CN1352204A - Process for preparing high molecular double active center olefine polymerization catalyst - Google Patents

Abstract

The present invention relates to a preparation method of a polymerized double-active center olefin polymerization catalyst. In the method, an iron-based pyridine bisimine compound containing an olefin group, a metallocene compound containing an olefin group, and styrene are synthesized under the action of an initiator. The metal compound is connected to the polymer chain through the C-Cα bond to form a polymerized double-active center olefin polymerization catalyst, and its expression is [P(ComFe-co-S-co-Com M)], P represents the copolymer, S It is polystyrene, co means copolymerization, Com Fe means iron-based catalyst, and Com M means metallocene catalyst. The dual active centers catalyze simultaneously during the polymerization process and produce synergistic effects. This kind of catalyst has high catalytic activity in catalyzing ethylene polymerization, and the obtained polymer has unique properties, which are suitable for gas phase and slurry polymerization processes.

Description

Preparation method of polymerized double active center olefin polymerization catalyst

Technical field: the present invention relates to an olefin polymerization catalyst, in particular to a polymerized double-active center olefin polymerization catalyst;

The present invention also relates to a preparation method of the above-mentioned catalyst;

The invention also relates to the use of the aforementioned catalysts in the polymerization of olefins, especially in the polymerization of ethylene.

Background technology: polyolefin is the pillar industry of modern polymer material industry, and catalyst is the core of polyolefin industry. In recent years, the development of olefin polymerization catalysts has gone far beyond the scope of the traditional active center being the early transition metals of IVB group, and the late transition metal olefin polymerization catalysts have become a new hotspot of research (Lettl S.D, Johnson L.K, Brookhart M, Chem. Rev 2000, 100, 1169; Britovsek G.J.P, Gibson V.C, Wass D.F, Angew. Chem. Iht. Ed, 1999, 38, 428). However, traditional early transition metal catalysts are playing a huge role in modern industrial production. How to combine the advantages of early transition metal catalysts and late transition metal catalysts to prepare polyolefin materials with novel structures and properties has become an important research direction. Chinese patents (98125651.1, 1998; 00121820.4, 2000) respectively disclose a preparation method of a polymerized metallocene olefin polymerization catalyst and a preparation method of a polymerized post-transition metal "post-molecular" olefin polymerization catalyst. Both methods are suitable for the polymer support of single metal center catalysts.

Summary of the invention: The purpose of the present invention is to provide a high molecular weight double active center olefin polymer catalyst, which has two active centers in the catalyst structure, and these two active centers simultaneously catalyze and cooperate with each other when catalyzing olefin polymerization .

Another object of the present invention is to provide a method for preparing a polymerized double active center olefin polymerization catalyst, which has a simple process and is easy to control.

Another object of the present invention is to provide a polymerized double-active-center olefin polymer catalyst for use in olefin polymerization, especially in ethylene polymerization, and the obtained polyolefin product has unique properties.

In order to achieve the above object, the polymerized double active center olefin polymer catalyst provided by the present invention is composed of A and B two components, and the expression of A component is [P(Com Fe-co-S-co-Com M)] , P represents a copolymer, S represents polystyrene, co represents a copolymerization, Com Fe represents an iron-based catalyst, ComM represents a metallocene catalyst, and the specific structural formula is as follows:

ComFe: R ₁ , R ₂ , R ₃ , R ₄ are one of H, CH ₃ , i-Pr, t-Bu; R ₅ is H or allyl, X is Cl or Br;

其中之一；M为Ti，Zr或Hf；X为Cl或Br；

ComM: R ₆ are H, One of them; R ₇ are

One of them; M is Ti, Zr or Hf; X is Cl or Br;

High molecular weight double active center olefin polymerization catalyst model: R ₁ =R ₂ =R ₃ =R ₄ =CH ₃ ; R ₅ =R ₆ =R ₇ =allyl; M = Zr; X = Cl;

Component B is methylalumoxane (MAO), modified methylalumoxane (MMAO) or pentafluorophenylboron.

