Honeycomb Films from Perfluoropolyether-Based Star and Micelle Architectures

A perfluoropolyether-b-poly(t-butyl acrylate) (PFPE-b-PtBA) block copolymer macroinitiator was used to prepare both core cross-linked star (CCS) polymers and micelles, whereby the outer shell and core, respectively, are comprised of fluorinated segments. The star polymer complete with PFPE outer shell was synthesised via atom transfer radical polymerisation (ATRP) and the arm-first approach, through cross-linking of the PFPE-b-PtBA macroinitiator with ethylene glycol diacrylate (EGDA). Alternatively, the PFPE-b-PtBA block copolymer could be self-assembled in benzene to form micelles with a PtBA shell and PFPE core. Both the micelle and CCS polymer were subsequently fabricated into non-cracking honeycomb (HC) patterned films on both planar and non-planar surfaces via the ‘Breath Figure’ (BF) technique using a static casting system.