CN1371923A - Process for preparing high molecular double-activity centre olefine polymerizing catalyst containing silicon bridged group metallocene - Google Patents

Process for preparing high molecular double-activity centre olefine polymerizing catalyst containing silicon bridged group metallocene Download PDF

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CN1371923A
CN1371923A CN 02104273 CN02104273A CN1371923A CN 1371923 A CN1371923 A CN 1371923A CN 02104273 CN02104273 CN 02104273 CN 02104273 A CN02104273 A CN 02104273A CN 1371923 A CN1371923 A CN 1371923A
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alkylene
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金国新
诸海滨
刘长坤
汤光荣
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The catalyst of formed from A and B. The expression formiula of A ios [P(ComM-co-S-co-Com Fe)], in which P represents copolymer, S is polystyrene, Co represents copolymerization, Com M represents cyclopentadienyl metal containing silicon bridge group and Com Fe represents iron series catalyst. The B is methyl aluminium oxoalkane (MAO) or modified methyl aluminium oxoalkane (MMAO). Said catalyst possesses high catalytic activity, is suitable for polymerization process of gas phase and slurry, and its polymer possesses special properties.

Description

The preparation method of double activity center's olefin polymerization catalysis of the siliceous bridged group metallocene of high molecular
Technical field:
The invention belongs to the preparation method of double activity center's olefin polymerization catalysis of the siliceous bridged group metallocene of high molecular.
Background technology:
Olefin polymerization catalysis is the core of polyolefin industry, its development is from traditional Ziegleg-Natta catalyzer, metallocene catalyst has experienced three phases to late transition metal catalyst, metallocene catalyst has different separately characteristics with the late transition metal catalyst that is now just becoming the research focus, how the advantages of two class catalyzer is got up, the polyolefine material of preparation structure and performance novelty will become a new research direction.Chinese patent 98125651.1,1998; 00121820.4 2000 openly are applicable to the method for the macromolecule loadingization of single metal center catalyzer respectively.Chinese patent 01140471.X then provides the preparation method of polymer double activity center olefin polymerization catalysis, is that late transition metal catalyst is connected to polymer carrier simultaneously with the metallocene catalyst and the iron of non-bridging.
Summary of the invention:
An object of the present invention is to provide double activity center's olefin polymerization catalysis of the siliceous bridged group metallocene of a kind of high molecular, another purpose provides the preparation method of double activity center's olefin polymerization catalysis of the siliceous bridged group metallocene of a kind of high molecular, and the 3rd purpose of the present invention provides the application of double activity center's olefin polymerization catalysis in olefinic polymerization of the siliceous bridged group metallocene of a kind of high molecular.The metallocene compound that the present invention contains silicon bridge alkylene is pyridine diimine compound and vinylbenzene are connected to the metallic compound copolymerization formation high molecular load on the macromolecular chain under action of evocating double activity center's olefin polymerization catalysis with the iron that contains alkylene.Two active centre are arranged in such catalyst structure, and katalysis takes place in these two active centre simultaneously when catalysis in olefine polymerization, and cooperation mutually, makes the gained polyolefin products have particular performances.
The catalyzer of the present invention's preparation is made up of A and B two components, A component expression formula is [P (ComM-co-S-co-Com Fe)], P represents multipolymer, S is a polystyrene, co represents copolymerization, Com M represents the silyl-bridged metallocene catalyst, and Com Fe represents Fe-series catalyst, and the B component is methylaluminoxane (MAO) or improves methylaluminoxane (MMAO).
