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Chromium, zinc or copper complexed conjugated microporous polymer catalysts, as well as preparation method and application thereof

A technology of conjugated micropores and copper complexation, applied in organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problem of low catalyst utilization and harsh conditions problem, achieve the effect of overcoming the limitation of high temperature and high pressure conditions, increasing solubility and shortening reaction time

Active Publication Date: 2014-02-12
ZHANGJIAGANG IND TECH RES INST CO LTD DALIAN INST OF CHEM PHYSICS CHINESE ACADEMY OF SCI
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Problems solved by technology

In recent years, through the efforts of researchers from various countries, CO 2 Fixing or chemical conversion into organic matter is the main way to deal with CO 2 means, where, utilizing CO 2 The organic chemical, cycloaddition reaction with cycloalkanes to the corresponding cyclic carbonates, is a promising approach, but the catalysts used in such reactions catalyze the conversion of CO 2 The conditions are relatively harsh, and its catalytic activity is limited by high temperature and high pressure conditions. At the same time, many catalysts used are limited by problems such as separation, resulting in relatively low catalyst utilization. Therefore, in order to overcome the above difficulties, it is necessary to find a simple separation , can achieve CO under relatively mild conditions 2 Catalysts for the catalytic conversion of

Method used

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  • Chromium, zinc or copper complexed conjugated microporous polymer catalysts, as well as preparation method and application thereof
  • Chromium, zinc or copper complexed conjugated microporous polymer catalysts, as well as preparation method and application thereof
  • Chromium, zinc or copper complexed conjugated microporous polymer catalysts, as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0064] 1), the synthesis method of Salen-Cr-Cl: 0.6mmol Salen (N,N-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane) and 0.8mmol CrCl 2 Dissolve in 12ml of dry tetrahydrofuran, under the protection of argon, stir at 25°C for 24h, and continue stirring for 24h under atmospheric atmosphere to obtain the desired Salen-Cr-Cl compound;

[0065] 2), the synthesis method of CMP-1:

[0066] ①. Synthesis of CMP-1-1: 0.4mmol Salen-Cr-Cl, 1.2mmol 1,3,5-triethynylbenzene, 40mg CuI, 80mg tetrakis(triphenylphosphopalladium), 12ml toluene and 4ml Tris Ethylamine was used as a solvent, and refluxed at 80°C for 72h to obtain the desired CMP-1-1 compound; the IR spectrum of the polymer was as follows Figure 12 ; Solid NMR such as Figure 16 .

[0067] ②. Synthesis of CMP-1-2: 0.45mmol Salen-Cr-Cl, 1.35mmol 1,4-diethynylbenzene, 30mg CuI, 60mg tetrakis(triphenylphosphopalladium), 15ml toluene and 5ml triethylamine As a solvent, reflux at 80°C for 72h to obtain the desired CMP-1...

Embodiment 2

[0078] 1), the synthesis method of Salen-Zn: 0.4mmol Salen (N,N-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane) and 0.4ml Et 2 Zn (1.0M in hexane) was dissolved in 20ml of dry tetrahydrofuran, protected by argon, and stirred at 25°C for 24h to obtain the desired Salen-Zn compound;

[0079]2), the synthesis method of CMP-2:

[0080] ①. Synthesis of CMP-2-1: 0.35mmol Salen-Zn, 1.05mmol 1,3,5-triethynylbenzene, 40mg CuI, 70mg tetrakis(triphenylphosphopalladium), 12ml toluene and 4ml triethylamine As a solvent, reflux at 85°C for 72h to obtain the desired CMP-2-1 compound; the IR spectrum of the polymer is as follows Figure 13 ; Solid NMR such as Figure 17 .

[0081] ② Synthesis of CMP-2-2: 0.4mmol Salen-Zn, 1.2mmol 1,4-diethynylbenzene, 35mg CuI, 70mg tetrakis(triphenylphosphopalladium), 15ml toluene and 5ml triethylamine as solvent , reflux at 85°C for 72h to obtain the desired CMP-2-2 compound;

[0082] ③. Synthesis of CMP-2-3: 0.4mmol Salen-Cr-Cl, 1.2mmol...

Embodiment 3

[0092] 1), the synthesis method of Salen-Cu: 0.5mmol Salen (N,N-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane) and 0.5mmol Cu(OAc) 2 Dissolve in 20ml of dry absolute ethanol, reflux at 80°C for 24h to obtain the desired Salen-Cu compound;

[0093] 2), the synthesis method of CMP-3:

[0094] ①. Synthesis of CMP-3-1: 0.46mmol Salen-Cu, 1.32mmol 1,3,5-triethynylbenzene, 40mg CuI, 80mg tetrakis(triphenylphosphopalladium), 15ml toluene and 5ml triethylamine As a solvent, reflux at 80°C for 72h to obtain the desired CMP-3-1 compound; the IR spectrum of the polymer is as follows Figure 14 ; Solid NMR such as Figure 18 .

[0095] ②. Synthesis of CMP-3-2: 0.4mmol Salen-Cu, 1.2mmol 1,4-diethynylbenzene, 40mg CuI, 70mg tetrakis(triphenylphosphopalladium), 12ml toluene and 4ml triethylamine as solvent , reflux at 80°C for 72h to obtain the desired CMP-3-2 compound;

[0096] ③. Synthesis of CMP-3-3: 0.45mmol Salen-Cu, 1.35mmol tetrakis(4-ethynylphenyl)methane, 40mg C...

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Abstract

The invention develops novel catalysts which can be used for catalyzing the cycloaddition of CO2 and epoxy alkane at 0-160 DEG C and 0.1-6MPa to generate corresponding cyclic carbonates and a preparation method thereof. The catalysts provided by the invention are metal chromium, zinc or copper complexed conjugated microporous polymer (CMP) catalysts, wherein CMP-1 is one type of metal chromium complexed polymers, CMP-2 is one type of metal zinc complexed polymers, and CMP-3 is one type of metal copper complexed polymers; by using the polymer catalysts complexed by different metals to catalyze the reaction of CO2 and epoxy alkane at normal temperature and normal pressure, the yield of the obtained corresponding cyclic carbonates is 35-38%, the recovery of the catalysts is simple and convenient to operate, and the reuse of the catalysts can not affect the yield; meanwhile the reaction conditions are controlled, and the yield can achieve above 90% when the reaction is performed at the temperature of 50-120 DEG C and the CO2 pressure of 2-6MPa for 1-3 hours.

Description

technical field [0001] The present invention designs and synthesizes metal chromium, zinc and copper complexed conjugated microporous polymer CMP, and uses them as catalysts to catalyze CO under relatively mild experimental conditions. 2 Cycloaddition reaction with alkylene oxide to synthesize corresponding cyclic carbonates. At the same time, this type of polymer catalyst is easy to recover and operate, and repeated use has no effect on the yield of cyclic carbonates, which greatly improves the utilization rate of the catalyst. Background technique [0002] CO 2 It is one of the main greenhouse gases. At the same time, it also has many advantages such as large reserves, safety, non-toxicity, and cheapness. Since the industrial revolution, CO in the atmosphere 2 The content of CO2 is constantly rising, the greenhouse effect is constantly increasing, leading to global warming, and at the same time, disastrous weather is becoming more frequent. Therefore, how to process and u...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07D317/36
Inventor 邓伟侨谢勇刘晓焕
Owner ZHANGJIAGANG IND TECH RES INST CO LTD DALIAN INST OF CHEM PHYSICS CHINESE ACADEMY OF SCI
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