Low-fluorinated homopolymer from heterogeneous ATRP of 2,2,2-trifluoroethyl methacrylate mediated by copper complex with nitrogen-based ligand

We report the preparation of low-fluorinated homopolymer via heterogeneous atom transfer radical polymerization (ATRP) of 2,2,2-trifluoroethyl methacrylate (TFEMA) using 2,2′-bipyridine (bpy), N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA), and tris(2-(dimethylamino)ethyl)amine (Me6TREN) as representatives for di-, tri-, and tetradentate amine ligands, respectively. The ATRP was better controlled, yielding polymers with controlled molecular weights and low polydispersities (Mw/Mn ca. 1.11) when bpy was used as a ligand than when PMDETA was used. This was further supported by the results of our kinetic and chain extension studies. However, the ATRP of TFEMA had lower monomer conversions and gel formation when Me6TREN was used as the ligand. Further reported are the thermal-properties, as well as the surface properties of the films from the resulting polymers with different molecular weights.

Graphical abstractThis paper reports low-fluorinated homopolymer from heterogeneous atom transfer radical polymerization (ATRP) of 2,2,2-trifluoroethyl methacrylate (TFEMA) using bpy, PMDETA, Me6TREN as representative for di-, tri-, and tetradentate amines ligands, respectively.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► ATRP of 2,2,2-trifluoroethyl methacrylate was carried out using different ligands. ► Kinetic studies were conducted to elucidate the reason for controllabilty of ATRP. ► The thermal-properties of the resulting polymers with different Mn were reported. ► The surface properties of the films from polymers were reported.