Single metallocene-titanium catalyst containing phosphate ester ligand and preparation method and application thereof

A technology of phosphate-based dichloro titanocene and titanocene catalysts, which is applied in the field of titanocene catalysts containing phosphate ligands and their preparation and application, can solve the problems of poor solubility and difficulty, and achieve the effect of simple method

Active Publication Date: 2011-02-09
PETROCHINA CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN1065870C, CN1065871C ​​and CN1340551A provide a kind of synthetic method of oxygen-containing titanocene, the synthesized catalyst has good activity to the syndiotactic polymerization of styrene; CN1345887A and CN1593763A provide a kind of synthetic method of oxygen-containing titanocene, so The synthesized catalyst has good activity for the polymerization of ethylene or ethylene and propylene; the above-mentioned catalysts generally introduce oxygen atoms into the catalyst molecule through alkoxy and phenoxy groups to stabilize the molecular structure of the catalyst, and finally compound with aluminoxane , to form an efficient catalytic system for olefin polymerization; the above-mentioned catalysts generally have poor solubility in hexane, and are not easily used in homogeneous or slurry polymerization using hexane as a solvent

Method used

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  • Single metallocene-titanium catalyst containing phosphate ester ligand and preparation method and application thereof
  • Single metallocene-titanium catalyst containing phosphate ester ligand and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Embodiment 1: the preparation of diisooctyl phosphate titanium trichloride

[0019] Add 50 milliliters of hexane, 1.90 grams of TiCl 4 (10 mmol) to 0.025M 3 Nitrogen gas was introduced at the flow rate of / h, and 3.22 g of di-isooctyl phosphate (10 mmol was diluted with 20 ml of hexane) was added dropwise at a constant speed within 20 minutes, and reacted for 2 hours to generate a red solution. The solvent was evaporated to obtain 4.75 g of a reddish-brown liquid with a yield of 99.9%. Molecular formula C 16 h 34 PO 4 Cl 3 Ti has a molecular weight of 475.4. Elemental analysis: C (wt%), measured value (theoretical value): 40.39 (40.40); H (wt%), measured value (theoretical value): 7.15 (7.10); chemical analysis: Cl (wt%), measured value (Theoretical value): 22.38 (22.40).

Embodiment 2

[0020] Example 2: Preparation of Diisooctyl Phosphate Dichloromonocene Titanium

[0021] Add 50 ml of hexane, 0.2134 g of 1,2,3,4-tetramethyl-5-trimethylsilyl-cyclopentadiene (1.1 ml Mole) hexane suspension cloudy also turbid liquid, under stirring at room temperature dropwise added 0.4754 g of di-isooctyl phosphate titanium trichloride (1 mmol), reacted at 65 ° C for 24 hours after the dropwise addition, a red solution was formed. The precipitate was filtered off, and the solvent was evaporated to obtain 0.5048 g of a reddish-brown liquid with a yield of 90.1%. Molecular formula C 25 h 47 PO 4 Cl 2 Ti, the molecular weight is 561. Elemental analysis: C (wt%), measured value (theoretical value): 53.48 (53.50); ​​H (wt%), measured value (theoretical value): 8.38 (8.40); chemical analysis: Cl (wt%), measured value (Theoretical value): 12.63 (12.66).

Embodiment 3

[0022] Embodiment 3: Preparation of diisooctyl dichloromonoindene titanium

[0023] Add 50 ml of hexane, 0.2068 g of 5-trimethylsilyl-indene (1.1 mmol) hexane to a 100 mL stirred reaction flask that has been treated with anhydrous and oxygen-free solution, and add it dropwise at room temperature under stirring 0.4754 g of diisooctyl phosphate titanium trichloride (1 mmol), reacted at 65° C. for 24 hours after the dropwise addition, and a red solution was generated. The precipitate was filtered off, and the solvent was evaporated to obtain 0.4302 g of a reddish-brown liquid with a yield of 77.5%. Molecular formula C 25 h 41 PO 4 Cl 2 Ti, the molecular weight is 555. Elemental analysis: C (wt%), measured value (theoretical value): 54.05 (54.00); H (wt%), measured value (theoretical value): 7.39 (7.40); chemical analysis: Cl (wt%), measured value (Theoretical value): 12.75 (12.79).

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Abstract

The invention relates to a single metallocene-titanium catalyst containing a phosphate ester ligand and a preparation method and application thereof. The preparation method comprises the following steps: performing reaction on 0.2 mol / L titanium tetrachloride hexane solution and 0.5 mol / L phosphate ester hexane solution for 2 hours according to the mol ratio of 1.00-1.05, and obtaining greenish yellow phosphate ester titanium trichloride; performing reaction on trimethyl silicane compounds of metallocene groups, indene groups or one derivative of the metallocene groups and the indene groups, and the phosphate ester titanium trichloride for 24 hours at a temperature of between 60 and 70 DEG C according to the mol ratio of between 1.05 and 1.10, and obtaining phosphate ester dichloro-singlemetallocene-titanium; and performing reaction on phenols or alcohols, pyridine and the phosphate ester dichloro-single metallocene-titanium according to the mol ratio of between 1:1:1.05-1:1:1.1, andobtaining phosphate ester single metallocene-titanium compounds. The catalyst has a stable molecular structure in hexane and is easy to dissolve, and the synthesis method is simple and convenient, suitable for homogeneous polymerization or slurry polymerization by adopting the hexane as a solvent, and used for synthesizing homopolymers or copolymers by adopting ethylene and alpha-olefin as raw materials.

Description

technical field [0001] The invention relates to a mono-titanocene catalyst containing phosphate ligands, which is easily soluble in hexane and has relatively high polymerization activity for alpha-olefins, as well as its preparation method and application. Background technique [0002] The development of highly active olefin polymerization catalysts has always been the focus of researchers' work. In recent years, the synthesis and development of monocene ligand catalysts have been paid more and more attention. CN1065870C, CN1065871C ​​and CN1340551A provide a kind of synthetic method of oxygen-containing titanocene, the synthesized catalyst has good activity to the syndiotactic polymerization of styrene; CN1345887A and CN1593763A provide a kind of synthetic method of oxygen-containing titanocene, so The synthesized catalyst has good activity for the polymerization of ethylene or ethylene and propylene; the above-mentioned catalysts generally introduce oxygen atoms into the c...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F4/6592C08F10/00
Inventor 张红江蔡小平王笑海东升魁陈可佳金春玉陶青海刘洪伟
Owner PETROCHINA CO LTD
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