Reaction-induced phase separation in benzoxazine/bismaleimide/imidazole blend: Effects of different chemical structures on phase morphology

A phenol-4,4'-diaminodiphenyl methane-based benzoxazine (P-ddm)/N,N'-(1,1,2-trimethylhexane-1,6-diyl) bis (maleimide) (TBMI)/imidazole blend with bi-continuous phase structure was prepared. The phase structures, reaction mechanism and kinetic parameter of P-ddm/TBMI/imidazole were researched, and the influence of chemical structural differences on phase structure was discussed based on the calculated Flory-Huggins parameters. P-ddm/FBMI/imidazole had a bi-continuous phase structure while bisphenol A-aniline-based benzoxazine (BA-a)/TBMI/imidazole had a homogeneous one. The Flory-Huggins parameter of P-ddm/TBMI/imidazole was 0.048, which was lower than that of BA-aJTBMI/imidazole. However, since the amount of reacted P-ddm was higher than that of BA-a at lower temperature (120 degrees C), the critical Flory-Huggins parameter of P-ddm/FBMI/imidazole decreased faster than that of BA-a/FBMI/imidazole did. Therefore, P-ddm/TBMI/imidazole was unstable from the thermodynamic point and more prone to phase separation than BA-a/TBMI/imidazole. Fitting of viscosity curves at different temperatures showed that P-ddm/TBMI/imidazole had excellent mobility which benefited the formation of bi-continuous structure. The better mobility of P-ddm/TBMI/imidazole, may be caused by methylene in P-ddm. Compared with isopropylidene in BA-a, this structure had less hindrance effects on molecular flow, which may be the key point in phase separation. (C) 2016 Elsevier Ltd. All rights reserved.