Scope and limitations of 1,1‐diphenylethylene chemistry in anionic polymer synthesis

The scope and limitations of the addition reactions of simple and polymeric organolithium compounds with substituted 1,1‐diarylethylenes to prepare in chain‐ and chain‐end functionalized polymers is presented. The application of this general living functionalization reaction for the preparation of ω‐functionalized polymers is illustrated for hydroxyl, carboxyl, dimethylamine, and primary amine groups, as well as for the fluorescent naphthalene and pyrene labels. The use of this chemistry to prepare functionalized initiators is described, as well as the copolymerization of substituted 1,1‐diphenylethylenes with monomers to prepare in‐chain functionalized polymers with alternating structures.