Since the ring-opening of POT produces a styryl like radical, the predicted ktr value could be seen as a theoretical propagation rate coefficient. At 80 °C, the value is rather low compared to styrene. To find a more efficient kp value to reach acceptable polymerization kinetics, we plotted on Figure the evolution of ktr with temperature and compared it with the kp of styrene determined using the same level of theory. To have an efficient propagation rate constant, the use of 120 °C seems a better temperature to perform the polymerization. We thus investigated the homopolymerization of POT at this temperature. The polymerization was performed in the presence of anisole to solubilize the VAM-111 azo initiator (0.5 mol%). The polymerization was followed by 1 H NMR spectroscopy (see Figure ). After 22 hours, the conversion was complete, and a waxy polymer was obtained. A polythioester with a Mn of 5,500 g.mol -1 with a Đ of 2 and a Tg of 1°C was obtained. These preliminary results confirmed the interest of POT as a efficient route to prepare poly(thioester)s. This will be investigated in details in a further study.