Styrene‐vinylferrocene random and block copolymers by TEMPO‐mediated radical polymerization

TEMPO‐mediated free radical polymerization was employed for homo‐ and copolymerization of vinylferrocene (Vfc). Homopolymerization of Vfc resulted in relatively narrow polydispersities (M_w/M_n = 1.24–1.8), however, molecular weights were limited to 4 800. Copolymerization with styrene afforded random copolymers with molecular weights (M_n) up to 10 000, narrow polydispersity (1.2 > M_w/M_n > 1.4) and up to 42 mol‐% Vfc. Block copolymers with PS block and P(S‐co‐Vfc) block with molecular weights (M_n) in the range of 9 000 to 17 600 (M_w/M_n > 1.3) were also prepared with up to 17 mol‐% vinylferrocene. DSC revealed two glass transition temperatures (T_g) evidencing phase separation.