Synthesis and characterization of siloxane-containing benzoxazines with high thermal stability

Abstract

To understand the influence of phenyl substituents on silicon and to improve the glass transition temperature ( T g ) and thermal stability, phenol/bis ( p-aminophenoxyl) dimethylsiloxane-based benzoxazine (P-adms), phenol/bis ( p-aminophenoxyl) methylphenylsiloxane-based benzoxazine (P-amps), and phenol/bis ( p-aminophenoxyl) diphenylsiloxane-based benzoxazine (P-adps) were designed and synthesized. The structure of the siloxane-containing benzoxazines were confirmed by proton and carbon nuclear magnetic resonance imaging and Fourier transform infrared spectra. The curing reaction of the obtained benzoxazines was studied by differential scanning calorimetry (DSC) and in situ infrared spectra. The influence of the aromatic content on the T g and thermal stability were investigated by modulated DSC and thermogravimetric analysis. Compared to aminopropylsiloxane-based benzoxazines, the bis ( p-aminophenoxyl) siloxane-based benzoxazines possessed relatively higher T g about 140°C due to the replacement of flexible propyl chain by phenoxyl chain. With increasing phenyl substituents on silicon, the polybenzoxazines possessed lower T g and higher thermal stability. It is notedthat the phenol/bis ( p-aminophenoxyl) diphenylsiloxane-based benzoxazine (P-adps) still has low viscosity despite high aromatic content due to the flexible ether linkage (Ar–O–Si).