Direct Route to Well-Defined Poly(ionic liquid)s by
Controlled Radical Polymerization in Water
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Abstract
The precision synthesis of poly(ionic
liquid)s (PILs) in water
is achieved for the first time by the cobalt-mediated radical polymerization
(CMRP) of <i>N</i>-vinyl-3-alkylimidazolium-type monomers
following two distinct protocols. The first involves the CMRP of various
1-vinyl-3-alkylimidazolium bromides conducted in water in the presence
of an alkyl–cobalt(III) complex acting as a monocomponent initiator
and mediating agent. Excellent control over molar mass and dispersity
is achieved at 30 °C. Polymerizations are complete in a few hours,
and PIL chain-end fidelity is demonstrated up to high monomer conversions.
The second route uses the commercially available bis(acetylacetonato)cobalt(II)
(Co(acac)<sub>2</sub>) in conjunction with a simple hydroperoxide
initiator (<i>tert</i>-butyl hydroperoxide) at 30, 40, and
50 °C in water, facilitating the scaling-up of the technology.
Both routes prove robust and straightforward, opening new perspectives
onto the tailored synthesis of PILs under mild experimental conditions
in water
