Hu Yue, Weng Zhihuan, Qi Yu, Wang Jinyan, Zhang Shouhai, Liu Cheng, Zong Lishuai, Jian Xigao
State Key Laboratory of Fine Chemicals, Liaoning High Performance Resin Engineering Research Center, Department of Polymer Science & Materials, Dalian University of Technology Dalian 116024 China
RSC Adv. 2018 Sep 24;8(57):32899-32908. doi: 10.1039/c8ra06926c. eCollection 2018 Sep 18.
Major problems currently limiting the widespread application of phthalonitrile resins are the high precursor melting point and volatility of the curing agent. Herein, a novel self-curing triphenol A-based phthalonitrile resin precursor (TPPA-Ph) was successfully synthesized by reacting α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (TPPA) with 4-nitrophthalonitrile (NPh) nucleophilic substitution. The presence of residual phenolic hydroxyl groups in the TPPA-Ph precursor promoted the curing reaction of phthalonitrile resin in the absence of an additional curing reagent. Self-cured TPPA-Ph resins exhibited relatively low melting points (less than 100 °C), high thermal stability, and a wide processing window (116 °C). Furthermore, the TPPA-Ph precursors contained phenolic hydroxyl and cyano groups that can be used as flexibilizers and curing agents to optimize other phthalonitrile resins. Resorcinol-based phthalonitrile resin (DPPH) cured with various amounts of TPPA-Ph possessed excellent thermal and thermo-oxidative stability with a 5% weight loss temperature exceeding 530 °C, s above 380 °C, and a wide processing window and time. Therefore, as a novel precursor and curing agent for phthalonitrile resins, the triphenol A-based phthalonitrile resin is an ideal resin matrix for high-performance composites with broad application prospects in aerospace, shipping, machinery, and other high-tech fields.
目前限制邻苯二甲腈树脂广泛应用的主要问题是前体熔点高和固化剂挥发性大。在此,通过α,α,α'-三(4-羟基苯基)-1-乙基-4-异丙基苯(TPPA)与4-硝基邻苯二甲腈(NPh)进行亲核取代反应,成功合成了一种新型自固化三酚A基邻苯二甲腈树脂前体(TPPA-Ph)。TPPA-Ph前体中残留酚羟基的存在促进了邻苯二甲腈树脂在无额外固化剂情况下的固化反应。自固化TPPA-Ph树脂表现出相对较低的熔点(低于100℃)、高热稳定性和较宽的加工窗口(116℃)。此外,TPPA-Ph前体含有酚羟基和氰基,可作为增韧剂和固化剂来优化其他邻苯二甲腈树脂。用不同量的TPPA-Ph固化的间苯二酚基邻苯二甲腈树脂(DPPH)具有优异的热稳定性和热氧化稳定性,5%失重温度超过530℃,起始分解温度高于380℃,且加工窗口宽、时间长。因此,作为一种新型的邻苯二甲腈树脂前体和固化剂,三酚A基邻苯二甲腈树脂是一种理想的树脂基体,在航空航天、船舶、机械等高科技领域具有广阔的应用前景。