Structure and properties of amine-hardened epoxy/benzoxazine hybrids: Effect of epoxy resin functionality

Bifunctional, trifunctional, and tetrafunctional epoxy resins (EP) were hardened with stoichiometric amount of 4,4′‐diaminodiphenyl methane in presence and absence of benzoxazine (BOX). The EP/BOX ratio of the hybrid systems was 100/0, 75/25, 50/50, and 25/75 wt %, respectively. Information on the structure of the hybrid systems was received from differential scanning calorimetry, dynamic‐mechanical thermal analysis, atomic force microscopy, and fractographic studies. The flexural and fracture mechanical properties of the EP/BOX hybrids were determined and compared to those of the reference EPs. The thermal degradation and fire resistance of the hybrids were also studied. It was found that the polymerized BOX was built in the network in from of nanoscale inclusions and acted as antiplasticizer. Incorporation of BOX enhanced the flexural modulus and strength and reduced the glass transition temperature of the parent EP. The fracture toughness and energy were practically not improved by hybridization with BOX. The charring and flame resistance were improved with increasing amount of BOX in the EP/BOX hybrids. The relative improvement in the latter was most prominent for the bifunctional EP/BOX systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012