The effect of THF and the chelating modifier DTHFP on the copolymerisation of β-myrcene and styrene: kinetics, microstructures, morphologies, and mechanical properties

The statistical anionic copolymerisation of the biobased monomer β-myrcene with styrene in cyclohexane was investigated via in situ near-infrared (NIR) spectroscopy, focusing on the influence of the modifiers (i.e., Lewis bases) tetrahydrofuran (THF) and 2,2-di(2-tetrahydrofuryl)propane (DTHFP) on the reactivity ratios. With increasing [modifier]/[Li] ratio, the reactivity ratios in the system myrcene/styrene are adjustable from rS ≪ rMyrvia rS ≈ rMyr to rS ≫ rMyr. The bidentate modifier DTHFP affects the reactivity ratios much more than THF: minute amounts only (0.35 equivalent relative to Li) are required to randomize the copolymer, and one equivalent to invert the reactivity ratios. Usin…