CN103665197B - A kind of homogeneous phase rare earth catalyst and the application in conjugate diene polymerization thereof - Google Patents
A kind of homogeneous phase rare earth catalyst and the application in conjugate diene polymerization thereof Download PDFInfo
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Abstract
The present invention relates to a kind of homogeneous phase rare earth catalyst and application thereof, relate in particular to a kind of novel homogeneous rare earth catalyst and the application in conjugate diene polymerization thereof.Adopt this homogeneous phase rare earth catalyst, while guarantee high catalytic activity and stable in catalytic performance, by changing ratio and the polymeric reaction condition of catalyst components, can prepare along 1,4-structural content is greater than 98%, weight-average molecular weight is adjustable in 40 ~ 2,000,000 scopes, and molecular weight distribution is 1.5 ~ 3.0, and the polymkeric substance that system viscosity is relatively low.
Description
Technical field
The present invention relates to a kind of homogeneous phase rare earth catalyst and application thereof, relate in particular to a kind of novel homogeneous rare earth catalyst and the application in conjugate diene polymerization thereof.
Background technology
Conjugated diene carries out tactic polymerization under rare earth catalyst effect, can synthesize and have the high polymkeric substance (as rare earth polybutadiene rubber and rare-earth isoprene rubber) along Isosorbide-5-Nitrae-structural content (> 96%), high molecular.The small size raising of cis-content can make the performance of polydiolefin significantly improve, when cis-content as rare-earth isoprene rubber is increased to 96.9% by 95.7%, the tensile strength of its cross-linked rubber increases to 32.1MPa by 30.6MPa, 300% tensile modulus increases to 14.1MPa(rare earth catalyst synthetic rubber collected works by 12.6MPa, Science Press, 1980).Rare-earth isoprene rubber is better than titanium system polyisoprene rubber in microtexture and physical and mechanical properties simultaneously, and its microcosmic and macrostructure are closest to natural rubber, are the optimal substitutes of natural rubber.And rare earth polybutadiene rubber is compared with traditional titanium system, cobalt system, nickel polymerized BR, there is better green strength and cured properties, adapt to the requirement of galloping, can be used for manufacturing high-performance tire.
Have bibliographical information, the catalytic activity of catalyzer and the structure of polymkeric substance by rare earth catalyst form and preparation condition determines.As CN100448898C discloses a kind of homogeneous catalyst be made up of carboxylic acid neodymium/aluminum alkyls/halogenated organic hydrocarbon/conjugated alkene or carboxylic acid, be under the condition of 1:1 ~ 30:1 ~ 50:0 ~ 17:6 in catalyst component ratio, can synthesize along Isosorbide-5-Nitrae-structural content is 95.32%, and molecular weight is 5.75 × 10
5polyisoprene rubber.But due on the low side along Isosorbide-5-Nitrae-structural content, gained rare-earth isoprene rubber is not suitable for tire product.
Rare earth catalyst synthetic rubber collected works (Science Press, 1980) in mention the heterogeneous catalyst be made up of neodymium naphthenate/triisobutyl aluminium/diethyl aluminum chloride, can synthesize along 1,4-structural content lower than 95% polyisoprene, but due to suitable 1,4-structural content is on the low side, makes polymer performance undesirable.In addition, heterogeneous catalyst due to may dynamics model be there is, therefore its less stable, catalyst preparation process and the more difficult control of polymerization process.
And just can solve the problem to obtain homogeneous phase rare earth catalyst by changing catalyzer composition.A kind of homogeneous catalyst for conjugate diene polymerization is disclosed in CN102108105A.This process for synthetic catalyst is simple, and resulting polymers is greater than 98% along Isosorbide-5-Nitrae-structural content, and weight-average molecular weight is adjustable in 100 ~ 2,500,000 scopes.But because the molecular weight of prepared polymkeric substance is too high, soltion viscosity is too large.These bring difficulty to the processes such as the heat transfer in industrial production, conveying, glue spraying and cohesion.
