The effect of the transition metal and of halide initiator in the photomediated free radical and controlled radical polymerization (FRP, CRP) of vinylidene fluoride (VDF) was investigated with a series of unsubstituted and ligand substituted monomeric, dimeric and oligomeric group 6-11 transition metal carbonyls such as (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 and Ru3(CO)12, Co4(CO)12) in conjunction with a representative set of alkyl- and perfluoroalkyl initiators including with CH3(CH2)5-Br, CH3(CH2)5-I, CH3-I, CCl3-Cl, CCl3-Br, Br-(CF2)6-Br, CF3(CF2)3-I and I-(CF2)4,6-I. While Cl and Br initiators afforded a typical FRP, a CRP enabled by iodine degenerative transfer, was obtained using even catalytic levels of Mn2(CO)10 ~ Re2(CO)10 &gt;&gt; Cp2Mo2(CO)6 &gt;&gt; Cp2W2(CO)6 and perfluoroalkyl iodides. The effect of the reaction parameters on the CRP process and on the dependence of the relative ratios of the PVDF-CH2-CF2-I and PVDF-CF2-CH2-I chain ends on conversion was also evaluated.

Iodine transfer polymerization of vinylidene fluoride with transition metal carbonyls under visible light

254th National Meeting (2017)

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