Non-Toxic, Green Polyhydroxyurethanes Synthesized From Abundant Glucose Sources

A new 6-membered mono-cyclic carbonate was synthesized from abundant D-glucose, which was then used in a thiol-ene reaction to make two 6-membered bis-cyclic carbonates. These bis-cyclic carbonates were then used as non-toxic monomers to develop six non-isocyanate polyhydroxyurethanes (NIPU1-NIPU6) through carbonate-amine polymerization with various diamines, including amino acid-based diamines, without a catalyst, at a mild temperature. The new 6-membered mono-cyclic carbonate and both the bis-cyclic carbonates, that were produced in good to excellent yield in the range of 65%-80%, were identified by ¹H NMR, ¹³C NMR, FTIR, and HRMS methods. Different analytical tools such as NMR (¹H, ¹³C), FTIR, GPC, TGA, and DSC analyses were used to fully characterize all the NIPUs. These polymers have molecular weights ranging from ∼7500 to 16 000, glass transition temperatures between -7°C to -21°C, and degradation temperatures (T_d,10%) between 195°C and 245°C. Last but not the least, the enzymatic degradation behaviour and biocompatibility analysis of these NIPUs demonstrated that they were both enzymatically degradable and biocompatible. The presence of reactive hydroxyl functionalities throughout the polymer backbone that contains the sugar moiety can be helpful for further functionalization, in the biomedical area, and/or for curing reasons, and are anticipated to work well in applications like coating and adhesives.