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

## TL;DR

Scientists created fluorinated and POSS-containing polymers using a new method, resulting in materials with high thermal stability and water resistance.

## Contribution

A new organocatalyzed method for synthesizing fluorinated and POSS-containing (co)polymers with tunable structures and properties is introduced.

## Key findings

- Linear and star-shaped (co)polymers with high molecular weights were successfully synthesized.
- C–F activation induced chain transfer and branching, enabling structural diversity.
- The resulting polymer films showed high thermal stability and hydrophobicity.

## 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°.