The polymerized double active center olefin polymerization catalyst provided by the present invention has not been reported in literature or patents so far.

The invention provides a method for preparing a polymerized double-active center olefin polymerization catalyst. The iron-based pyridine bis-imine compound containing an alkene group and the metallocene compound containing an alkene group and styrene are used as an initiator to convert the metal The compound is connected to the polymer chain through a C-Cα bond to form a polymerized double active center olefin polymerization catalyst.

The preparation process of the catalyst is as follows:

1. Preparation of alkenyl arylamine

R为H，Me，i-Pr，t-Bu其中之一Its structural formula is:

R is one of H, Me, i-Pr, t-Bu

Aromatic amine and alkenyl chloride or alkenyl bromide in a molar ratio of 2:1, heating and reacting to obtain N-alkenyl arylamine, yield 30.0-84.3%, N-alkenyl arylamine and excess _ZnCl in toluene solvent Heated to reflux A rearrangement reaction occurs to generate 4-alkenyl arylamine or 2-alkenyl arylamine. Yield 25.2-70.9%.

2. Preparation of alkenyl cyclopentadiene

R为 其中之一Its structural formula is:

R is one of them

Equimolar cyclopentadiene reacts with chlorinated olefin or brominated olefin in NaOH aqueous solution under tetrabutylammonium bromide as a phase transfer agent to obtain alkene-substituted cyclopentadiene. Yield 40-70%.

3. Preparation of olefin-based iron-based catalyst Com Fe

First, 2.6-diacetylpyridine and alkenyl amine undergo two-step acid-catalyzed condensation reaction to prepare the corresponding pyridinediimine ligand. If the ligand structure is symmetrical, the two-step condensation reaction can be completed in one step. At this time, the amine and 2.6 - The diacetylpyridine molar ratio is 2:1. The alkene group-containing pyridine diimine compound can be prepared by reacting the prepared pyridine diimine ligand with _FeX2 , and the yield is 90-95%.

Its preparation reaction process is as follows:

With methanol as solvent and formic acid as catalyst, alkenyl arylamine is condensed with 2.6-diacetylpyridine to generate tridentate pyridinediimine ligand. The preparation of Com Fe was carried out under the protection conditions of anaerobic, anhydrous and high-purity argon. Use 30-40 mL of tetrahydrofuran as solvent, feed pyridinediimine ligand and FeCl ₂ 4H ₂ O at a molar ratio of 1.05:1, stir at room temperature for 2-3 hours to obtain a blue solution, concentrate in vacuo, add n-hexane to precipitate blue Color powder, filtered, vacuum-dried, yield 90-95%.

4. Preparation of olefin-based metallocene catalyst Com M

First, the lithium salt of the corresponding alkenyl cyclopentadiene is prepared by reacting alkenyl cyclopentadiene with equimolar n-butyllithium. If a structurally symmetrical alkenyl metallocene catalyst is to be prepared, the molar ratio is 2:1 The lithium salt of alkene-based cyclopentadiene reacts with MCl ₄ ; if an asymmetric alkene-based metallocene catalyst is to be prepared, two equimolar lithium salts of alkene-based cyclopentadiene are added to react with equimolar MCl ₄ . Yield 60-75%.

Its preparation reaction process is as follows:

Add alkenyl cyclopentadiene to tetrahydrofuran solution, under the condition of ice-salt bath, dropwise add equimolar n-butyllithium, stir at room temperature for 2-3 hours, then slowly add an equivalent amount of MCl ₄ tetrahydrofuran solution, the solution was dark red, stirred and reacted at room temperature for 6-8 hours, evaporated the solvent, added toluene and centrifuged to remove lithium salt, drained the clear liquid, and washed several times with hexane to obtain the product, the yield was 60 -75%.

