Synthesis of PEG‐Polycycloether Block Copolymers: Poloxamer Mimics Containing a Rigid Helical Block

Poloxamers are amphiphilic block copolymers consisting of poly(ethylene glycol) (PEG) and poly(propylene glycol) segments. Their self-assembly and interfacial properties are tied to the relative hydrophilicity and hydrophobicity of each block and can therefore be adjusted by changing block lengths. Here, a series of PEG-polycycloether block copolymers is synthesized that have the same structure as a poloxamer, but they encompass a rigid polycyclic backbone as the hydrophobic block. A variety of polymer structures are synthesized, for example diblock or triblock architectures, with/without olefinic units, atactic or isotactic backbone, and different block lengths. Due to their amphiphilicity, self-assembly into spherical aggregates (diameters ranging from 64 to 132 nm) at low concentrations (critical aggregation concentration as low as 0.04 mg mL