The structural formula of A component of the present invention is as follows:
Figure A0210427300081
R wherein 1, R 2, R 3, R 4Be respectively H, CH 3, i-Pr, t-Bu one of them; R 5Be H or allyl group; X is Cl or Br; M=0-4, M are Ti, Zr or Hf; X is Cl or Br; R 6Be Me, Et or Ph; R 7, R 8, R 9, R 9, R 10, R 7 ', R 8 ', R 9 ', R 10 'Be H, Me, tBu or SiMe 3
1): the preparation of silicon bridge olefine-containing group metallocene catalyst Com M:
(a) all join the preparation of type silyl-bridged metallocene catalyst
At first going out corresponding substituted cyclopentadienyl sodium salt by substituted-cyclopentadienyl and sodium prepared in reaction, is 2: 1 substituted cyclopentadienyl sodium salts and corresponding silyl-bridged reagent react by mol ratio, then with two times of molar weights nThe BuLi reaction generates dilithium salt, again with equimolar MCl 4Reaction, productive rate: 40%-50%, its preparation feedback process is as follows:
Figure A0210427300091
(b) preparation of the silyl-bridged metallocene catalyst of mixed matching
Earlier is 1: 2 a kind of substituted cyclopentadienyl sodium salt and corresponding silica reagent reaction, and then generates corresponding silyl-bridged part, then with two times of molar weights with another kind of substituted cyclopentadienyl sodium salt reaction with same mole by mol ratio nThe BuLi reaction generates corresponding part dilithium salt, then with equimolar MCl 4Reaction, productive rate: 40%-50%, its preparation feedback process is as follows:
2). the preparation of alkylene arylamine
Its structural formula is:
Figure A0210427300102
R is H, Me, i-Pr or t-Bu one of them;
Arylamine and alkylene chlorine or alkylene bromine get N-alkylene arylamine by amount of substance than 2: 1 reacting by heating, productive rate 30.0-84.3%, N-alkylene arylamine and excessive ZnCl 2Reflux generation rearrangement reaction generates 4-alkylene arylamine or 2-alkylene arylamine in toluene solvant.Productive rate 25.2-70.9%.
3). the preparation of alkylene Fe-series catalyst Com Fe
At first 2.6-diacetyl pyridine and alkylene amine carry out two the step acid catalyzed condensation reactions prepare the corresponding pyridine diimide ligand; if this ligand structure symmetry then two step condensation reactions can one the step finish, this moment, amine and 2.6-diacetyl pyridine mol ratio were 2: 1.By the pyridine diimine part and the FeX that have been prepared into 2Reaction can make the pyridine diimine compound that contains alkylene, productive rate 90-95%.Its preparation feedback process is as follows: R wherein 1, R 2, R 3, R 4, R 5, R 6Be respectively H, CH 3, i-Pr or t-Bu; X is Cl or Br.
4). the preparation of high molecular double activity center olefin polymerization catalysis
Under the anhydrous and oxygen-free condition, the metallocene catalyst Com M that silicon bridge is contained alkylene, the Fe-series catalyst Com Fe that contains alkylene, vinylbenzene, Diisopropyl azodicarboxylate, join successively in the exsiccant toluene and mix, copolymerization in water-bath is then made precipitation agent with normal hexane, gets the pressed powder of multipolymer, with normal hexane washing three times, oven dry gets final product again.
5). the catalyzed ethylene polymerization reaction
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50-500mL successively, methylaluminoxane (MAO) or improvement methylaluminoxane (MMAO), the catalyst A l/ of high molecular double activity center (Fe+M)=350-2200, ethene 1-20atm was in 0-60 ℃ of reaction 1 hour, with containing the ethanolic soln termination reaction that weight ratio is 1% hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 24 hours.
Embodiment is as follows:
Embodiment 1: the metallocene catalyst C of silicon bridge olefine-containing group 13H 14SiZrCl 2Preparation
Cyclopentadienyl sodium 15.32mmol is dissolved in Et 2Among the O, spend the night with vinyl dimethyl dichlorosilane (DMCS) 7.66mmol reaction.Add 15.32mmol 〃 BuLi hexane solution afterwards under the room temperature, reaction 24h forms dilithium salt.Dilithium salt is transferred to 7.66mmol ZrCl 4Et 2In the O solution, react 48h under the room temperature.Vacuum extracts solvent, and the toluene extraction is filtered, and the filtrate freezing and crystallizing promptly arrives product C 13H 14SiZrCl 20.828g, productive rate 30%.
