the hexanaphthene/solution of raffinating oil under 15 ℃ in polymerization reactor; hexanaphthene/raffinate oil=1/1) and above-mentioned catalyst solution (catalyzer/monomer=1.0mmol/mol) starts polymerization; behind the reaction 3.7h; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate.The weight-average molecular weight of product is 3.36 * 10
5-1,4 structural content suitable in the polyhutadiene is 98.39%, and anti--1,4 structural content is 0.74%, 1, and the 2-structural content is 0.87%.
Embodiment 4
At 30 ℃ and N
2Protection down; in neodymium octoate (0.06mmol), triisobutyl aluminium (0.96mmol), trichloromethane (1.74mmol) and sad (0.17mmol) adding exsiccant catalyst preparation bottle; mix, behind the ageing 1h, obtain the transparent homogeneous catalyst solution of grey blue.
At N
2Protection down; the divinyl and raffinate oil solution (wherein monomer mass concentration is 20%) and above-mentioned catalyst solution (catalyzer/monomer=0.77mmol/mol) startup polymerization that under 10 ℃, in polymerization reactor, add 35ml; behind the reaction 11.5h; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate.Monomer conversion is 45%, and the weight-average molecular weight of product is 2.40 * 10
6, molecular weight distributing index is 2.11.
Embodiment 5
At 15 ℃ and N
2Protection down; neodymium octoate (0.582mmol), triisobutyl aluminium (9.86mmol), diisobutylaluminium hydride (0.50mmol), trichloromethane (17.4mmol) and 2-phenyl-2 cbloropropane isopropyl chloride (0.015mmol) are added in the exsiccant catalyst preparation bottle; after mixing; ageing 6.3h obtains the transparent homogeneous catalyst solution of grey blue.
At N
2Protection adds the divinyl/solution of raffinating oil (wherein monomer mass concentration is 20%) and the above-mentioned catalyst solution (catalyzer/monomer=0.7mmol/mol) startup polymerization of 37.5ml down in polymerization reactor; after reacting 2.5h under 40 ℃; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.In polymerization process, temperature of charge only fluctuates in 40 ℃～48 ℃ scopes in the reaction system.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate.The weight-average molecular weight of product is 4.8 * 10
5, molecular weight distributing index is 2.48.-1,4 structural content suitable in the polyhutadiene is 97.32%, and anti--1,4 structural content is 2.42%, 1, and the 2-structural content is 0.25%.
Embodiment 6
At 50 ℃ and N
2Protection down; neodymium octoate (0.12mmol), triisobutyl aluminium (1.92mmol), diisobutylaluminium hydride (0.09mmol) and ethyl trichloroacetate (0.36mmol) are added in the exsiccant catalyst preparation bottle; after mixing, ageing 10min obtains the transparent homogeneous catalyst solution of grey blue.
At N
2Protection down; divinyl/the solution of raffinating oil (wherein monomer mass concentration is 20%) of adding 20ml and above-mentioned catalyst solution in polymerization reactor (catalyzer/monomer=2.7mmol/mol); behind 55 ℃ of following polyreaction 15h; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry, constant weight, obtain polymerisate.Monomer conversion is 50%, and the weight-average molecular weight of product is 2.6 * 10
5, molecular weight distributing index is 3.76.
Embodiment 7
At 20 ℃ and N
2Under the protection, with neodymium octoate (0.17mmol), triisobutyl aluminium Al (i-Bu)
3(3mmol), trichloromethane (5mmol) and trichloroethane (0.017mmol) add in the exsiccant catalyst preparation bottle, mixes, and behind the ageing 27h, obtains the transparent homogeneous catalyst solution of grey blue.
At N
2Protection down; the divinyl and raffinate oil solution (wherein monomer mass concentration is 20%) and above-mentioned catalyst solution (catalyzer/monomer=0.2mmol/mol) startup polymerization that in polymerization reactor, add 37.5ml; behind the reaction 4h; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry, constant weight, obtain polymerisate.The limiting viscosity of product is 7.47dL/g, and viscosity-average molecular weight is 1.12 * 10
6-1,4 structural content suitable in the polyhutadiene is 98.71%, and anti--1,4 structural content is 0.86%, 1, and the 2-structural content is 0.29%.
Embodiment 8
At 50 ℃ and N
2Under the protection, with neodymium naphthenate (0.16mmol), triisobutyl aluminium Al (i-Bu)
3(2.70mmol), trichloroethane (0.95mmol) and trichloromethane (0.005mmol) add in the exsiccant catalyst preparation bottle, mixes, and behind the ageing 3h, obtains the homogeneous phase transparent catalyst solution of grey blue.
