The metal and ligand effect of a
series of transition metal carbonyls
in conjunction with alkyl and perfluoroalkyl halides was investigated
in the initiation and control of the visible light, radical photopolymerizations
of vinylidene fluoride (VDF) and respectively, in the synthesis of
PVDF block copolymers. No polymerization was observed for CpMn(CO)3, CpCo(CO)2, Cp2Fe2(CO)4, Cp*2Cr2(CO)4, Mo(CO)6, Fe(CO)5, Cr(CO)6, Co2(CO)8, Co4(CO)12, Fe3(CO)12, Ru3(CO)12, (PPh3)2Ni(CO)2, Cp2Ti(CO)2, and
Au(CO)Cl. A free radical polymerization, and respectively an iodine
degenerative transfer, controlled radical polymerization was obtained
for Mn2(CO)10 ∼ Re2(CO)10 ≫ Cp2Mo2(CO)6 ≫
Cp2W2(CO)6 with CH3(CH2)5–Br, CH3(CH2)5–I, CH3–I, CCl3–Cl,
CCl3–Br, Br–(CF2)6–Br,
and respectively with CF3(CF2)3–I
and I–(CF2)4,6–I. Furthermore,
while Fe(CO)5, Cp*Cr2(CO)4 and Co4(CO)12 led to ∼ CF2–I
bond insertion, Re2(CO)10, Mn2(CO)10, Cp2W2(CO)6, Cp2Mo2(CO)6 and Cp2Fe2(CO)4 provided quantitative radical activation of both PVDF–CH2–CF2–I and PVDF–CF2–CH2–I chain ends, and were employed in
the synthesis of well-defined ABA triblock PVDF copolymers with vinyl
acetate, tert-butyl acrylate, methyl methacrylate,
isoprene, styrene, and acrylonitrile.
