A kind of p-containing organic polymer and its preparation method and application

Abstract

A P-containing organic polymer, the organic polymer is a multi-dentate organic phosphine monomer containing P and olefin groups, and the organic phosphine with a large specific surface area and a hierarchical porous structure is formed after the polymerization reaction is initiated by an initiator by a solvothermal polymerization method polymer. The organophosphine polymer is used in the preparation of heterogeneous reaction catalysts, and has the dual functions of a carrier and a ligand. In the metal-supported catalyst prepared by supporting the active metal component on the carrier, the metal component is highly dispersed on the carrier. It can also be used as a ligand similar to active metal ions in homogeneous complex catalysis. The active metal component is highly dispersed in this type of organic polymer in the form of a single atom, which greatly improves the utilization efficiency of the metal; In the acylation reaction, the catalyst prepared by using the polymer as a carrier can significantly improve the stereoselectivity of the product.

Description

technical field [0001] The invention relates to a P-containing organic polymer and a preparation method thereof, belonging to the technical field of material synthesis and application. Background technique [0002] In recent years, the design and synthesis of porous organic materials (Macromolecules, 2013, 34, 471) has gradually become one of the new hotspots in the research field of microporous materials. Compared with traditional inorganic microporous materials and organo-metallic coordination polymers, organic microporous The skeleton of the porous polymer is composed of pure organic molecules, which are connected to each other by covalent bonds, and have open pores 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 organic molecular building block precursors and molecular networks. The final material has corresponding proper...

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Problems solved by technology

However, the homogeneous reaction catalyst is not easy to recycle, and the production cost is very high

[0005] In the patent CN1210514A, the olefin hydroformylation reaction is carried out under the catalysis of the rhodium complex, and the rhodium complex has a multi-dentate, phosphorus-free organic nitrogen compound that can form a complex with the VIII metal for coordination The rhodium complex also contains at least one tertiary nitrogen group that can be protonated in a weak acid, but the catalyst also faces the problem of difficult recovery

[0006] In the patent CN102911021A, a composite catalytic system composed of a rhodium complex, a biphenyl skeleton or a binaphthyl skeleton diphosphine ligand, and a triphenylphosphine or phosphite triphenyl ester monophosphine ligand is used as a catalyst. In the formylation reaction, normal aldehydes have high selectivity, which reduces the amount of expensive bisphosphine ligands, but the catalytic system is still homogeneous, and the catalyst cannot be reused.

In the patent CN1986055A, bisphosphite and triphenylphosphine are also used to cooperate with Rh, and the composition conforms to the catalytic system. In the hydroformylation reaction of propylene, the molar ratio of n-butyraldehyde and isobutyraldehyde is greater than 20, which significantly prolongs the bisphosphite The service life of the phosphate ligand significantly reduces the amount of triarylphosphine, but it is still a homogeneous reaction in nature, and it also faces the problem of difficulty in catalyst recycling

[0007] In 2014, Xiao Fengshou, Ding Yunjie and others (Chem.Commun., 2014, 50, 11844) used solvothermal polymerization to polymerize tris (4-vinylphenyl) phosphine and named it POLs. The organic polymer was prepared The catalyst obtained in the olefin hydroformylation reaction has good activity, and the active component is not easy to lose, but due to the polymerization of monophosphine ligands, the catalyst prepared with the polymer as a carrier can be used in the hydroformylation of high carbon olefins. Good stereoselectivity was not achieved in the acylation reaction

However, the use of porous organic matter as a carrier for heterogeneous reactions also exposes some problems that need to be solved and overcome, such as poor thermal stability of polymer materials, cumbersome material synthesis process and other materials that are sensitive to air and water. Organic polymers as carriers The reaction selectivity is not high enough, and it is difficult to introduce target monomers in a general and concise manner.

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