Fully bio-based and intrinsically flame retardant unsaturated polyester cross-linked with isosorbide-based diluents

Unsaturated polyester resins (UPR) are composed of prepolymers and styrene diluents, while the former are produced by co-polycondensation between diol, unsaturated diacid and saturated diacid. In this work, bio-based UPR prepolymers were synthesized from bio-based oxalic acid, itaconic acid, and ethylene glycol, which were then diluted with bio-based isosorbide methacrylate (MI). Meanwhile, the phenylphosphonate were introduced into the molecular chains of prepolymers to achieve intrinsic flame retardancy of bio-based UPR. The potential of the reactive MI diluents as substitutes of volatile styrene, was also assessed through the volatility test, curing kinetics and gel contents analysis. For UPR materials with styrene diluents, the UPR materials can achieve UL-94 V⁰ level and the 28% of limiting oxygen index (LOI) with 2.63 wt% of phosphorus contents. By contrast, the UPR materials with MI diluents can reach UL-94 V⁰ level with only 2.14 wt% of phosphorus contents. As the phosphorus contents were further increased to 2.63 wt%, UPR materials can achieve highest 29%, while the peak of heat release rate (PHRR) and total heat release (THR) were decreased by 68.01% and 48.62%, respectively. The Flame Retardancy Index (FRI) was also used to comprehensively evaluate the flame retardant performance of UPR composites. Compared with neat UPR, the composites with MI diluents and phosphorus containing structures increased from 1.00 to 6.46. The mechanism for improved flame retardancy was analyzed from gaseous and condensed phase. Additionally, the tensile strengths of bio-based UPR materials with styrene and MI diluents were studied. This work provides an effective method to prepared high-performance and fully bio-based UPR materials with improved flame retardant properties and safety application of reactive diluents.