Organocatalyzed Atom Transfer Radical (Co)Polymerization of Fluorinated and POSS-Containing Methacrylates: Synthesis and Properties of Linear and Star-Shaped (Co)Polymers

Hybrid fluorinated copolymers containing POSS moieties along with fluorinated homopolymers were synthesized via organocatalyzed atom transfer radical (co)polymerization (O-ATRP) of fluoroalkyl methacrylate (<b>FMA</b>) and a POSS-based monomer (<b>IBSS</b>) using perylene as a photocatalyst. Linear and four- and eight-armed star-shaped (co)polymers in a wide range of molecular weights with M_n(SEC) up to 53,100 g/mol for poly(<b>FMA</b>), 22,700 g/mol for poly(<b>IBSS</b>) and 87,300 g/mol for poly(<b>FMA</b><i>-co-</i><b>IBSS</b>) were successfully prepared. During polymerization, C-F activation was found to induce chain transfer and branching reactions, contributing to structural diversity. A mechanism for chain transfer to the polymer resulting in branching was proposed, applying density functional theory (DFT). Films based on the obtained (co)polymers showed tunable morphology, high thermal stability (up to 306 °C) and hydrophobicity, with water contact angles reaching 98°.