Fluorinated Cyclic Olefin Copolymers (COCs) and Cyclic Olefin Polymers (COPs)

Abstract The demand for insulating materials with superior dielectric properties has increased. Among these materials, polymers containing cyclic structure including cyclic olefin copolymer (COC) and cyclic olefin polymer (COP) stand out because of their excellent dielectric properties originating from the pure hydrocarbon structure. Introducing fluorine into polymers is one efficient strategy for optimizing the dielectric and the related important properties. Here, three fluorinated norbornene derivatives with high fluorine content are synthesized and copolymerized via coordination‐insertion polymerization (CIP) and ring‐opening metathesis polymerization (ROMP). The obtained fluorinated COCs and COPs have high fluorine contents (up to 48.2 wt.%) and exhibit excellent dielectric properties with dielectric constant ( D k ) of 2.11‐2.24 and dielectric loss ( D f ) of 0.0021‐0.0031 at 10 GHz. Moreover, these fluoropolymers show good solvent tolerance, high toughness (elongation at break up to 779%), enhanced thermal stability ( T d,5% of 427–440 °C), low hydrophilicity (water uptake <0.01%), and excellent gas separation properties. These results imply that these fluoropolymers are suitable as a potential candidate for substrate material utilized in the application of insulating materials.