Embodiment 2: the metallocene catalyst C of silicon bridge olefine-containing group 14H 16SiZrCl 2Preparation
Cyclopentadienyl sodium 13.76mmol is dissolved among the 50mL DME, adds allyl methyl dichlorosilane 6.88mmol reaction under the room temperature and spends the night.Add 13.76mmol 〃 BuLi hexane solution afterwards under the room temperature, reaction 24h forms dilithium salt.Dilithium salt is transferred to 6.88mmol ZrCl 4DME solution in, react 48h under the room temperature.Vacuum extracts solvent, and the toluene extraction is filtered, and the filtrate freezing and crystallizing promptly arrives product C 14H 16SiZrCl 21.287g, productive rate 50%.
Embodiment 3: the metallocene catalyst C of silicon bridge olefine-containing group 18H 24SiHfCl 2Preparation
2,4-dimethyl cyclopentadienyl sodium 15.32mmol is dissolved among the DME (glycol dimethyl ether), spends the night with vinyl ethyl dichlorosilane 7.66mmol reaction.-78 ℃ add 15.32mmol 〃 BuLi hexane solution down, and reaction 24h forms dilithium salt under the room temperature.Dilithium salt is transferred to 7.66mmol HfCl 4DME solution in, 70 ℃ the reaction 48h.Vacuum extracts solvent, and the toluene extraction is filtered, and the filtrate freezing and crystallizing promptly arrives product C 18H 24SiHfCl 21.625g, productive rate 41%.
Embodiment 4: the metallocene catalyst C of silicon bridge olefine-containing group 26H 32SiTiBr 2Preparation
Cyclopentadienyl sodium 6.88mmol is dissolved among the 50mL THF and spends the night with alkene hexyl diphenyl dichlorosilane 13.76mmol reaction, vacuum extracts solvent and excessive alkene hexyl diphenyl dichlorosilane, add 6.88mmol tertiary butyl cyclopentadienyl sodium reaction 12h then,-78 ℃ add 13.76mmol 〃 BuLi hexane solution, reaction 24h forms dilithium salt under the room temperature, then with 6.88mmolTiBr 4THF solution reaction 48h, extract solvent, the extraction, freezing and crystallizing promptly gets product C 26H 32SiTiBr 21.277g, productive rate 32%.
Embodiment 5: the preparation of alkylene arylamine
2.6-diisopropyl aniline 0.2mol and chlorallylene 0.1mol reflux 10 hours, cooling was placed after 12 hours, in the impouring 400mL water, adding sodium hydroxide makes solution be alkalescence, extracted with diethyl ether, vacuum decompression distill N-allyl group aniline 18.33g, productive rate 84.3%. is that solvent adds N-allyl group aniline 0.084mol and excessive ZnCl with 100mL toluene 2, refluxed 5 hours under the argon atmospher, in the aqueous solution of cooling impouring sodium hydroxide, separate organic layer, after lower floor's insolubles is dissolved in the concentrated hydrochloric acid of heat again in the above-mentioned alkaline solution of impouring extracted with diethyl ether merge organic layer, anhydrous magnesium sulfate drying, underpressure distillation gets 4-allyl group aniline 12.92g behind the vacuum concentration.Productive rate 70.9%.
Embodiment 6: the preparation of alkylene arylamine
Aniline 0.24mol and allyl bromide 98 0.12mol reflux 8 hours, cooling was placed after 10 hours, in the impouring 200mL water, adding sodium hydroxide makes solution be alkalescence, extracted with diethyl ether, vacuum decompression distill N-allyl group aniline 8.645g, productive rate 54.17%. is that solvent adds N-allyl group aniline 0.065mol and excessive ZnCl with 200mL toluene 2, refluxed 8 hours under the argon atmospher, in the aqueous solution of cooling impouring sodium hydroxide, separate organic layer, after lower floor's insolubles is dissolved in the concentrated hydrochloric acid of heat again in the above-mentioned alkaline solution of impouring extracted with diethyl ether merge organic layer, anhydrous magnesium sulfate drying, underpressure distillation gets 2-allyl group aniline 2.18g behind the vacuum concentration.Productive rate 25.2%.
