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Nickel(ii) complexes containing p-diphenylmethyl-substituted α-diimine for catalyzing the polymerization of ethylene and 2-hexene

A technology of benzhydryl and diimide nickel is applied in the field of olefin polymerization to achieve the effect of high activity and high branching degree

Active Publication Date: 2021-01-29
CHANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, reports on the polymerization of 2-olefins are rarely seen

Method used

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  • Nickel(ii) complexes containing p-diphenylmethyl-substituted α-diimine for catalyzing the polymerization of ethylene and 2-hexene
  • Nickel(ii) complexes containing p-diphenylmethyl-substituted α-diimine for catalyzing the polymerization of ethylene and 2-hexene
  • Nickel(ii) complexes containing p-diphenylmethyl-substituted α-diimine for catalyzing the polymerization of ethylene and 2-hexene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] (1) Synthesis of 4-benzhydryl-2,6-dimethylaniline:

[0035]

[0036] 2,6-Dimethylaniline (1.21g, 10mmol) and diphenylmethanol (1.84g, 10mmol) were placed in a 50ml round-bottomed flask, stirred and heated to 120°C, then anhydrous chloride was added to the mixture Zinc (0.681g, 5mmol), concentrated hydrochloric acid (37%, H 2 O, 0.365g, 10mmol), heated to 160°C, reacted for 1 hour (exothermic and vigorous bubbling), after cooling to room temperature, the solid was dissolved in CH 2 Cl 2 (70 mL), washed with saturated NaOH aqueous solution, washed with anhydrous MgSO 4 Dry, concentrate under reduced pressure, add a large amount of ethanol to precipitate a white solid, filter and dry to obtain 2.33 g of 4-benzhydryl-2,6-dimethylaniline, and the yield is 81%.

[0037] 1 H NMR (500MHz, CDCl 3 ,ppm):δ7.33–7.29(m,4H,C9),7.25–7.22 (m,2H,C10),7.17(d,J=7.0Hz,4H,C8),6.74(s,2H,C3) ,5.46(s, H,C6),3.50(s,2H,-NH 2 ), 2.16(s,6H,C5). 13 C NMR (125MHz, CDCl 3 ,ppm): δ144.75(C6)...

Embodiment 2

[0056] (1) Synthesis of 4-benzhydryl-2,6-diisopropylaniline:

[0057]

[0058] 2,6-diisopropylaniline (1.77g, 10mmol) and diphenylmethanol (1.84g, 10mmol) were placed in a 50ml round bottom flask, and after heating up to 120°C, anhydrous zinc chloride was added to the mixture (0.681g, 5mmol), concentrated hydrochloric acid (37%, H 2 O, 0.365g, 10mmol), the temperature was raised to 160°C, and the reaction was carried out for 1 hour (exothermic and strong bubbling). After cooling to room temperature, the solid was dissolved in CH 2 Cl 2 (60 mL), washed with saturated NaOH aqueous solution, washed with anhydrous MgSO 4 Dry, concentrate under reduced pressure, add a large amount of ethanol to precipitate a white solid, filter and dry to obtain 2.85 g of 4-benzhydryl-2,6-dimethylaniline, and the yield is 83%.

[0059] 1 H NMR (500MHz, CDCl 3 ,ppm):δ7.32–7.29(m,4H,C8),7.24–7.21(m,2H,C9),7.16(d,J=7.5Hz,4H,C7),6.84(s,2H,C3) ,5.50(s,H,C5),3.02(s,2H,-NH 2 ),2.21(s,4H,C10),1....

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Abstract

Novel late-transition-metal alpha-diimine nickel (II) complexes containing p-benzhydryl substitutes are disclosed. According to the complexes, two bulky groups which are benzhydryl are introduced to the para positions of imine nitrogen atoms on aromatic rings, and therefore ethylene insertion is accelerated, catalyst activity is improved, the transferring rate of active chains to a monomer is reduced, and a polymer having a high molecular weight is prepared. Under activation by a cocatalyst that is diethylaluminium chloride, a catalytic system catalyzing ethylene polymerization has high catalytic activity (can be 10<6> g PE / (mol Ni h)), and prepared polyethylene having a high molecular weight has a high degree of branching (can be 131 branches per 1000 C). Because of ortho-position small-steric-hindrance substitution and immobilization by para-position bulky benzhydryl, 2-hexene can be easily inserted to a metal center, and therefore chain shuttling polymerization of the 2-hexene has ahigh conversion ratio (88%), and a branch polymer having a high molecular weight and a low degree of dispersion is obtained. Accordingly, the catalyst has good potential application value in industrial polyolefin production.

Description

technical field [0001] The invention belongs to the technical field of olefin polymerization, relates to a class of late-transition metal olefin polymerization catalysts, in particular to a class of α-diimine nickel (II) complexes containing p-diphenylmethyl substitution, and also relates to the complexes Preparation method and its use in the polymerization of ethylene and 2-hexene. Background technique [0002] Since the Ni(II) and Pd(II) complexes of α-diimine ligands reported by Brookhart et al. in the 1990s can catalyze ethylene or α-olefin polymerization with high activity to obtain high molecular weight polymers, post-transition Metal catalysts have attracted widespread attention from scientists. These catalysts have unique chain walking properties, so that highly branched polymer materials can be obtained, and some polar monomers can be inserted to produce functionalized polyolefin materials with excellent performance. Compared with transition metal catalysts, this ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F110/02C08F110/14C08F4/70C07F15/04
CPCC07F15/045C08F110/02C08F110/14C08F4/7006C08F2500/01C08F2500/10C08F2500/03
Inventor 李为民田素素王福周李瑞萍陈昶乐
Owner CHANGZHOU UNIV
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