LAUSR

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−1) is observed in water. Low surface tensions (as low as 26.7 mN m−1) are observed as well as the formation of stable high internal phase emulsions (HIPEs) irrespective of the oil/water ratio. This contrasts with the properties of the commonly used poloxamers P188 or P407 and illustrates the significance of the rigid polycycloether block. These new colloidal properties offer new prospects for applications in emulsion formulations for biomedicine, cosmetics, and the food industry.