Double-ligand zinc complex catalyst and application thereof

A technology of zinc complexes and catalysts, applied in the direction of organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, zinc organic compounds, etc., can solve poor corrosion and water resistance, slow release of corrosion inhibitors Poor performance, expensive and other problems, to achieve the effect of reducing corrosion and water resistance, easy recycling, and less by-product high polymer generation

Inactive Publication Date: 2015-04-08
NANJING UNIV OF TECH +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] It can be seen that the combination of metal salts and ionic liquids, quaternary ammonium salts, and quaternary phosphonium salt catalysts into one composite catalyst has a good effect on CO 2 The cycloaddition reaction with epoxides has high catalytic activity. These catalysts have applied the concept of ionic liquids to varying degrees, and the preparation of ionic liquids is complicated and expensive. Further demonstration and discussion are needed.
In particular, in view of the obvious corrosion and poor water resistance of Lew

Method used

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  • Double-ligand zinc complex catalyst and application thereof
  • Double-ligand zinc complex catalyst and application thereof
  • Double-ligand zinc complex catalyst and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Weigh 0.1mol ZnBr 2 Dissolve in 100mL of absolute ethanol, 0.1mol of methyltriphenylphosphonium bromide in 25ml of absolute ethanol, and 0.1mol of N-methylimidazole in 25mL of absolute ethanol. Add ZnBr to phosphine solution 2 After adding N-methylimidazole solution to the above-mentioned mixture, the mixture is prepared by heating and boiling to 50°C and maintaining it for about 30 minutes, cooling to room temperature, filtering, and drying at 60°C under vacuum to obtain white Powdery complex [(CH 3 )(C 6 H 5 ) 3 P][C 4 H 6 N 2 ]ZnBr 3 catalyst.

Embodiment 2

[0042] Under the conditions of implementation case 1, weigh out 0.1 mol ZnI 2 Dissolved in 100mL of absolute ethanol, 0.1mol of tetraphenylphosphine iodide dissolved in 25ml of absolute ethanol, a white powdery complex [(C 6 H 5 ) 4 P][C 4 H 6 N 2 ]ZnI 3 catalyst.

Embodiment 3

[0044] 3mmol prepared in Example 1 [(CH 3 )(C 6 H 5 ) 3 P][C 4 H 6 N 2 ]ZnBr 3 The complex was dissolved in 0.5 mol of reactant propylene oxide, and added to the reaction kettle, sealed and stirred to make it fully mixed, and pass CO 2 Replace the air 2 to 3 times, then pass in CO 2 The gas maintains a pressure of 2.5MPa, and the temperature is raised to 100℃ to react for 30 minutes. During the reaction, when the pressure is lower than 4MPa, CO is added 2 To 4MPa, until the kettle pressure remains unchanged; cooling, removing the kettle liquid, using vacuum distillation to obtain the propylene carbonate product, weighing, measuring its pH with a pH meter to be 7.75, and analyzing the yield of propylene carbonate by gas chromatography to be 99.2 %; On this basis, the product of propylene carbonate was separated by vacuum distillation, and the catalyst was recycled for 10 times. The yield of propylene carbonate was greater than 95%; and through gas chromatography analysis, no glycol...

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Abstract

The invention discloses a double-ligand zinc complex catalyst which is prepared from an active main body zinc halide salt, an active functional ligand L1 and a corrosion-inhibition functional ligand L2, wherein the active functional ligand L1 is tetramethyl ammonium halide, tetraethyl ammonium halide, tetrapropyl ammonium halide, tetraethyl phosphonium halide, tetraphenyl phosphonium halide, methyl tri-tert-butyl phosphonium halide or methyl triphenyl phosphonium halide; and the corrosion-inhibition functional ligand L2 is N-methylimidazole, iminazole, isoquinoline, quinoline, 2-toluquinoline, 4-toluquinoline, biquinoline, pyridine, 3-methylpyridine or 1,10-o-phenanthroline. The invention also discloses application of the catalyst in preparing corresponding cyclic carbonate by CO2-epoxy compound cycloaddition. The catalyst has the advantages of low temperature, high catalytic activity, low corrosivity, easy separation, high stability, favorable recovery performance and the like, can form a homogeneous catalytic system, and has favorable industrial application prospects.

Description

Technical field [0001] The invention belongs to the field of chemical catalysts, and specifically relates to a dual-ligand zinc complex catalyst and its application. Background technique [0002] CO 2 It is not only the main greenhouse gas, but also the abundant, cheap, and non-toxic C1 resource. Under the trend of "atomic economy", "sustainable development" and "green chemistry", how to realize CO under relatively mild conditions 2 The chemical fixation has become one of the hot topics in international research and development. Take CO 2 It is very rare to synthesize corresponding cyclic carbonate with epoxide as raw material. 2 One of the routes to achieve industrialization as a raw material. By CO 2 Propylene carbonate obtained by cycloaddition reaction with propylene oxide is an excellent organic solvent and organic synthesis intermediate. It has the advantages of high boiling point, high polarity, low toxicity and low corrosiveness. It is widely used in plastics, printing an...

Claims

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Application Information

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IPC IPC(8): B01J31/22B01J31/24C07F3/06C07D317/36C07D317/38
Inventor 刘定华史艳丽刘晓勤孙林兵卢伟陈贤召
Owner NANJING UNIV OF TECH
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