In Situ Synthesis of Incompatible Polymers within Hollow Porous Organic Nanosphere Networks for Cascade Reactions

In the paper, the novel hollow porous organic nanosphere networks (H-PONNs) with remaining Z-type chain transfer agent (CTA) inside the cavity are synthesized via a hypercrosslinking mediated self-assembly method using the polystyrene-b-polylactide as precursors. The resultant Z-type CTA functionalized H-PONNs can be utilized to mediate reversible addition-fragmentation chain transfer polymerization and the acidic or basic monomer (phenyl 4-vinylbenzene sulfonate (PVBS), 4-N-(4-vinylbenzyl)-N-methylaminopyridine (VBMAP)) can be in situ polymerized in the cavity of nanospheres to produce acid/base-functionalized hollow porous organic nanosphere networks (poly(phenyl 4-vinylbenzene sulfonate) (PPVBS)/H-PONNs and poly(4-N-(4-vinylbenzyl)-N-methylaminopyridine) (PVBMAP)/H-PONNs). These PPVBS/H-PONNs and PVBMAP/H-PONNs possess the large surface area, hierarchically porous structure, and robust organic framework, which exhibit the excellent catalytic performance for acid–base cascade reactions. Furthermore, the turnover frequency is up to 51 h⁻¹ that shows the catalysts have a great advantage over other similar materials for one-pot reactions.