取代基对氰基官能化苯并噁嗪树脂固化反应及热稳定性的影响  

Effects of Substituent Groups on Curing Reaction and Thermal Stability of Nitrile Functional Benzoxazine Resins

作　　者：文蔚 方雄 陈贵勇 闫宁 周奕雪 孟凡盛[2] 冉起超[2] WEN Wei;FANG Xiong;CHEN Guiyong;YAN Ning;ZHOU Yixue;MENG Fansheng;RAN Qichao(AVIC Chengdu Aircraft Industrial(Group)Co.LTD,Chengdu 610092,China;State Key Laboratory of Polymer Materials Engineering,College of Polymer Science and Engineering,Sichuan University,Chengdu 610065,China)

机构地区：[1]成都飞机工业(集团)有限责任公司,成都610092 [2]四川大学高分子科学与工程学院,高分子材料工程国家重点实验室,成都610065

出　　处：《功能高分子学报》2024年第5期416-423,共8页Journal of Functional Polymers

摘　　要：基于含不同取代基的酚与间氨基苯甲腈合成了3种含氰基苯并噁嗪单体(PH-bn、mPHbn、aPH-bn),并固化得到苯并噁嗪树脂(poly(PH-bn)、poly(mPH-bn)、poly(aPH-bn))。采用傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(^(1)H-NMR)、凝胶渗透色谱(GPC)对苯并噁嗪单体的结构与组成进行了表征,通过差示扫描量热分析(DSC)比较了取代基对固化行为的影响,并进一步探讨了固化反应机理。此外,采用热重分析(TGA)和热重分析-红外联用(TGA-FTIR)研究了3种固化物的热稳定性和热解机理。结果表明:噁嗪环与部分氰基在固化过程中同时发生交联反应。给电性甲基的存在使得体系的固化反应峰值温度增加、热稳定性降低;而吸电性醛基使得体系的固化反应峰值温度降低,同时醛基的交联反应使体系的热稳定性显著增加。poly(aPH-bn)的5%失重温度为380℃,800℃时N_(2)气氛下残炭率高达67.3%。Three nitrile functional benzoxazine monomers(PH-bn,mPH-bn,aPH-bn)were synthesized based on phenols containing different substituents and m-aminobenzonitrile,and their cured products(poly(PH-bn)、poly(mPH-bn)、poly(aPHbn))were obtained.The structures and compositions of benzoxazine monomers were characterized by Fourier Transform Infrared spectroscopy(FT-IR),Nuclear Magnetic Resonance spectroscopy(^(1)H-NMR)and Gel Permeation Chromatography(GPC).The effect of the substituents on curing behaviors was compared by differential scanning calorimetry(DSC),and the curing reaction mechanism was further discussed.In addition,thermogravimetric analysis(TGA)and TGA-FTIR were used to compare the thermal stability and pyrolysis mechanism of the three cured products.The results showed that the crosslinking reactions of the oxazine rings and a part of nitrile groups occurred simultaneously during the curing process.Due to the presence of the electric-donating methyl group,the peak temperature of the curing reaction increased and the thermal stability decreased.However,the electric-absorbing aldehyde group made the curing peak temperature decrease.Moreover,the thermal stability significantly increased because of the crosslinking reaction of the aldehyde groups.The 5%mass loss temperature of poly(aPH-bn)was 380℃,and its char yield was as high as 67.3%in N_(2) atmosphere at 800℃.

关 键 词：苯并噁嗪 氰基 热稳定性 固化反应 树脂 

分 类 号：TQ332[化学工程—橡胶工业]