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Boroxol cyclopentadienyl zirconium metal catalyzer and preparation method and application thereof

A metal catalyst, boroxy zirconocene technology, applied in the field of boroxy zirconocene metal olefin polymerization catalysts and its preparation, can solve the problems of low solubility limiting the application of metallocene catalysts, the inability to synthesize ethylene-propylene rubber activity, etc., and achieve excellent Solubility, cheap synthesis raw materials, and simple synthesis process

Active Publication Date: 2008-08-27
PETROCHINA CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0002] The development of highly active metallocene catalysts for olefin polymerization has always been the focus of researchers' work. However, the low solubility of general metallocene catalysts in hexane limits the application of metallocene catalysts in polymerization systems using hexane as a solvent.
CN200410070449 patent provides a vanadium catalyst and its preparation method and application. The catalyst is a Ziegler-Natta catalyst using phosphoric acid ester as a ligand, which is easily soluble in hexane and has good activity for the copolymerization of ethylene and propylene. Zirconocene metal catalysts with phosphate ester ligands cannot synthesize ethylene-propylene rubber and have low activity
Metallocene catalysts with borates as ligands have not been reported

Method used

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  • Boroxol cyclopentadienyl zirconium metal catalyzer and preparation method and application thereof
  • Boroxol cyclopentadienyl zirconium metal catalyzer and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] Preparation of racemic ethyl-bridged bis-indenylboronate diisooctyl zirconium chloride.

[0015] Add 50 milliliters of ethylene glycol dimethyl ether (anhydrous), 0.4185 grams of racemic ethyl bridged bisindene zirconium dichloride to the stirred reaction flask of 100 milliliters that has been treated with anhydrous and anaerobic treatment. A mixed solvent of 0.2860 g of diisooctyl borate and 0.0790 g of pyridine (diluted with 20 ml of hexane) was added dropwise, and reacted for 8 hours to generate a yellow solution. Filtration and evaporation of the filtrate gave 0.6586 g of a yellow solid. Molecular formula C 36 h 50 BO 3 ClZr, the molecular weight is 668.36. Elemental analysis (%), measured value (theoretical value): C, 64.61 (64.64); H, 7.49 (7.48); chemical analysis: Cl (wt%), measured value (theoretical value): 5.28 (5.31).

Embodiment 2

[0017] Add 50 ml of hexane, 0.4 ml of ethyl aluminoxane (2.5M hexane solution), and 0.4 ml of isobutylaluminum into a 200 ml reaction flask with a bottom tube and agitation after anhydrous and anaerobic treatment. Oxane (2.5M hexane solution), warming up to 50°C, adding 1 ml of the catalyst synthesized in Example 1 (0.0668 g of catalyst dissolved in 100 ml of hexane solution), and feeding ethylene and propylene mixed gas through the dip tube (weight ratio 1:2.5), react at normal pressure for 1 hour, stop ventilation. Add 5 ml of 10% hydrochloric acid ethanol solution to terminate the reaction. Wash with 20% alkaline solution, and evaporate the solvent in vacuo to obtain 8.1330 g of ethylene-propylene rubber. The catalytic efficiency is 8.13×10 6 g ethylene propylene rubber per mole of catalyst. per hour.

Embodiment 3

[0019] Preparation of diisooctyl borate zirconocene chloride.

[0020] Add 50 milliliters of ethylene glycol dimethyl ether (anhydrous) and 0.2920 grams of zirconocene dichloride to a 100 milliliter stirred reaction flask that has been treated with anhydrous and anaerobic treatment, and add 0.2860 diisooctyl borate dropwise at a uniform speed within 20 minutes. gram, pyridine 0.0790 gram mixed solvent (diluted with 20 milliliters of hexane), reacted for 8 hours, and generated a yellow solution. After filtration and evaporation of the filtrate, 0.5351 g of yellow viscous liquid was obtained. Molecular formula C 26 h 44 BO 3 ClZr, the molecular weight is 541.67. Elemental analysis (%), found value (theoretical value): C, 57.61 (57.60); H, 8.09 (8.12); chemical analysis: Cl (wt%), found value (theoretical value): 6.55 (6.54).

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Abstract

The invention relates to a boroxol cyclopentadienyl zirconium metal catalyst, a preparation method and an application. The preparation method comprises adding zirconium dichloride ethylene glycol dimethyl ether solution containing bis (cyclopentadienyl), bis (lindenyl) or relative derivative groups, whose density is 0.02mol / L, mixing and slowly adding boric acid dibasic ester compound and the ethylene glycol dimethyl ether solution of pyridine in 20min, while the pyridine density is 0.02mol / L and the density of boric acid dibasic ester is 0.02mol / L, wherein the mol ratio of boric acid dibasic ester compound, pyridine and the irconium dichloride containing bis (cyclopentadienyl), bis (lindenyl) or relative derivative groups is 1:1:1-1:1:1.05, reacting for 8h, and after the reaction, and evaporating the ethylene glycol dimethyl ether solution to obtain boroxol cyclopentadienyl zirconium metal catalyst. The synthesis materials are cheap, the process is simple, the yield is high, the catalystic polymerization activity is high, the product can be used for the homopolymerization or copolymerization of ethylene and alpha olefin and the synthesized copolymer has adjustable structure.

Description

technical field [0001] The invention relates to a boronoxy zirconocene metal olefin polymerization catalyst with relatively high polymerization activity for α-olefins, a preparation method and application thereof. Background technique [0002] The development of highly active metallocene catalysts for olefin polymerization has always been the focus of researchers' work. However, the low solubility of general metallocene catalysts in hexane limits the application of metallocene catalysts in polymerization systems using hexane as a solvent. CN200410070449 patent provides a vanadium catalyst and its preparation method and application. The catalyst is a Ziegler-Natta catalyst using phosphoric acid ester as a ligand, which is easily soluble in hexane and has good activity for the copolymerization of ethylene and propylene. Zirconocene metal catalysts with phosphate esters as ligands cannot synthesize ethylene-propylene rubber and are less active. Metallocene catalysts with borat...

Claims

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Application Information

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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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