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Updated: Sep 3, 2026

Particles without a Box: Brush-first Synthesis of Photodegradable PEG Star Polymers under Ambient Conditions
Published on: October 10, 2013
Organocatalyzed Atom Transfer Radical (Co)Polymerization of Fluorinated and POSS-Containing Methacrylates: Synthesis
Hleb Baravoi1,2, Heorhi Belavusau1,2,3, Aliaksei Vaitusionak1,3
1Research Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya St., 220006 Minsk, Belarus.
Abstract:
Hybrid fluorinated copolymers containing POSS moieties along with fluorinated homopolymers were synthesized via organocatalyzed atom transfer radical (co)polymerization (O-ATRP) of fluoroalkyl methacrylate (FMA) and a POSS-based monomer (IBSS) using perylene as a photocatalyst. Linear and four- and eight-armed star-shaped (co)polymers in a wide range of molecular weights with Mn(SEC) up to 53,100 g/mol for poly(FMA), 22,700 g/mol for poly(IBSS) and 87,300 g/mol for poly(FMA-co-IBSS) 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°.
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