CN1134461C - Process for preparing metallocene catalyst with high-molecular shell-nucleus structure - Google Patents
Process for preparing metallocene catalyst with high-molecular shell-nucleus structure Download PDFInfo
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- CN1134461C CN1134461C CNB991212452A CN99121245A CN1134461C CN 1134461 C CN1134461 C CN 1134461C CN B991212452 A CNB991212452 A CN B991212452A CN 99121245 A CN99121245 A CN 99121245A CN 1134461 C CN1134461 C CN 1134461C
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Abstract
The present invention belongs to a process for preparing a high molecular metallocene catalyst with a core-shell structure, which is used for the homopolymerization and the copolymerization of ethylene and alpha-olefin. The catalyst prepared by the process is composed of a component A, a component B and a component C, wherein the expression formula of A is P(S-co-(R1)m(R2)nM), and A is a high molecular metallocene compound; B is the core of the catalyst and comprises SiO2, Al2O3, MgCl2 and polystyrenes microspheres; C is methylaluminoxane (MAO) or B(C6F5)3, etc. The catalyst has uniform granules and good fluidity and is suitable for a gas phase polymerization process and a slurry polymerization process. The catalytic efficiency of the catalyst is from 0.6 to 10.5*10<6>gPolym/molM. hr.
Description
The invention belongs to the preparation method of the metallocene catalyst of shell-nuclear high molecular.
Since the 1980s, some metallocene compounds such as Cp have been it is found that
2ZrCl
2, Cp
2Zr (CH
3)
2The catalyst system of forming Deng (Cp is a cyclopentadienyl) and MAO (methylaluminoxane) has the catalytic activity of superelevation and the polyethylene product excellent property of gained to ethene.German Patent Application 2,608,863 disclose the olefin polymerization catalysis of a kind of cyclopentadiene titanium compound and methylaluminoxane composition, German Patent Application2,608,933 and European PatentApplication 0035242 similar luxuriant zirconium metal catalyzer is disclosed.Above-mentioned catalyzer is used for the ethylene polymerization activity height, the molecular weight of product narrowly distributing, and the big I of molecular weight is by catalyst concn and temperature of reaction control simultaneously.On the other hand, the reaction system of polymerization in homogeneous phase can not satisfy the requirement of vapour phase polymerization fluidized-bed process, and the product bulk density is low, and therefore poor morphology improves catalyst form and mobile people's the very big interest that caused.Japanese Laid-Patent NO.35006,35007 disclose a kind of preparation method of carried catalyst, utilize MAO that metallocene compound is carried on inorganic carrier SiO
2Or Al
2O
3On.United states Patent 5,006,500 and European Patent358,264,367,503,368,644, a kind of preparation method of carried catalyst is disclosed, the inorganic carrier that utilization contains part of hydroxyl reacts with metallocene compound with the aluminum alkyls reaction earlier again, thereby reaches the purpose that metallocene compound is immobilized.
The preparation method who the purpose of this invention is to provide a kind of metallocene catalyst of heterogeneous high-molecular shell-nucleus structure.This method adopts SiO
2, Al
2O
3, MgCl
2, polystyrene is as the nuclear of catalyzer, adopts the shell of the multipolymer of the metallocene catalyst compound that contains the alkene substituted radical and vinylbenzene and Vinylstyrene as catalyzer, the metallocene catalyst of formation high-molecular shell-nucleus structure.
Principle according to the olefinic polymerization template effect; inorganic carrier combines with metallocene catalyst and forms heterogeneous metallocene catalysis system; help the form granulating though can improve the bulk density of polyolefin product, the activity of its catalysis in olefine polymerization of metallocene catalyst after immobilized then reduces greatly.The feature that promptly will keep the metallocene catalyst high catalytic activity guarantees the form of polymerisate and the research emphasis that performance is metallocene catalyst again.Adopt the metallocene catalyst of high-molecular shell-nucleus structure, the effective constituent of catalyzer is distributed on the surface of carrier, and,, be difficult for leaving away so connect firmly because metallocene catalyst is keyed on the surface of catalyzer shell by σ.The catalytic efficiency of this catalyzer can reach 0.6-10.5 * 10
6GPolym./molMhr.
