Robust hollow nanocomposites with ruthenium-bipyridine complexes for heterogeneous catalysis of logic-controlled RAFT...

Photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization has become a powerful and eco-friendly toolkit to create well-defined macromolecular buildups while exhibiting composition, sequence and spatiotemporal control. Although PET-RAFT polymerization is generally much more convenient than living ionic polymerization, it is still a great challenge to regulate the polymerization upon multiple external stimuli and to simplify the procedures of post-polymerization purification. In this contribution, hHPGE-PFPPNRu nanocomposites were engineered as catalyst supports to firmly accommodate ruthenium-bipyridine complexes for heterogeneous catalysis of PET-RAFT polymerization. The manipulation of reaction temperature modulated the performance of the nanocatalysts, with a pronounced acceleration of the polymerization kinetics being identified at a temperature above the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAM) brushes compared to that below it. Consequently, the control of RAFT polymerization can be achieved upon the dual-stimuli of light and heat. Moreover, these nanocatalysts conferred radical polymerizations with myriad attractive features such as the adaptability of diverse monomer formulations and reaction media, exquisite control over the molecular variables, oxygen tolerance, and catalyst doses in the ppm range. Owing to the robust mechanical nature of nanocomposites, the separation and reuse of the nanocatalysts were readily realized by rapid centrifugation, and they showed inappreciable catalyst leakage along with consistent catalytic performance even after multiple polymerization runs.