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Metal complex catalyzer and application thereof for synthesizing cyclic carbonate

A technology of metal complexes and cyclic carbonates, applied in the direction of organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, chemical recovery, etc., can solve the problem of lack of suitable catalysts and low usage of homogeneous catalysts , high catalytic activity, etc., to achieve the effects of stable catalyst structure, good repeated use performance, and simple preparation process

Inactive Publication Date: 2012-09-19
NANJING UNIV OF TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] It can be seen that the combination of metal salts, ionic liquids and quaternary ammonium salt catalysts into one composite catalyst has a good effect on CO 2 The cycloaddition reaction with epoxy compounds has obvious high activity, but these catalyst systems all apply the concept of ionic liquids to varying degrees, and the preparation of ionic liquids is complicated, expensive and corrosive. Further demonstration and discussion
[0013] The obvious advantage of homogeneous catalysts is less usage and high catalytic activity, but the disadvantage is that subsequent separation and reuse are difficult
Chinese patent CN1789258A discloses a kind of using NaOH, NaCO 3 etc. Modified strongly basic ion exchange resin loaded gold, and Chinese patent CN1568851A disclosed activated carbon loaded tetraethylammonium bromide, CN1796384A disclosed chitosan loaded zinc bromide and CN101239965A disclosed resin loaded ionic liquid, etc. Solid catalysts are used to achieve CO 2 It has achieved certain effects in the cycloaddition reaction activity of epoxy compounds and catalyst separation performance, but the life of heterogeneous catalysts needs further research, and there is still a long way to go before industrial applications.
[0020] However, there are currently no catalysts on the market that meet these criteria

Method used

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  • Metal complex catalyzer and application thereof for synthesizing cyclic carbonate

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Weigh 22.52gZnBr 2 and 42.03g of tetraethylammonium bromide were dissolved in 100ml and 50ml of absolute ethanol respectively, then the two were mixed, heated and boiled to 50°C, and maintained for about 30min, cooled to room temperature, filtered, and dried at 60°C under vacuum , to obtain 59.56g white powder [(C 2 h 5 ) 4 N] 2 ZnBr 4 catalyst.

Embodiment 2

[0045] In the autoclave, add the zinc complex [(C 2 h 5 ) 4 N] 2 ZnBr 4 Catalyst 0.17mmol; CO was introduced after sealing 2 Replace the air 2-3 times, measure and press 0.5mol of ethylene oxide, add CO 2 Increase the pressure to 2.5MPa; raise the temperature to 90°C for 40 minutes, when the pressure is lower than 3MPa, add CO 2 to 3MPa, until the still pressure remains constant; cooling, taking out the still liquid and adopting rectification under reduced pressure to obtain the ethylene carbonate product, weighing and analyzing with gas chromatography, the yield of ethylene carbonate is 99.5%, and the TOF in terms of metal complexes is 4390h -1 .

Embodiment 3

[0047] In the autoclave, the zinc complex [(C 2 h 5 ) 4 N] 2 ZnBr 4 Catalyst 0.22mmol and propylene oxide 0.5mol; 2 Replace the air 2-3 times, increase the pressure to 2.5MPa; raise the temperature to 90°C for 40 minutes, when the pressure is lower than 3MPa, add CO 2 To 3MPa, until the pressure of the still remains constant; cooling, taking out the still liquid and adopting vacuum distillation to obtain the propylene carbonate product, weighing and analyzing with gas chromatography. The yield of propylene carbonate is 99.2%, and the TOF calculated as metal complex is 3382h -1 .

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Abstract

The invention belongs to the field of chemicals and discloses a metal complex catalyzer and application thereof for synthesizing cyclic carbonate. The catalyzer is one of metal complexes of zinc element, copper element, cadmium element, aluminum element, tin element, iron element, cobalt element or nickel element and can also be composited with metal salt synergistic adjuvant to prepare a composite catalyzer, and CO2 (carbon dioxide) and epoxy compound are utilized to prepare the cyclic carbonate by cycloaddition. The metal complex catalyzer for synthesizing the cyclic carbonate is simple to prepare, high in catalytic activity, low in cost, easy to separate, good in stability and reusability, can form a homogeneous catalyzer system, and has a good industrial application prospect. Besides, the metal salt synergistic adjuvant is easy to obtain.

Description

technical field [0001] The invention belongs to the field of chemical industry, and relates to a metal complex catalyst for synthesizing cyclic carbonate and application thereof. Specifically involving a CO 2 Zinc (copper, cadmium, aluminum, tin, iron, cobalt or nickel) metal complex catalysts and complex main catalysts and potassium (lithium or sodium) metal salt coordinating additives to form composite catalysts and their applications. Background technique [0002] With the intensification of the global "greenhouse effect" and the energy crisis, CO 2 Abundant, inexpensive and CO-reducing as C1 starting material for some chemicals 2 emission and reduce the harm to the environment. Due to CO 2 The nature of the extremely inactive, in the fixation of CO 2 One of the most successful and typical reactions is the use of CO 2 Synthesis of cyclic carbonates by cycloaddition with epoxy compounds. The general formula of cyclic carbonates can be expressed as: Because of its...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J31/40C07D317/38C07D317/36
CPCY02P20/584
Inventor 刘定华严家进刘晓勤孙林兵朱志敏梅支舵殷芳喜
Owner NANJING UNIV OF TECH
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