Synthesis of end‐functionalized polymer by means of living anionic polymerization, 7. Reaction of anionic living polymers with perfluoroalkyl halides

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.