Optimizing Poly(hydroxyurethane) Synthesis via Cyclic Carbonate Aminolysis: A Comprehensive Review

Abstract

This review provides a comprehensive overview of optimization strategies for the synthesis of poly(hydroxyurethane)s (PHUs) via the most common route: cyclic carbonate (CC) aminolysis with amines. PHUs represent a sustainable alternative to conventional polyurethanes, eliminating toxic isocyanates and allowing the use of bio-based monomers. Despite these advantages, their broader industrial adoption is limited by slow polymerization kinetics, modest molecular weights, side reactions, and scalability challenges. Key factors affecting the reaction are examined, including the structure and substituents of CCs and amines, reaction conditions (temperature, time, molar ratios), solvent selection, and the use of plasticizers to mitigate hydrogen bonding limitations. Special attention is given to catalytic approaches, including fundamental catalysts, ionic liquids, dual catalysis, and catalyst-free methods. Strategies to control regioselectivity, side reactions and the influence of solvent choice are also discussed. The potential of bio-based materials for sustainable PHU production is also highlighted. Finally, perspectives are provided on enhancing PHU reactivity and advancing industrial scalability.