In order to reduce polymer solution viscosity, patent CN1342718A adds 3d group 4 transition metal organic compound (as neodecanoic acid nickel) in catalyst preparation process, polymer intrinsic viscosity is down to 5.3dL/g by 7.5dL/g, but also cause polyisoprene structural unit to be down to 97.6% along Isosorbide-5-Nitrae-structural content by 98.9% simultaneously.CN1295087A adds m-xylene in catalyst preparation process, makes polymer intrinsic viscosity reduce to 5.2dL/g by 7.3dL/g, but divinyl and isoprene structures unit reduce along Isosorbide-5-Nitrae-structural content simultaneously, are respectively 97.6% and 95.3%.
CN1295087A discloses double-olefine polymerizing rare earth catalyst of a kind of aromatic hydrocarbons improvement and preparation method thereof.In catalyst formulation process, introduce aromatic hydrocarbons as benzene,toluene,xylene, trimethylbenzene, mellitene, vinyl benzene, Vinylstyrene, naphthalene, anthracene, phenanthrene etc., not only increase the molecular weight of catalyst activity also adjustable polymerisate.But use the polymkeric substance prepared by this catalyzer to be linear structure, its soltion viscosity is still very large, makes troubles to large-scale commercial production.
In anionic polymerisation, in order to reduce soltion viscosity, usually polymer chain is made branched structure.Branched polymer has good physical and mechanical properties, splendid flowing property (lower melting, soltion viscosity), excellent processing characteristics because of it, and higher resistance to cold flow energy, is more and more subject to the attention of rubber industry.Simultaneously, scientists starts gradually by the concept of branched polymer, be incorporated in rare-earth catalysis system polyreaction, to reduce the viscosity of polymer solution system, after rare-earth catalysis system butadiene polymerization terminates, epoxidation vinyl benzene is added as IwakazuHattori reports, by the reaction of epoxidation vinyl benzene and the rare earth polybutadiene rubber polymer end of the chain, make the final polymkeric substance formed be star-branched structure, thus reduce the soltion viscosity of final polymerisate.（ChemicalModificationofNeodymiumHighcis-1,4PolybutadienewithStyreneoxide,PolymersforAdvancedTechnologies,1999,4:450~456）。
Therefore, develop for the preparation of high along Isosorbide-5-Nitrae-structural content, the novel homogeneous rare earth catalyst of the conjugated diene polymer of low system viscosity is worth paying close attention in the industry.
Summary of the invention
The object of the invention is to propose a kind of novel homogeneous rare earth catalyst and the application in conjugate diene polymerization thereof.Adopt this homogeneous phase rare earth catalyst, conjugated diene structural unit can be prepared and be greater than 98% along Isosorbide-5-Nitrae-structural content, weight-average molecular weight (M
w) be 3.0 × 10
5~ 1.6 × 10
6, low solution viscosity polymkeric substance.
Specifically, a kind of homogeneous phase rare earth catalyst disclosed in this invention, it mainly consists of:
A) carboxylic acid neodymium compound;
B) having general formula is AlR
3or AlHR
2aluminum alkyls or alkyl aluminium hydride, Organoaluminoxy alkane or their mixture;
C) halogen compounds;
D) olefin(e) compound;
E) such as formula the compound of structure shown in I
(formula I)
Wherein R
1for the one in H, methyl or ethyl.
Wherein each component molar ratio is: a ︰ b ︰ c ︰ d ︰ e=1 ︰ 5 ~ 40 ︰ 1 ~ 6 ︰ 5 ~ 30 ︰ 0.1 ~ 20.
A kind of homogeneous phase rare earth catalyst disclosed in this invention, described component is a) one in neodymium octoate, neodymium iso-octanate, n-nonanoic acid neodymium, capric acid neodymium or neodymium caprate.
A kind of homogeneous phase rare earth catalyst disclosed in this invention, described components b) be trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three amyl group aluminium, a kind of in diethyl aluminium hydride, hydrogenation dibutyl aluminium, diisobutylaluminium hydride, methylaluminoxane or their mixture.Described components b) be preferably triisobutyl aluminium, diisobutylaluminium hydride, a kind of in methylaluminoxane or their mixture.
