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Conjugated diene efficient polymerization rare earth catalyst composition and application thereof

A rare earth catalyst and conjugated diene technology, applied in the field of polymer materials, can solve the problems of hindering the industrial application of single active site rare earth catalysts, complex synthesis of organic boron salts, and high cost.

Active Publication Date: 2021-08-20
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the complex synthesis and high cost of organoboron salts seriously hinder the industrial application of this single-site rare earth catalyst.

Method used

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  • Conjugated diene efficient polymerization rare earth catalyst composition and application thereof
  • Conjugated diene efficient polymerization rare earth catalyst composition and application thereof
  • Conjugated diene efficient polymerization rare earth catalyst composition and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0063]

[0064] In the glove box, take 10mmolY(CH 2 C 6 h 4 NMe 2 -o) 3 Add it into a 100mL pressure bottle, add 20mL of toluene and dissolve it under stirring with a stirrer, then slowly add 10mmol non-phenocene ligand PNP-1 dissolved in toluene into the pressure bottle, after the dropwise addition, put the pressure The bottle was placed in a constant temperature oil bath at 50°C and reacted for 3 hours. After the reaction solution was concentrated in vacuo, it was recrystallized at -30°C to obtain Rare Earth Complex 1 with a yield of 89%.

Embodiment 2

[0066]

[0067] In the glove box, take 10mmol Ho(CH 2 C 6 h 4 NMe 2 -o) 3 Add it into a 100mL pressure bottle, add 20mL of toluene and dissolve it under stirring with a stirrer, then slowly add 10mmol non-phenocene ligand PNP-2 dissolved in toluene into the pressure bottle, after the dropwise addition, put the pressure The bottle was placed in a constant temperature oil bath at 50°C and reacted for 3 hours. After the reaction solution was concentrated in vacuum, it was recrystallized at -30°C to obtain Rare Earth Complex 2 with a yield of 86%.

Embodiment 3

[0069]

[0070] In the glove box, take 10mmol Er(CH 2 C 6 h 4 Me-p) 3 Add to a 100mL reaction bottle, add 20mL of toluene and dissolve it under stirring with a stirrer, then slowly add 10mmol of non-phenocene ligand PNP-1 dissolved in toluene into the pressure bottle, after the dropwise addition, react at room temperature for 2 Hour. After the reaction solution was concentrated in vacuo, it was recrystallized at -30°C to obtain Rare Earth Complex 3 with a yield of 79%.

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Abstract

The invention provides a conjugated diene efficient polymerization rare earth catalyst composition and application thereof. The composition is composed of a rare earth complex shown in a formula I defined in the description, aluminoxane and a main group metal alkyl reagent in a molar ratio of 1: (10-5000): (0-5000). According to the invention, commercial low-price aluminoxane is adopted to replace high-price organic boron salt to serve as a cocatalyst, a tridentate carbazole ligand chelated rare earth complex shown in the formula I is activated, and the high-activity and high-cis-1, 4-selectivity rare earth catalyst composition is prepared; and the rare earth complex represented by the formula I and aluminoxane form the positive and negative ion pair with the right distance, such that the high catalytic activity of the catalyst is maintained, and the cis-1, 4-selectivity of the catalyst is maintained at the high temperature or in the presence of the main group alkyl reagent.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and in particular relates to a rare earth catalyst composition for high-efficiency polymerization of conjugated diene and its application. Background technique [0002] Cocatalysts play a very important role in the process of transition metal catalysts exhibiting high catalytic activity. The Ziegler-Natta catalytic system has very high catalytic activity and stereoselectivity for the polymerization of ethylene, propylene and α-olefins under the action of alkylaluminum or alkylaluminum chloride. However, the catalysts of Group IV metallocenes activated by alkylaluminum or alkylaluminum chloride have very low catalytic activity for olefin polymerization and have no industrial development value. It was not until the discovery of methylaluminoxane that the catalytic activity of group four metallocene catalysts for olefin polymerization was greatly improved. Similarly, the Ziegler-Natta ca...

Claims

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Application Information

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IPC IPC(8): C08F136/08C08F236/08C08F136/06C08F4/54
CPCC08F136/08C08F236/08C08F136/06
Inventor 崔冬梅李世辉
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI