In this work, the catalyst-free multicomponent polymerizations of diisocyanides, N,N′-dimethylbarbituric acid, and dialdehyde for highly substituted poly(furopyrimidine)s has been achieved. All the experimental conditions such as polymerization solvents, temperature and time were investigated in detail. Through the systematic optimization of the polymerization conditions, the obtained polymers could have molecular weights of up to 16 400 g mol−1, and excellent yields (up to 84%) can be achieved. All the polymers were well characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy. The thermal properties of the polymers were investigated and the decomposition temperature (Td, 5%) was 277 °C.
