One-pot controlled synthesis of double thermoresponsive N-vinylcaprolactam-based copolymers with tunable LCSTs

in Polymer Chemistry (2013), 4(8), 2575-2583

N-Vinylcaprolactam (NVCL) was copolymerized statistically for the first time in a controlled manner with hydrophilic N-vinylamide or hydrophobic vinylester monomers in order to precisely tune up and down ... [more ▼]

N-Vinylcaprolactam (NVCL) was copolymerized statistically for the first time in a controlled manner with hydrophilic N-vinylamide or hydrophobic vinylester monomers in order to precisely tune up and down the lower critical solution temperature (LCST) of the resulting copolymers. The incorporation of these segments in complex architectures was also considered. Several narrowly distributed NVCL-based copolymers were prepared by cobalt-mediated radical polymerization (CMRP) using the bis-(acetylacetonato)cobalt(II) complex as a controlling agent and N-methyl-N-vinylacetamide (NMVA), N-vinylacetamide (NVA), vinyl acetate (VAc) or vinyl pivalate (VPi) as comonomers. PNVCL-containing block copolymers having two discrete LCSTs were also synthesized following a one-pot strategy based on the sequential CMRP of NVCL followed by the copolymerization of NMVA with the residual NVCL. Upon gradual heating of aqueous solutions of such double thermoresponsive copolymers, we noticed a transition from free chains to micelles before full dehydration and collapse of the block copolymers. These advances represent a significant step towards the development of a platform based on thermoresponsive PNVCL copolymers with a single phase separation or multistep assembly behaviors. [less ▲]

Organometallic-mediated radical polymerization of vinyl amides: Effect of metal coordination

Conference (2012, September 04)

Key role of intramolecular metal chelation and hydrogen bonding in the cobalt-mediated radical polymerization of N-vinyl amides

in Chemistry : A European Journal (2012), 18

This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt ... [more ▼]

This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex, i.e. the bis(acetylacetonato)cobalt(II). The cobalt-mediated radical polymerization (CMRP) of a series of N-vinyl amides was considered in order to evidence the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt-polymer bond in the order N-vinylpyrrolidone < N-vinyl caprolactam < N-methyl-N-vinyl acetamide, and is responsible for the optimal control of the polymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, via a covalent bond and a dative one, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. The possible hydrogen bond formation is also taken into account in the case of N-vinyl acetamide and N-vinyl formamide. These results are essential for understanding factors influencing a Co-C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N-vinyl amide)s, an important class of polymers which sustains numerous applications today. [less ▲]