All-Polycarbonate Graft Copolymers with Tunable Morphologies by Metal-Free Copolymerization of CO₂ with Epoxides

Brush-type macromolecules (BMs) have attracted much attention over the past decades because of their unique properties and potential applications in nanoscience, drug-delivery systems, photonics. A two-step strategy synthesis polycarbonate-grafted copolymers with either star-shaped or brush-typed morphologies using a “grafting from” approach is reported; backbone these all-polycarbonate graft made poly(cyclohexene carbonate) (PCHC), side grafts are poly(propylene (PPC). In first step, poly (vinyl-cyclohexene (PVCHC) backbones two different sizes (PVCHC35, PVCHC283) were prepared by copolymerization vinyl-cyclohexene oxide (VCHO) CO2 presence triethylborane (TEB), tetrabutyl ammonium succinate (TBAS) as initiator. second dangling vinyl double bonds PVCHC transformed into carboxylic acid groups. After partial neutralization latter hydroxide, PPC could be grown from sites propylene (PO) TEB. Before attempting above grafted copolymers, we check viability synthetic preparing polymethacrylate grafts. case, was generated reversible addition–fragmentation chain-transfer (RAFT) polymerization methacrylic (MAA), followed growth carboxylates initiating sites. both cases (PVCHC-g-PPC PMAA-g-PPC), types architectures corresponding to synthesized: obtained rather short backbones, relatively long grafts, on one hand, semiflexible cylinders These various structures characterized nuclear magnetic resonance (NMR) gel permeation chromatography/light scattering (GPC/LS), further investigated atomic force microscopy (AFM). The reported method provides robust way synthesize well-defined polycarbonates star-type brush-type polyacrylate polycarbonate Thermal mechanical also investigated.