At N
2Protection down; the isoprene of adding 20ml and cyclohexane solution (wherein monomer mass concentration is 50%) and above-mentioned catalyst solution in polymerization reactor (catalyzer/monomer=1.5mmol/mol); behind polyreaction 19h under 50 ℃ of constant temperature; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry, constant weight, obtain polymerisate.Monomer conversion is 87%, and the weight-average molecular weight of product is 5.75 * 10
5, molecular weight distributing index is 2.86.-1,4 structural content suitable in the polyisoprene is 95.32%, and anti--1,4 structural content is 0.43%, 3, and the 4-structural content is 4.25%.
Embodiment 9
At 50 ℃ and N
2Under the protection, with neodymium octoate (0.11mmol), triisobutyl aluminium Al (i-Bu)
3(1.74mmol), trichloromethane (3.89mmol), 1,4-two (2-chloro-propyl) benzene (0.01mmol) and divinyl (0.15mmol) add in the exsiccant catalyst preparation bottle, mix ageing after, obtain the homogeneous phase transparent catalyst solution of shallow grey blue.
At N
2Protection adds divinyl and the hexanaphthene/C of 30ml down in polymerization reactor under-10 ℃
6～C
8(wherein monomer concentration is 26% quality to the alkane mixing solutions, hexanaphthene/C
6～C
8Alkane mixing solutions=1/1) and above-mentioned catalyst solution (catalyzer/monomer=0.85mmol/mol) starts polymerization, behind the reaction 4h, adds the ethanolic soln that contains 0.1% (quality) 2,6 ditertiary butyl p cresol and hydrochloric acid and stops polymerization.With remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate.Monomer conversion is 92%, and the weight-average molecular weight of product is 7.22 * 10
5, molecular weight distributing index is 2.52.
Embodiment 10
At 40 ℃ and N
2Under the protection, with neodymium octoate (0.08mmol), triisobutyl aluminium Al (i-Bu)
3(1.2mmol), 1,4-two (2-chloro-propyl) benzene (0.76mmol) and trichloroethane (0.03mmol) add in the exsiccant catalyst preparation bottle, mix ageing 1.5h after, obtain the transparent homogeneous catalyst solution of shallow grey blue.
At N
2Protection down; (wherein monomer mass concentration is 20% to add the divinyl of 30ml and the hexanaphthene/solution of raffinating oil under 20 ℃ in polymerization reactor; hexanaphthene/raffinate oil=1/1) and above-mentioned catalyst solution (catalyzer/monomer=1.0mmol/mol) starts polymerization; behind the reaction 3.7h; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate.The weight-average molecular weight of product is 4.95 * 10
5, molecular weight distributing index is 2.05.
Embodiment 11
At 40 ℃ and N
2Under the protection, with neodymium octoate (0.25mmol), triisobutyl aluminium Al (i-Bu)
3(4.20mmol), diisobutylaluminium hydride (0.21mmol) and ethyl trichloroacetate (0.25mmol) add in the exsiccant catalyst preparation bottle, after mixing, ageing 10min obtains the transparent homogeneous catalyst solution of sky-blue.
At N
2Protection down; the divinyl that in polymerization reactor, adds 20ml and raffinate oil solution (wherein monomer mass concentration is 21.9%) and above-mentioned catalyst solution (catalyzer/monomer=3.0mmol/mol); behind 55 ℃ of following polyreaction 15h; adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry, constant weight, obtain polymerisate.Monomer conversion is 73%, and the viscosity-average molecular weight of polymerisate is 6.8 * 10
4
Embodiment 12
At 50 ℃ and N
2Protection down; with neodymium octoate (0.045mmol), triisobutyl aluminium (0.45mmol), diisobutylaluminium hydride (0.03mmol), trichloromethane (1.6mmol) and 1; 4-two (2-chloro-propyl) benzene (0.05mmol) adds in the exsiccant catalyst preparation bottle; mix; behind the ageing 2h, obtain the transparent homogeneous catalyst solution of shallow grey blue.
At N
2Protection down, adding the divinyl of 30ml and hexanaphthene/raffinate oil in polymerization reactor (is C
6～C
8The alkane mixing solutions) (wherein monomer mass concentration is 20%, hexanaphthene/raffinate oil=1/1) and above-mentioned catalyst solution (catalyzer/monomer=1.0mmol/mol) starts polymerization, after reacting 5h under 50 ℃, adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate.Monomer conversion is 58%, and the weight-average molecular weight of product is 9.41 * 10
5, molecular weight distributing index is 1.59.
Embodiment 13
At 50 ℃ and N
2Protection down; neodymium octoate (0.045mmol), triisobutyl aluminium (1.07mmol), diisobutylaluminium hydride (0.11mmol), trichloromethane (1.6mmol) and trichloroethane (0.002mmol) are added in the exsiccant catalyst preparation bottle; mix; behind the ageing 2h, obtain the transparent homogeneous catalyst solution of shallow grey blue.
