丙氧基化双酚A缩水甘油醚的合成与固化性能  

Synthesis and curing properties of propoxylated bisphenol A glycidyl ether

作　　者：李书香 汪宁 李娅 付博[1] 朱新宝[1,2] LI Shuxiang;WANG Ning;LI Ya;FU Bo;ZHU Xinbao(College of Chemical Engineering,Nanjing Forestry University,Nanjing 210037,Jiangsu,China;Anhui Engineering Research Center of Epoxy Resin and Additives,Huangshan 245900,Anhui,China)

机构地区：[1]南京林业大学化学工程学院,江苏南京210037 [2]安徽省环氧树脂及助剂工程技术研究中心,安徽黄山245900

出　　处：《化工进展》2019年第6期2961-2967,共7页Chemical Industry and Engineering Progress

基　　金：安徽省科技重大专项(17030901077);江苏省产学研前瞻性联合研究项目(BY2016006-02)

摘　　要：以丙氧基化双酚A(D33)、环氧氯丙烷(ECH)和液碱为主要原料,采用两步法工艺合成了丙氧基化双酚A缩水甘油醚(DGEPBA)。考察了原料配比、催化剂用量、反应温度、反应时间等因素对反应的影响。结果表明:开环催化剂三氟化硼-乙醚(BF3-Et2O),质量分数0.1%,D33与ECH的质量比为1∶2.0,反应温度70℃,反应时间2.5h;闭环催化剂苄基三乙基氯化铵质量分数0.2%,D33与NaOH的质量比为1∶2.2,反应温度40℃,反应时间6h时,产物环氧值为0.291eq/100g,产率95.4%,黏度为1180mPa·s。通过FTIR和1H NMR对产物结构进行表征,并将不同质量分数的DEEBAPO掺入到E-51环氧树脂中,与二乙烯三胺(DETA)进行固化,并对其固化物力学性能进行测试。因为DGEPBA的掺入,使得E-51固化物在抗拉伸、抗冲击方面均有明显提高。热失重(TGA)分析表明固化物热稳定性稍有提高,扫描电镜(SEM)显示断裂面为韧性断裂。Diglycidyl ether of propoxylated bisphenol A(DGEPBA) was synthesized by a two-step process using propoxylated bisphenol A(D33), epichlorohydrin(ECH) and liquid alkali as the main starting materials. The effects of the substrates ratio, catalyst loading, reaction temperature and reaction time were investigated for this reaction. The results showed that the 0.1% of BF3-Et2O, 1∶2.0 ratio of D33 to ECH, at 70℃ and reaction for 2.5 h was the best condition for the ring-opening reaction. The optimized condition for the second step was the use of 0.2% triethylammonium chloride at 40℃ for 6 h with the 1∶2.2 molar ratio of D33 to NaOH, which provided the desired product in 95.4% yield with0.291 eq/100 g epoxy value and 1180 mPa·s viscosity. The structure of the product was characterized by FTIR and 1H NMR, and the different amounts of DEEBAPO were incorporated into E-51 epoxy resin and cured with diethylenetriamine(DETA). The properties of the cured product were tested, and the tensile strength and impact resistance of the E-51 cured product were significantly improved with the incorporation of DGEPBA. The thermogravimetric analysis(TGA) showed that the thermal stability of the cured product was slightly improved, and the scanning electron microscopy(SEM) indicated that the fracture surface was a ductile fracture.

关 键 词：丙氧基化双酚A 环氧氯丙烷 合成 固化性能 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]