Embodiment 7: the preparation of alkylene arylamine
4-tertiary butyl aniline 0.2mol and chlorallylene 0.1mol reflux 9 hours, cooling was placed after 11 hours, in the impouring 300mL water, adding sodium hydroxide makes solution be alkalescence, extracted with diethyl ether, vacuum decompression distill N-allyl group-2-tertiary butyl aniline 5.67g, productive rate 30.0%. is that solvent adds N-allyl group-2-tertiary butyl aniline 0.03mol and excessive ZnCl with 50mL toluene 2Refluxed 6 hours under the argon atmospher, in the aqueous solution of cooling impouring sodium hydroxide, separate organic layer, after lower floor's insolubles is dissolved in the concentrated hydrochloric acid of heat again in the above-mentioned alkaline solution of impouring extracted with diethyl ether merge organic layer, anhydrous magnesium sulfate drying, underpressure distillation gets 4-allyl group-2-tertiary butyl aniline 3.54g, productive rate 62.4% behind the vacuum concentration.
Embodiment 8: the preparation of alkylene Fe-series catalyst Com Fe
With methyl alcohol is solvent, and formic acid is catalyzer, 4-allyl group-2.6-diisopropyl aniline, and 2.6-diisopropyl aniline and the condensation reaction of 2.6-diacetyl pyridine generate tridentate pyridine diimide ligand C 36H 47N 3The preparation of Com Fe is carried out under the anhydrous and high-purity argon gas protective condition in anaerobic.With THF 40mL is solvent, this pyridine diimine part 4.0mmol and FeCl 24H 2O3.8mmol stirring at room 2 hours gets blue solution, and vacuum concentration adds normal hexane and is settled out blue powder, filters, and vacuum-drying gets C 36H 47N 3FeCl 22.34g, productive rate 95%.
Embodiment 9: the preparation of alkylene Fe-series catalyst Com Fe
With methyl alcohol is solvent, and formic acid is catalyzer, 2-tertiary butyl-4-allyl group aniline, and 2.6-xylidine and the condensation reaction of 2.6-diacetyl pyridine generate tridentate pyridine diimide ligand C 30H 35N 3The preparation of Com Fe is carried out under the anhydrous and high-purity argon gas protective condition in anaerobic.With THF 40mL is solvent, this pyridine diimine ligand 1 .51mmol and FeCl 24H 2O1.44mmol stirring at room 3 hours gets blue solution, and vacuum concentration adds normal hexane and is settled out blue powder, filters, and vacuum-drying gets C 30H 35N 3FeCl 20.731g, productive rate 90%.
Embodiment 10: the preparation of alkylene Fe-series catalyst Com Fe
With methyl alcohol is solvent, and formic acid is catalyzer, and 2-allyl group aniline and the condensation reaction of 2.6-diacetyl pyridine generate tridentate pyridine diimide ligand C 27H 27N 3The preparation of Com Fe is carried out under the anhydrous and high-purity argon gas protective condition in anaerobic.With THF 35mL is solvent, this pyridine diimine part 2.27mmol and FeCl 24H 2O 2.16mmol stirring at room 2.5 hours gets blue solution, and vacuum concentration adds normal hexane and is settled out blue powder, filters, and vacuum-drying gets C 27H 27N 3FeCl 21.044g, productive rate 93%.