At N
2Protection down, adding the divinyl of 30ml and hexamethylene institute/raffinate oil in polymerization reactor (is C
6～C
8The alkane mixing solutions) (wherein monomer mass concentration is 20%, hexanaphthene/raffinate oil=1/1) and above-mentioned catalyst solution (catalyzer/monomer=1.0mmol/mol) starts polymerization, after reacting 2h under 50 ℃, adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate, monomer conversion is 96.4%, the viscosity-average molecular weight of product is 3.8 * 10
5
Embodiment 14
At 50 ℃ and N
2Protection down; neodymium octoate (0.045mmol), triisobutyl aluminium (0.77mmol), diisobutylaluminium hydride (0.038mmol), trichloromethane (2.1mmol) and trichloroethane (0.006mmol) are added in the exsiccant catalyst preparation bottle; mix; behind the ageing 3h, obtain the transparent homogeneous catalyst solution of shallow grey blue.
At N
2Protection down, adding the divinyl of 30ml and hexanaphthene/raffinate oil in polymerization reactor (is C
6～C
8The alkane mixing solutions) (wherein monomer mass concentration is 12%, hexanaphthene/raffinate oil=0.77) and above-mentioned catalyst solution (catalyzer/monomer=2.1mmol/mol) starts polymerization, after reacting 37h under 35 ℃, adding contains the 2,6 ditertiary butyl p cresol of quality 0.1% and the ethanolic soln of hydrochloric acid stops polymerization.Remove desolvate and unreacted monomer after, after repeatedly ethanol/water washing, dry constant weight, obtain polymerisate, monomer conversion is 55%, the viscosity-average molecular weight of product is 2.95 * 10
5
Claims (9)
1. rare earth catalyst, it mainly consists of:
A. rare earth carboxylate compound;
B. organo-aluminium compound is AlR
3Or AlHR
2Or both miscellanys, wherein R is C
1-C
6Alkyl;
C. activator, be any in the following material group or their mixture: 2-phenyl-2 cbloropropane isopropyl chloride, 1,4-two (2-chloro-propyl group) benzene, methylene dichloride, ethylene dichloride, propylene dichloride, dichlorobutane, trichloromethane, trichloroethane, three chlorobutanes, three chloropentanes, methyl chloroacetate, ethyl chloroacetate, the Mono Chloro Acetic Acid propyl ester, methyl dichloroacetate, ethyl dichloroacetate, the dichloro acetic acid propyl ester, the dichloro acetic acid butyl ester, the Tripon ethyl ester, the dichloro-butyric acid ethyl ester, methyl trichloroacetate, ethyl trichloroacetate, the trichoroacetic acid(TCA) propyl ester, butyl trichloroacetate, the chloropon ethyl ester, the trichlorobutyric acid ethyl ester;
D. conjugated alkene or C
6-C
10Carboxylic acid;
The mol ratio of each component is A: B: C: D=1: 1～30: 1～50: 0～17/6.
2. according to the catalyzer of claim 1, it is characterized in that: the rare earth carboxylate compound is C
6-C
10Neodymium naphthenate or branched alkyl carboxylic acid's neodymium.
3. according to the catalyzer of claim 2, it is characterized in that: said branched alkyl carboxylic acid's neodymium is neodymium octoate, n-nonanoic acid neodymium or capric acid neodymium.
4. according to the catalyzer of claim 1, it is characterized in that: organo-aluminium compound is any in the following material group or their mixture: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride, hydrogenation dibutyl aluminium.
5. according to the catalyzer of claim 4, it is characterized in that: organo-aluminium compound is tri-butyl aluminum, hydrogenation dibutyl aluminium or both mixtures.
6. according to the catalyzer of claim 1, it is characterized in that: activator is any in the following material group or their mixture: 2-phenyl-2 cbloropropane isopropyl chloride, 1,4-two (2-chloro-propyl) benzene, ethylene dichloride, propylene dichloride, dichlorobutane, trichloromethane, trichloroethane, three chlorobutanes, three chloropentanes, methyl trichloroacetate, ethyl trichloroacetate, trichoroacetic acid(TCA) propyl ester, butyl trichloroacetate, chloropon ethyl ester, trichlorobutyric acid ethyl ester.
7. according to the catalyzer of claim 1, it is characterized in that: conjugated alkene is any in the following material group or their mixture: divinyl, isoprene, vinylbenzene.
8. the polymerization process of a conjugated diene in the presence of any catalyzer of claim 1 to 7, is a polymer solvent with the hydrocarbon compound, and-70～70 ℃ of temperature actuated polyreactions, catalyst consumption is 0.08～5mmol/mol monomer.
9. polymerization process according to Claim 8 is characterized in that: said polymer solvent is any in the following material group or their mixture: hexane, hexanaphthene, heptane, octane, methylcyclohexane.
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