Synthesis of Polypeptoid-Polycaprolactone-Polytetrahydrofuran Heterograft Molecular Polymer Brushes via a Combination...

Janus polymerization is a novel and efficient way to synthesize diblock and multiblock copolymers in one step by using Lu(OTf)₃ and propylene epoxide as a catalytic system. By modifying the epoxide initiator, which is located at the block junction with various functional groups, the possibility for future topological design is provided. Herein, 2-bicyclo[2.2.1]hept-5-en-2-yl oxirane (NB-EO) is used as an alternative for propylene epoxide to synthesize a poly(THF-co-CL)-b-PCL diblock copolymer featuring a norbornene group at this position. This also results in multiblock [poly(THF-co-CL)-b-PCL]_m copolymers carrying multiple norbornene moieties through Janus polymerization. Subsequent ring-opening metathesis copolymerization (ROMP) of the resulting poly(THF-co-CL)-b-PCL macromonomers with norbornenyl-terminated polysarcosine (PSar-NB) allows the facile preparation of heterograft molecular polymer brushes (MPBs). The MPBs feature three heterografts of PCL, P(CL-co-THF) and PSar, potentially equipping these structures with biocompatibility, biodegradability, semi-crystallinity, and amphiphilicity. A phase separation is observed after annealing in both TEM and AFM analysis. Due to their amphiphilic nature, the MPBs also undergo self-assembly into micelles in aqueous solution. Such materials combining polypeptoids, polyesters, and polyethers segments are expected to attract wide attention in drug delivery applications.