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J Am Chem Soc. 2012 Apr 11;134(14):6080-3. doi: 10.1021/ja300178r. Epub 2012 Apr 2.

Mild-temperature Mn2(CO)10-photomediated controlled radical polymerization of vinylidene fluoride and synthesis of well-defined poly(vinylidene fluoride) block copolymers.

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Institute of Materials Science and Department of Chemistry, University of Connecticut, Storrs, Connecticut 06069-3136, USA.


By contrast to typical high-temperature (100-250 °C) telo-/polymerizations of gaseous fluorinated monomers, carried out in high-pressure metal reactors, the visible light, Mn(2)(CO)(10)-photomediated initiation of vinylidene fluoride (bp = -83 °C) polymerization occurs readily from a variety of alkyl, semifluorinated, and perfluorinated halides at 40 °C, in low-pressure glass tubes and in a variety of solvents, including water and alkyl carbonates. Perfluorinated alkyl iodide initiators also induce a controlled radical polymerization via iodine degenerative transfer (IDT). While IDT proceeds with accumulation of the less reactive P(m)-CF(2)-CH(2)-I vs the P(n)-CH(2)-CF(2)-I chain ends, Mn(2)(CO)(10) enables their subsequent quantitative activation toward the synthesis of well-defined poly(vinylidene fluoride) block copolymers with a variety of other monomers.


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