Green perspective drives the renaissance of anionic diene polymerization

Polymers based on 1,3-diene monomers play a pivotal role in many commercial elastomers and thermoplastic elastomers. This perspective summarizes the state of the art and recent developments in the living anionic polymerization of dienes, permitting to finely tune the properties of the resulting polymers. An emphasis is placed on novel biobased diene monomers (myrcene, farnesene, etc. ) and polymerization solvents, which bear promise for more sustainable elastomers in the future. Furthermore, statistical copolymerization of dienes with vinyl monomers and the in situ monitoring of monomer gradients and formation of tapered di- and triblock copolymers due to disparate reactivity ratios is also reviewed. Thermoplastic elastomers based on tri- and multiblock architectures as well as recently reported diene-based polymer architectures are discussed as well. A summary of current challenges and future options for carbanionic diene polymerization concludes this short review article.