Application Of Phosphine-Containing Porous Polymers And Water-Soluble Phosphine Ligands In Heterogeneous Synthesis Of Aldehydes

Aldehyds are an important class of fine chemicals and have a wide range of industrial applications.They are also important raw materials for the preparation of alcohols,esters,acids,and amines.In most industrial applications,aldehydes can be synthesized by hydroformylation of alkenes.Homogeneous catalysts are widely used in hydroformylation of olefins,but they are still plagued by stability,reusability and separation.Therefore,the development of heterogeneous olefin hydroformylation catalysts has broader application prospects in industry.This thesis consists of two parts:（1）A series of phosphorus-containing porous organic polymer supported transition metal catalysts for heterogeneous hydroformylation were synthesized;（2）The catalytic reaction of C-C bond cleavage to synthesize aldehydes in two-phase of water and oil was studied.1.Synthesis of porous organic polymer-supported Rh catalyst and its application in hydroformylation of olefins.The phosphorus-containing porous polymer ligands were synthesized by copolymerization of 2v BINAPa monomer with divinyl group and the monomer（3v PPh₃and 3v Ph Ph₃）,which coordinated with Rh to obtain Rh/POL-BINAPa＆PPh₃and Rh/POL-BINAPa＆Ph Ph₃,respectively.These two heterogeneous rhodium catalysts were used in hydroformylation of alkenes.Rh/POL-BINAPa＆PPh₃showed better catalytic performance.1-Pentene,1-hexene,and long-chain 1-octene and1-decene were all suitable for this reaction,affording the corresponding aldehydes with high regioselectivity（l/b=85.6-133.7）and TON（up to 1.0×10~4）.Subsequently,a series of characterization datas such as NMR,FT-IR and DFT calculations were used to analyze and study the active Rh-H species in detail.The results show that the BINAPa polymerization unit in the carrier is beneficial to improve the activity of hydroformylation reaction,and PPh₃unit can improve the stability of Rh-H species.BINAPa and PPh₃units can coordinate with Rh to form a large group of triphosphine coordinated Rh-H active intermediates,which further improves the regional selectivity of the reaction.The Rh/POL-BINAPa＆PPh₃catalyst could maintain good activity and selectivity in five cycles.2.C-C bond cleavage of aliphatic aldehydes/ketones catalyzed by Cu in water-oil two phasesThe BINAP ligand was sulfonated to form a water-soluble sulfonated BINAP ligand,which was complexed with Cu（OAc）₂to obtain a water-soluble copper catalyst and the catalyst was used for the selective oxidation of carbon-carbon bonds of aliphatic aldehydes or ketones.Substrates containing different functional groups can be applied to the reaction system to obtain corresponding aldehydes.The catalyst has good stability,and it can still maintain good catalytic activity after five runs in the process of catalytic oxidation.