Sustainable myrcene‐based elastomers via a convenient anionic polymerization

Soluble heterocomplexes consisting of sodium hydride in combination with trialkylalu-minum derivatives have been used as anionic initiating systems at 100 °C in toluene for convenient homo‐, co‐ and ter‐polymerization of myrcene with styrene and isoprene. In this way it has been possible to obtain elastomeric materials in a wide range of compositions with interesting thermal profiles and different polymeric architectures by simply modulating the alimentation feed and the (monomers)/(initiator systems) ratio. Especially, a complete study of the myrcene‐styrene copoly-mers (PMS) was carried out, highlighting their tapered microstructures with high molecular weights (up to 159.8 KDa) and a single glass transition temperature. For PMS copolymer reactivity ratios, rmyr = 0.12 ± 0.003 and rsty = 3.18 ± 0.65 and rmyr = 0.10 ± 0.004 and rsty = 3.32 ± 0.68 were deter-mined according to the Kelen–Tudos (KT) and extended Kelen–Tudos (exKT) methods, respec-tively. Finally, this study showed an easy accessible approach for the production of various elasto-mers by anionic copolymerization of renewable terpenes, such as myrcene, with commodities.