CN1257875A - Process for preparing high-molecular metallocene catalyst - Google Patents
Process for preparing high-molecular metallocene catalyst Download PDFInfo
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- CN1257875A CN1257875A CN 98125651 CN98125651A CN1257875A CN 1257875 A CN1257875 A CN 1257875A CN 98125651 CN98125651 CN 98125651 CN 98125651 A CN98125651 A CN 98125651A CN 1257875 A CN1257875 A CN 1257875A
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- metallocene catalyst
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Abstract
A process for preparing high-molecular metallocene catalyst used for the homopolymerization and copolymerization of ethylene and alpha-olefin is disclosed. Said catalyst is composed of two components A and B. The A is a high-molecular metallocene compound and has the formula of P(S-co-(R1)m (R2)nM). The B is the methyl aluminoxane (MAO) or B(C6F5)3. Its advantages are high catalytic activity and no content of inorganic ash in polymerized product.
Description
The invention belongs to the preparation method of the metallocene catalyst of high molecular.
Since the 1980s, some metallocene compounds such as Cp have been it is found that
2ZrCl
2, CpZr (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 Aprplicaqtion 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 metallocene catalyst 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, above-mentioned catalyzer is homogeneous phase in reaction system, and the product bulk density is low, and poor morphology can not satisfy the requirement of vapour phase polymerization fluidized-bed process, so the modification of catalyzer has caused people's very big interest.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 EuropeanPatent358,264,367,503,368,644, a kind of preparation method of carried catalyst is disclosed, the inorganic carrier that utilization contains part moisture 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 high molecular.This method adopt contain the alkene substituting group because of metallocene catalyst compound and vinylbenzene under action of evocating, metallocene catalyst is keyed to the metallocene catalyst of formation high molecular on the macromolecular chain by σ.
The metallocene catalyst of high molecular has very high catalytic activity to vinyl polymerization, is suitable for gas phase and slurry polymerization processes.The metallocene catalyst high molecular can be controlled composition, the distribution of metallocene catalyst on polymer at an easy rate.Metallocene compound with inorganic carrier is compared, and polymerisate does not contain inorganic ash content.
The catalyzer of the present invention's preparation is made up of A and B two components, 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, transition metal such as Hf, R
1For the cyclopentadienyl of alkene replacement, the indenyl that alkene replaces, the fluorenyl that alkene replaces, can be C wherein as substituent alkene
2～C
10And two keys can be at the alkene of different positions; R
2Be Cl, CH
3, OMe, OBu, NMe
2, m+n=4; B is methylaluminoxane (MAO) or B (C
6F
5)
3
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, the NaOH of 100ml 30-35% is under the condition of solvent, stirs 2hr in the ice-water bath, stirs 6hr under the room temperature and makes.
By the fulvene conversion method: 6,6-dialkyl group fulvene is a solvent at tetrahydrofuran (THF), adds equimolar diisopropylamine lithium, stirs 1hr. in ice-water bath, stirs 2hr. under the room temperature and makes.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 2hr down, stirs 2hr under the room temperature.Drip the tetrahydrofuran solution 2.5-5mmol of metal chloride then under ice-water bath, reaction is spent the night.Reaction mixture through taking out tetrahydrofuran (THF), 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
Under the condition of anhydrous and oxygen-free, will contain the metallocene catalyst 2-10mmol of olefin group, vinylbenzene 5-10ml, Vinylstyrene 0.5-1ml, Diisopropyl azodicarboxylate 0.5wt% joins in the toluene successively, mixes, then copolymerization 3-6hr. in 80 ℃ water-bath.Adopt anhydrous hexane as precipitation agent, the precipitation that obtains is washed 3-5 time with hexane again and can be obtained.
Ethene (or ethylene/alpha-olefin) is aggregated under the anhydrous and oxygen-free condition and carries out, 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 for several times, in 40 ℃ of vacuum-drying 24hr..
Embodiment provided by the invention is as follows:
The preparation of embodiment 1 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%.
The preparation of embodiment 2 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 contains the preparation of the metallocene compound of alkylene
With butenyl cyclopentadiene C
4H
7C
5H
50.600g (5mmol) join in the 20ml tetrahydrofuran solution, under the condition of ice-water bath, the n-BuLi of mole numbers such as dropping at room temperature stirs 2hr., adds lentamente then and contains CpTiCl
30.56g tetrahydrofuran THF 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.
The preparation of embodiment 4 catalyst component A
(C with 5ml 0.4M
3H
5C
5H
4) (C
5H
5) TiCl
2Join in the 20ml toluene solution with 5ml vinylbenzene, add the 0.02g Diisopropyl azodicarboxylate, reaction solution is placed 80 ℃ of waters bath with thermostatic control, react 5hr., after reaction mixture is concentrated, precipitate with hexane, preserve solid, wash five times with toluene then, to remove (the C of not copolymerization
3H
5C
5H
4) (C
5H
5) TiCl
2, wash five times with hexane, to remove the vinylbenzene of not copolymerization, vacuum is taken out solution, obtains the solid catalyst powder, and measuring Ti content is 0.33wt%.
The preparation of embodiment 5 catalyst component A
(C with 5ml 0.5M
10H
19C
5H
4)
2TiMe
2Join in the 20ml toluene solution with 5ml vinylbenzene, add the 0.02g Diisopropyl azodicarboxylate, reaction solution is placed 80 ℃ of waters bath with thermostatic control, reaction 5hr., all the other steps are with embodiment 4, and Ti content is 0.38wt% in the mensuration catalyzer.
