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 PPh 3 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 PPh 3 were uniformly dispersed and interacted with each other, leading to different structure and PPh 3 microenvironment in HC-3vPPh 3 -POLs.