Precise preparation of four-arm-poly(ethylene glycol)-block-poly(trimethylene carbonate) star block copolymers via activated monomer mechanism and examination of their solution properties

The polymerization of trimethylene carbonate (TMC) in the presence of HCl·Et₂O via activated monomer mechanism was performed to synthesize 4a-PEG-b-PTMC star block copolymers composed of poly(ethylene glycol) (PEG) and poly(trimethylene carbonate) (PTMC) using four-arm (4a) PEG as an initiator. The TMC conversion and molecular weight of PTMC increased linearly with the polymerization time or the feed ratios of the TMC to 4a-PEG in the presence of HCl·Et₂O in CH₂Cl₂ at 25 °C. The obtained PTMC had molecular weights close to the theoretical value calculated from TMC to PEG molar ratio and exhibited monomodal GPC curve. We prepared successfully 4a-PEG-b-PTMC star block copolymers without metal catalyst at room temperature via living ring-opening polymerization (ROP) of TMC from 4a-PEG as an initiator in the presence of HCl·Et₂O as a monomer activator. The CMCs of the 4a-PEG-b-PTMC star block copolymers determined from fluorescence measurements. The CMCs of the 4a-PEG-b-PTMC star block copolymers decreased in the order of the increase in the PTMC segment. The partition equilibrium constant, K_v, which is an indicator of the hydrophobicity of the micelles of the 4a-PEG-b-PTMC star block copolymers in aqueous media, increased with the increase in the PTMC segment. In conclusion, we confirmed that the 4a-PEG-b-PTMC star block copolymers form micelles and hence may be potential hydrophobic-drug delivery vehicles.