Polymer properties. After studying the homopolymerization behaviour of DOT, the pDOT product was characterised. At RT and at concentrations of 10 g/L, pDOT was soluble in DMF, THF, DCM, chloroform, anisole, and toluene, and insoluble in water, methanol, isopropanol, acetone, DMSO, acetonitrile, ethyl acetate, petroleum ether, and hexane. PDOT was stable for at least 18 months when stored at RT under air with samples showing no change of SEC-measured Mn after this time. A BF3•Et2O-initiated sample (Table , entry 1) had a measured glass transition temperature of 97 °C (Figure ), which was slightly higher than the value of 95 °C reported for a radically made oligomer. The thermal stability of the polymers was analysed using TGA (Figure , S8, S9). Interestingly, the choice of initiator had an influence on the thermal stability. While BF3•Et2O-initiated pDOT (Table , entry 4) was found to be stable until 270 °C, a MeOTf-initiated sample (Table , entry 8) started to decompose at 170 °C. The TGA profile of this MeOTf-initiated sample was similar to that of DTO (Figure ), see below for further discussion. With labile thioester linkages in every repeat unit, pDOT holds the potential for complete degradation into small molecules. Three degradation conditions were evaluated in detail: aminolysis, thiolysis, and thermal degradation in the absence of solvent.