A series of polyfunctional benzoxazine monomers containing aromatic and fluorene group (AMFB) were used as modified agents to improve the performance of typical bifunctional bisphenol-A-aniline-based (BA-a) benzoxazine resins. The polymerization behaviors of BA-a/AMFB blends were investigated by using the differential scanning calorimetry (DSC), while the dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were used to analyze the thermomechanical and thermal properties of BA-a/AMFB copolymers [poly(BA-a/AMFB)]. Moreover, the cross-section morphologies of poly(BA-a/AMFB) were observed by scanning electron microscope (SEM). The experimental results showed that BA-a monomer has good catalytic activity for AMFB monomers during the curing process. Compared with BA-a polymer [poly(BA-a)], due to the introduction of heat-resistant fluorene ring and the increase of the crosslinking degree of copolymers, the copolymers showed higher glass transition temperature and better thermal properties. For poly(BA-a/AMFB), the T5, T10, and Yc were higher than those of poly(BA-a). With the increase of the alkyl chain length of AMFB monomers, the cross-section creases gradually changed from linear to dendritic, and the number of creases increased significantly, which indicated that the toughness of the copolymers was significantly improved.
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