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Cobalt catalyst and application thereof in 1,3-butadiene polymerization reaction

A polymerization reaction and catalyst technology, which is applied to cobalt-based catalysts and the application field of cobalt-based catalysts in 1,3-butadiene polymerization, can solve problems such as transition metal complexes that have not yet been found, and achieve broad industrial application prospects, The effect of high product cis selectivity and excellent catalytic activity

Inactive Publication Date: 2014-05-07
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But so far, there is no report on the use of transition metal complexes containing PNP ligands for the polymerization of butadiene

Method used

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  • Cobalt catalyst and application thereof in 1,3-butadiene polymerization reaction
  • Cobalt catalyst and application thereof in 1,3-butadiene polymerization reaction
  • Cobalt catalyst and application thereof in 1,3-butadiene polymerization reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0072] 1. Bis[2-(diphenylphosphino)ethyl]amine hydrochloride (ligand L1·HCl ) preparation: under nitrogen protection, diphenylphosphine (2.8 ml, 3.0 g, 16.1 mmol), potassium tert-butoxide (4.68 g, 41.7 mmol) were added into dry tetrahydrofuran (100 ml), stirred for 20 minutes, The reaction solution changed from dark red to orange red, and then powdered bis(2-chloroethyl)amine hydrochloride (1.42 g, 8.0 mmol) was added, and heated to reflux for 28 hours. Then add 100 ml of 1 mol / L dilute hydrochloric acid solution, separate the organic layer, dry with anhydrous sodium sulfate, remove the solvent to obtain a white precipitate, and the separated white precipitate is recrystallized from dichloromethane-ether and washed with acetonitrile , and dried to obtain 1.605 g of white solid with a yield of 42%.

[0073] FT-IR (KBr disc, cm -1 ): 3422 (ν N–H ), 1585, 1480, 1433, 1388, 748, 738, 695, 513.

[0074] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm): 9.95 (s, 2 H, N H 2 Cl), 7.38–...

Embodiment 2

[0081] 1. Complex 1a The preparation is with embodiment 1.

[0082] 2. Butadiene solution polymerization: under the protection of nitrogen, take the complex 1a (3.0 mg, 5.0 μmol) in a polymerization vial, sealed with a rubber stopper, vacuumed and vented with nitrogen three times, and dissolved by adding 4.34 ml of purified toluene. Then, 0.063 ml of cocatalyst sesquiethylaluminum chloride (EASC, 0.4 mol / L n-hexane solution) was added with a syringe, so that [Al] / [Co] was 10, and the catalyst composition was stirred at 25 °C After two minutes, 5.6 ml of butadiene (1.78 mol / L toluene solution) was added with a syringe, so that [BD] / [Co] was 2000, and the polymerization reaction started. Unless otherwise stated, the total volume of the polymerization reaction was controlled at 10 ml by adjusting the amount of solvent toluene. After one hour, the reaction solution was poured into 200 ml of terminator to terminate the polymerization. The terminator was 5% hydrochloric acid eth...

Embodiment 3

[0084] 1. Complex 1a The preparation is with embodiment 1.

[0085] 2. Butadiene solution polymerization: under the protection of nitrogen, take the complex 1a (3.0 mg, 5.0 μmol) in a polymerization vial, sealed with a rubber stopper, vacuumed and vented with nitrogen three times, and dissolved by adding 4.275 ml of purified toluene. Then, 0.125 ml of cocatalyst sesquiethylaluminum chloride (EASC, 0.4 mol / L n-hexane solution) was added with a syringe, so that [Al] / [Co] was 20, and the catalyst composition was stirred at 25 °C After two minutes, 5.6 ml of butadiene (1.78 mol / L toluene solution) was added with a syringe, so that [BD] / [Co] was 2000, and the polymerization reaction started. Unless otherwise stated, the total volume of the polymerization reaction was controlled at 10 ml by adjusting the amount of solvent toluene. After one hour, the reaction solution was poured into 200 ml of terminator to terminate the polymerization. The terminator was 5% hydrochloric acid et...

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Abstract

The invention discloses a cobalt catalyst and application thereof in 1,3-butadiene polymerization reaction. The cobalt catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is a cobalt complex containing PNP ligand; and the cocatalyst is composed of one or more of aluminoxane, alkyl aluminum compounds and chlorinated alkyl aluminum compounds. The mol ratio of the metal aluminum in the cocatalyst to the metal cobalt in the main catalyst is (10-2000):1. The application method comprises the following steps: mixing the main catalyst and the cocatalyst in a solvent, aging for 1 minute to 1 hour, and adding the monomer butadiene to carry out the polymerization reaction. When being used for catalyzing 1,3-butadiene polymerization reaction, the cobalt catalyst has excellent catalytic activity and high product cis selectivity, thereby having wide industrial application prospects.

Description

technical field [0001] The invention relates to a catalyst, in particular to a cobalt-based catalyst and the application of the cobalt-based catalyst in 1,3-butadiene polymerization. Background technique [0002] The polymerization of 1,3-butadiene has two ways of 1,4-insertion and 1,2-insertion to generate cis-1,4, trans-1,4 or 1,2-vinyl polybutadiene respectively Alkenes, whose properties mainly depend on the microstructure of the polymer. Among these different isomers, high cis-1,4 polybutadiene, that is, butadiene rubber, has become an important industrial product due to its excellent rubber properties, and its output is second only to styrene-butadiene rubber. The second most common synthetic rubber. [0003] The catalysts used in the industrial production of butadiene rubber are mainly Ziegler-Natta catalysts, the central metals are mainly transition metals titanium, nickel, cobalt and rare earth metal neodymium, etc. High cis polybutadiene is prepared by solution p...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F4/70C08F36/06
Inventor 介素云李伯耿陈琳艾朋飞
Owner ZHEJIANG UNIV
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