Kinetics of 1,3‐cyclohexadiene polymerization initiated by organolithium compounds in a non‐polar medium, 2. Secondary reactions in the propagation step

Abstract

Abstract It is confirmed that during the polymerization of 1,3‐cyclohexadiene initiated by polystyryllithium in cyclohexane a tranfer to the monomer takes place, as previously reported. It is shown that a part of the metallated monomer reinitiates the polymerization and another part decomposes to inert lithium hydride. The formation of 1,4‐cyclohexadiene is observed and interpreted. The transfer constant is deduced from measured molecular weights. The propagation constants were reported in a previous paper of this series. Knowing these values, the ratio between reinitiation and decomposition constants is deduced from a comparison between experimental kinetics and a numerical resolution of kinetic equations. This study allows a prediction of the best conditions for the synthesis of block copolymers including poly(1,3‐cyclohexadiene) sequences in 1–4 addition.