Organic porous copolymer multifunctional biomimetic heterogeneous catalyst and preparation method thereof

Abstract

The invention relates to a multifunctional biomimetic heterogeneous catalyst formed by an organic porous copolymer based on metalloporphyrin and a quaternary phosphonium salt, and a preparation methodthereof, wherein the metalloporphyrin and the quaternary phosphonium salt functional group are used as the main active component of the heterogeneous catalyst, the metalloporphyrin group is used as aLewis acid, the halogen ion in the quaternary phosphonium salt is used as a nucleophilic reagent, and the organic porous copolymer carrier containing metalloporphyrin and a quaternary phosphonium group is formed by carrying out co-polymerization on alkylene-functionalized metalloporphyrin and a quaternary phosphonium salt monomer. According to the present invention, the heterogeneous catalyst isused for the coupling reaction process of epoxy compounds and carbon dioxide, wherein the abundant N and P atoms in the polymer skeleton can increase the adsorption of CO2; and the porous organic polymer material can seal and limit the reaction substrate in the nano-scale pores and increase the concentration of the substrate at the catalytic site, such that the catalyst has double advantages of extremely high activity and extremely high stability.

Description

technical field [0001] The field of the invention belongs to the field of heterogeneous catalysis, and specifically relates to a multifunctional biomimetic heterogeneous catalyst containing metal porphyrin and quaternary phosphonium salt copolymer used in the coupling reaction of carbon dioxide and epoxy compounds and a preparation method thereof. Background technique [0002] The design and synthesis of porous organic polymer materials has gradually become one of the new hotspots in the field of porous materials research. Compared with traditional inorganic microporous materials and metal-organic frameworks (MOFs), the framework of organic microporous polymers is composed of pure organic molecules, which are connected to each other by covalent bonds, and have open channels and excellent pore properties. . More importantly, due to the diversity of organic chemical synthesis methods, it provides a wealth of synthetic routes and construction methods for the construction of or...

AI Technical Summary

Problems solved by technology

A Lewis acid / base composite catalytic system composed of zinc chloride and hexyltetradecyl phosphonium salt ionic liquid was prepared, and it was used in the addition reaction of alkylene oxide ring and carbon dioxide, showing high Catalytic activity, but it is a homogeneous catalytic system, facing problems such as difficult catalyst recovery and use

[0005] In 2013, Ema et al. (Green Chem, 2013, 15, 2485) prepared an organic-inorganic hybrid catalyst, that is, rigid porphyrin molecules were supported on iron oxide through covalent bonds. 2 In the addition reaction with epoxide, it shows high catalytic activity, but its cycle stability is poor, and the active components are easy to lose

[0006] In 2014, Ema et al. (J.Am.Chem.Soc.2014,136,15270) synthesized a bifunctional porphyrin catalyst, that is, the ionic liquid was grafted onto the porphyrin molecule through a covalent bond. 2 In the addition reaction with epoxide, it shows super high catalytic activity, but it still belongs to the homogeneous catalytic system, and still faces problems such as difficulty in catalyst recovery.

However, the above catalytic system requires the addition of quaternary ammonium salt cocatalysts, resulting in difficulties in product separation and purification.

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