Embodiment 11: the preparation of high molecular double activity center olefin polymerization catalysis
Under the anhydrous and oxygen-free condition, with the silyl-bridged metallocene catalyst C of embodiment 1 preparation 13H 14SiZrCl 21.5mmol, embodiment 8 preparation Fe-series catalyst C 36H 47N 3FeCl 20.4mmol, vinylbenzene 10mL, Diisopropyl azodicarboxylate 1.0wt% joins successively in the exsiccant toluene and mixes, then copolymer-1 after 2 hours in 80 ℃ water-bath, be cooled to room temperature, centrifugal, supernatant liquid is made precipitation agent with normal hexane, gets pressed powder, with normal hexane washing three times, oven dry gets final product again.Measuring zirconium content is 1.75wt%, and iron level is 0.467wt%.
Embodiment 12: the preparation of high molecular double activity center olefin polymerization catalysis
Under the anhydrous and oxygen-free condition, with the silyl-bridged metallocene catalyst C of embodiment 2 preparations 14H 16SiZrCl 21.0mmol, the Fe-series catalyst C of embodiment 8 preparations 36H 47N 3FeCl 20.04mmol, vinylbenzene 10mL, Diisopropyl azodicarboxylate 1.0wt% joins successively in the exsiccant toluene and mixes, then copolymer-1 after 2 hours in 80 ℃ water-bath, be cooled to room temperature, centrifugal, supernatant liquid is made precipitation agent with normal hexane, gets pressed powder, with normal hexane washing three times, oven dry gets final product again.Measuring zirconium content is 1.88wt%, and iron level is 0.095wt%.
Embodiment 13: the preparation of high molecular double activity center olefin polymerization catalysis
Under the anhydrous and oxygen-free condition, with the silyl-bridged metallocene catalyst C of embodiment 3 preparations 18H 24SiHfCl 22.0mmol, embodiment 9 preparation Fe-series catalyst C 30H 35N 3FeCl 20.5mmol, vinylbenzene 10mL, Diisopropyl azodicarboxylate 1.0wt% joins successively in the exsiccant toluene and mixes, then copolymer-1 2 hours in 80 ℃ water-bath. after, be cooled to room temperature, centrifugal, supernatant liquid is made precipitation agent with normal hexane, gets pressed powder, with normal hexane washing three times, oven dry gets final product again.Measuring hafnium content is 1.82wt%, and iron level is 0.560wt%.
Embodiment 14: the preparation of high molecular double activity center olefin polymerization catalysis
Under the anhydrous and oxygen-free condition, with the silyl-bridged metallocene catalyst C of embodiment 4 preparations 26H 32SiTiBr 20.6mmol, embodiment 10 preparation Fe-series catalyst C 27H 27N 3FeCl 20.3mmol, vinylbenzene 10mL, Diisopropyl azodicarboxylate 1.0wt% joins successively in the exsiccant toluene and mixes, then copolymer-1 2 hours in 80 ℃ water-bath. after, be cooled to room temperature, centrifugal, supernatant liquid is made precipitation agent with normal hexane, gets pressed powder, with normal hexane washing three times, oven dry gets final product again.The mensuration titanium content is 0.458wt%, and iron level is 0.516wt%.
Embodiment 15: vinyl polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50mL successively, methylaluminoxane, the catalyzer 0.011g of high molecular double activity center of embodiment 11 preparations, Al/ (Fe+Zr)=367, ethene 1atm, in 18 ℃ of reactions 1 hour,, products therefrom is filtered with containing the ethanolic soln termination reaction that weight ratio is 1% hydrochloric acid, with washing with alcohol for several times, got polyethylene 0.440g in 24 hours in 40 ℃ of vacuum-dryings.
Embodiment 16: vinyl polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 200mL successively, improve methylaluminoxane, the catalyzer 0.011g of high molecular double activity center of embodiment 11 preparations, Al/ (Fe+Zr)=1467, ethene 4atm, in 50 ℃ of reactions 1 hour,, products therefrom is filtered with containing the ethanolic soln termination reaction that weight ratio is 1% hydrochloric acid, with washing with alcohol for several times, got polyethylene 31.03g in 24 hours in 40 ℃ of vacuum-dryings.
