Preparation Of Porous Organic Polymers And Hydroformylation Of 1-octene Catalyzed By Supported Rhodium

Hydroformylation has important applications in industry.However,there is a problem of separation between catalyst and product in homogeneous phase,so it is necessary to prepare the support of supported catalyst.As one of the carriers of hydroformylation reaction,porous materials have rich pore structure,which can support rhodium in the pores,so it has important research significance.In this thesis,several porous organic polymer materials were prepared by organic synthesis,and used as supports to prepare supported rhodium catalysts for hydroformylation of 1-octene.Firstly,N-POP,P-POP and N+P-POP were obtained by hydrothermal polymerization with 4-vinyl pyridine(containing N),divinylbenzene and diphenyl(4-vinyl phenyl)phosphine(containing P)as monomers.The organic functional groups,pore structure and morphology in the polymer were characterized by infrared,specific surface analyzer,scanning electron microscope and transmission electron microscope,and the structure of porous organic polymer was confirmed.The three polymers have microporous and mesoporous porous structures,and the specific surface area is between230 m~2/g and 530 m~2/g.Compared with the other two polymers containing P atoms,N-POP synthesized from 4-vinylpyridine and divinylbenzene has a larger specific surface area because the former has a larger triphenylphosphine group.Secondly,the supported rhodium catalyst was obtained by the reaction of three polymers with homogeneous rhodium,which was used for the hydroformylation of 1-octene.The results showed that in the hydroformylation reaction of 1-octene with syngas,when no ligand was added,the hydroformylation activities of Rh-P-POP and Rh-N+P-POP were weak,and Rh-N-POP-I had no hydroformylation activity.When auxiliary ligands(TPP or TPPO)were used,the hydroformylation activities of the three catalysts were significantly improved.As an auxiliary phosphine ligand,TPP can improve the yield of aldehyde more than TPPO.In the reaction with TPP,Rh-N-POP-I showed the best catalytic performance for hydroformylation because of its large surface area and pore volume.Rh-P-POP has the worst catalytic performance for hydroformylation,because its large number of basic phosphine centers limit the activity of hydroformylation reaction.Finally,a nitrogen rich porous organic polymer(S-POP)was prepared by aldehyde amine condensation reaction.It was also characterized by infrared,BET,SEM and TEM.It was proved that an ideal porous material was obtained.The pore size was concentrated in 1-4 nm.It was a microporous-mesoporous material.The hydroformylation reaction of1-octene was carried out after loading rhodium(Rh-S-POP).When TPP was added as ligand,the hydroformylation activity was weaker than that of Rh-N-POP-I,Rh-P-POP and Rh-N+P-POP.This is because the P-center of the synthesized S-pop is highly alkaline,resulting in low hydroformylation activity.