Ligated anionic polymerization: An innovative elf‐atochem technology for the polymerization of (meth)acrylates

Admittedly performing materials, (meth)acrylic polymers, used in a wide variety of applications, are traditionally produced by radical polymerization processes. The extension of living polymerization, originally developed for dienes and vinyl-aromatics, to (meth)acrylic polymers, would be an interesting opening to a variety of products with a large scope of properties and applications. However, this method suffers from chemical and technical limitations when applied to (meth)acrylates under the usual conditions of solvent and temperature. We report how alkoxy alkoxides-based systems combined with a recent Elf Atochem process offer attractive conditions for ultra-fast anionic polymerization of (meth)acrylates at high solid content. Applications to cost effective syndiotactic poly(methyl methacrylate) and block copolymers syntheses are described.