The catalyzer of the present invention preparation is by A, and B and C three components are formed, and A is expressed as P (S-co-(R
1) m (R
2) nM), S is a vinylbenzene, co represents copolymerization, (R
1) m (R
2) nM is metallocene compound, M is Ti, Zr, transition metal such as Hf, R
1For cyclopentadienyl, the indenyl that contains the alkene replacement that contains the alkene replacement, the fluorenyl that contains the alkene replacement, can be C wherein as substituent alkene
2～C
10And two keys can be at the alkene of different positions; R
2Be F, Cl, Br, I, CH
3, OMe, OBu, NMe
2Deng, m+n=4; B is the nuclear of catalyzer, and they are SiO
2, Al
2O
3, MgCl
2, polystyrene microsphere; C is methylaluminoxane (MAO) or B (C
6F
5)
3Deng.
The Preparation of catalysts process is as follows:
1. the preparation of alkylene cyclopentadiene:
The alkylene cyclopentadiene adopts phase transfer method or is prepared by fulvene.
Phase transfer method: cyclopentadiene, alkylene chlorine or alkylene bromine are consisting of phase-transferring agent at Tetrabutyl amonium bromide, under the condition of the NaOH solvent of 100ml 30-35%, stir 2-3hr in the ice-water bath, stir 5-6hr under the room temperature.Through washing, drying, decompression makes product, yield 40-70%;
By the fulvene conversion method: adopting 6-methyl fulvene is reactant, is solvent with the tetrahydrofuran (THF), adds equimolar diisopropylamine lithium, stirs 1-1.5hr in ice-water bath, stirs 2-3hr under the room temperature, makes product, yield 70-90%.
2. contain the preparation of the metallocene catalyst of olefin group on the cyclopentadiene
The all operations of Preparation of Catalyst all carries out under anhydrous and oxygen-free and high-purity argon gas protection.At tetrahydrofuran (THF) is under the situation of solvent, in reaction flask, add successively 5-10mmol alkylene cyclopentadiene, etc. the butyllithium of mole number, ice-water bath stirs 1-2hr down, stirs 2-3hr under the room temperature.Drip the tetrahydrofuran solution 2.5-5mmol of metal chloride then under ice-water bath, metal chloride is TiCl
4, ZrCl
4, HfCl
4, reacted 12-20 hour.Reaction mixture through taking out the tetrachloro furans, is changed toluene solution again, and the centrifugal lithium salts of removing, clear liquid are drained and can be obtained.
3. the preparation of the metallocene catalyst of high-molecular shell-nucleus structure
Under the condition of anhydrous and oxygen-free, with B compound 1-2g, vinylbenzene 5-10ml, Vinylstyrene 0.5-1.0ml joins in the toluene successively, mixes, and at room temperature adds the butyllithium of 0.5-1.0mmol then.Keep 50-60 ℃ polymerization 20-30 minute, add the metallocene compound 1-2mmol contain olefin group, repolymerization 1-2 hour.Use the toluene wash products at last, the precipitation that obtains promptly can be used for polymerization.
Ethene or alpha-olefine polymerizing and copolymerization are carried out under the anhydrous and oxygen-free condition, in reaction system, add toluene or ethane 100-2000ml, methylaluminoxane, the catalyst A l/M=500-5000 of high molecular, ethene successively, in 30-80 ℃ of reaction 1hr., with the ethanolic soln termination reaction that contains 1% (weight ratio) hydrochloric acid, products therefrom is filtered, with washing with alcohol 2-5 time, in 40 ℃ of vacuum-drying 12-24hr..
Embodiment provided by the invention is as follows:
Embodiment 1: the preparation of alkylene cyclopentadiene
The NaOH that in 200ml glass Schlenk bottle, adds 100ml 33% successively, cyclopentadiene, the hexenyl bromine is a consisting of phase-transferring agent at Tetrabutyl amonium bromide, stir 2hr in the ice-water bath, stir after the 6hr under the room temperature, oil phase is washed till neutrality, adopt the dry 12hr. of Anhydrous potassium carbonate after, obtain the hexenyl cyclopentadiene under 68 ℃ of the decompressions (40mmHg).Productive rate 50%.
Embodiment 2: the preparation of alkylene cyclopentadiene
6-methyl fulvene is a solvent with the hexane in 200ml glass Schlenk bottle, adds equimolar diisopropylamine lithium, stirs 1hr. in ice-water bath, stirs 2hr. under the room temperature.The centrifugal solid that obtains of reaction solution is washed 2 times with hexane again, and the product that obtains is the lithium salts of vinyl cyclopentadiene, productive rate 85%.