5. Preparation of polymerized double-active center olefin polymerization catalyst

Under anhydrous and oxygen-free conditions, the iron-based catalyst Com Fe containing olefin groups, the metallocene catalyst Com M containing olefin groups, styrene, and azobisisobutyronitrile were sequentially added to dry toluene and mixed evenly, and then Copolymerize in a water bath and use n-hexane as a precipitating agent to obtain a solid powder of the copolymer, which is then washed three times with n-hexane and dried.

The polymerized double active center olefin polymer catalyst provided by the present invention is carried out under anhydrous and oxygen-free conditions in olefin polymerization, especially in catalyzing ethylene polymerization reaction, and 100-2000 mL of toluene, methyl aluminum Oxane (MAO) or improved methylalumoxane (MMAO), the molar ratio of polymerized double-active center catalyst to MAO or MMAO is Al/(Fe+M)=350-3500, ethylene 1-20atm, at -15- React at 80°C for 1 hour, terminate the reaction with ethanol solution containing 1% hydrochloric acid by weight, filter the obtained product, wash with ethanol several times, and dry in vacuum at 40°C for 24 hours.

The specific implementation is as follows:

Example 1 Preparation of alkenyl arylamine

2. 0.2 mol of 6-diisopropylaniline and 0.1 mol of allyl chloride were heated and refluxed for 10 hours, cooled and placed for 12 hours, poured into 400 mL of water, added sodium hydroxide to make the solution alkaline, extracted with ether, and distilled under vacuum to obtain 18.33 g of N-allyl aniline, yield 84.3%. Add 0.084 mol of N-allyl aniline and excess ZnCl ₂ with 100 mL of toluene as a solvent, reflux for 5 hours under an argon atmosphere, cool and pour into an aqueous solution of sodium hydroxide, The organic layer was separated, and the insoluble matter in the lower layer was dissolved in hot concentrated hydrochloric acid, and then poured into the above alkali solution to extract with ether and the combined organic layer was dried over anhydrous magnesium sulfate, concentrated in vacuo, and distilled under reduced pressure to obtain 12.92 g of 4-allylaniline. Yield 70.9%.

Example 2 Preparation of alkenyl arylamine

0.24mol of aniline and 0.12mol of allyl bromide were heated and refluxed for 8 hours, cooled and placed for 10 hours, poured into 200mL of water, added sodium hydroxide to make the solution alkaline, extracted with ether, and distilled under vacuum to obtain N-allyl aniline 8.645g, yield 54.17%. Add 0.065mol of N-allylaniline and excess ZnCl ₂ to 200mL of toluene as solvent, reflux for 8 hours under argon atmosphere, cool and pour into aqueous solution of sodium hydroxide, separate the organic layer, the lower layer is insoluble The product was dissolved in hot concentrated hydrochloric acid, and then poured into the above alkali solution for ether extraction and combined organic layers, dried over anhydrous magnesium sulfate, concentrated in vacuo, and distilled under reduced pressure to obtain 2.18 g of 2-allylaniline. Yield 25.2%.

Example 3 Preparation of alkenyl arylamine

0.2 mol of 4-tert-butylaniline and 0.1 mol of allyl chloride were heated and refluxed for 9 hours, cooled and placed for 11 hours, poured into 300 mL of water, added sodium hydroxide to make the solution alkaline, extracted with ether, and distilled under vacuum to obtain N -Allyl-2-tert-butylaniline 5.67g, yield 30.0%. Add 0.03mol of N-allyl-2-tert-butylaniline and excess ZnCl ₂ with 50mL of toluene as solvent, and reflux for 6 hours under argon atmosphere , cooled and poured into an aqueous solution of sodium hydroxide, the organic layer was separated, the insoluble matter in the lower layer was dissolved in hot concentrated hydrochloric acid, and then poured into the above alkali solution to extract the combined organic layer, dried over anhydrous magnesium sulfate, concentrated in vacuo and then decompressed Distillation gave 3.54 g of 4-allyl-2-tert-butylaniline. Yield 62.4%.

