Mild-Temperature Mn<sub>2</sub>(CO)<sub>10</sub>-Photomediated
Controlled Radical Polymerization of Vinylidene Fluoride and Synthesis
of Well-Defined Poly(vinylidene fluoride) Block Copolymers
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Abstract
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<sub>2</sub>(CO)<sub>10</sub>-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<sub><i>m</i></sub>-CF<sub>2</sub>-CH<sub>2</sub>-I vs
the P<sub><i>n</i></sub>-CH<sub>2</sub>-CF<sub>2</sub>-I
chain ends, Mn<sub>2</sub>(CO)<sub>10</sub> enables their subsequent
quantitative activation toward the synthesis of well-defined poly(vinylidene
fluoride) block copolymers with a variety of other monomers
