磷杂菲-厚朴酚基环氧低聚物的合成及其固化树脂阻燃性能  

Synthesis and flame-retardant properties of the epoxy resin based on phenanthroline and magnolol

作　　者：谢煜彬 胡国梁 张笑晴 雷彩红[1] XIE Yubin;HU Guoliang;ZHANG Xiaoqing;LEI Caihong(School of Materials and Energy,Guangdong University of Technology,Guangzhou 510006,China)

机构地区：[1]广东工业大学材料与能源学院,广州510006

出　　处：《复合材料学报》2024年第12期6545-6558,共14页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金面上项目(52073065)。

摘　　要：商用环氧树脂主要由不可再生的石油基原料制得,且存在易燃、离火不自熄的问题,限制了它在电子电气和轨道交通等领域的广泛应用。因此,以生物质化合物厚朴酚、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和环氧氯丙烷为原料,合成了一种磷杂菲-厚朴酚基环氧低聚物(ED-0.5),并以4,4'-二氨基二苯基甲烷(DDM)为环氧固化剂,制备高阻燃效率的环氧固化树脂(ED-0.5/DDM)。通过FTIR、NMR表征了其化学结构,利用DSC和TGA研究了环氧固化树脂的固化动力学和热稳定性,采用极限氧指数、垂直燃烧、锥形量热仪探究了环氧固化树脂的阻燃性能,通过TG-FTIR和SEM分别对固化物热解气相组成和燃烧后残炭形貌结构进行了分析,探究其阻燃机制。结果表明,ED-0.5/DDM树脂热稳定性和热机械性能均优于传统双酚A环氧树脂,固化反应活化能略高。ED-0.5/DDM环氧固化树脂极限氧指数(LOI)可达到52.5%,UL-94测试达到V-0等级,热释放速率峰值和总热释放量分别降低70.9%和58.2%,残炭增加1 565.2%。ED-0.5/DDM环氧固化树脂可通过捕获猝灭自由基,产生大量不燃气体,形成致密炭层,发挥气相和凝聚相协同阻燃作用。Commercial epoxy resin is mainly made from non renewable petroleum-based raw materials,and it has the problem of flammability and non self extinguishing,which limits its widespread application in fields such as electronics,electrical engineering,and rail transit.Therefore,a novel epoxy oligomer with magnolol phosphaphenanthrene(ED-0.5) was successfully synthesized with biomass compound magnolol,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO),and epichlorohydrin,and then a high flame retardant epoxy resin(ED-0.5/DDM) was prepared by using 4,4'-diaminodiphenylmethane(DDM) as the epoxy curing agent.The chemical structure was characterized by FTIR and NMR,and the curing kinetics and thermal stability of epoxy resin were studied by DSC and TGA.The flame retardancy of epoxy resin was investigated by limiting oxygen index,vertical combustion,and cone calorimeter.The thermal decomposition gas phase composition of the cured resin and the morphology of the carbon layer after combustion of the epoxy resin were analyzed by TG-FTIR and SEM,respectively,to study its flame retardancy mechanism.The results show that the thermal stability and thermal mechanical properties of ED-0.5/DDM epoxy resin are better than traditional bisphenol A epoxy resin,but the activating energy of the curing reaction is higher.The limiting oxygen index(LOI) of ED-0.5/DDM epoxy cured resin can reach 52.5%,passing the V-0 level of UL-94,reducing the peak heat release rate and total heat release by 70.9% and 58.2% respectively,and increasing the residual carbon by 1 565.2%.ED-0.5/DDM epoxy resin can capture and quenching active radicals,generate a large amount of non-burning gases,form a dense carbon layer,and exert the synergistic flame retardant effect of gas phase and condensed phase.

关 键 词：环氧低聚物 厚朴酚 磷杂菲 阻燃 协同阻燃 

分 类 号：TQ322[化学工程—合成树脂塑料工业] TB332[一般工业技术—材料科学与工程]