Embodiment 3: contain the preparation of the metallocene compound of alkylene
With propenyl cyclopentadiene C
3H
5C
5H
50.530g (5mmol) join in the 20ml tetrahydrofuran solution, under the condition of ice-water bath, the butyllithium of mole numbers such as dropping at room temperature stirs 2hr., adds lentamente then and contains CpTiCl
30.56g tetrahydrofuran solution (2.5mmol), stirring reaction 12hr. boils off solvent under the room temperature, adds toluene 50ml, and the centrifugal lithium salts of removing is drained clear liquid, again with hexane wash promptly for several times.
Embodiment 4: catalyst component A, the preparation of B
Under the condition of anhydrous and oxygen-free, with 1gSiO
2, 8ml vinylbenzene, the 0.5ml Vinylstyrene joins in the toluene successively, mixes, and at room temperature adds the butyllithium of 1.0ml1.0M then, keeps 50 ℃ of polyase 13s 0 minute.(the C that adds 5ml0.5M
3H
5C
5H
4) (C
5H
4) TiCl
2, repolymerization 1 hour.With toluene washed product repeatedly, in filtrate, do not have till metallocene compound and the polystyrene at last.The precipitation that obtains is product, and product is yellow.Ti content is 0.96wt%
Embodiment 5: catalyst component A, the preparation of B
Under the condition of anhydrous and oxygen-free, with 1g MgCl
2, 8ml vinylbenzene, the 0.5ml Vinylstyrene joins in the toluene successively, mixes, and at room temperature adds the butyllithium of a certain amount of 1.0ml1.0M then, keeps 60 ℃ of polymerizations 20 minutes.(the C that adds 5ml0.5M
3H
5C
9H
7)
2ZrCl
2, repolymerization 1 hour.All the other steps are with embodiment 4, and Zr content is 0.43wt% in the catalyzer.
Embodiment 6: catalyst component A, the preparation of B
Under the condition of anhydrous and oxygen-free, with the 1g polystyrene microsphere, 8ml vinylbenzene, the 0.5ml Vinylstyrene joins in the toluene successively, mixes, and at room temperature adds the butyllithium of a certain amount of 1.0ml1.0M then, keeps 50 ℃ of polyase 13s 0 minute.(the C that adds 5ml0.5M
5H
4) (C
4H
7C
13H
9) Hf (OMe)
2, repolymerization 1 hour.All the other steps are with embodiment 4, and Hf content is 1.7wt% in the catalyzer.
Embodiment 7: catalyst component A, the preparation of B
Under the condition of anhydrous and oxygen-free, with 1g Al
2O
3, 8ml vinylbenzene, the 0.5ml Vinylstyrene joins in the toluene successively, mixes, and at room temperature adds the butyllithium of a certain amount of 1.0ml1.0M then, keeps 50 ℃ of polyase 13s 0 minute.(the C that adds 5ml0.5M
6H
11C
5H
4)
2Zr (NMe
2)
2, repolymerization 1 hour.All the other steps are with embodiment 4, and Zr content is 1.3wt% in the catalyzer.
Embodiment 8: vinyl polymerization
In 200ml glass reaction bottle, add 100ml toluene, normal pressure feeds ethylene gas, the MAO toluene solution and the toluene suspension that contains catalyst A component prepared among the embodiment 5 of 0.5 μ mol Ti that under agitation add 2ml1M (2mmol) concentration successively, polyreaction are in 25 ℃ of following polymerization 1hr., with the ethanolic soln termination reaction that contains 1% hydrochloric acid, resulting polymers is filtered, washs, in 40 ℃ of vacuum-drying 24hr., get product 0.75g, catalytic efficiency is 1.25 * 10
6GPE/molZrhr.
Embodiment 9: propylene polymerization
In 200ml glass reaction bottle, add 100ml toluene, normal pressure feeds propylene gas, the MAO toluene solution and the toluene suspension that contains catalyst A component prepared among the embodiment 5 of 1.5 μ molZr that under agitation add 2ml1M (2mmol) concentration successively, polyreaction are in 50 ℃ of following polymerization 1hr., with the ethanolic soln termination reaction that contains 1% hydrochloric acid, resulting polymers is filtered, washs, in 40 ℃ of vacuum-drying 24hr., obtain product 1.0g, catalytic efficiency is 0.67 * 10
6GPP/molZrhr.
