含膦固化剂的制备及其阻燃环氧树脂的性能  

Preparation of Curing Agent Containing Phosphine and Properties of It Flame Retardant Epoxy Resin

作　　者：冯才敏[1] 姜佳丽[1] 农彦彦[1] 练翠霞 黄健光[1] 黄志鑫 刘云香 谢荣华 李景汉 Feng Caimin;Jiang Jiali;Nong Yanyan;Lian Cuixia;Huang Jianguang;Huang Zhixin;Liu Yunxiang;Xie Ronghua;Li Jinghan(College of Light Chemical Industry and Materials Engineering,Shunde Polytechnic,Foshan 528333,China;Dongguan Hongke New Material Technology Co.,Ltd.,Dongguan 523000,China;Guangdong Jinke New Materials Co.,Ltd.,Guangzhou 510000,China)

机构地区：[1]顺德职业技术学院轻化与材料学院,广东佛山528333 [2]东莞弘科新材料科技有限公司,广东东莞523000 [3]广东金科新材料有限公司,广州510000

出　　处：《工程塑料应用》2021年第8期37-42,共6页Engineering Plastics Application

基　　金：广东省自然科学基金项目(2021A1515012274);2021年攀登计划(pdjh2021)。

摘　　要：选用乙基膦酰二氯和乙二胺制备了乙基含膦二胺固化剂(EDE),采用傅立叶变换红外光谱(FTIR)表征了EDE的结构,并跟踪了9,10-二氢-9-氧杂-10-磷杂菲-10氧化物(DOPO)改性环氧树脂(DOPO-EP)与EDE的固化反应过程,制备了EDE固化的DOPO改性环氧树脂(EDE-DOPO-EP)。分析比较了纯环氧树脂、DOPO-EP和EDE-DOPO-EP固化物的阻燃性能、透明性、力学性能和热稳定性能,采用FTIR和扫描电子显微镜(SEM)对残炭的结构和形貌进行分析。结果表明,在80℃固化2 h可以完成EDE-DOPO-EP的固化;当EDE的用量为23.04份(磷质量分数为3.07%)时,EDE-DOPO-EP极限氧指数达到30.5%,垂直燃烧阻燃等级达到UL 94 V-0级;EDE-DOPOEP具有良好的透明性,在波长200~800 nm内保持了纯环氧树脂固化物透光率的80%~90%;与纯环氧树脂固化物相比,EDE-DOPO-EP的力学性能下降幅度相对较小,初始分解温度虽下降明显,但600℃和800℃的残炭率分别从2.1%和0.9%提高到23.4%和12.0%;FTIR和SEM对残炭的分析表明,EDE-DOPO-EP残炭中形成了更多的P—O—C和P=O的结构,形成了更致密的炭层,从而提高了阻燃性能。The ethyl diamine curing agent containing phosphine(EDE)was prepared by ethylphosphonous dichloride and ethylenediamine,and the structure of EDE was characterized by Fourier transform infrared spectroscopy(FTIR),the reaction routine of EDE and 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)modified epoxy resin(DOPO-EP)was tracked by FTIR.The DOPO-EP cured by EDE(EDE-DOPO-EP)was prepared.The flame retardant properties,transparency,mechanical properties and thermal stability of cured pure epoxy resin,DOPO-EP and EDE-DOPO-EP were characterized.The molecular structure and morphology of residual char were analyzed by FTIR and scanning electron microscopy(SEM).It is found that it cured completely after heated at 80℃for 2 hours for EDE-DOPO-EP.The limit oxygen index value of EDE-DOPO-EP is 30.5%,and the flame retardant grade of vertical combustion reaches UL 94 V-0,when the content of EDE is 23.04 phr(mass fraction of P is 3.07%).EDE-DOPO-EP has good transparence and it can keep 80%-90%of the transmittance of cured pure epoxy resin at the wavelength of 200-800 nm.Compared with cured pure epoxy resin,the decrease of the mechanical properties of EDE-DOPO-EP are relatively little,the initial degradation temperature decreases obviously but the carbon residue rate at 600℃and 800℃increase from 2.1%and 0.9%to 23.4%and 12.0%respectively.The analysis of residual char characterized by FTIR and SEM illustrates that more P—O—C and P=O bonds during combustion are formed in the residual char of EDE-DOPO-EP,and more compact char layer is formed to improve the flame retardant properties.

关 键 词：环氧树脂 9 10-二氢-9-氧杂-10-磷杂菲-10氧化物 含膦固化剂 本征阻燃 阻燃机理 

分 类 号：TQ314.248[化学工程—高聚物工业]