Abstract: The flame retardant of polymer materials greatly depends on their thermal degradation behaviors and research on the thermal degradation kinetics has a critical role in revealing the flame retardant mechanism. Based on the analysis of the flame retardant and thermal stability of epoxy resin DOPS derivative (EP/MAH-DOPS), the thermal degradation behavior was studied, the morphology of the char residue was analyzed, and the flame retardant mechanism was finally discussed. The results showed that when the amount of flame retardant was 7.5wt%, the limiting oxygen index (LOI) value of EP/MAH-DOPS increased to 29.3%, and reached UL-94 V-0 rating. Compared with pure EP, the peak heat release rate (PHRR) and total heat release (THR) of EP/MAH-DOPS-7.5% were decreased by 43.83% and 7.43%, respectively. The initial decomposition temperature of EP/MAH-DOPS-7.5% (T5%, 333.81 ℃) was lower than that of pure EP (376.84 ℃), and the amount of char residue increased to 22.12% at 600 ℃. The addition of MAH-DOPS promoted the EP to decompose in advance and the char forming of EP, which further reduced the activation energy of EP. The results of thermogravimetric-fourier transform infrared spectroscopy (TG-FTIR) showed that the flame retardant MAH-DOPS mainly play a flame retardant role in gas phase through the generation of phosphorus oxygen radicals during pyrolysis. The results of scanning electron microscopy (SEM) showed that EP/MAH-DOPS could form a more complete and dense char layer. From the flame retardant mechanism, MAH-DOPS plays a flame retardant role in the gas phase and condensed phase through quenching free radicals and char formation respectively, and the gas phase flame retardant mechanism is the main one.
通讯作者:
* 宝冬梅,贵州民族大学化学工程学院教授、硕士研究生导师。2003年6月于辽宁师范大学化学与化工学院获得学士学位,2007年6月于贵州师范大学理学院获得硕士学位,同年7月到贵州民族大学任教至今,2013年6月于北京理工大学材料学院获得博士学位。目前主要从事聚合物基阻燃复合材料方面的研究工作。在Materials Letters、Chemical Physics Letters、Journal of Physics and Chemistry of Solids、《复合材料学报》等国内外期刊上发表论文30余篇。dongtian1314521@163.com
1 Xu Z G, Song P A, Zhang J, et al. Composites Science and Technology, 2018, 168, 363. 2 Qian L J, Ye L J, Qiu Y, et al. Polymer, 2011, 52(24), 5486. 3 Wang Y Z, Yuan Y C, Zhao Y, et al. High Performance Polymers, 2017, 29(1), 94. 4 Liu W, Chen K P, Zhao X L. Journal of Chongqing Technology and Business University(Natural Science Edition), 2022, 39(3), 1(in Chinese). 刘文, 陈可平, 赵秀丽. 重庆工商大学学报(自然科学版), 2022, 39(3), 1. 5 Jin S L, Qian L J, Qiu Y, et al. Polymer Degradation and Stability, 2019, 166, 344. 6 Wang P, Cai Z S. Polymer Degradation and Stability, 2017, 137, 138. 7 Zhang S, Jiang Y C, Sun Y Y, et al. Polymers for Advanced Technologies, 2021, 32(5), 2093. 8 Zhang Q Q, Yang S, Wang J, et al. Polymer Degradation and Stability, 2019, 167, 10. 9 Luo J Y, Zhang D H, Zhou M, et al. Chemical Industry and Engineering Progress, 2020, 39(8), 3221(in Chinese). 罗继永, 张道海, 周密, 等. 化工进展, 2020, 39(8), 3221. 10 Liu P, Liu M, Gao C, et al. Journal of Applied Polymer Science, 2013, 130(2), 1301. 