Kinetics of the anionic homopolymerizations of ß–myrcene and 4–methylstyrene in cyclohexane initiated by n–butyllithium

The kinetics of isothermal anionic homopolymerization of ß–myrcene (MYR) and 4–methylstyrene (4MS) in cyclohexane, initiated by n–butyllithium was studied at different temperatures (55, 63, and 71 ° C). The kinetic information obtained from the homopolymerizations was used to estimate the parameters of the Eyring equation, ΔH^?= 84080 J/mol and ΔS^?= ?21.9 J/mol·K for the MYR, and ΔH^?= 51250 J/mol and ΔS^?= ?116.8 J/mol·K for the 4MS, to calculate the apparent propagation coefficients $k_p^{\mathrm{app}}$ as a function of temperature. Finally, the parameters obtained for the Eyring equation were validated by applying them in a mathematical model representing the kinetics of nonisothermal (quasi‐adiabatic) polymerization experiments of MYR and 4MS. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2157–2165