Preparation method for complex containing o-benzhydryl substituted alpha-diimine nickel (II) used for fluorination of ethylene polymerization

A technology of benzhydryl and nickel diimide, which is applied in the field of olefin polymerization, can solve the problems of limited research and achieve the effect of large steric hindrance, promotion of chain growth rate, and reduction of transfer rate

Active Publication Date: 2018-12-21
CHANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In previous studies, the research on the ortho-F group on α-diimine ligands and corresponding catalysts is very limited.

Method used

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  • Preparation method for complex containing o-benzhydryl substituted alpha-diimine nickel (II) used for fluorination of ethylene polymerization
  • Preparation method for complex containing o-benzhydryl substituted alpha-diimine nickel (II) used for fluorination of ethylene polymerization
  • Preparation method for complex containing o-benzhydryl substituted alpha-diimine nickel (II) used for fluorination of ethylene polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] (1) Synthesis of 2-benzhydryl-4-bromo-6-fluoroaniline:

[0044]

[0045] In a 50ml round bottom flask, add 2-fluoro-4-bromoaniline (1.89g, 10mmol) and diphenylmethanol (1.84g, 10mmol), stir the mixture and slowly heat up to 120°C, add anhydrous chlorine to the mixture Zinc chloride (0.68g, 5mmol), concentrated hydrochloric acid (37%, 0.37g, 10mmol), heated to 160°C, reacted for 1 hour (exothermic and strong bubbling), after cooling to room temperature, the solid was dissolved in 50mL CH 2 Cl 2 , washed three times with saturated NaOH aqueous solution, and the organic layer was washed with anhydrous MgSO 4 Dry, concentrate under reduced pressure, add ethanol to precipitate a white solid, filter and dry to obtain 2.91 g of 2-benzhydryl-4-bromo-6-fluoroaniline with a yield of 82%.

[0046] Its reaction formula is as follows:

[0047]

[0048] (2) Ligand (2-CHPh 2 -4-Br-6-FPh) 2 Synthesis of DABAn:

[0049]

[0050] Dissolve 2-benzhydryl-4-bromo-6-fluoroanili...

Embodiment 2

[0060] (1) Synthesis of 2-benzhydryl-4-chloro-6-fluoroaniline:

[0061]

[0062] In a 50ml round bottom flask, add 2-fluoro-4-chloroaniline (1.45g, 10mmol) and diphenylmethanol (1.84g, 10mmol), stir the mixture and slowly heat up to 120°C, add anhydrous chlorine to the mixture Zinc chloride (0.68g, 5mmol), concentrated hydrochloric acid (37%, 0.37g, 10mmol), heated to 160°C, reacted for 1 hour (exothermic and strong bubbling), after cooling to room temperature, the solid was dissolved in 50mL CH 2 Cl 2 , washed three times with saturated NaOH aqueous solution, and the organic layer was washed with anhydrous MgSO 4 Dry, concentrate under reduced pressure, add ethanol to precipitate a white solid, filter and dry to obtain 2.61 g of 2-benzhydryl-4-chloro-6-fluoroaniline with a yield of 84%.

[0063] Its reaction formula is as follows:

[0064]

[0065] (2) Ligand (2-CHPh 2 -4-Cl-6-FPh) 2 Synthesis of DABAn:

[0066]

[0067] Dissolve 2-benzhydryl-4-chloro-6-fluoroa...

Embodiment 3

[0077] (1) Synthesis of 2-benzhydryl-4,6-difluoroaniline:

[0078]

[0079] In a 50ml round bottom flask, add 2,4-difluoroaniline (1.29g, 10mmol) and diphenylmethanol (1.84g, 10mmol), stir the mixture and slowly raise the temperature to 120°C, add anhydrous chloride Zinc (0.68g, 5mmol), concentrated hydrochloric acid (37%, 0.37g, 10mmol), heated to 160°C, reacted for 1 hour (exothermic and strong bubbling), after cooling to room temperature, the solid was dissolved in 50mL CH 2 Cl 2 , washed three times with saturated NaOH aqueous solution, and the organic layer was washed with anhydrous MgSO 4 Dry, concentrate under reduced pressure, add ethanol to precipitate a white solid, filter and dry to obtain 2.36 g of 2-benzhydryl-4,6-difluoroaniline, and the yield is 80%.

[0080] Its reaction formula is as follows:

[0081]

[0082] (2) Ligand (2-CHPh 2 -4,6-diFPh) 2 Synthesis of DABAn:

[0083]

[0084] Dissolve 2-benzhydryl-4,6-difluoroaniline (1.24g, 4.2mmol) and a...

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Abstract

The invention belongs to the technical field of olefin polymerization, and discloses a novel complex containing o-benzhydryl substituted alpha-diimine nickel used for fluorination of ethylene polymerization. Large-steric-hindrance benzhydryl and an F group are led to the ortho-position of phenyl of a catalyst, so that a coordination environment (steric hindrance and electronic density) of a metalcenter is changed; under activation of a co-catalyst MAO, catalytic activity, polymer molecular weight and a micro branched structure can be effectively controlled. The complex catalytic ethylene polymerization has relatively high heat stability; and high-molecular-weight low-branching-degree polyethylene is obtained.

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 fluorinated α-diimine nickel (II) complexes containing ortho benzhydryl substitutions, and also relates to the The preparation method of the complex and its application in ethylene polymerization. Background technique [0002] Polyolefin materials are rich in raw materials, low in price, easy to process and shape, and have excellent comprehensive properties. They are the most consumed synthetic resins, and polyethylene is the most important polyolefin, which greatly improves people's daily life. Since the Ni(II) and Pd(II) complexes of α-diimine ligands reported by Brookhart et al. in the 1990s catalyzed the polymerization of ethylene or α-olefins to obtain high molecular weight polymers (Johnson, L.K.; Killian, C.M. ; Brookhart, M.J.Am.Chem.Soc.1995,117,6414-6415.; Johnson, L.K...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/04C08F110/02C08F4/70
CPCC07F15/045C08F110/02C08F4/7006C08F2500/01C08F2500/24
Inventor 李为民李瑞萍王福周田素素张杨陈昶乐郭登峰
Owner CHANGZHOU UNIV
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