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Naphthol skeleton phenol-phosphine neutral nickel catalyst preparation method and application in preparing ethylene/vinyl polar monomer co-polymer

A nickel catalyst and catalyst technology, applied in the direction of nickel organic compounds, etc., can solve problems such as unsuitable for industrialization and expensive metal palladium

Active Publication Date: 2019-02-12
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] At present, the catalysts that can realize the direct coordination polymerization of ethylene and vinyl polar monomers are mainly palladium complexes, but metal palladium is expensive and not suitable for industrial promotion

Method used

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  • Naphthol skeleton phenol-phosphine neutral nickel catalyst preparation method and application in preparing ethylene/vinyl polar monomer co-polymer
  • Naphthol skeleton phenol-phosphine neutral nickel catalyst preparation method and application in preparing ethylene/vinyl polar monomer co-polymer
  • Naphthol skeleton phenol-phosphine neutral nickel catalyst preparation method and application in preparing ethylene/vinyl polar monomer co-polymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] A-1 ligand is naphthol-phosphine L1, its structural formula is:

[0047]

[0048] Synthetic steps of L1:

[0049] Under a nitrogen atmosphere, α-naphthol (11.5 g, 50 mmol) was reacted with dihydropyran at room temperature for 10 h with stirring to obtain product b with a tetrahydropyran group. It was dissolved in 100 mL of tetrahydrofuran, stabilized at -78°C for 5 minutes, and n-BuLi solution (25 mL, 60 mmol) was added dropwise, and gradually returned to room temperature after 0.5 h of reaction. The reaction was continued for 2h, and a large amount of white precipitate c was obtained. 10.7 mL of diphenylphosphine chloride (PPh 2 Cl) was uniformly dispersed in 20 mL of tetrahydrofuran, and added dropwise to the original reaction system under an ice-water bath, slowly raised to room temperature, and stirred overnight. TLC monitored until the reaction was completed, quenched with water, extracted the organic phase with diethyl ether, concentrated the obtained organi...

Embodiment 2

[0051] A-2 ligand is naphthol-phosphine L2, its structural formula is:

[0052]

[0053] Synthetic steps of L2:

[0054] Under nitrogen atmosphere, dissolve α-naphthol (7.2g, 50mmol), iodobenzene (12.3g, 60mmol), cesium carbonate (19.5g, 60mmol) in 150mL DMF, then add palladium chloride (0.13g, 0.75 mmol) was used as a catalyst, heated to reflux at 115° C. for 12 h, and the reaction progress was monitored by TLC. After the reaction was completed and cooled to room temperature, the organic phase was extracted with ether, and the anhydrous MgSO 4 Dry, filter and concentrate. Column chromatography gave dark brown oily product d. It was stirred and reacted with dihydropyran at room temperature for 10 h to obtain light yellow solid e with tetrahydropyran group.

[0055] Under a nitrogen atmosphere, the intermediate product e (9.2 g, 30 mmol) was dissolved in 50 mL of diethyl ether, stabilized in an ice-water bath for 5 minutes, and n-BuLi solution (14 mL, 33 mmol) was added ...

Embodiment 3

[0057] A-3 ligand is naphthol-phosphine L3, its structural formula is:

[0058]

[0059] Synthetic steps of L3:

[0060] Under nitrogen atmosphere, dissolve α-naphthol (7.2g, 50mmol), 3,5-dimethyliodobenzene (13.9g, 60mmol), cesium carbonate (19.5g, 60mmol) in 150mL DMF, and then add chlorine Palladium chloride (0.13g, 0.75mmol) was used as a catalyst, heated to reflux at 115°C for 12h, and the reaction progress was monitored by TLC. After the reaction was completed and cooled to room temperature, the organic phase was extracted with ether, and the anhydrous MgSO 4 Dry, filter and concentrate. Column chromatography gave dark brown oily product g. It was stirred and reacted with dihydropyran at room temperature for 10 h to obtain light yellow solid h with tetrahydropyran group.

[0061] Under a nitrogen atmosphere, the intermediate product h (9.9 g, 30 mmol) was dissolved in 50 mL of diethyl ether, stabilized in an ice-water bath for 5 minutes, and n-BuLi solution (14 mL...

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Abstract

The invention relates to a naphthol skeleton phenol-phosphine neutral nickel catalyst preparation method and application in preparing an ethylene / vinyl polar monomer co-polymer. Naphthol-phosphine ligands containing different R and Ar substituent groups and a metal nickle source are subjected to coordination reaction to obtain a series of phenol-phosphine complexes with the different substituent groups. The phenol-phosphine complexes can be used as a high-activity neutral catalyst single component for triggering vinyl polymerization, wherein vinyl homopolymerization activity is up to 2.9*107 g / (molNi.h). By means of the type of catalysts, efficient copolymerization of ethylene and vinyl polar monomer is achieved, the copolymerization activity can reach 1.4*105 g / (molNi.h). Through nuclearmagnetic spectroscopy calculation, the methyl acrylate insertion rate can be up to 6.5 mol%; the methyl methacrylate insertion rate can be up to 4.4 mol%.

Description

technical field [0001] The invention relates to the synthesis of a naphthol skeleton phenol-phosphine nickel complex and its application in the copolymerization of ethylene and vinyl polar monomers. The naphthol skeleton phenol-phosphine neutral nickel complex is used as an olefin polymerization catalyst for the preparation of linear polyethylene and ethylene / methyl (meth)acrylate random copolymer. Background technique [0002] Due to the abundance of raw materials, low price, easy processing and molding, and corrosion resistance, polyolefin has become the largest and most widely used polymer material in the world. However, most traditional polyolefins are non-polar polymers, so their hydrophilicity, colorability, and poor compatibility with polar polymers have seriously hindered their application in many fields. The simple and effective functional modification of polyolefin can greatly improve the surface polarity of polyolefin, increase its added value, and expand its app...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/04C08F110/02C08F210/02C08F220/14C08F4/80
CPCC07F15/04C08F110/02C08F210/02C08F4/80C08F220/14
Inventor 李悦生王旭灵张艳平潘莉
Owner TIANJIN UNIV
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