Embodiment 17: vinyl polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 100mL successively, improve methylaluminoxane, the catalyzer 0.013g of high molecular double activity center of embodiment 12 preparations, Al/ (Fe+Zr)=2200, ethene 1atm, in 0 ℃ of reaction 1 hour,, products therefrom is filtered with containing the ethanolic soln termination reaction that weight ratio is 1% hydrochloric acid, with washing with alcohol for several times, got polyethylene 1.746g in 24 hours in 40 ℃ of vacuum-dryings.
Embodiment 18: vinyl polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 500mL successively, methylaluminoxane, the catalyzer 0.013g of high molecular double activity center of embodiment 12 preparations, Al/ (Fe+Zr)=1833 ethene 4atm was in 60 ℃ of reactions 1 hour, with containing the ethanolic soln termination reaction that weight ratio is 1% hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, got polyethylene 10.79g in 24 hours in 40 ℃ of vacuum-dryings.
Embodiment 19: vinyl polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 200mL successively, methylaluminoxane, the catalyzer 0.020g of high molecular double activity center of embodiment 13 preparations, Al/ (Fe+Hf)=1700 ethene 8atm was in 45 ℃ of reactions 1 hour, with containing the ethanolic soln termination reaction that weight ratio is 1% hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, got polyethylene 20.58g in 24 hours in 40 ℃ of vacuum-dryings.
Embodiment 20: vinyl polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 300mL successively, methylaluminoxane, the catalyzer 0.013g of high molecular double activity center of embodiment 14 preparations, Al/ (Fe+Ti)=2200 ethene 20atm was in 25 ℃ of reactions 1 hour, with containing the ethanolic soln termination reaction that weight ratio is 1% hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, got polyethylene 19.59g in 24 hours in 40 ℃ of vacuum-dryings.

Claims (6)

1. family macromoleculeization double activity center's olefin polymerization catalysis of containing silicon bridge base metallocene is made up of A and B two components, A component expression formula is [P (Com M-co-S-co-Com Fe)], P represents multipolymer, S is a polystyrene, co represents copolymerization, Com M represents the silyl-bridged metallocene catalyst, and Com Fe represents Fe-series catalyst, and the B component is methylaluminoxane (MAO) or improves methylaluminoxane (MMAO);
Its structural formula is as follows: R wherein 1, R 2, R 3, R 4Be respectively H, CH 3, i-Pr, t-Bu one of them; R 5Be H or allyl group; X is Cl or Br; M=0-4, M are Ti, Zr or Hf; X is Cl or Br; R 6Be Me, Et or Ph; R 7, R 8, R 9, R 10, R 7 ', R 8 ', R 9 ', R 10 'Be H, Me or tBu;
1). the preparation of silicon bridge olefine-containing group metallocene catalyst Com M:
At first going out the substituted cyclopentadienyl sodium salt by substituted-cyclopentadienyl and sodium prepared in reaction, is 2: 1 substituted cyclopentadienyl sodium salts and silyl-bridged reagent react by mol ratio, then with two times of molar weights nThe BuLi reaction generates dilithium salt, again with equimolar MCl 4Reaction, productive rate: 40%-50%, its preparation feedback process is as follows:
Figure A0210427300031
2). the preparation of alkylene arylamine
Its structural formula is: R is H, Me, i-Pr or t-Bu one of them;
Arylamine and alkylene chlorine or alkylene bromine get N-alkylene arylamine by amount of substance than 2: 1 reacting by heating, productive rate 30.0-84.3%, N-alkylene arylamine and excessive ZnCl 2Reflux generation rearrangement reaction generates 4-alkylene arylamine or 2-alkylene arylamine, productive rate 25.2-70.9% in toluene solvant;
3). the preparation of alkylene Fe-series catalyst Com Fe
At first 2.6-diacetyl pyridine and alkylene amine carry out two acid catalyzed condensation reactions of step and prepare the pyridine diimine part, if this ligand structure symmetry then two step condensation reactions can one the step finish, this moment, amine and 2.6-diacetyl pyridine mol ratio were 2: 1; By the pyridine diimine part and the FeX that have been prepared into 2Reaction promptly makes the pyridine diimine compound that contains alkylene, productive rate 90-95%, and its preparation feedback process is as follows:
