Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization

A bimetallic catalyst and catalyst technology, which is applied in the field of olefin coordination polymerization, can solve the problems such as the inability to effectively regulate the proportion of comonomers, and achieve high catalytic efficiency

Active Publication Date: 2010-10-20
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This type of catalyst has good olefin catalytic activity. For example, salicylaldimine-nickel catalyst changed the situation that nickel catalysts could only obtain oligomers in the past, and obtained polyethylene with a certain degree of branching (Science 2000, 287, 460) and the salicylaldimine titanium catalyst can highly active catalytically synthesize homopolymers such as polyethylene and polypropylene (J.Am.Chem.Soc.2001,123,5134; J.Am.Chem.Soc.2002,124, 3327), and can realize the polymerization of ethylene and olefins with functional groups, but the ratio of comonomer in the polymer obtained is only 3%, and the ratio of comonomer in the polymer cannot be effectively regulated (J.Am.Chem.Soc .2008, 130, 17636)

Method used

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  • Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization
  • Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization
  • Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] The preparation of bimetallic catalyst precursor shown in formula II

[0047] With 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethyl-9H-oxanthene as the starting material, in the presence of palladium catalyst with 3-tert-butyl-5 -(4,4,5,5-Tetramethyl-1,3,2-dioxaborolane-2-substituted) salicylaldehyde was obtained by Suzuki coupling to 5,5'-(2,7-ditert Butyl-9,9-dimethyl-9H-xanthene-4,5-disubstituted)bis(3-tert-butylsalicylaldehyde). Then, under the catalysis of p-toluenesulfonic acid, it is condensed with pentafluoroaniline to obtain (E)-4,4'-(2,7-di-tert-butyl-9,9-dimethyl-9H-oxanthene-4 , 5-disubstituted) bis(3-tert-butyl-(E)-salicylaldehyde pentafluoroaniline). Then react with di(tetrahydrofuran)titanium tetrachloride in dichloromethane to obtain bimetallic catalyst precursor II. Such as figure 2 As shown, the specific synthesis steps are as follows:

[0048] 1) Preparation of 5,5'-(2,7-di-tert-butyl-9,9-dimethyl-9H-oxanthene-4,5-disubstituted) bis(3-tert-butyl salic...

Embodiment 2

[0057] Synthesis of polyethylene: evacuate the 250ml polymerization bottle after heating and drying, and pass nitrogen twice, and then pass ethylene gas after vacuuming, and then add 6.8ml of toluene solution of methylaluminoxane (MAO) in sequence (concentration is 1.47 mol / l), 23.2ml of toluene through anhydrous and oxygen-free treatment, 20ml of toluene solution of metal catalyst II (0.55mg / ml). Feed ethylene with a pressure of 1 atm under magnetic stirring, and react at 25°C for 10 minutes under this pressure, then add an acidified solution of ethanol to terminate the reaction, and obtain 0.054 g of a polymer with an activity of 4.1×104 g·mol -1 h -1 .

[0058] The melting point measured by DSC is 137°C; the M value of polyethylene measured by GPC w 5.1×10 5 ,M w / M n is 15.2.

Embodiment 3

[0060] Synthesis of polyethylene: evacuate the 250ml polymerization bottle after heating and drying, and pass nitrogen twice, and then pass ethylene gas after vacuuming, and then add 6.8ml of toluene solution of methylaluminoxane (MAO) in sequence (concentration is 1.47 mol / l), 23.2ml of toluene through anhydrous and oxygen-free treatment, 20ml of toluene solution of metal catalyst II (0.55mg / ml). Feed ethylene with a pressure of 1 atm under magnetic stirring, and react at 25°C for 5.0 min under this pressure, then add an acidified solution of ethanol to terminate the reaction, and obtain 0.027 g of a polymer with an activity of 4.1×10 4 g·mol -1 h -1 .

[0061] The melting point measured by DSC is 136°C; the M value of polyethylene measured by GPC w 4.0×10 5 ,M w / M n is 7.7.

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Abstract

The invention discloses a bimetallic catalyst precursor for catalyzing olefin to polymerize or copolymerize and belongs to the field of olefin coordination polymerization. The catalyst precursor is based on a salicvlaldimine ligand and an IV group transition metal. Compared with a monometallic catalyst, with the synergistic effect of bimetals, a catalyst consisting of the precursor and alkyl aluminum has higher activity when used for catalyzing the olefin to homopolymerize or copolymerize; particularly, the activity of the catalyst can reach 5.2*104g/mol<-1>h<-1> at the ethylene pressure of 1atm when used for catalyzing 1,5-hexadiene to be copolymerized with the ethylene; and in addition, the catalyst has higher ratio of inducing a comonomer into a polymer.

Description

technical field [0001] The invention belongs to the field of olefin coordination polymerization, and relates to the synthesis of a bimetallic catalyst precursor and the application of the catalyst composed of it in catalyzing olefin polymerization and copolymerization. Specifically, a group IV transition metal dinuclear catalyst precursor based on salicylaldimine ligands was synthesized, and the catalyst composed of the precursor and alkylaluminoxane can effectively catalyze the homopolymerization of ethylene and the substitution of ethylene and ethylene. Copolymerization of olefins. Background technique [0002] Over the years, the functionalization of olefins has been a research hotspot. The synthesis of functionalized polyolefins is mainly through conventional olefins (such as ethylene, propylene, etc.) and functionalized olefins (also known as polar olefin monomers, such as methyl acrylate, Vinyl acetate) copolymerized. Such polyolefins have various types of organic fu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/70C08F10/02C08F10/00C08F36/02
Inventor 马玉国韩书亮秦伟
Owner PEKING UNIV
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