A kind of homogeneous phase rare earth catalyst disclosed in this invention, described amount of component b) be the one in diethylaluminum chloride, chlorination dipropyl aluminium, chlorination di-isopropyl aluminium, chlorination dibutyl aluminium, di-isobutyl aluminum chloride, sesquialter ethylmercury chloride aluminium.Described amount of component b) be preferably one in di-isobutyl aluminum chloride or sesquialter ethylmercury chloride aluminium.
A kind of homogeneous phase rare earth catalyst disclosed in this invention, described component d) be a kind of in divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene or their mixture.Described component d) be preferably isoprene.
Shown in Chinese style I of the present invention, the compound of structure is prepared by the following method: under argon shield; in round-bottomed bottle, add tetrahydrofuran (THF) (50 ~ 200mL) successively, 1，3-cyclopentadiene or alkyl replace 1; 3-cyclopentadiene (50 ~ 500mmol), NaH or CaH
2after (60 ~ 500mmol) induction stirring reflux 0.5 ~ 2h, then add 1,3,5-tribromo-benzene (30 ~ 150mmol), continue backflow 0.5 ~ 3h.After cooling, reaction solution is transferred in separating funnel, and adds ethyl acetate (100 ~ 400mL), organic layer washed with water three times (each 50 ~ 100mL).By organic solvent under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal, and mass yield is 90 ~ 97%.
A kind of preparation method of catalyzer of the present invention is as follows: under argon shield; to drying catalyzer configuration bottle in add successively component a), components b), amount of component b), component d) and component e); in 10 ~ 60 DEG C of ageing 5 ~ 100min after mixing, prepare homogeneous catalyst.
The invention also discloses any one homogeneous phase rare earth catalyst application in conjugate diene polymerization above-mentioned.Namely in the solution formed at inert solvent and conjugated diene, add any one homogeneous phase rare earth catalyst above-mentioned start in 0 DEG C ~ 90 DEG C temperature ranges conjugate diene polymerization reaction, wherein catalyzer add-on for make catalyst component a) with monomer mole ratio be 2 × 10
-5~ 3 × 10
-4.
The application of homogeneous phase rare earth catalyst disclosed in this invention in conjugate diene polymerization, described inert solvent is a kind of in hexane, hexanaphthene, pentamethylene, heptane or their mixture.
The application of homogeneous phase rare earth catalyst disclosed in this invention in conjugate diene polymerization, described conjugated diene is a kind of in divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadienes or their mixture.Described conjugated diene is preferably a kind of in divinyl, isoprene or their mixture.
Major advantage of the present invention and effect: due to the acting in conjunction of each component, rare earth catalyst disclosed in this invention has high catalytic activity, the polyreaction of conjugated diene can be started very soon, and obtain high conversion, narrow molecular weight distributions and the height polymerisate along Isosorbide-5-Nitrae-structural content.Catalyzer is homogeneous phase, easy to use, stable in catalytic performance, and reaction easily controls.
Especially catalyst component e) add, make prepared catalyzer be star structure, shown in II, wherein
for polyisoprene segments, Nd is catalyst activity point, and in the course of the polymerization process, monomer conjugated diene carries out chainpropagation along neodymium (Nd) active site in catalyzer, finally obtains the polymerisate in star-branched structure; Do not reduce at maintenance catalyst activity, under the narrow and suitable Isosorbide-5-Nitrae-structural content of molecular weight distribution is greater than the prerequisite of 98%, significantly can reduces the soltion viscosity of polymkeric substance, bring convenience to processes such as the heat transfer in industrial production, conveying, glue spraying and cohesions.
(formula II)
Use homogeneous phase rare earth catalyst disclosed in this invention to synthesize and be greater than 98% along Isosorbide-5-Nitrae-structural content, weight-average molecular weight is adjustable in 40 ~ 2,000,000 scopes, and molecular weight distribution is 1.5 ~ 3.0, the polymkeric substance that soltion viscosity (η) is 2.6dL/g ~ 4.5dL/g.
Accompanying drawing illustrates:
Fig. 1: gel permeation chromatography (GPC) spectrogram of embodiment 3 product, the molecular weight of resulting polymers is unimodal distribution as seen from the figure, and molecular weight distribution is narrower, and molecular weight distributing index is 1.6.
