缩水甘油酯型自固化环氧树脂的高效合成  

Efficient Synthesis of Glycidic Ester Self-Curing Epoxy Resin

作　　者：刘钰[1] 王胜鹏 陈八斤 王嘉骏[1] 冯连芳[1] 顾雪萍[1] Yu Liu;Shengpeng Wang;Bajin Chen;Jiajun Wang;Lianfang Feng;Xueping Gu(College of Chemical and Biological Engineering,State Key Laboratory of Chemical Engineering,Zhejiang University,Hangzhou 310027,China;Transfar Zhilian Co.,Ltd.,Hangzhou 311215,China)

机构地区：[1]浙江大学化学工程与生物工程学院化学工程联合国家重点实验室,浙江杭州310027 [2]传化智联股份有限公司,浙江杭州311215

出　　处：《高分子材料科学与工程》2020年第9期1-8,共8页Polymer Materials Science & Engineering

基　　金：国家重点研发计划(2017YFB0307702)。

摘　　要：以四甲基氢氧化铵五水合物(THP)作为催化剂,环氧氯丙烷(ECH)与2,5-二羟基对苯二甲酸(DHTA)为原料,制备了具有自固化特性的缩水甘油酯型环氧树脂。考察了温度、溶剂、催化剂等因素对制备过程的影响,用傅里叶变换红外光谱对反应过程中羧基转化情况进行了表征。结果表明,在90℃条件下,反应物与催化剂摩尔比n(DHTA)∶n(ECH)∶n(THP)=1∶17.5∶0.12时,DHTA内羧基可在2 h内完成酯化且温升较小。使用核磁碳谱及氢谱表征树脂,确认产物结构。使用凝胶渗透色谱对树脂相对分子质量分布进行表征,由于反应物平均官能度较低,产物内主要为小分子的二聚体及四聚体。该路线反应时间短、反应温升小、废液排放少且树脂稳定性较好,实现了具有工业基础的低介电缩水甘油酯型自固化环氧树脂的绿色高效合成。Glycidic ester epoxy resin with self-curing properties was prepared from epichlorohydrin(ECH)and 2,5-dihydroxyterephthalic acid(DHTA)using tetramethylammonium hydroxide pentahydrate(THP)as catalyst.The influence of temperature,solvent and catalyst on the preparation process was investigated.The carboxyl conversion was characterized by FT-IR.The results show that the esterification of carboxyl in DHTA could be completed within 2 h and the temperature rise is small,when the mole ratio of reactant to catalyst is n(DHTA)∶n(ECH)∶n(THP)=1∶17.5∶0.12 at 90℃.1H-NMR and 13C-NMR were used to characterize the resin and confirm the structure of the product.The molecular weight distribution of resins was characterized by gel permeation chromatography(GPC).The resins were mainly composed of dimer and tetramer.The route has the advantages of short reaction time,small temperature changes in reaction process,less waste liquid discharge and good room temperature stability for more than 270 d.This route realizes the green and efficient synthesis of low dielectric constant glycidyl ester self-curing epoxy resin and has a certain industrial application foundation.

关 键 词：自固化 环氧树脂 催化剂 缩水甘油酯 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]