The iodine degenerative transfer (IDT) polymerization of vinylidene fluoride (VDF) proceeds with the unavoidable accumulation of the least reactive PVDF-CF2-CH2-I chain end to the detriment of the more reactive PVDF-CH2-CF2-I counterpart. Therefore, the synthesis of well-defined PVDF block copolymers requires the quantitative activation of both PVDF-I termini. Such activation was tested under visible light irradiation with a series of photolabile group 6-11 transition metal carbonyls including Mo(CO)6, Fe(CO)5, Cr(CO)6), CpMn(CO)3, CpCo(CO)2, Cp2Ti(CO)2, (PPh3)2Ni(CO)2, AuCOCl, Mn2(CO)10, Re2(CO)10 Co2(CO)8, Cp2Fe2(CO)4, Cp*2Cr2(CO)4, Cp2Mo2(CO)6 Cp2W2(CO)6, Fe3(CO)12, Ru3(CO)12, and Co4(CO)12. Depending of the complex, the activation of both PVDF-I chain ends was observed by either metal insertion or by radical iodide abstraction pathways. Mn2(CO)10, Re2(CO)10, Cp2W2(CO)6, Cp2Fe2(CO)4 and Cp2Mo2(CO)6 afforded the desired complete radical activation of both PVDF-CH2-CF2-I and PVDF-CF2-CH2-I chain ends, and were used in the synthesis of well-defined ABA triblock PVDF copolymers with styrene, methyl methacrylate, t-butyl acrylate, vinyl acetate, acrylonitrile and isoprene.

Synthesis of PVDF block copolymers by the quantitative radical activation of both PVDF-CH2-CF2-I and PVDF-CF2-CH2-I chain ends with transition metal carbonyls under visible light

254th National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.