Embodiment
Following examples are further described feature of the present invention, but protection scope of the present invention is not by the restriction of these embodiments.
1, primary analysis method
The limiting viscosity of polymkeric substance utilizes dark type viscometer to test at 30 DEG C, and using toluene as solvent, calculation formula is [η]=[2 (η
sp-ln η
r)]
1/2/ c, wherein η
r=t/t
0, η
sp=η
r-1, t is concentration is the flowing time of the polymkeric substance toluene solution of c, t
0for the flowing time of toluene; Middle average molecular weight (the M of multipolymer
w) and molecular weight distribution (M
w/ M
n) utilize gel permeation chromatography (GPC) to characterize, take polystyrene standards as calibration curve; Suitable Isosorbide-5-Nitrae-the structural content of multipolymer utilizes fourier infrared (FTIR) to characterize.Nucleus magnetic resonance
1hNMR data come from BrukerAC-300 nuclear magnetic resonance analyser, and chemical shift δ unit is ppm, is inside designated as tetramethylsilane.
2, raw material specification and source
Divinyl, isoprene Petrochina Lanzhou Petrochemical Company, polymerization-grade;
High and new technology industrial development zone, carboxylic acid neodymium Ningbo Yu Ling Chemical Industry Science Co., Ltd, 0.5M hexane solution;
Aluminum alkyls and alkyl-al hydride Nanjing communications and liaison Chemical Co., Ltd., purity > 97%;
Alkyl aluminum halide lark prestige Science and Technology Ltd., 0.8M hexane solution;
Other reagent AlfaAesar (Tianjin) Chemical Co., Ltd., SILVER REAGENT.
Embodiment 1
Catalyst component e) synthesis:
Work as R
1for methyl: under argon shield; tetrahydrofuran (THF) (150mL) is added successively, 5-methyl isophthalic acid, 3-cyclopentadiene (24g in 250mL round-bottomed bottle; 300mmol); NaH(7.92g, 330mmol) after induction stirring reflux 1h, then add 1; 3; 5-tribromo-benzene (28.3g, 90mmol), continues backflow 2h.After cooling, reaction solution is transferred in separating funnel, and adds ethyl acetate (200mL), organic layer washed with water three times (each 50mL).
By organic solvent under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal, yield 95%.
1H-NMR（300MHz，CDCl
3，ppm）：δ1.56（s，9H，CH
3），6.25（d，6H，CH），6.35（t，6H，CH），6.90（s，3H，PhH）。
Work as R
1for H: step is the same, and now raw material is 1，3-cyclopentadiene, yield 90%.Nucleus magnetic resonance:
1h-NMR(300MHz, CDCl
3, ppm): δ 4.02(d, 3H, CH), 6.21(t, 6H, CH) and, 6.32(t, 6H, CH), 6.82(s, 3H, PhH).
Work as R
1for ethyl: step is the same, and now raw material is 5-ethyl-1，3-cyclopentadiene, yield 93%.Nucleus magnetic resonance:
1h-NMR(300MHz, CDCl
3, ppm): δ 0.82(t, 9H, CH
3), 1.53(q, 6H, CH
2), 6.33(d, 6H, CH), 6.43(t, 6H, CH), 6.96(s, 3H, PhH).
Embodiment 2
Catalyst component e) synthesis:
Work as R
1for methyl: under argon shield, add tetrahydrofuran (THF) (20mL) successively in 50mL round-bottomed bottle, 5-methyl isophthalic acid, 3-cyclopentadiene (4g, 50mmol), CaH
2after (1.3g, 30mmol) induction stirring reflux 0.8h, then add 1,3,5-trichlorobenzene (2.7g, 15mmol), continue backflow 1.5h.After cooling, reaction solution is transferred in separating funnel, and adds ethyl acetate (70mL), organic layer washed with water three times (each 50mL).By organic solvent under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal, obtains clear crystal (4.3g, yield 92%).
Work as R
1for H: step is the same, and now raw material is 1，3-cyclopentadiene, yield 90%.
