生物基苯并噁嗪作为环氧树脂潜伏性固化剂的研究  

Latent Curing Agent of Epoxy Resin Based on Bio-Benzoxazine

作　　者：王汉武 贾瑞明 冉起超[1] WANG Hanwu;JIA Ruiming;RAN Qichao(State Key Laboratory of Polymer Materials Engineering,College of Polymer Science and Engineering,Sichuan University,Chengdu 610065,China)

机构地区：[1]四川大学高分子科学与工程学院,高分子材料与工程国家重点实验室,成都610065

出　　处：《功能高分子学报》2022年第3期236-243,共8页Journal of Functional Polymers

基　　金：国家自然科学基金(52073188)。

摘　　要：以糠胺、香草醛、多聚甲醛为原料合成了一种生物基苯并噁嗪(V-fa)。选择双环戊二烯-苯酚型环氧树脂(DCPD-ER)为研究对象,将V-fa作为固化剂按不同比例加入到DCPD-ER中,同时以二氨基二苯甲烷(DDM)为固化剂进行对比研究。通过傅里叶红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)对V-fa的化学结构进行表征,确认了其结构。采用差示扫描量热(DSC)、FTIR系统研究了树脂体系的固化反应。此外,使用动态热机械分析(DMA)、热失重分析(TGA)考察了固化物的热性能。研究表明,与DCPD-ER/DDM相比,DCPD-ER/V-fa的起始固化反应温度和固化反应活化能较高。DCPD-ER/V-fa固化物的玻璃化转变温度(T_(g))、初始分解温度和800℃氮气下的残炭率(Y_(c))均高于DCPD-ER/DDM的相应值,其T_(g)与Yc分别高达192℃与44%。同时,V-fa的加入能够改善树脂体系的阻燃性能。A bio-based benzoxazine(V-fa)was synthesized from furfuramine,vanillin and paraformaldehyde.Its chemical structure was characterized by Fourier-transformed Infrared spectra(FT-IR)and 1H-Nuclear Magnetic Resonance(1H-NMR)spectra.Results show that this new benzoxazine monomer is synthesized successfully.Dicyclopentadiene-phenol epoxy resin(DCPD-ER)was selected as a research object.V-fa was added into DCPD-ER in different proportions as a latent curing agent.At the same time,a usual curing agent,diaminodiphenylmethane(DDM),was also used as a comparative study.The curing reaction of the resin system was studied by Differential Scanning Calorimetry(DSC)and FT-IR spectra.Compared with DCPD-ER/DDM,DCPD-ER/V-fa has a higher initial curing reaction temperature and curing reaction activation energy.DCPD-ER/V-fa can cure at a high temperature,which is attributed to the reaction between phenolic hydroxyl groups produced by ring-opening reaction of the benzoxazine and epoxy groups.In addition,the thermal properties of the cured products were investigated by Dynamic Mechanical Analysis(DMA)and Thermogravimetric Analysis(TGA).The addition of V-fa can improve the heat resistance and thermal stability of the resin system.The glass transition temperature(T_(g)),initial decomposition temperature and char yield under nitrogen at 800℃(Y_(c))of DCPD-ER/V-fa are higher than those of DCPD-ER/DDM,and the T_(g) and Yc can reach as high as 192 oC and 44%,respectively.Moreover,the flame retardancy of DCPD-ER/V-fa was evaluated on the basis of the results from TGA measurements.The limiting oxygen index(LOI)of DCPD-ER/V-fa can reach as high as 35.1,suggesting that the addition of V-fa improves the flame retardancy of the epoxy resin.

关 键 词：环氧树脂 苯并噁嗪 生物基 潜伏性固化剂 热性能 

分 类 号：TB35[一般工业技术—材料科学与工程]