LAUSR

A total of 1/2/4/6-armed molecular architectured polyhedral oligomeric silsesquioxane (POSS) fluoropolymers were synthesized via atom transfer radical polymerization (ATRP) by linear (L), dicephalus (D), four-arm (T), and six-arm (S) initiators initiating same content of methyl methacrylate (MMA), methacrylate POSS (MA-POSS), and dodecafluoroheptyl methacrylate (DFHM). The obtained L/D/T/S-(PMMA-b-PMAPOSS-b-PDFHM)1/2/4/6 had increased molecular weight with arm increase. Driven by the stereo-hindrance and curvature effects of segments in tetrahydrofuran (THF), they assembled into the decreased spherical core-shell micelles (250–100 nm) with arm increase as PMA-POSS/PDFHM core and PMMA shell. Because of easy surface migration of fluorine-containing groups in small micelles, the casted film by S-(PMMA-b-PMAPOSS-b-PDFHM)6 performed the fluorine-rich (46.44%) and rough (5.41 nm) surface, and therefore with the hydrophobic (112°) and low water adsorption surface (1522 ng/cm2). Also, POSS-fluoropolymers obtained the enhanced thermostability with arm increase. It is believed that this research will provide a bright view for design and application of POSS-fluoropolymers. Graphical abstract Graphical abstract