Kinetics of anionic polymerization of β ‐myrcene in hydrocarbon solvents

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Abstract The kinetics of anionic polymerization of β‐myrcene initiated by sec‐butyllithium were examined in saturated and unsaturated hydrocarbon solvents, i.e. cyclohexane, cyclohexene, 4‐vinylcyclohexene and dl‐limonene. Polymerizations usually proceeded in a living manner, i.e. in the absence of termination and chain transfer reactions, in all solvents, to produce well‐defined polymyrcenes with high content (>85%) of cis‐1,4 units. However, polymyrcenyllithium chains exhibited limited long‐term stability in 4‐vinylcyclohexene solution, most probably due to chain transfer to solvent. Reaction orders with respect to the concentration of active chains were found to be one‐quarter in cyclohexane increasing to one‐half in unsaturated solvents, indicating that the polymyrcenyllithium chains are present as tetrameric or dimeric associates, respectively. Apparent activation energies were found to be 81 kJ mol−1 in cyclohexane and 77 kJ mol−1 in dl‐limonene solution, which are close to the values obtained by quantum chemical calculations. © 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

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