Example 4 Preparation of alkenyl cyclopentadiene

Add 100 mL of 33% NaOH, 0.5 mol cyclopentadiene, and 0.5 mol allyl chloride to a glass Schlenk bottle successively, and stir in an ice bath for 2 hours under the condition of 2 g of tetrabutylammonium bromide as a phase transfer agent. After stirring at low temperature for 6 hours, the oil phase was washed to neutrality, dried with anhydrous potassium carbonate, and distilled under reduced pressure to obtain allyl cyclopentadiene 36.75. Yield 70.0%.

Example 5 Preparation of alkenyl cyclopentadiene

Add 120 mL of 33% NaOH, 0.6 mol cyclopentadiene, and 0.5 mol 3-bromo-1-butene to a glass Schlenk bottle, and stir in an ice-water bath for 2 After stirring at room temperature for 7 hours, the oil phase was washed to neutrality, dried with anhydrous potassium carbonate, and then distilled under reduced pressure to obtain 26.78 g of 3-cyclopentadienyl-1-butene. Yield 45.01%.

Example 6 Preparation of alkenyl cyclopentadiene

Add 110 mL of 33% NaOH, 0.5 mol cyclopentadiene, and 0.5 mol 4-bromostyrene in a glass Schlenk bottle, and stir in an ice-water bath for 2 hours under 2.5 g of tetrabutylammonium bromide as a phase transfer agent. After stirring at room temperature for 6.5 hours, the oil phase was washed to neutrality, dried with anhydrous potassium carbonate, and distilled under reduced pressure to obtain 33.40 g of styrylcyclopentadiene. Yield 40.0%.

Example 7 Preparation of olefin-based iron-based catalyst Com Fe

Using methanol as a solvent and formic acid as a catalyst, 4-allylaniline and 2.6-diacetylpyridine are condensed to generate tridentate pyridinediimine ligand C ₃₉ H ₅₁ N ₃ . The preparation of Com Fe was carried out under the protection of oxygen, anhydrous and high-purity argon. Using tetrahydrofuran as solvent 30mL, 4.0mmol of the pyridinediimine ligand and FeCl ₂ 4H ₂ O 3.8mmol were stirred at room temperature for 2 hours to obtain a blue solution, which was concentrated in vacuo, added n-hexane to precipitate a blue powder, filtered, and dried in vacuo 2.48 g of C ₃₉ H ₅₁ N ₃ FeCl ₂ was obtained with a yield of 95%.

Example 8 Preparation of olefin-based iron-based catalyst Com Fe

With methanol as solvent and formic acid as catalyst, 2-tert-butyl-4-allylaniline, 2.6-dimethylaniline and 2.6-diacetylpyridine are condensed to generate tridentate pyridinediimine ligand C ₃₀ H ₃₅ N ₃ . The preparation of Com Fe was carried out under the protection conditions of anaerobic, anhydrous and high-purity argon. Using tetrahydrofuran as solvent 40mL, 1.51mmol of the pyridinediimine ligand and FeCl ₂ 4H ₂ O 1.44mmol were stirred at room temperature for 3 hours to obtain a blue solution, which was concentrated in vacuo, added n-hexane to precipitate a blue powder, filtered, and dried in vacuo 0.73 lg of C ₃₀ H ₃₅ N ₃ FeCl ₂ was obtained with a yield of 90%.

Example 9 Preparation of olefin-based iron-based catalyst Com Fe

With methanol as solvent and formic acid as catalyst, 2-allylaniline and 2.6-diacetylpyridine are condensed to generate tridentate pyridinediimine ligand C ₂₇ H ₂₇ N ₃ . The preparation of Com Fe was carried out under the protection conditions of anaerobic, anhydrous and high-purity argon. Using tetrahydrofuran as solvent 35mL, 2.27mmol of the pyridinediimine ligand and FeCl ₂ 4H ₂ O 2.16mmol were stirred at room temperature for 2.5 hours to obtain a blue solution, concentrated in vacuo, added n-hexane to precipitate a blue powder, filtered, and dried in vacuo 1.044 g of C ₂₇ H ₂₇ N ₃ FeCl ₂ was obtained with a yield of 93%.

