Recent Advances in the Low‐Temperature Curing of Benzoxazine Resins: Mechanisms, Strategies, and Performance Trade‐Offs

ABSTRACT

Polybenzoxazine, a high‐performance thermosetting resin, offers exceptional thermal stability, mechanical properties, and near‐zero curing shrinkage, but its inherently high curing temperature (180°C–250°C) remains a critical bottleneck for broader industrial adoption. This review systematically and critically evaluates five key strategies developed to reduce curing temperature: molecular design modification, exogenous catalysts, blending/copolymerization modification, nanomaterial modification, and reaction‐condition optimization. For each strategy, we analyze underlying mechanisms, assess curing‐temperature reductions (approximately 8°C to over 80°C depending on the approach), and examine associated trade‐offs in thermal stability, mechanical performance, dielectric properties, processability, and long‐term reliability. While combustion synthesis and microwave curing achieve the most pronounced reductions, no single strategy simultaneously delivers ultra‐low curing temperatures, superior comprehensive performance, low cost, and industrial scalability. Each approach carries inherent limitations, such as residual catalytic species, phase separation, nanofiller aggregation, or specialized equipment. The review's scientific contribution is an integrated comparative framework that consolidates dispersed literature and provides a balanced roadmap for navigating complex multi‐property trade‐offs essential for practical applications. We further identify emerging opportunities in multi‐strategy synergies, bio‐based feedstocks, and machine‐learning‐assisted formulation design. Ultimately, this review guides the rational and efficient design of low‐temperature‐curing benzoxazines that balance processing efficiency, high performance, cost‐effectiveness, and environmental sustainability.