Green crosslinking agents for hydrogels: eco-friendly innovations shaping the future of polymer science
摘要
The growing environmental and toxicological concerns associated with conventional crosslinkers have driven a transition toward sustainable alternatives in hydrogel fabrication. This review highlights recent advances in green crosslinking technologies, analyzing their mechanisms, performance, and industrial potential within the global crosslinking market, valued at USD 9.9 billion in 2023 and projected to reach USD 13.6 billion by 2028. Green crosslinkers are categorized into three classes: natural agents from renewable biological sources, synthetic green crosslinkers with enhanced biocompatibility, and biodegradable agents designed for controlled degradation. Mechanistic pathways include Schiff base chemistry, esterification, ionic and hydrogen-bond interactions, and enzymatic catalysis with transglutaminase or horseradish peroxidase. Performance data underscore their advantages. Genipin shows 5000–10,000-fold lower cytotoxicity than glutaraldehyde while offering higher thermal stability (268.45 °C vs. 251.67 °C). Life cycle analyses demonstrate 30–50% lower carbon footprints and 35% reduced cumulative energy demand in renewable feedstock systems. Tunable mechanical strengths (10–100 kPa) with pH-responsive swelling (100–500%) enhance versatility. Environmental applications report over 90% heavy metal removal within 30 min and regeneration over five cycles. Biodegradable agents achieve complete hydrolytic or enzymatic degradation in 7–14 days, easing end-of-life management. Yet, barriers remain: cost disparities ($1.5–500/kg), natural extract variability, scalability challenges, and stringent regulatory approvals under TSCA, REACH, and FDA. Emerging strategies-natural deep eutectic solvents (NADES), agricultural by-product utilization, and continuous-flow processing-offer 30–40% cost reduction and improved reproducibility. Future opportunities lie in dynamic covalent networks and upcycled waste resources, enabling sustainable, economically viable, and regulatory-compliant polymer manufacturing.
Graphical abstract