Synthesis, curing characteristics, and kinetics of tetra-functional fluorene-based benzoxazines having saturated aliphatic groups

In this paper, a novel series of tetra-functional fluorene-based benzoxazine monomers (SAMFB) were obtained by o-hydroxy-benzylamine method combining with Mannich condensation reaction. Compared with the traditional three-step method, the synthesis of asymmetric benzoxazine reduced the treatment process of the intermediate product, greatly shortened the reaction time and experimental period, improved the yield of the intermediate product, and reduced the production cost. In the traditional three-step synthesis method, the double bond reduction process took 8–12 h, but in this paper, it only took 15 min to complete this process. The curing characteristics, kinetics, thermal stabilities, and thermomechanical properties of SAMFB monomers and their polymers were analyzed. Non-isothermal curing kinetics studies showed that the polymerization process of SAMFB monomers was an autocatalytic reaction. The introduction of fluorene rings and polymerizable groups and the increase of oxazine rings in the polymer network structure can result in an obvious increase in the crosslinking density of polymers. Therefore, SAMFB polymers (poly(SAMFB)) exhibited higher glass transition temperature (Tg, 314–317 °C) and better thermal stability properties, higher than that of traditional bisphenol A-aniline-based and reported bifunctional fluorene-based polybenzoxazine resins. The TGA results showed that the T5 and T10of poly(SAMFB)were 334−368 °C and 370−414 °C, respectively, and Yc at 800 °C was 45.7–61.6 %. Moreover, the toughness of poly(SAMFB) was greatly improved due to the introduction of the flexible alkyl chain. © 2020 Elsevier Ltd