Abstract
Reactions of anionic living polymers of styrene, tert‐butyl methacrylate, and 2‐(trimethylsiloxy)ethyl methacrylate with perfluoroalkyl (Rf) halides, such as C~4~F~9~(CH~2~)~3~I(1), (CF~3~)~2~CF(CF~2~)~6~I (2), C~4~F~9~(CH~2~)~2~I (3), C~8~F~17~(CH~2~)~2~O(CH~2~)~4~Br (4), were investigated to synthesize well‐defined polymers with Rf groups at the chain end. Nucleophilic attack of living polystyryl anions on 1 and 4 quantitatively proceeds to give the Rf‐terminated polystyrenes with predictable molecular weights and narrow molecular weight distributions, while low functionalities (0–50 mol‐%) were obtained in the cases of 2 and 3, on account of electron transfer and ß‐proton elimination. The anionic propagating ends of the methacrylates with potassium countercation react with 1 and 4 to afford the Rf‐terminated poly(methacrylate)s in high efficiency. Poly[2‐(trimethylsiloxy)ethyl methacrylate] produced was deprotected under acidic conditions to give poly(2‐hydroxyethyl methacrylate) bearing the Rf‐terminal group. However, the reactions of the propagating enolate with lithium countercation with 1 and 4 result in low yields of the Rf‐terminated polymers. From the surface analyses of the Rf‐terminated polymer films by X‐ray photoelectron spectroscopy and contact angle measurements, a remarkable enrichment of the Rf group at the dry surface and a surface restructuring corresponding to the environmental change are indicated.