Ren Dengxun, Fan Zexu, Zhang Jiaqu, Xu Yi, Tang Xianzhong, Xu Mingzhen
School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 610054, China.
Molecules. 2024 Nov 29;29(23):5668. doi: 10.3390/molecules29235668.
To study the properties of cyclotriphosphazene (CTP)-containing phthalonitriles, a branched phthalonitrile containing CTP (CTP-PN) with self-catalytic behavior was designed and synthesized. The structure of CTP-PN was characterized by FT-IR (Fourier transform infrared spectroscopy), MS (mass spectroscopy), H-NMR (proton nuclear magnetic resonance spectroscopy), and C-NMR (carbon nuclear magnetic resonance spectroscopy). Then, the curing reaction of CTP-PN was studied using DSC (differential scanning calorimetry) and DRA (dynamic rheological analysis). The results show that the curing reaction of CTP-PN is initiated at 200 °C. Additionally, the change in the viscosity of CTP-PN as a function of the temperature was investigated. After curing at different temperatures, the generated structures were characterized by FT-IR. The fracture morphology and thermomechanical properties of cured CTP-PN were scanned and studied using SEM (scanning electron microscopy) and TMA (thermomechanical analysis), respectively. The results demonstrate that CTP-PN exhibits a smooth fracture surface and possesses a relatively low CTE (coefficient of linear thermal expansion) of approximately 25 ppm/°C at 285 °C. A (temperature at which 5% weight loss occurs) of as high as 405 °C can be obtained for cured CTP-PN, and its char yield at 800 °C exceeds 70% in N. FT-IR and XPS (X-ray photoelectron spectroscopy) were used to study the thermal decomposition of cured CTP-PN, indicating that it remains stable below 350 °C. With an increasing temperature, there is decomposition first of CTP and P-NH-Ph and C-O-C bonds (>350 °C) and then nitrogen-containing aromatic heterocycles (>500 °C), ultimately resulting in the formation of P-containing residual char.
为研究含环三磷腈(CTP)的邻苯二甲腈的性能,设计并合成了一种具有自催化行为的含CTP的支化邻苯二甲腈(CTP-PN)。通过傅里叶变换红外光谱(FT-IR)、质谱(MS)、质子核磁共振光谱(H-NMR)和碳核磁共振光谱(C-NMR)对CTP-PN的结构进行了表征。然后,采用差示扫描量热法(DSC)和动态流变分析(DRA)研究了CTP-PN的固化反应。结果表明,CTP-PN的固化反应在200℃开始。此外,还研究了CTP-PN粘度随温度的变化。在不同温度下固化后,用FT-IR对生成的结构进行了表征。分别使用扫描电子显微镜(SEM)和热机械分析(TMA)对固化CTP-PN的断裂形态和热机械性能进行了扫描和研究。结果表明,CTP-PN呈现出光滑的断裂表面,在285℃时具有约25 ppm/℃的相对较低的线性热膨胀系数(CTE)。固化后的CTP-PN可获得高达405℃的5%失重温度(T5%),在氮气中800℃时的残炭率超过70%。采用FT-IR和X射线光电子能谱(XPS)研究了固化CTP-PN的热分解,结果表明其在350℃以下保持稳定。随着温度升高,首先是CTP以及P-NH-Ph和C-O-C键(>350℃)分解,然后是含氮芳香杂环(>500℃)分解,最终形成含磷残余炭。