Wu Minjie, Xu Jianjun, Bai Shengnan, Chen Xinggang, Yu Xiaoyan, Naito Kimiyoshi, Zhang Zhenjiang, Zhang Qingxin
Hebei Key Laboratory of Functional Polymers, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China.
National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba 305-0047, Japan.
Soft Matter. 2020 Feb 19;16(7):1888-1896. doi: 10.1039/c9sm02328c.
A monomer of fluorinated phthalonitrile, namely 4,4'-bis(p-perfluoro-phenol-(bis(p-phenol)propane-2,2-diyl)-p-oxy-diphthalonitrile) (PBDP), was synthesized by the nucleophilic substitution reaction of bisphenol A, decafluorobiphenyl and 4-nitrophthalonitrile. The structure of the monomer was characterized by nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The results indicated that the PBDP monomer was synthesized successfully. The monomer was cured in the presence of 4-(aminophenoxy)phthalonitrile (APPH) and the curing behaviour was investigated by differential scanning calorimetry (DSC), suggesting a low melting point of 96 °C and an excellent processing window (96-262 °C). Thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) showed that the fluorinated phthalonitrile resin possessed outstanding thermal and thermo-oxidative stabilities as well as good mechanical properties. The glass transition temperature was >400 °C and the 5% thermal degradation temperature was 501 °C. When the frequency was 50 MHz, the dielectric constant and dielectric loss of the polymer were 2.84 and 0.007, respectively. The PBDP resin has ultra-low water absorption of 0.77% and 1.4%, when exposed to an aqueous environment for 50 days at 24 °C and for 24 h at 100 °C, respectively. The prepared PBDP resin with outstanding thermal stability and low dielectric constant is an ideal candidate for aerospace industries, and microelectronic and other electronic packaging materials.
一种氟化邻苯二甲腈单体，即4,4'-双（对-全氟-苯酚-（双（对-苯酚）丙烷-2,2-二亚基）-对-氧基-二邻苯二甲腈）（PBDP），通过双酚A、十氟联苯和4-硝基邻苯二甲腈的亲核取代反应合成。该单体的结构通过核磁共振（NMR）光谱和傅里叶变换红外（FTIR）光谱进行表征。结果表明PBDP单体成功合成。该单体在4-（氨基苯氧基）邻苯二甲腈（APPH）存在下固化，并通过差示扫描量热法（DSC）研究其固化行为，结果表明其熔点低至96℃，加工窗口优异（96-262℃）。热重分析（TGA）和动态力学分析（DMA）表明，氟化邻苯二甲腈树脂具有出色的热稳定性和热氧化稳定性以及良好的机械性能。玻璃化转变温度>400℃，5%热降解温度为501℃。当频率为50MHz时，该聚合物的介电常数和介电损耗分别为2.84和0.007。PBDP树脂在24℃下暴露于水环境50天以及在100℃下暴露24小时时，吸水率分别为0.77%和1.4%，吸水率极低。所制备的具有出色热稳定性和低介电常数的PBDP树脂是航空航天工业以及微电子和其他电子封装材料的理想候选材料。