Example 10 Preparation of olefin-based metallocene catalyst Com M

Add 4.14mmol of allylcyclopentadiene to the tetrahydrofuran solution, under the condition of ice-salt bath, dropwise add n-butyllithium of equimolar number, stir at room temperature for 2 hours, then slowly add The tetrahydrofuran solution of ZrCl ₄ , the solution is dark red, stirred and reacted at room temperature for 6 hours, evaporated the solvent, added toluene and centrifuged to remove lithium salt, drained the clear liquid, and washed several times with hexane to obtain the product C ₁₆ H ₁₆ ZrCl ₂ 0.574g, yield 75%.

Example 11 Preparation of olefin-based metallocene catalyst Com M

2.17mmol of 3-cyclopentadienyl-1-butene and 2.17mmol of allylcyclopentadiene were added to the tetrahydrofuran solution, and 4.34mmol of n-butyllithium was added dropwise under the condition of an ice-salt bath. Stir at room temperature for 3 hours, then slowly add tetrahydrofuran solution containing equivalent _TiCl4 , the solution is dark red, stir and react at room temperature for 8 hours, evaporate the solvent, add toluene and centrifuge to remove lithium salt, drain the clear liquid, and then After washing several times with hexane, 0.444 g of the product C ₁₇ H ₁₈ TiCl ₂ was obtained, with a yield of 60%.

Example 12 Preparation of olefin-based metallocene catalyst Com M

Add 1.79 mmol of styryl cyclopentadiene and 1.79 mmol of cyclopentadiene to the tetrahydrofuran solution, add 3.58 mmol of n-butyllithium dropwise under the condition of an ice-salt bath, stir at room temperature for 2.5 hours, and then slowly Add the tetrahydrofuran solution containing equivalent _ZrCl4 , the solution is deep red, stir and react at room temperature for 7.5 hours, evaporate the solvent, add toluene and centrifuge to remove lithium salt, drain the clear liquid, and wash it several times with hexane to obtain Product C ₁₈ H ₁₄ ZrCl ₂ 0.431 g, yield 61.4%.

Example 13 Preparation of polymerized double-active center olefin polymerization catalyst

Under anhydrous and oxygen-free conditions, 0.2 mmol of the iron-based catalyst C ₃₉ H ₅₁ N ₃ FeCl ₂ prepared in Example 7, 0.7 mmol of the metallocene catalyst C ₁₆ H ₁₆ ZrCl ₂ prepared in Example 10, 5 mL of styrene, and azo 1.0 wt% of diisobutyronitrile was added to dry toluene and mixed evenly, then copolymerized in a water bath at 80°C for 10 hours, cooled to room temperature, centrifuged, and the supernatant was made of n-hexane as a precipitating agent to obtain a solid powder. Then wash it three times with n-hexane and dry it. The iron content was determined to be 0.256 wt%, and the zirconium content was 1.57 wt%.

Example 14 Preparation of high molecular weight double active center olefin polymerization catalyst

Under anhydrous and oxygen-free conditions, 0.5 mmol of the iron-based catalyst C ₃₀ H ₃₅ N ₃ FeCl ₂ prepared in Example 8, 0.5 mmol of the metallocene catalyst C ₁₈ H ₁₄ ZrCl ₂ prepared in Example 12, 8 mL of styrene, and Add 1.0wt% nitrogen bisisobutyronitrile to dry toluene and mix evenly, then copolymerize in a water bath at 80°C for 11 hours, cool to room temperature, centrifuge, and use n-hexane as a precipitating agent in the supernatant to obtain a solid powder , then washed three times with n-hexane and dried. The iron content was determined to be 0.214 wt%, and the zirconium content was 0.419 wt%.

