Catalysts for the Controlled Polymerization of Conjugated Dienes

Since the beginning of the 1960s, the coordinative polymerization of conjugated dienes has continuously improved. Today, chemists know how to polymerize conjugated dienes stereospecifically and in a controlled fashion, both petro-sourced (nowadays also bio-sourced) and those of natural origin. The industry has greatly improved the performances of the catalytic systems—covering a wide range of elements including metals from groups 4–6 and 8–10, and rare earths—with the aim of optimizing the preparation of synthetic polymers for a large range of industrial applications. Nowadays, there is a better understanding of the polymerization mechanism involving allyl-active species, thanks in particular to the support of more efficient calculation methods. In addition, statistical copolymerization of 1,3-dienes with olefin or styrene comonomers and innovative approaches to coordinative chain transfer polymerization allow the production of copolymers with controlled topology, while a last challenge is about to be solved with the preparation of stereoregular polydienes that are also end-functionalized. This issue brings together several important aspects of this chemistry that remain at the forefront of both academic and industrial research.