Synthesis of poly(t-butyl acrylate) macromonomers

Teyssié et al. have recently shown that anionic polymerization of hindered acrylates exhibits the characteristic features of ‘living’ systems, provided LiCl is used in order to decrease the nucleophilicity of the growing carbanion. This paper extends Teyssié's method to the synthesis of various model poly(t-butyl acrylate)s, emphasis being put on the macromolecular engineering aspect. We have synthesized linear poly(t-butyl acrylate) over a broad range of molecular weights (3000–200000), using successively monofunctional and difunctional initiators. Tailor-made poly(t-butyl acrylate) macromonomers were also obtained by deactivation of the living sites with an electrophilic unsaturation either styrenic or methacrylic. Accurate characterization of the various model polymers (gel permeation chromatography, light scattering, end-group analysis) was performed.