Example 15 Preparation of high molecular weight double active center olefin polymerization catalyst

Under anhydrous and oxygen-free conditions, iron-based catalyst C ₂₇ H ₂₇ N ₃ FeCl ₂ 0.7 mmol prepared in Example 9, metallocene catalyst C ₁₇ H ₁₈ TiCl ₂ 0.4 mmol prepared in Example 11, styrene 10 mL, azo 1.0 wt% of diisobutyronitrile was sequentially added to dry toluene and mixed uniformly, then copolymerized in a water bath at 80°C for 12 hours, cooled to room temperature, centrifuged, and the supernatant was made of n-hexane as a precipitating agent to obtain a solid powder. Then wash it three times with n-hexane and dry it. The iron content was determined to be 0.532 wt%, and the titanium content was 0.467 wt%.

Example 16 Ethylene Polymerization

Ethylene polymerization is carried out under anhydrous and oxygen-free conditions, and 100 mL of toluene, methyl aluminoxane, and 0.02 g of the polymerized double-active center catalyst prepared in Example 13 are successively added to the reaction system, Al/(Fe+Zr)=350 , ethylene 1atm, reacted at -15°C for 1 hour, terminated the reaction with an ethanol solution containing 1% hydrochloric acid by weight, filtered the resulting product, washed several times with ethanol, and dried in vacuum at 40°C for 24 hours to obtain 1.76g of polyethylene.

Example 17 Ethylene Polymerization

Ethylene polymerization is carried out under anhydrous and oxygen-free conditions, 500 mL of toluene is added to the reaction system successively, and methyl aluminoxane is improved, and the polymerized double-active center catalyst prepared in Example 13 is 0.02 g, Al/(Fe+Zr)= 1400, ethylene 5 atm, reacted at 30°C for 1 hour, terminated the reaction with ethanol solution containing 1% hydrochloric acid by weight, filtered the resulting product, washed several times with ethanol, and dried in vacuum at 40°C for 24 hours to obtain 19.25 g of polyethylene.

Example 18 Ethylene Polymerization

Ethylene polymerization is carried out under anhydrous and oxygen-free conditions, and 2000 mL of toluene is added successively to the reaction system to improve methyl aluminoxane, 0.04 g of the polymerized double-active center catalyst prepared in Example 14, Al/(Fe+Zr)= 3500, ethylene 4atm, reacted at 45°C for 1 hour, terminated the reaction with ethanol solution containing 1% hydrochloric acid by weight, filtered the obtained product, washed several times with ethanol, and dried in vacuum at 40°C for 24 hours to obtain 6.48g of polyethylene.

Example 19 Ethylene Polymerization

Ethylene polymerization is carried out under anhydrous and oxygen-free conditions, and 2000 mL of toluene, methyl aluminoxane, and 0.02 g of the polymerized double-active center catalyst prepared in Example 15 are successively added to the reaction system, Al/(Fe+Ti)=1700 , Ethylene 20atm, reacted for 1 hour at 80°C, terminated the reaction with an ethanol solution containing 1% hydrochloric acid by weight, filtered the resulting product, washed several times with ethanol, and dried in vacuum at 40°C for 24 hours to obtain 21.74g of polyethylene.