Embodiment 10: vinyl polymerization
In 21 reactors, add 600ml toluene, the MAO toluene solution and the toluene suspension that contains catalyst A component prepared among the embodiment 5 of 4 μ molTi that under agitation add 6ml1M (6mmol) concentration successively, 0.4MPa following feeding ethylene gas, polyreaction are in 80 ℃ of following polymerization 1hr., with the ethanolic soln termination reaction that contains 1% hydrochloric acid, resulting polymers is filtered, washs, in 40 ℃ of vacuum-drying 24hr., obtain product 42 grams, catalytic efficiency is 1.05 * 10
7GPE/molTi.hr.
Claims (3)
1. the preparation method of the metallocene catalyst of a high-molecular shell-nucleus structure is characterized in that catalyzer by A, and B and C three components are formed, and the expression formula of A is P (S-co-(R
1) m (R
2) nM), S is a vinylbenzene, co represents copolymerization, (R
1) m (R
2) nM is metallocene compound, M is Ti, Zr, Hf transition metal, R
1For cyclopentadienyl, the indenyl that contains the alkene replacement that contains the alkene replacement, the fluorenyl that contains the alkene replacement, can be C wherein as substituent alkene
2～C
10And two keys can be at the alkene of different positions; R
2Be F, Cl, Br, I, CH
3, OMe, OBu
2, m+n=4; B is the nuclear of catalyzer, and they are SiO
2, Al
2O
3, MgCL
2, polystyrene microsphere; C is methylaluminoxane (MAO) or B (C
6F
5)
3, the Preparation of catalysts process is as follows:
(1). the preparation of alkylene cyclopentadiene:
Phase transfer method: cyclopentadiene, alkylene chlorine or alkylene bromine are consisting of phase-transferring agent at Tetrabutyl amonium bromide, the NaOH of 100ml 30-50% is under the condition of solvent, stirred 2-3 hour in the ice-water bath, stirred 5-6 hour under the room temperature, through washing, drying, decompression makes product, yield 40-70%;
By the fulvene conversion method: adopting 6-methyl fulvene is reactant, is solvent at tetrahydrofuran (THF), adds equimolar diisopropylamine lithium, stirs 1-1.5 hour in ice-water bath, stirs 2-3 hour under the room temperature, makes product, yield 70-90%;
(2). contain the preparation of the metallocene catalyst of olefin group on the cyclopentadiene;
The all operations of Preparation of Catalyst all carries out under anhydrous and oxygen-free and high-purity argon gas protection; at tetrahydrofuran (THF) is under the situation of solvent; in reaction flask, add successively 5-10mmol alkylene cyclopentadiene, etc. the butyllithium of mole number; ice-water bath stirred 1-2 hour down; stirred 2-3 hour under the room temperature; drip the tetrahydrofuran solution 2.5-5mmol of metal chloride then under ice-water bath, metal chloride is TiCl
4, ZrCl
4, HfCl
4, reacting 12-20 hour, reaction mixture through taking out the tetrachloro furans, is changed toluene solution again, and the centrifugal lithium salts of removing, clear liquid are drained and can be obtained;
(3). the preparation of the metallocene catalyst of high-molecular shell-nucleus structure;
Under the condition of anhydrous and oxygen-free, with B compound 1-2g, vinylbenzene 5-10ml, Vinylstyrene 0.5-1.0ml, join in the toluene successively, mix, at room temperature add the butyllithium of 0.5-1.0mmol then, keep 50-60 ℃ polymerization 20-30 minute, add the metallocene compound 1-2mmol that contains olefin group, repolymerization 1-2 hour, use the toluene wash products at last, the precipitation that obtains promptly can be used for polymerization.
2. the preparation method of the metallocene catalyst of the high molecular of shell-core structure as claimed in claim 1 is characterized in that described catalyst component C is a methylaluminoxane.
3. the preparation method of the metallocene catalyst of the high molecular of shell-core structure as claimed in claim 1, the preparation that it is characterized in that described alkylene cyclopentadiene adopts that its reactant is the alkylene bromine in the phase transfer method.
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|---|---|---|---|
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| US7176158B2 (en) | 2002-10-25 | 2007-02-13 | Exxonmobil Chemical Patents Inc. | Polymerization catalyst composition |
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