Acyclic Diene Metathesis with a Monomer from Renewable Resources: Control of Molecular Weight and One‐Step Preparation of Block Copolymers

The preparation of a long-chain aliphatic alpha,omega-diene from plant oil derivatives and its subsequent polymerization through acyclic diene metathesis (ADMET) is described. The ADMET bulk polymerization of the thus-obtained monomer, undecyl undecenoate, was investigated and optimized by applying ruthenium-based metathesis catalysts from Grubbs and Hoveyda-Grubbs, leading to high-molecular-weight polyesters. Moreover, by applying different amounts of methyl 10-undecenoate as a chain stopper in this ADMET step growth polymerization, the molecular weight of the resulting polyester could be tuned in a range from approximately 10 to 45 kDa. Finally, the application of a poly(ethylene glycol) methyl ether acrylate as the chain stopper led to the preparation of ABA triblock copolymers in a one-step, one-pot procedure.