Reversible deactivation radical (co)polymerization of dimethyl methylene oxazolidinone towards responsive vicinal aminoalcohol-containing copolymers

Abstract

Radical polymerization of exo-methylene cyclic monomers is a straightforward strategy for preparing polymers with pendant heterocycles used as protective groups for reactive functions. In spite of their availability and possible chemical transformations, so far, methylene oxazolidinones have been disregarded in the field of macromolecular synthesis. This work reports the radical (co)polymerization of 4,4-dimethyl-5-methyleneoxazolidin-2-one (DMOx) and the transformation of the pendant oxazolidinone groups into vicinal amino-alcohol functions. DMOx was produced through an optimized procedure of carboxylative cyclization of dimethylpropargylamine. In addition to the conventional radical (co)polymerization of DMOx, we considered its reversible deactivation radical copolymerization with VAc by organometallic-mediated radical polymerization (OMRP) and reversible addition fragmentation chain transfer (RAFT). The ability of these methods to produce well-defined copolymers was studied as well as their respective reactivity ratios. Finally, the poly(DMOx-co-VAc) was converted into vicinal amino-alcohol functional poly(vinyl alcohol)s presenting peculiar multi-responsive behavior, namely pH-, thermal- and metal-ion sensitivity.