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Olefinic polymerization non-metallocene metal catalyst system and preparation and application thereof

A non-metallocene and olefin polymerization technology, applied in the field of copolymerization non-metallocene catalyst system, can solve the problems such as catalyst research report, large amount of MAO, etc., and achieves less amount of MAO, high catalyst activity, and polymer molecular weight. high effect

Active Publication Date: 2011-04-27
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

When the catalysts studied above catalyze olefin polymerization, the amount of MAO is relatively large
There have been no research reports on such catalysts

Method used

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  • Olefinic polymerization non-metallocene metal catalyst system and preparation and application thereof
  • Olefinic polymerization non-metallocene metal catalyst system and preparation and application thereof
  • Olefinic polymerization non-metallocene metal catalyst system and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] 1) Preparation of the ligand: under the protection of an inert gas, add 0.68g (5mmol) o-phthalaldehyde and 1.26g (10mmol) 2-amino-4-methylphenol to 50mL of absolute ethanol in sequence, and reflux at 80°C Reaction 8h. Cool to room temperature, obtain solid precipitation, wash three times with anhydrous ether, then recrystallize with the mixed solution (3:1) of toluene and chloroform, obtain 1.57g ligand L1 (see general formula (2)), productive rate 91%.

[0045] 2) Preparation of non-metallocene main catalyst for olefin polymerization: anhydrous and oxygen-free and under the protection of high-purity nitrogen, 0.69g (2mmol) ligand L1 was dissolved in 80mL toluene / tetrahydrofuran (1:1) mixed solvent, at 0 0.22mL (2mmol) TiCl was added dropwise at ℃ (ice-water bath) 4 After the dropwise addition, the temperature was slowly raised to 40° C. for 6 h, the solvent was removed in vacuo, the precipitate was washed 3 times with n-hexane, filtered, and vacuum-dried to obtain th...

Embodiment 2

[0050] 1) Preparation of ligands: under the protection of inert gas, add 1.02g (5mmol) 4-trifluoromethyl-phthalaldehyde, 1.26g (10mmol) 2-amino-4-methyl Phenol, reflux reaction at 90°C for 8h. Cool to room temperature, obtain solid precipitation, wash three times with anhydrous ether, then recrystallize with the mixed solution (3:1) of toluene and chloroform, obtain 1.82g ligand L2 (see general formula (2)), productive rate 88%.

[0051] 2) Preparation of non-metallocene main catalyst for olefin polymerization: anhydrous and oxygen-free and under the protection of high-purity nitrogen, 0.83g (2mmol) ligand L2 was dissolved in 50mL toluene / tetrahydrofuran (1:1) mixed solvent, in- Add 0.22mL (2mmol) TiCl dropwise at 10°C (ice-water bath) 4 , after the dropwise addition was completed, the temperature was slowly raised to 30° C. for 8 h, the solvent was removed in vacuo, the precipitate was washed 3 times with n-hexane, filtered, and vacuum-dried to obtain the main catalyst comp...

Embodiment 3

[0054] 1) Preparation of the ligand: under the protection of an inert gas, add 0.96g (5mmol) 4-tert-butylphthalaldehyde and 1.26g (10mmol) 2-amino-4-methylphenol successively to 50mL of absolute ethanol. 80 ° C reflux reaction for 12h. Cool to room temperature, obtain solid precipitation, wash three times with anhydrous ether, then recrystallize with the mixed solution (3:1) of toluene and chloroform, obtain 1.74g ligand L3 (see general formula (2)), productive rate 87%.

[0055] 2) Preparation of non-metallocene main catalyst for olefin polymerization: anhydrous and oxygen-free and under the protection of high-purity nitrogen, 0.80g (2mmol) of ligand L3 was dissolved in 50mL of toluene / tetrahydrofuran (1:1) mixed solvent, in 10 Add 0.22mL (2mmol) TiCl dropwise at ℃ 4 , after the dropwise addition was completed, the temperature was slowly raised to 60° C. for 6 h, the solvent was removed in vacuo, the precipitate was washed 3 times with n-hexane, filtered, and vacuum-dried t...

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Abstract

The invention relates to an olefinic polymerization non-metallocene metal catalyst system and preparation and application thereof. A main catalyst is shown as a structural formula (1), wherein M represents Ti, Zr, Hf, Sc, Y, La, Nd or Sm; methylaluminoxane or modified methylaluminoxane is taken as a cocatalyst; and the molar ratio of the main catalyst to the cocatalyst is 1:100-5,000. The catalyst has high activity and high polymer molecular weight; when the catalyst is applied to copolymerization of ethylene and alpha-olefin or a polar alkene monomer, the insertion rate of the alpha-olefin or the polar alkene monomer is high; and the main catalyst has high stability and small monoamine oxidase (MAO) using amount.

Description

technical field [0001] The invention relates to a non-metallocene catalyst system for ethylene polymerization or copolymerization of ethylene and α-olefin or copolymerization of ethylene and polar olefinic monomers and its preparation and application. Background technique [0002] In the history of olefin polymerization industry, the traditional Ziegler-Natta (Z-N) catalyst has occupied a dominant position for a long time. In 1980, Kaminsky and Sinn discovered methylalumoxane (MAO) with a special catalytic effect, making the metallocene catalyst a new catalyst system with much higher activity than the traditional Ziegler-Natta catalyst, but its cost is high and stable Poor performance, high consumption of MAO, and difficulty in structural modification have limited the development of metallocene catalysts to a certain extent, while "post-metallocene" olefin polymerization catalysts with low cost and high stability have become a new hot spot in research and development. "Post...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F110/02C08F210/02C08F210/16C08F4/642C08F4/52
Inventor 义建军李红明陈曦豆秀丽黄启谷姜凯
Owner PETROCHINA CO LTD
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