Controlled Radical Polymerization of Myrcene in Bulk: Mapping the Effect of Conditions on the System

Solvent-free reversible deactivation radical polymerization of myrcene, a naturally occurring terpenoid monomer, with high regioselectivity was developed recently. Here, this green polymerization system is further improved to reach increased yields and produce polymers with high molar mass but still low dispersity and regioregular microstructure. To this end, two initiators (dibenzoyl peroxide, DBPO; azobis­(isobutyro­nitrile), AIBN) at 65, 90, and 130 °C were applied, and it was demonstrated that these varying conditions have a huge effect not only on the monomer conversion and the molar mass of the product, but also on the microstructure of the resulting polymyrcene. The polymerizations utilized two trithio­carbonate chain-transfer agents, and were similar in yields, molar masses, and dispersity of the produced polymyrcene, but progressed differently for the diverse initiator–temperature pairs. Generally, in all systems, pseudo-first-order kinetics, linear increase of molar mass with conversion, and low <i>Đ</i> values were found as a result of controlled polymerization. The systems using AIBN and DBPO initiators at 90 and 130 °C, respectively, have rate constants of propagation (<i>k</i><sub>p</sub><sup>app</sup>) lower than the decomposition rates (<i>k</i><sub>d</sub>) of initiators, likewise important to control the polymerizations. At 130 °C, also branching occurred at the higher stage of the reaction, and lower regioregularity developed during the polymerization as a consequence of the favorable junction formation at elevated temperature and increased viscosity. Generally, compared to the previous study on the reversible deactivation radical polymerization of myrcene via reversible addition–fragmentation chain-transfer polymerization process, significantly higher conversions (30 → 65%) and increased chain length (9 → 40 kDa) were reached. The dispersity values for these polymerizations remained as low as 1.3–1.6, and also regioregular microstructures (up to 94%) were detected.