Using this approach, we attempted to homopolymerize internal olefin monomers, but no polymers were yielded even after trying with various substrates (Figure ). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to evaluate the thermal properties of these ABC sequence-regulated polymers. Depending on the different A and B units, a wide range of glass transition temperature (Tg) from -27. Tg can be achieved with P22 and P23 due to the cyclohexanes within the polymer backbone, causing mobility restrictions. Most of the polymers exhibit good thermal stability (Td, 5% > 200 °C). The Td, 5% of P20 is much lower than P19 even though they have similar structures. That is probably due to the thermal deprotection of tert-butyl ester and decarboxylation, resulting in α-cyano anion. The anion triggered the polymer chain scission by the retro thia-Michael reaction.