The preparation of embodiment 6 catalyst component A
(C with 5ml 0.4M
8H
17C
5H
4) (C
5H
5) Zr (NMe
2)
2, 5ml vinylbenzene and 0.8ml Vinylstyrene join in the 20ml toluene solution, adds the 0.02g Diisopropyl azodicarboxylate, reaction solution placed 80 ℃ of waters bath with thermostatic control, reaction 5hr..After reaction mixture concentrated,, preserve solid, wash five times with toluene then, to remove (the C of not copolymerization with the hexane precipitation
8H
17C
5H
4) (C
5H
5) Zr (Nme
2)
2, wash five times with hexane, to remove the vinylbenzene of not copolymerization, vacuum is taken out solution, obtains the solid catalyst powder.
The preparation of embodiment 7 catalyst component A
(C with 5ml 0.4M
5H
9C
5H
4)
2Hf (OMe)
2, 5ml vinylbenzene and 0.8ml Vinylstyrene join in the 20ml toluene solution, adds the 0.02g Diisopropyl azodicarboxylate, reaction solution placed 80 ℃ of waters bath with thermostatic control, reaction 5hr..After reaction mixture concentrated,, preserve solid, wash five times with toluene then, to remove (the C of not copolymerization with the hexane precipitation
5H
9C
5H
4)
2Hf (OMe)
2, wash five times with hexane, to remove the vinylbenzene of not copolymerization, vacuum is taken out solution, obtains the solid catalyst powder.
Embodiment 8 vinyl polymerizations
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 4 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 4.5g, catalytic efficiency is 9.0 * 10
6GPE/molTi.hr.
Embodiment 9 propylene polymerizations
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 6 of 0.5 μ molZr that under agitation add 2ml1M (2mmol) concentration successively, polyreaction, is filtered resulting polymers, wash with the ethanolic soln termination reaction that contains 1% hydrochloric acid in 50 ℃ of following polymerization 1hr., in 40 ℃ of vacuum-drying 24hr., obtain product.
Embodiment 10 vinyl polymerizations
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 40.12 grams, catalytic efficiency is 1.03 * 10
7GPE/molTi.hr..
Claims (4)
1, a kind of preparation method of metallocene catalyst of high molecular is characterized in that catalyzer is made up of A and B two components, 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 the cyclopentadienyl of alkene replacement, the indenyl that alkene replaces, the fluorenyl that alkene replaces, be C wherein as substituent alkene
2～C
10And two keys can be at the alkene of different positions; R
2Be Cl, CH
3, OMe, OBu, NMe
2, m+n=4; B is methylaluminoxane (MAO) or B (C
6F
5)
3
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, the NaOH of 33-35% is under the condition of solvent, stirs 2hr. in the ice-water bath, stirs 6hr. under the room temperature and makes;
By the fulvene conversion method: 6,6-dialkyl group fulvene is a solvent at tetrahydrofuran (THF), adds equimolar diisopropylamine lithium, stirs 1hr. in ice-water bath, stirs 2hr. under the room temperature and makes; (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, add alkylene cyclopentadiene, butyllithium successively in reaction flask, ice-water bath stirs 2hr. down, stirs 2hr. under the room temperature, under ice-water bath, drip the tetrahydrofuran solution of metal chloride then, reaction is spent the night, and reaction mixture through taking out tetrahydrofuran (THF), is changed toluene solution again, the centrifugal lithium salts of removing, clear liquid are drained and can be obtained; (3). the preparation of the metallocene catalyst of high molecular
Under the condition of anhydrous and oxygen-free, the metallocene catalyst that will contain olefin group, vinylbenzene, Vinylstyrene, Diisopropyl azodicarboxylate joins in the toluene successively, mixes, then copolymerization 3-6hr. in 80 ℃ water-bath, adopt anhydrous hexane as precipitation agent, the precipitation that obtains is washed 3-5 time with hexane again and can be obtained.
2, the preparation method of metallocene catalyst as claimed in claim 1 is characterized in that the R in the described A component
1Cyclopentadienyl for the alkene replacement.
3, the preparation method of metallocene catalyst as claimed in claim 1 is characterized in that the R in the described A component
2Be Cl, CH
3, OMe, NMe
2
4, the preparation method of metallocene catalyst as claimed in claim 1 is characterized in that described B component is methylaluminoxane (MAO).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98125651 CN1257875A (en) | 1998-12-24 | 1998-12-24 | Process for preparing high-molecular metallocene catalyst |
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|---|---|---|---|
| CN 98125651 CN1257875A (en) | 1998-12-24 | 1998-12-24 | Process for preparing high-molecular metallocene catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7119155B2 (en) | 2002-10-25 | 2006-10-10 | Exxonmobil Chemical Patents Inc. | Polymerized catalyst composition II |
| US7176158B2 (en) | 2002-10-25 | 2007-02-13 | Exxonmobil Chemical Patents Inc. | Polymerization catalyst composition |
| US7319083B2 (en) | 2002-10-25 | 2008-01-15 | Exxonmobil Chemical Patents Inc. | Polymerized catalyst composition |
| CN104558265A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Metallocene catalyst system and preparation method thereof |
-
1998
- 1998-12-24 CN CN 98125651 patent/CN1257875A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7119155B2 (en) | 2002-10-25 | 2006-10-10 | Exxonmobil Chemical Patents Inc. | Polymerized catalyst composition II |
| US7176158B2 (en) | 2002-10-25 | 2007-02-13 | Exxonmobil Chemical Patents Inc. | Polymerization catalyst composition |
| US7319083B2 (en) | 2002-10-25 | 2008-01-15 | Exxonmobil Chemical Patents Inc. | Polymerized catalyst composition |
| CN104558265A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Metallocene catalyst system and preparation method thereof |
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