Work as R
1for ethyl: step is the same, and now raw material is 5-ethyl-1，3-cyclopentadiene, yield 96%.
Embodiment 3
Under argon shield, in the catalyzer configuration bottle of drying, add 0.03mmol neodymium iso-octanate, 0.75mmol triisobutyl aluminium, 0.15mmol diethyl aluminium hydride, 0.09mmol diethylaluminum chloride, 0.3mmol isoprene, 0.02mmol component e) (R
1for methyl) mix after in 25 DEG C of ageing 60min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.3mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 1 × 10 with the mol ratio of monomer
-4.Be polymerized after 5 hours at 50 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 89.0%, weight-average molecular weight (M
w) be 6 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.9, polymkeric substance is 98.3% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.4dL/g.
Comparative example 3
In catalyst preparation process, component e) be toluene, other condition is with embodiment 3.Polymer yield is 89.7%, weight-average molecular weight (M
w) be 5.7 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.4, polymkeric substance is 98.3% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.2dL/g.
Embodiment 4
Under argon shield, in the catalyzer configuration bottle of drying, add 0.036mmol n-nonanoic acid neodymium, 0.6mmol triisobutyl aluminium, 0.4mmol hydrogenation dibutyl aluminium, 0.08mmol di-isobutyl aluminum chloride, 0.8mmol isoprene, 0.06mmol component e) (R
1for ethyl) mix after in 27 DEG C of ageing 50min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.6mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 6 × 10 with the mol ratio of monomer
-5.Be polymerized after 4 hours at 55 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 85.0%, weight-average molecular weight (M
w) be 8.3 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.6, polymkeric substance is 98.7% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.3dL/g.
Comparative example 4
In catalyst preparation process, component e) be vinyl benzene, other condition is with embodiment 4.Polymer yield is 84.5%, weight-average molecular weight (M
w) be 8.0 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.7, polymkeric substance is 98.8% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.7dL/g.
Embodiment 5
Under argon shield, in the catalyzer configuration bottle of drying, add 0.02mmol neodymium caprate, 0.8mmol diisobutylaluminium hydride, 0.03mmol sesquialter ethylmercury chloride aluminium, 0.1mmol isoprene, 0.1mmol component e) (R
1for H) mix after in 35 DEG C of ageing 60min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 1mol isoprene in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 2 × 10 with the mol ratio of monomer
-5.Be polymerized after 5 hours at 70 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 92.0%, weight-average molecular weight (M
w) be 7.3 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.7, polymkeric substance is 98.9% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.2dL/g.
Comparative example 5
In catalyst preparation process, component e) be dimethylbenzene, other condition is with embodiment 5.Polymer yield is 91.5%, weight-average molecular weight (M
w) be 9.0 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.8, polymkeric substance is 98.8% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.0dL/g.
Embodiment 6
Under argon shield, in the catalyzer configuration bottle of drying, add 0.05mmol capric acid neodymium, 0.25mmol tri-butyl aluminum, 1.5mmol diethyl aluminium hydride, 0.15mmol chlorination dibutyl aluminium, 1.25mmol isoprene, 0.1mmol component e) (R
1for methyl) mix after in 20 DEG C of ageing 30min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.25mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 2 × 10 with the mol ratio of monomer
-4.Be polymerized after 4.5 hours at 40 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 80.0%, weight-average molecular weight (M
w) be 4.5 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.1, polymkeric substance is 99.0% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.6dL/g.
Comparative example 6
In catalyst preparation process, component e) be Vinylstyrene, other condition is with embodiment 6.Polymer yield is 79.5%, weight-average molecular weight (M
w) be 4.2 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.1, polymkeric substance is 98.9% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.3dL/g.
Embodiment 7
Under argon shield, in the catalyzer configuration bottle of drying, add 0.01mmol neodymium iso-octanate, 0.05mmol triethyl aluminum, 0.30mmol hydrogenation dibutyl aluminium, 0.04mmol di-isobutyl aluminum chloride, 0.05mmol isoprene, 0.15mmol component e) (R
1for methyl) mix after in 25 DEG C of ageing 45min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.05mol divinyl and 0.05mol isoprene in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 1 × 10 with the mol ratio of monomer
-4.Be polymerized after 5.5 hours at 80 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 78.0%, weight-average molecular weight (M
w) be 6.5 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.6, polymkeric substance is 98.2% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.0dL/g.
