3,4,5-三羟基苯甲酸基水性含磷环氧固化剂的合成与性能  

Synthesis of gallic acid-based aqueous-phosphorous epoxy curing agent and its properties

作　　者：周继亮[1] 张俊珩[1] 张道洪[1] 李廷成[1] ZHOU Jiliang;ZHANG Junheng;ZHANG Daohong;LI Tingcheng(School of Chemistry and Materials Science,South-Central Minzu University,Wuhan 430074,China)

机构地区：[1]中南民族大学化学与材料科学学院,武汉430074

出　　处：《中南民族大学学报（自然科学版）》2022年第4期385-391,共7页Journal of South-Central University for Nationalities：Natural Science Edition

基　　金：湖北省自然科学基金资助项目(2015CFC875);中央高校基本科研业务费专项资金资助项目(CZY19008)。

摘　　要：先用生物基原料3,4,5-三羟基苯甲酸(GA)与环氧氯丙烷反应制备了3,4,5-三羟基苯甲酸基环氧树脂(GAE),然后在初始的GAE的环氧基与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的物料摩尔比为2︰1条件下,GAE与DOPO在乙二醇丁醚溶剂中在催化剂(三苯基膦)作用下反应生成了GAE-2DOPO加成物.探讨了反应温度、反应时间、催化剂量对GAE环氧基转化率的影响,结果表明其适宜工艺条件为:催化剂用量是GAE、DOPO质量和的2%、反应温度150℃、反应时间4 h.再将GAE-2DOPO加成物与自制的长碳链聚醚多胺化合物(TETA-PEGGEAGE)在丙二醇甲醚溶剂中进一步加成反应生成GAE-2DOPO-TETA-PEGGE-AGE加成物,探讨了反应温度、反应时间对GAE-2DOPO环氧基转化率的影响,结果表明其适宜的工艺条件为:反应温度65℃、反应时间7 h.真空蒸馏去除有机溶剂后,将其在水中分散制备出3,4,5-三羟基苯甲酸基水性含磷环氧固化剂.其综合性能优良:具有良好的水分散性、涂膜透明且机械性能良好,并且具有良好的耐热性和阻燃性能.透明的固化膜表明不同组分在膜中均匀分散且相容性良好;其阻燃性比传统的双酚A衍生物类固化剂得到有效提高;LOI值从22.3提高到28.2,达到V1的阻燃等级;其耐热性和残炭率(450~900℃)也得到明显提高:如在800℃下,其残炭率从4.65%提高到18.7%.Gallic acid-based epoxy resin(GAE)was synthesized from the reaction of gallic acid(GA,3,4,5-trihydroxybenzoic acid)and epichlorohydrin first,then with the initial molar ratio of the epoxy group of GAE and DOPO being 2︰1,GAE reacted with DOPO in butyl glycol ether using triphenylphosphine as catalyst to synthesize the GAE-2DOPO adduct.The effects of reaction temperature,reaction time and catalyst dosage on epoxy transformation rate were studied.And the suitable reaction conditions were as follows:weight percentage of catalyst 2% of the sum of GAE and DOPO mass,reaction temperature 150℃,and reaction time 4 h.The GAE-2DOPO adduct then reacted with self-prepared polyether polyamine compound(TETA-PEGGE-AGE)which contained long carbon chain to synthesize the GAE-2DOPO-TETA-PEGGE-AGE adduct.The effects of reaction temperature and reaction time on the epoxy transformation rate were studied,which showed that reacting 7 h at temperature 65℃ was most suitable.The organic solvent was removed subsequently by vacuum distillation,then distilled water was added to disperse the adduct and afford the gallic acid(GA)based aqueous phosphorous-containing curing agent.The thus prepared curing agent showed excellent comprehensive properties,including good water dispersion,film transparency,film mechanical property,heat resistance and flame retardancy.The cured films were transparent and uniform,indicating that the components were well compatible and evenly dispersed.The flame retardancy was significantly improved compared to the common water-based epoxy curing agent.The LOI value was improved from 22.3 to 28.2,reaching a flame retardancy grade of V1.The heat resistance and carbon residue rate were also significantly improved at the temperatures of 450‒900℃,e.g.,at 800℃,the char yield was increased from 4.65% to 18.7%.

关 键 词：3 4 5-三羟基苯甲酸 环氧固化剂 水性 合成 

分 类 号：TQ63[化学工程—精细化工]