Figure A0210427300041
R wherein 1, R 2, R 3, R 4, R 5, R 6Dividing in addition is H, CH 3, i-Pr or t-Bu; X is Cl or Br;
4). the preparation of high molecular double activity center olefin polymerization catalysis
Under the anhydrous and oxygen-free condition, the metallocene catalyst Com M that silicon bridge is contained alkylene, the Fe-series catalyst Com Fe that contains alkylene, vinylbenzene, Diisopropyl azodicarboxylate, join successively in the exsiccant toluene and mix, copolymerization in water-bath is then made precipitation agent with normal hexane, gets the pressed powder of multipolymer, again with normal hexane washing three times, oven dry;
5). the catalyzed ethylene polymerization reaction
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50-500mL successively, methylaluminoxane (MAO) or improvement methylaluminoxane (MMAO), the catalyst A l/ of high molecular double activity center (Fe+M)=350-2200, ethene 1-20atm was in 0-60 ℃ of reaction 1 hour, with containing the ethanolic soln termination reaction that weight ratio is 1% hydrochloric acid, products therefrom is filtered, use washing with alcohol, in 40 ℃ of vacuum-dryings 24 hours.
2. the preparation method of double activity center's olefin polymerization catalysis of the siliceous bridged group metallocene of high molecular as claimed in claim 1, it is characterized in that the preparation of described silicon bridge olefine-containing group metallocene catalyst ComM, by mol ratio earlier 1: 2 a kind of substituted cyclopentadienyl sodium salt and silica reagent reaction, generate the silyl-bridged part with another kind of substituted cyclopentadienyl sodium salt reaction with same mole again, then with two times of molar weights nThe BuLi reaction generates the part dilithium salt, then with equimolar MCl 4Reaction, productive rate: 40%-50%, its preparation feedback process is as follows:
3. the method for Com Fe in the double activity center's olefin polymerization catalysis for preparing the siliceous bridged group metallocene of the described high molecular of claim 1 comprises:
At formic acid, acetate, CF 3Under the catalysis of COOH and hydrochloric acid, the condensation reaction of the alkylene substituted aromatic amines shown in 2.6-diacetyl pyridine and the following formula in acid and alcoholic solvent system
4. the preparation method of double activity center's olefin polymerization catalysis of the siliceous bridged group metallocene of high molecular as claimed in claim 1, it is characterized in that described vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50-500mL, methylaluminoxane successively.
5. the preparation method of double activity center's olefin polymerization catalysis of the siliceous bridged group metallocene of high molecular as claimed in claim 1, it is characterized in that described vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene 50-500mL successively, improve methylaluminoxane (MMAO).
6. produce poly method for one kind, comprising the synthesis step of the olefin polymerization catalysis A of the double activity center component of using the siliceous bridged group metallocene of high molecular shown in the claim 1.
CN 02104273 2002-03-04 2002-03-04 Process for preparing high molecular double-activity centre olefine polymerizing catalyst containing silicon bridged group metallocene Pending CN1371923A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7034157B2 (en) * 2003-10-23 2006-04-25 Fina Technology, Inc. Catalyst components, process for their preparation and their use as catalyst components in polymerization of olefins
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

Cited By (4)

* Cited by examiner, † Cited by third party
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
US7034157B2 (en) * 2003-10-23 2006-04-25 Fina Technology, Inc. Catalyst components, process for their preparation and their use as catalyst components in polymerization of olefins

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