带羟基邻苯二甲腈衍生物的自加速热聚合研究

利用酚类化合物与4-硝基邻苯二甲腈的亲核取代反应合成出了3种带羟基的邻苯二甲腈衍生物:4-(4-羟基苯氧基)邻苯二甲腈(化合物1),4-(4-羟基联苯氧基)邻苯二甲腈(化合物2)和2-(4-羟基苯基)-2′-(4-(3,4-二腈基苯氧基)苯基)丙烷(化合物3)。这类化合物无须外加催化剂,因而不会发生由于催化剂挥发或分解而使材料产生孔隙的问题。核磁共振氢谱(1H-NMR)和傅里叶转变红外光谱(FT-IR)的分析结果证实了所合成化合物的结构。利用示差扫描量热计(DSC)和热重分析(TGA)技术,对这3种邻苯二甲腈衍生物的热行为进行了对比研究。热分析研究显示出化合物3在290℃附近表现出与化合物1类似的自加速热聚合行为,而化合物2并未表现出明显的自加速热聚合反应行为。利用核磁共振氢谱技术(1H-NMR)分析了化合物1、2、3的酚羟基质子NMR化学位移,以研究分子结构与其自加速热聚合反应能力的关系。

Investigation on characteristics of the auto-accelerated thermo-polymerization of hydroxy-containing phthalonitrile derivatives

4-(4-hydroxyphenoxy) phthalonitrile(compound 1),4-(4′-hydroxybiphenyl-4-yloxy) phthalonitrile(compound 2) and 4-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenoxy)phthalonitrile(compound 3) were synthesized by nucleophilic displacement between phenolic compouds and 4-nitrophthalonitrile.These compounds needn′t additionnal catalyst,materials made of that had no voids for without volatilization and decomoposion of catalyst.The structures of these phthalonitrile-based compounds were confirmed by FT-IR and 1H-NMR.These compounds were comparatively investigated for their thermo-polymerization characteristics by different scanning calorimetry(DSC) and thermogravemetric analysis(TGA).Being similar to compound 1,compound 3 exhibited the characteristic of the auto-accelerated thermo-polymerization near 290 ℃.However,compound 2 did′t exhibit this characteristic.The relationship between molecular structure and reactity of the auto-accelerated thermo-polymerization was also studied by the 1H-NMR chemical shift of the phenolic hydroxy of the these compounds.