Catalyst composition for olefin polymerization, use thereof and method for polymerization of conjugated diene monomer

A technology of olefin polymerization and composition, which is applied in the field of conjugated diene monomer polymerization, can solve the problems of catalyst deactivation, difficult realization of copolymerization, easy destruction of catalytic active centers, etc., and achieve high content of cis structure and high conversion rate Effect

Active Publication Date: 2020-02-18
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the copolymerization of conjugated dienes with other olefins, polar monomers, etc. is not easy to achieve, especially polar monomers can easily destroy the catalytic active center, resulting in catalyst deactivation

Method used

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  • Catalyst composition for olefin polymerization, use thereof and method for polymerization of conjugated diene monomer
  • Catalyst composition for olefin polymerization, use thereof and method for polymerization of conjugated diene monomer
  • Catalyst composition for olefin polymerization, use thereof and method for polymerization of conjugated diene monomer

Examples

Experimental program
Comparison scheme
Effect test

preparation example 1

[0108] (1) prepare the compound of structure shown in formula (2), wherein, X is Br; R 1 for CH 3 ; 2 for CH 3 .

[0109] 1. Dissolve 2,6-dimethylbromobenzene (10mmol), NBS (30mmol) and AIBN (0.2mmol) in 50mL of CCl 4 After reflux for 10 hours, cool and filter, and spin the filtrate to dryness. To this was added 88% by weight formic acid (35 mL) and reflux was continued for 12 h. After that, the solvent was evaporated under reduced pressure, and the volume ratio was 1:1.5 with CH 2 Cl 2 / H 2 O extraction, the organic phase was separated and washed with anhydrous Na 2 SO 4 Dry, then use petroleum ether: CH 2 Cl 2 =5:1 (volume ratio) column chromatography separation to obtain the intermediate product 2-bromo-3-benzyl bromide-benzaldehyde;

[0110] 2. Dissolve 2-bromo-3-benzyl bromide-benzaldehyde (3.6mmol) in 30mL of methanol, then add 2,6-dimethyl-aniline (3.6mmol), and add acetic acid to make the pH of the solution After reacting at 25°C for 8 hours, the precipita...

preparation example 2

[0118] (1) prepare the compound of structure shown in formula (2), wherein, X is Br; R 1 for CH 3 CH 2 ; 2 for CH 3 CH 2 .

[0119] The compound with the structure represented by formula (2) was prepared by a method similar to Preparation Example 1 to obtain a bis-Schiff base compound with a yield of 75%.

[0120] The characterization data of gained bis-Schiff base compound are as follows:

[0121] 1 H NMR (CDCl 3 ,400MHz,δ,ppm):8.74(s,2H),8.14(d,2H),7.37(t,4H),7.10(d,4H),7.18(t,2H),2.61(m,8H), 1.36(s,12H).

[0122] Elemental Analysis: C 36 h 38 N 2 Br 2 Calculated: C, 65.67; H, 5.78; N, 4.26. Found: C, 65.69; H, 5.78; N, 4.23.

[0123] (2) The compound with the structure shown in formula (1) was prepared by a method similar to Preparation Example 1, wherein Ln is Nd.

[0124] Dissolve the obtained bis-Schiff base compound (1 mmol) in THF to form a 0.04M solution, add butyllithium (1.05 mmol) in hexane solution (20 mL), stir the reaction at minus 78 ° C for 1 h...

preparation example 3

[0126] (1) prepare the compound of structure shown in formula (2), wherein, X is Br; R 1 for CH(CH 3 ) 2 ; 2 for CH(CH 3 ) 2 .

[0127] The compound represented by the formula (2) was prepared by a method similar to that of Preparation Example 1 to obtain a bis-Schiff base compound with a yield of 73%.

[0128] The characterization data of gained bis-Schiff base compound are as follows:

[0129] 1 H NMR (CDCl3 ,400MHz,δ,ppm):8.74(s,2H),8.14(d,2H),7.37(t,4H),7.08~7.12(m,6H),3.02~3.08(m,4H),1.23(d ,12H).

[0130] Elemental Analysis: C 40 h 46 N 2 Br 2 Calculated: C, 67.24; H, 6.44; N, 3.92. Found: C, 67.23; H, 6.44; N, 3.91.

[0131] (2) The compound with the structure shown in formula (1) was prepared by a method similar to Preparation Example 2, wherein Ln is Nd.

[0132] The bis-Schiff base rare earth complex P3 was obtained.

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Abstract

The present invention relates to the field of catalysts for polymerization, and discloses a catalyst composition for olefin polymerization, and applications thereof, and a conjugated diene monomer polymerization method, wherein the catalyst composition for olefin polymerization contains a main catalyst and a cocatalyst, the main catalyst is a double Schiff base rare earth coordination compound, the coordination compound has a structure represented by a formula (1), and the cocatalyst comprises an alkylating reagent and / or an organoboron compound. The conjugated diene monomer polymerization method comprises that a raw material containing a conjugated diene monomer contacts a catalyst composition to carry out a polymerization reaction. According to the present invention, the catalyst composition for olefin polymerization can catalyze the homopolymerization reaction of conjugated diene monomers and the copolymerization reaction between conjugated diene monomers and polar monomers; and thecatalyst composition for olefin polymerization has advantages of high conversion rate and high cis structure content in the catalysis of the homopolymerization and the copolymerization of conjugateddiene monomers. The formula (1) is defined in the specification.

Description

technical field [0001] The present invention relates to the field of polymerization catalysts, in particular to a catalyst composition for olefin polymerization, the application of the catalyst composition for olefin polymerization in catalyzing the polymerization of conjugated diene monomers, and a method for the polymerization of conjugated diene monomers. method. Background technique [0002] Conjugated dienes (such as butadiene and isoprene) can be synthesized into stereoregular polymers by coordination polymerization to produce important synthetic rubber varieties, such as cis-1,4-polybutadiene and cis-1 , 4-polyisoprene. [0003] Various organic complexes of transition metals, late transition metals and rare earth metals can be used as catalysts for the polymerization of conjugated dienes. However, the copolymerization of conjugated dienes with other olefins and polar monomers is not easy to realize, especially the polar monomers are very easy to destroy the catalyti...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F136/08C08F10/00C08F4/52C08G63/08C08G63/84
CPCC08F10/00C08F136/08C08G63/08C08G63/823C08F4/52
Inventor 谭金枚徐林董江舟张杰王超
Owner CHINA PETROLEUM & CHEM CORP
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