Comparative example 7
In catalyst preparation process, component e) be naphthalene, other condition is with embodiment 7.Polymer yield is 79.0%, weight-average molecular weight (M
w) be 6.2 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.6, polymkeric substance is 98.1% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 4.0dL/g.
As can be seen from above embodiment and comparative example result, relative to prior art, star-shaped catalyst of the present invention is used in conjugate diene polymerization process, do not reduce at maintenance catalyst activity, molecular weight distribution is narrow and along 1, under 4-structural content is greater than the prerequisite of 98%, significantly can reduce the soltion viscosity of polymkeric substance.
Claims (7)
1. a homogeneous phase rare earth catalyst, is characterized in that comprising:
A) carboxylic acid neodymium compound;
B) having general formula is AlR
3or AlHR
2aluminum alkyls or alkyl aluminium hydride, Organoaluminoxy alkane or their mixture;
C) halogen compounds;
D) olefin(e) compound;
E) such as formula the compound of structure shown in I
(formula I)
Wherein R
1for the one in H, methyl or ethyl;
Described halogen compounds is the one in diethylaluminum chloride, chlorination di-isopropyl aluminium, di-isobutyl aluminum chloride, sesquialter ethylmercury chloride aluminium;
Described olefin(e) compound is a kind of in divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene or their mixture.
2. homogeneous phase rare earth catalyst according to claim 1, is characterized in that each component molar ratio is: a ︰ b ︰ c ︰ d ︰ e=1 ︰ 5 ~ 40 ︰ 1 ~ 6 ︰ 5 ~ 30 ︰ 0.1 ~ 20.
3. homogeneous phase rare earth catalyst according to claim 1, is characterized in that component is a) one in neodymium iso-octanate, n-nonanoic acid neodymium or neodymium caprate.
4. homogeneous phase rare earth catalyst according to claim 1, it is characterized in that components b) be trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three amyl group aluminium, a kind of in diethyl aluminium hydride, diisobutylaluminium hydride, methylaluminoxane or their mixture.
5. the application of a homogeneous phase rare earth catalyst according to claim 1 in conjugate diene polymerization, it is characterized in that in the solution formed at inert solvent and conjugated diene, add described homogeneous phase rare earth catalyst, start in 0 DEG C ~ 90 DEG C temperature ranges conjugate diene polymerization reaction, wherein catalyzer add-on for make catalyst component a) with monomer mole ratio be 2 × 10
-5~ 3 × 10
-4.
6. application according to claim 5, is characterized in that inert solvent is a kind of in hexane, hexanaphthene, pentamethylene, heptane or their mixture.
7. application according to claim 5, is characterized in that conjugated diene is a kind of in divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadienes or their mixture.
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| CN1136548A (en) * | 1995-01-23 | 1996-11-27 | 蒙特尔技术有限公司 | Process for preparation of cyclopentadinyl compounds and compounds obtained therefrom |
| CN1342719A (en) * | 2001-10-12 | 2002-04-03 | 中国科学院长春应用化学研究所 | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene |
| US20050004333A1 (en) * | 2001-12-07 | 2005-01-06 | Michelin Recherche Et Technique S.A. | Method for preparing butadiene/isoprene copolymers and resulting copolymers |
| US20050130835A1 (en) * | 2002-05-16 | 2005-06-16 | Michelin Recherche Et Technique S.A. | Catalytic system for the preparation of polybutadienes and preparation process |
| CN101045768A (en) * | 2007-04-12 | 2007-10-03 | 中国科学院长春应用化学研究所 | Rare earth catalyst for preparing polyisoprene and preparation method and method for preparing polyisoprene |
| CN101812151A (en) * | 2010-05-26 | 2010-08-25 | 中国科学院长春应用化学研究所 | Method for preparing polybutadiene |
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