Metal miscellaneous ligand catalyst precursor based on salicylaldehyde imine ligand, as well as preparation and application thereof

A catalyst and precursor technology, applied in chemical instruments and methods, organic chemistry, titanium organic compounds, etc., can solve the problems of increasing the difficulty of catalyst synthesis and separation, and the inability to adjust catalyst activity. It is easy to achieve equivalent, simple and gentle operation, The effect of less side effects

Active Publication Date: 2013-08-21
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] There are three problems in this synthetic method: 1) adopt low temperature (-78 ℃) and liquid flammable and explosive substance (butyllithium solution) as raw material, in industry and laboratory synthesis, have inconvenience more, and exist butyl The side reaction of lithium to imine addition in the ligand; 2) in the existing reports, the highest yield of this reactio

Method used

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  • Metal miscellaneous ligand catalyst precursor based on salicylaldehyde imine ligand, as well as preparation and application thereof
  • Metal miscellaneous ligand catalyst precursor based on salicylaldehyde imine ligand, as well as preparation and application thereof
  • Metal miscellaneous ligand catalyst precursor based on salicylaldehyde imine ligand, as well as preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] The preparation of metal heteroligand catalyst precursor shown in formula IIa

[0043]

[0044] In a glove box, (E)-2-((pentafluorophenylimino)methyl)phenol (0.29 g, 1.00 mmol) was dissolved in anhydrous dichloromethane (DCM) solvent, An equivalent amount of potassium hydride was added to the solution and reacted for 1 hour. Afterwards, this solution is added dropwise to titanium metal monoligand complex (R in the compound shown in formula IV) at normal temperature 1 = H, R 4 =t-Bu, M=Ti) (0.56g, 1.00mmol) in dichloromethane solution, and reacted at this temperature for 3 hours. After the reaction was finished, the solvent was removed with a vacuum line, the residue was washed with dichloromethane and filtered through celite, the filtrate was sucked dry, and the crude product was recrystallized with dichloromethane / n-hexane to obtain a reddish-brown powder (0.37g, 75%). 1 H NMR (CDCl 3 , 400MHz): δ8.30(s, 1H, CH=N), 8.18(s, 1H, CH=N), 7.70(d, 1H, J=7.2Hz, ArH), ...

Embodiment 2

[0046] The preparation of metal heteroligand catalyst precursor shown in formula IIb

[0047]

[0048] In the glove box, (E)-3-methyl-2-((pentafluorophenylimino)methyl)phenol (0.53g, 1.76mmol) was dissolved in anhydrous dichloromethane solvent, at room temperature Next, an equivalent amount of potassium hydride was added to the solution and reacted for 1 hour. Afterwards, this solution is added dropwise to titanium metal monoligand complex (R in the compound shown in formula IV) at normal temperature 1 = H, R 4 =t-Bu, M=Ti) (1.00 g, 1.76 mmol) in dichloromethane solution, and reacted at this temperature for 3 hours. After the reaction was finished, the solvent was removed with a vacuum line, the residue was washed with dichloromethane and filtered through diatomaceous earth, the filtrate was sucked dry, and the crude product was recrystallized with dichloromethane / n-hexane to obtain a reddish-brown powder (0.50 g, 37%). 1 H NMR (CDCl 3 , 400MHz): δ8.29(s, 1H, CH=N), 8....

Embodiment 3

[0050] The preparation of metal heteroligand catalyst precursor shown in formula IIc

[0051]

[0052] In a glove box, (E)-3-((pentafluorophenylimino)methyl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol (0.42 g, 1.00 mmol) was dissolved in anhydrous dichloromethane solvent, and an equivalent amount of potassium hydride was added to the solution at room temperature to react for 1 hour. Afterwards, this solution is added dropwise to titanium metal monoligand complex (R in the compound shown in formula IV) at normal temperature 1 =R 4 =t-Bu, M=Ti) (0.624g, 1.00mmol) in dichloromethane solution, and reacted at this temperature for 3 hours. After the reaction was finished, the solvent was removed with a vacuum line, the residue was washed with dichloromethane and filtered through diatomaceous earth, the filtrate was sucked dry, and the crude product was recrystallized with dichloromethane / n-hexane to obtain a reddish-brown powder (0.43g, 46%). 1 H NMR (CDCl 3 , 400MHz): δ8.31(s, 1...

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Abstract

The invention discloses a metal miscellaneous ligand catalyst precursor based on a salicylaldehyde imine ligand, as well as a synthesis method of the catalyst precursor and an application of the catalyst precursor in olefin polymerization. The catalyst precursor comprises two different salicylaldehyde imine ligands and transition metal of the IV group and can be rapidly synthesized by raw materials including the salicylaldehyde imine ligands, titanium tetrachloride and potassium hydride at normal temperature, the operation is simple and time-saving, and the yield is doubled compared with that of a conventional method. When a catalyst formed of the precursor and alkylaluminoxane catalyzes olefin homopolymerization or copolymerization, the activity is in the magnitude order of 106g.mol<-1>(Ti).h<-1>, the molecular weight of the obtained copolymer is about 150,000, and the dispersity is between 1.2 and 3.5. Compared with a single ligand metal catalyst, a miscellaneous ligand catalyst shows the advantages of both parent bodies or even exceeds a parent catalyst.

Description

technical field [0001] The invention belongs to the field of olefin coordination polymerization, and relates to the synthesis of a metal heteroligand catalyst precursor and the application of the catalyst composed of it in catalyzing olefin polymerization and copolymerization. Specifically, the present invention synthesizes a metal heteroligand catalyst precursor based on a group IV transition metal of salicylaldimine ligand, and the catalyst composed of the precursor and alkylaluminoxane can efficiently catalyze ethylene homogeneity. Copolymerization of polyethylene and ethylene with substituted olefins. Background technique [0002] Since the beginning of the 21st century, with the improvement of the national economy and the needs of the national defense industry, polymer materials, especially polyolefin materials, have played an increasingly important role: due to the abundance and low cost of polyolefin raw materials, easy processing and molding, every year in the world ...

Claims

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Application Information

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IPC IPC(8): C08F4/642C07F7/28C07F7/00C08F10/00C08F10/02C08F110/02C08F210/16C08F210/02
Inventor 马玉国姚二冬
Owner PEKING UNIV
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