Bio-Based Bisbenzoxazines with Flame Retardant Linker

Abstract

This work explores the strategy of incorporating a highly substituted reactive flame retardant into a benzoxazine moiety. For this purpose, a DOPO-based flame retardant received a chain extension via reaction with ethylene carbonate. It was then reacted with phloretic acid to obtain a diphenol end-capped molecule, and further reacted with furfurylamine and paraformaldehyde to obtain a benzoxazine monomer via a Mannich-like ring closure reaction. This four-step synthesis yielded a partly bio-based halogen-free flame retardant benzoxazine monomer (DOPO-PA-fa). The successful synthesis was proven via NMR, IR and MS analysis. The polymerization behavior was monitored by DSC and rheological analysis both showing the polymerization starts at 200 °C to yield pDOPO-PA-fa. pDOPO-PA-fa has a significant thermal stability with a residual mass of 30% at 800 °C under ambient atmosphere. Furthermore, it reached a V-0 rating against small flames and an <i>OI</i> of 35%. Blended with other benzoxazines, it significantly improves their thermal stability and fire resistance. It emphasizes its potential as flame retardant agent.