Itaconic acid as a platform chemical for bio-based polymers: from green polymerization strategies to structure-driven applications

Abstract

As a promising bio-based platform chemical, itaconic acid (IA) combines two carboxyl groups with an activated vinyl group, enabling extensive derivatization and multiple polymerization pathways. This review provides a comprehensive overview of IA-derived polymers, focusing on their green polymerization strategies, structure-performance relationships, and especially structure-driven applications. Whenever possible, we also evaluate the sustainability of reported polymerization routes by calculating E-factor values to compare waste generation across different processes. We first discuss two main classes: poly(itaconate)s and itaconate polyesters. Poly(itaconate)s produced by chain-growth polymerization exhibit tunable flexibility and polarity, supporting applications in green tires, high-temperature oil-resistant gaskets, pressure-sensitive adhesives, organic glass, dielectric elastomer actuators, and 3D printing, thereby serving as practical alternatives to certain petroleum-based poly(meth)acrylates. In parallel, itaconate polyesters produced by step-growth polycondensation, which are potentially hydrolytically degradable, enable applications in fully biodegradable shoes, bio-based engineering elastomers, UV-curable materials, and biomedical fields. Additionally, we discuss other IA-derived polymer families obtained through diverse polymerization strategies, including polyurethanes, itaconic anhydride-containing polymers, epoxy thermosets, and polyamides. These polymers highlight the chemical versatility of IA as a bio-based platform and extend its utility to superabsorbent resins, heat-resistant materials, and functional coatings. Finally, we offer our perspective on challenges and opportunities in shifting toward application-driven structural design and industrial-scale production of IA-derived polymers to reduce reliance on fossil resources, decrease costs, and enhance performance.