Claims (3)

1. high molecular double activity center olefin polymerization catalysis, form by A and B two components, it is characterized in that A component expression formula is [P (Com Fe-co-S-co-Com M)], P represents multipolymer, S is a polystyrene, and co represents copolymerization, and Com Fe represents Fe-series catalyst, Com M represents metallocene catalyst, and the concrete structure formula is as follows:

Com Fe:R ₁, R ₂, R ₃, R ₄Be respectively H, CH ₃, i-Pr, t-Bu one of them; R ₅Be H or allyl, X is Cl or Br;

ComM:R ₆Be respectively H, One of them; R ₇Be respectively

One of them; M is Ti, Zr or Hf; X is Cl or Br;

High molecular double activity center olefin polymerization catalysis model: R ₁=R ₂=R ₃=R ₄=CH ₃R ₅=R ₆=R ₇=allyl; M=Zr; X=Cl;

The B component is methylaluminoxane (MAO), improvement methylaluminoxane (MMAO) or penta phenyl fluoride boron.

2, the preparation method of a kind of high molecular double activity center olefin polymerization catalysis is characterized in that

The Preparation of catalysts process is as follows:

1), the preparation of alkylene arylamine

Its structural formula is: R is H, Me, i-Pr, t-Bu one of them

Arylamine and alkylene chlorine or alkylene bromine 2: 1 in molar ratio, reacting by heating get N-alkylene arylamine, 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;

2), the preparation of alkylene cyclopentadiene

Its structural formula is:

R is One of them

Equimolar cyclopentadiene and chloro-alkenes or bromo alkene are to react under the consisting of phase-transferring agent to obtain the cyclopentadiene that alkylene replaces, productive rate 40-70% in the NaOH aqueous solution at Tetrabutyl amonium bromide;

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:

With methyl alcohol is solvent, and formic acid is catalyzer, and alkylene arylamine and the condensation reaction of 2.6-diacetyl pyridine generate the tridentate pyridine diimide ligand, and the preparation of Com Fe is carried out under the anhydrous and high-purity argon gas protective condition in anaerobic; With tetrahydrofuran (THF) 30-40mL is solvent, pyridine diimine part and FeCl ₂4H ₂O fed intake by 1.05: 1, and stirring at room 2-3 hour, get blue solution, vacuum concentration adds normal hexane and is settled out blue powder, filters vacuum-drying, productive rate 90-95%;

4), the preparation of alkylene metallocene catalyst Com M

At first gone out the lithium salts of corresponding alkene basic ring pentadiene by alkylene cyclopentadiene and equimolar n-Butyl Lithium prepared in reaction, the alkylene metallocene catalyst of preparation symmetrical configuration then is 2: 1 alkylene cyclopentadiene lithium salts and MCl by mol ratio ₄Reaction; The asymmetric alkylene metallocene catalyst of preparation structure adds the lithium salts and the equimolar MCl of equimolar two kinds of alkylene cyclopentadiene respectively ₄Reaction, productive rate 60-75%;

Its preparation feedback process is as follows:

The alkylene cyclopentadiene is joined in the tetrahydrofuran solution, and under the condition that cryosel is bathed, the n-Butyl Lithium of mole numbers such as dropping at room temperature stirred 2-3 hour, added the MCl that contains equivalent then lentamente ₄Tetrahydrofuran solution, solution is scarlet, under the room temperature stirring reaction 6-8 hour, boil off solvent, add the centrifugal lithium salts of removing of toluene, clear liquid is drained, promptly get product, productive rate 60-75% for several times with hexane wash again;

5), the preparation of high molecular double activity center olefin polymerization catalysis

Under the anhydrous and oxygen-free condition, the Fe-series catalyst Com Fe that will contain alkylene, the metallocene catalyst Com M 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 promptly obtains high molecular double activity center olefin polymerization catalysis again.

3, the application of a kind of high molecular double activity center olefin polymerization catalysis, it is characterized in that in the catalyzed ethylene polymerization reaction, be under the anhydrous and oxygen-free condition, to carry out, in reaction system, add toluene 100-2000mL successively, methylaluminoxane (MAO) or improvement methylaluminoxane (MMAO), high molecular double activity center catalyzer and methylaluminoxane (MAO) or improvement methylaluminoxane (MMAO) mol ratio Al/ (Fe+M)=350-3500, ethene 1-20atm, in-15-80 ℃ 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.