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A linear oligobenzoxazine precursor with cyclotriphosphazene ring was prepared through the Schiff base route. The resulting polymers showed higher molecular weight and better thermal stability than those from the traditional Mannich polycondensation method. The oligomeric benzoxazine precursor can form a high-quality transparent yellow film; however, it was fragile after being cured. In order to identify the effect of end groups on the cured polymer, an aniline-capped polymer was prepared by the same Schiff base method and then was changed into a benzoxazine end group. The results indicated that the uncapped polymer exhibited higher stability than the capped polymer. This can be ascribed to different chemical structures resulting from different end groups. [ABSTRACT FROM AUTHOR]

The synthesis and mesomorphic properties of a class of cyclotriphosphazenes containing cyanostilbene groups with different terminal substituents (-H, -CH3, -OCH3, -CN) are described. All the resulting compounds are characterized by 1H, 13C, and 31P NMR, matrix-assisted laser desorption/ionization time of flight, and elemental analysis. The thermal behaviors of cyclotriphosphazene derivatives are studied by the means of differential scanning calorimetry and polarizing optical microscopy. Nematic phases are observed in cyclotriphosphazenes with terminal substituents (-CH3, -OCH3, -CN). [ABSTRACT FROM AUTHOR]

Abstract: Well-defined organic–inorganic hybrid benzoxazine monomers based on cyclotriphosphazene (CP) cores have been synthesized. Theses monomers possessed controllable number of organic benzoxazine moieties and biphenyl groups distributed on the inorganic ring of CP. Corresponding ring-opening polymerization under heat led to highly cross-linked polymers with different number of crosslinking sites. The ring-opening polymerization behaviors of the new benzoxazine monomers were investigated by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMA). The results indicated that the polymerization activity of the monomers depended on the number of benzoxazine moiety of corresponding monomers. Those monomers with more benzoxazine moieties resulted in higher polymerization rate. Due to the high crosslinking nature with rigid and stable inorganic CP ring and biphenyl groups in the networks, the resulted polybenzoxazines from the monomers showed excellent thermal stability, mechanic property and humidity resistance. [Copyright &y& Elsevier]

Abstract: A hyperbranched organic–inorganic hybrid benzoxazine monomer based on cyclotriphosphazene (CP) has been synthesized, which possesses six organic benzoxazine moieties distributed on the inorganic ring of CP. The high molecular weight (1491 g/mol) monomer showed excellent solubility in common organic solvents. Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) were used to study the thermal ring-opening polymerization reaction of the novel benzoxazine monomer. FT-IR spectrum implied that the characteristic absorption peaks of the benzoxazine ring disappeared completely after curing at 240 °C for 1 h, which illustrated that the completion of polymerization reaction. DSC plots indicated that the melting point of the new monomer was 77 °C and an exothermic peak was 225 °C owing to the ring-opening polymerization of the monomer. Due to its highly steric crosslinking structure with rigid and thermal stable inorganic CP as the core, the polybenzoxazine based on the new monomer showed excellent thermal stability and mechanic properties. The char yield of the polymer at 850 °C was 66.9% in nitrogen, and the Tg of the polybenzoxazine was 152 °C. [Copyright &y& Elsevier]