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Rare-earth catalyst of nitrogen-containing heterocyclic carbene ligand and olefin polymerization catalyzing method of rare-earth catalyst

A nitrogen-heterocyclic carbene and rare-earth catalyst technology, applied in the field of rare-earth catalysts, can solve problems such as poor inhibition ability, difficulty in preparing high molecular weight polymers, and low polymerization activity

Active Publication Date: 2017-05-10
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The rare earth catalysts reported so far have poor ability to inhibit the chain transfer reaction of monomers such as propylene and isobutylene during the polymerization process, resulting in low polymerization activity and difficulty in preparing high molecular weight polymers.

Method used

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  • Rare-earth catalyst of nitrogen-containing heterocyclic carbene ligand and olefin polymerization catalyzing method of rare-earth catalyst
  • Rare-earth catalyst of nitrogen-containing heterocyclic carbene ligand and olefin polymerization catalyzing method of rare-earth catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0011] Example 1 Preparation of nitrogen-containing heterocyclic carbene rare earth catalyst

[0012] Different methenyl ligands and different azacyclic carbenes can be prepared by the following methods:

[0013] (1) In the glove box, weigh ScCl 3 (15mmol) was put into a Schlenk bottle filled with a magnetic stirrer, and 50mL of tetrahydrofuran was added. After sealing the Schlenk bottle, the Schlenk bottle was taken out of the glove box and stirred overnight at 80°C. Activated ScCl 3 (THF) 3 The white suspension was taken into the glove box, and the LiCH 2 SiMe 3 (45mmol) was dissolved in 15mL tetrahydrofuran, and slowly added dropwise to ScCl 3 (THF) 3 In the white suspension, react for 30min. Then, remove the solvent THF under reduced pressure, add 60mL of n-hexane for extraction, freeze the extract to remove by-products and filter while cold, and finally remove the n-hexane in the filtrate to obtain a white powder Sc(CH 2 SiMe 3 ) 3 (THF) 2 .

[0014] (2) In t...

Embodiment 2

[0017] Example 2 Preparation of polypropylene

[0018] In a glove box under the protection of inert gas nitrogen, add 20ml of toluene solution to a 100ml stainless steel reaction kettle, use a constant temperature bath to control the polymerization temperature, the polymerization temperature is -30°C, add propylene, the pressure of propylene is maintained at 0.1MPa, turn on the stirring, Add a rare earth catalyst, adopt the method provided in Example 1 to prepare a rare earth catalyst, and select 1,3-bis(trimethylsilyl)indenyl ligand (1,3-(Me 3 Si) 2 C 9 h 5 ), the nitrogen heterocyclic carbene ligand is selected from 1,3-diisopropyl-imidazolyl carbene, the amount of rare earth catalyst Sc is 2umol, the rare earth catalyst Sc and organoboron reagent [Ph 3 C][B(C 6 f 5 ) 4 ] molar ratio [Sc] / [B] is 1, after 30 minutes of polymerization reaction, methanol is added to terminate the reaction, the product is post-treated, vacuum-dried, analysis test: the number average molecu...

Embodiment 3

[0019] Example 3 Preparation of polypropylene

[0020] The polymerization reaction temperature is -20 ℃, and other polymerization reaction conditions are identical with embodiment 2, analysis test: the number average molecular weight of polypropylene is 123.9 * 10 4 g / mol, molecular weight distribution HI is 1.49.

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Abstract

The invention provides a rare-earth catalyst of a nitrogen-containing heterocyclic carbene ligand and an olefin polymerization catalyzing method of the rare-earth catalyst. The rare-earth catalyst comprises a part A and a part B, wherein the part A is nitrogen-containing heterocyclic carbene coordinated rare-earth complex LMR2X, L is a cyclopentadienyl ligand selected from a cyclopentadienyl ligand, an indenyl ligand and a fluorenyl ligand, X is the nitrogen-containing heterocyclic carbene ligand selected from imidazolyl carbene, imidazolinyl carbene, triazolyl carbene and thiazolyl carbene, M is rare-earth metal selected from Sc, Y, Lu, Gd, Sm and Nd, and R is alkyl directly connected with the rare-earth metal; the part B is organoboron reagents. By using the rare-earth catalyst of the nitrogen-containing heterocyclic carbene ligand, the chain transfer reaction of propylene monomers can be effectively inhibited so as to prepare the homopolymer and copolymer, with higher molecular weight and narrower molecular distribution, of the propylene monomers.

Description

technical field [0001] The invention belongs to the technical field of advanced manufacturing of high-performance polymer materials, and relates to a rare earth catalyst of nitrogen-containing heterocyclic carbene ligands that can be used for olefin polymerization. Background technique [0002] The chain transfer reaction is a bottleneck that restricts the wide application of rare earth catalysts, such as propylene monomers containing one methyl group and isobutylene monomers containing two methyl groups. Due to the severe chain transfer reaction, it is difficult to use rare earth catalysts to prepare higher molecular weight polymers thing. Therefore, designing and synthesizing rare earth catalysts that can effectively inhibit the chain transfer reaction of propylene and isobutene monomers has always been a challenging work in this field. Due to the high activity of rare earth catalysts, stable valence state, wide selection range of olefin monomers, and effective regulation...

Claims

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Application Information

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IPC IPC(8): C08F110/06C08F110/10C08F110/02C08F210/06C08F210/16C08F210/12C08F236/08C08F232/08C08F212/14C08F4/52
Inventor 李杨谭睿郭方牛慧史正海李婷婷杨珂
Owner DALIAN UNIV OF TECH
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