Precisely design PPh3-based polymer by hybrid coupling of monomers for high efficient hydroformylation

A series of hybrid coupling porous organic polymers (HC-3vPPh(3)-POLs) were designed and synthesized through copolymerizing any two of tris(4-vinphenyl) phosphine (p-3vPPh(3)), tris(3-vinphenyl) phosphine (m-3vPPh(3)) and tris(2-vinphenyl) phosphine (o-3vPPh(3)) in different proportions by solvothermal polymerization. The BET surface area of obtained HC-3vPPh(3)-POLs is varied from 534 to 1124 m(2).g(-1) while the pore volume is changed from 0.43 to 2.25 cm(3).g(-1), and the amount of micropores could also be regulated from 43.5 to 66.8%. The afforded Rh/HC-3vPPh(3)-POLs exhibit different conversions from 91% to 98%, selectivity to aldehyde from 79% to 90%, and the 1/b ratios from 4.0 to 11.1 (the ratio of the linear aldehydes to the branched aldehydes) by adjusting the PPh3 microenvironment and their quantities. The superior recyclability in an autoclave reactor and stability in a fixed-bed reactor of Rh/HC-3vPPh(3)-POLs demonstrate the excellent potential of this method in preparing functional materials for heterogeneous catalysis. Combined characterization methods were employed and demonstrated that P atoms from different vinyl functional PPh3 were uniformly dispersed and interacted with each other, leading to different structure and PPh3 microenvironment in HC-3vPPh(3)-POLs.

Automated summary

A series of hybrid coupling porous organic polymers were designed and synthesized through solvothermal polymerization, showing excellent potential in heterogeneous catalysis. The properties of the obtained materials can be regulated by adjusting the microenvironment and quantities, with superior recyclability and stability demonstrated in catalytic reactions.