Nanoseeded Catalytic Terpolymerization of CO, Ethylene, and Propylene by Size-Controlled SiO₂@Sulfonated Microporous Organic Polymer

Abstract

Nanoseeds with silica@sulfonated microporous organic polymer (SiO2@S-MOP) structure were prepared by the formation of MOP layers on the surface of SiO2 spheres and the successive sulfonation of the MOPs. Using the SiO2@S-MOPs as seed materials, catalytic terpolymerization of CO, ethylene, and propylene was studied. The designed SiO2@S-MOP nanoseeds not only activated catalyst precursors but also controlled the catalytic formation of polyketones. While the homogeneous system showed a severe reactor fouling and a wide molecular weight distribution of terpolymer, the SiO2-190@S-MOP system resulted in the narrow molecular weight distribution of terpolymers without a reactor fouling. The size of nanoseeds was critical to obtaining the granular terpolymers. Moreover, the SiO2-190@S-MOP system showed a good activity of 17.2 kg of polymer/g of Pd, comparable to the homogeneous system with 19.6 kg of polymer/g of Pd. We believe that more various nanoseeded catalytic polymerizations can be developed using new nanoseed materials adopting the MOP chemistry.

The rise of morphology-engineered microporous organic polymers (ME-MOPs): synthesis and benefits

“…20). 63,64 In the conventional synthesis of polymers, reactor fouling is a critical and technical problem (Fig. 20a and d).…”

“…Photographs of (d) polyketones obtained with reactor fouling, (e) antifouling polyketone synthesis using SiO 2 @sulfonated MOP nanoseeds, and (f) polyketone powders obtained through seed-mediated antifouling polymerization. 64 Copyright 2017 ACS.…”

“…20b-f). 63,64 Recently, PK has attracted signicant attention of scientists because PK contains 50 wt% carbonyl groups that originate from carbon monoxide. 81 Shell's Pd catalyst is known to show high activity in the PK synthesis.…”

“…[54][55][56][57][58] Moreover, ME-MOPs can open new application elds. [59][60][61][62][63][64][65][66] Whilst there have been recent reviews on the synthesis and application of MOPs, [1][2][3][4][5][6][7][8]20 this review article focuses on the synthetic methods for ME-MOPs as well as the benets provided over conventional MOPs.…”

(Iminopyridine)Pd (II) complexes as versatile catalysts for copolymerization and terpolymerization of vinyl arene, ethylene, and carbon monoxide

“…Our research group previously developed highly efficient palladium catalysts for the synthesis of polyketone from ethylene and CO. [ 21–24 ] Yet the diphosphine ligands used in our previous work do not efficiently introduce aromatic alkenes into polyketone chains that comprise ethylene and CO. Thus, we explored the utility of amine ligand‐modified palladium catalysts for this purpose.…”