11 Wang Y, Luo Y, Zhang Z. Insulating Materials, 2010, 43(3), 20(in Chinese). 王昱, 罗炎, 张桢. 绝缘材料, 2010, 43(3), 20. 12 Wang J H, Xu Z Y, Ye X L, et al. Fine Chemicals, 2022, 39(2), 396 (in Chinese). 王建航, 许志彦, 叶小林, 等. 精细化工, 2022, 39(2), 396. 13 Xu Z Y, Hou Z M, Ye X L, et al. Acta Materiae Compositae Sinica, 2022, 39(10), 4518(in Chinese). 许志彦, 侯泽明, 叶小林, 等. 复合材料学报, 2022, 39(10), 4518. 14 He W T, Long Y H, Xu H H. Journal of Huanggang Normal University, 2020, 40(6), 67 (in Chinese). 何文涛, 龙雨宏, 徐花卉. 黄冈师范学院学报, 2020, 40(6), 67. 15 Wang J H, Xu Z Y, Zhang Y P, et al. Journal of Functional Materials, 2020, 51(11), 11152 (in Chinese). 王建航, 许志彦, 张玉鹏, 等. 功能材料, 2020, 51(11), 11152. 16 Standardization Administration of the People's Republic of China. Plastics—Determination of burning behaviour by oxygen index—Part 1: Guidance: GB/T 2406. 1-2008, China Standards Press, China, 2008 (in Chinese). 中国国家标准化管理委员会. 塑料用氧指数法测定燃烧行为第1部分:导则:GB/T 2406. 1-2008, 中国标准出版社, 2008. 17 Standardization Administration of the People's Republic of China. Plastics—Determination of burning characteristics: Horizontal and vertical test: GB/T2408-2008, China Standards Press, China, 2008 (in Chinese). 中国国家标准化管理委员会. 塑料燃烧性能的测定:水平法和垂直法:GB/T2408-2008, 中国标准出版社, 2008. 18 International Organization for Standardization. Reaction-to-fire tests-Heat release, smoke production and mass loss rate—Part 1:Heat release rate(cone calorimeter method): ISO5660-1-2002. International, 2002. 19 Ni Z, Wang Y H, Luo H W, et al. Chemistry and Adhesion, 2021, 43(1), 1(in Chinese). 倪卓, 王英浩, 罗汉伟, 等. 化学与粘合, 2021, 43(1), 1. 20 Ye X L, Xu Z Y, Hou Z M, et al. Materials Reports, 2022, 36(19), 222(in Chinese). 叶小林, 许志彦, 侯泽明, 等. 材料导报, 2022, 36(19), 222. 21 Zhang W C. The research on the mechanism and application of blowing-out flame retarded epoxy resins. Ph. D. Thesis, Beijing Institute of Technology, China, 2013 (in Chinese). 张文超. 吹熄阻燃环氧树脂机理及应用研究. 博士学位论文, 北京理工大学, 2013. 22 Chen S M. Synthesis of flame retardant based on phosphaphenanthrene and its application in epoxy resin. Master's Thesis, Guizhou Normal University, China, 2018 (in Chinese). 陈仕梅. 磷杂菲类阻燃剂的合成及在环氧树脂中的应用. 硕士学位论文, 贵州师范大学, 2018. 23 Liu Q Y, Liu C B, Peng X L. Plastics Science and Technology, 2021, 49(8), 39 (in Chinese). 刘全义, 刘传邦, 彭孝亮. 塑料科技, 2021, 49(8), 39. 24 Fan J J, Min Y, Yang J, et al. Materials Reports, 2021, 35(10), 10189 (in Chinese). 范娟娟, 闵样, 杨吉, 等. 材料导报, 2021, 35(10), 10189. 25 Lu Y Z, Geng H C, Shen J R, et al. Acta Materiae Compositae Sinica, 2023, 40(4), 2119(in Chinese). 陆亦洲, 耿海春, 沈金荣, 等.复合材料学报, 2023, 40(4), 2119. 26 You G Y, Cheng Z Q, Peng H, et al. Journal of Applied Polymer Science, 2015, 132(16), 1. 27 Zhang Q Q, Wang J, Yang S, et al. Composites Part B:Engineering, 2019, 177, 107380. 28 Peng X L, Li Z K, Wang D H, et al. Chemical Engineering Journal,2021, 424, 130404. 29 Tan Y, Shao Z B, Yu L X, et al. Polymer Chemistry, 2016, 7(17), 3003. 30 Carja L D, Serbezeanu D, Vladbubulac T, et al. Journal of Materials Chemistry A, 2014, 2(38), 16230.
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2023, Vol. 37 
