Synthesis of partially fluorinated polyolefins via copolymerization of ethylene with fluorinated norbornene-based comonomers†

Abstract

Partially fluorinated polyolefins are widely utilized due to their outstanding properties, including low surface energy, high thermal stability, and high chemical stability. In this contribution, we report the design and synthesis of a series of fluorinated mono and disubstituted norbornene-based comonomers, and investigate their copolymerization with ethylene to produce partially fluorinated polyolefins using phosphine–sulfonate palladium catalysts. These fluorinated norbornene-based comonomers lead to remarkable catalytic activities (up to 5.7 × 10⁶ g mol⁻¹ h⁻¹), high molecular weights (up to 358 kg mol⁻¹), high comonomer incorporation ratios (up to 28.9 mol%) and high fluorine contents (up to 52.0 wt%). Compared to previously reported studies, this work demonstrates superior comprehensive performances in terms of various copolymerization parameters. More importantly, these fluorinated norbornene-based comonomers can impart widely tunable thermal, mechanical, surface, and optical properties to the resulting partially fluorinated polyolefins.