Abstract: In recent years, phosphaphenanthrene-based flame retardants have been extensively studied due to their good compatibility and flame retardancy. In this work, PLA/MAH-DOPS flame retardant composites were prepared by adding maleic anhydride-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide (MAH-DOPS) as flame retardant into polylactic acid (PLA), then the thermal degradation process was studied by TG/DTG method, finally the thermal degradation kinetic parameters, including the activation energy (E) and pre-exponential factor (A), the thermal degradation kinetic mechanism function and reaction order were calculated by Kissinger method, Flynn-Wall-Ozawa method and Coats-Redfern method. The results indicate that compared with pure PLA, the initial decomposition temperature(T5%), maximum thermal weight loss rate (Rmax) and peak temperature (TP) of PLA/MAH-DOPS are all decreased, while the carbon residue rate is increased. The thermal degradation kinetic parameters are EK(PLA)=174.02 kJ/mol, EO(PLA)=178.45 kJ/mol, lnAK(PLA)=31.90, EK(PLA/MAH-DOPS) =124.93 kJ/mol, EO(PLA/MAH-DOPS)=126.37 kJ/mol and lnAK(PLA/MAH-DOPS)=24.43. The mechanism functions of the thermal degradation of PLA and PLA/MAH-DOPS are both g(α)=[-ln(1-α)]3/4, with the reaction order n=3/4, and the thermal degradation mechanism is random nucleation and its subsequent growth.
作者简介: 叶小林,2019年7月毕业于贵州民族大学,获得理学学士学位。现为贵州民族大学化学工程学院硕士研究生,师从宝冬梅教授,目前主要研究领域为磷系阻燃材料。 宝冬梅,贵州民族大学化学工程学院教授。2003年于辽宁师范大学化学化工学院获得学士学位,2007年于贵州师范大学理学院获得硕士学位,同年到贵州民族大学任教至今,2013年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的研究。在Materials Letters、Chemical Physics Letters、Journal of Physics and Chemistry of Solids和《复合材料学报》等国内外期刊上发表论文30余篇。
引用本文:
叶小林, 许志彦, 侯泽明, 王建航, 谭芳, 张道海, 蔡晓东, 周国永, 吴中立, 宝冬梅. 聚乳酸/DOPS衍生物阻燃复合材料的非等温热降解动力学研究[J]. 材料导报, 2022, 36(19): 21090131-6.
YE Xiaolin, XU Zhiyan, HOU Zeming, WANG Jianhang, TAN Fang, ZHANG Daohai, CAI Xiaodong, ZHOU Guoyong, WU Zhongli, BAO Dongmei. Non-isothermal Thermal Degradation Kinetics of Polylactic Acid/DOPS Derivatives Flame Retardant Composites. Materials Reports, 2022, 36(19): 21090131-6.
1 Yu S L, Xiang H X, Zhou J L, et al. Progress in Natural Science:Mate-rials International, 2018,28(5), 590. 2 Lin Z N, Gou X M, He Z P, et al. Polymer Engineering & Science, 2021, 61(1), 201. 3 Yang Y F, Wang X G, Fei B, et al. Polymers for Advanced Technologies, 2021, 32(8), 3039. 4 Xu L F, Wu X D, Li L S, et al. Polymers for Advanced Technologies, 2019,30(6),1375. 5 Long L J, Chang Q F, He W T, et al. Polymer Degradation and Stability, 2017, 139, 55. 6 Wang L Q, Li L Y, Liang J, et al. Journal of Safety and Environment, 2021,21(3),1040 (in Chinese). 王丽琼, 李立影, 梁洁, 等. 安全与环境学报, 2021, 21(3), 1040. 7 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. 8 Chen S M, Lai F, Li P, et al. Acta Polymerica Sinica, 2017(8), 1358 (in Chinese). 陈仕梅, 来方, 李霈, 等. 高分子学报, 2017(8), 1358. 9 Wei K, Zhang D H, Qin S H, et al. Polymer Materials Science & Engineering, 2019,35(5), 184 (in Chinese). 魏柯, 张道海, 秦舒浩, 等. 高分子材料科学与工程, 2019, 35(5), 184. 10 Zhou Y, Zhang D H, Qin S H. Materials Reports A:Review Papers, 2019, 33(3), 901 (in Chinese). 周颖, 张道海, 秦舒浩. 材料导报:综述篇, 2019, 33(3), 901. 11 Liu P, Liu M M, Gao C, et al. Journal of Applied Polymer Science, 2013, 130(2), 1301. 12 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. 13 Zhao W. Synthesis of phosphorus-containing polymeric flame retardant and its flame retardant mechanism on epoxy resins. Ph.D. Thesis, Beijing Institute of Technology, China, 2016 (in Chinese). 赵伟. 聚合型磷基阻燃剂合成及对环氧树脂的阻燃机理研究. 博士学位论文,北京理工大学, 2016. 14 Lu L G, Zhang Q, Xu X N, et al. Polymer Materials Science & Enginee-ring, 2010,26(11), 39 (in Chinese). 卢林刚, 张晴, 徐晓楠, 等. 高分子材料科学与工程, 2010, 26(11), 39. 15 Kuang J Z, Liu P F, Luo D F, et al. Materials Reports B:Research Papers, 2018, 32(7), 2376 (in Chinese). 匡敬忠, 刘鹏飞, 罗大芳, 等.材料导报:研究篇, 2018, 32(7), 2376. 16 Ren Y, Cheng B, Zhang J, et al. Frontiers of Chemistry in China, 2009, 4(2), 136. 17 Li S T, Zhu Z H, Wen C, et al. China Plastics, 2016, 30(5), 13 (in Chinese). 李沈婷, 朱志华, 文超, 等.中国塑料, 2016, 30(5), 13. 18 Ding M H. Study on heat resistance and decomposition kinetics of nitrile rubber. Master's Thesis, Qingdao University of Science and Technology, China, 2019 (in Chinese). 丁明辉. 丁腈橡胶耐热性和分解动力学研究. 硕士学位论文, 青岛科技大学, 2019. 19 Lu L G, Han Z K, Yang S S, et al. Journal of Molecular Science, 2010, 26(4), 261 (in Chinese). 卢林刚, 韩中凯, 杨守生, 等. 分子科学学报, 2010, 26(4), 261. 20 Ren Y L, Wang Y L, Wang L J, et al. Construction and Building Mate-rials, 2015,76,273. 21 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. 22 Bao D M, Fang L, Wen Z, et al. Journal of Functional Materials, 2018, 49(11), 11089 (in Chinese). 宝冬梅, 方丽, 文竹, 等.功能材料, 2018, 49(11), 11089. 23 Ren Y L, Cheng B W, Xu L, et al. Acta Chimica Sinica, 2009, 67(18), 2127 (in Chinese). 任元林, 程博闻, 徐玲, 等.化学学报, 2009, 67(18), 2127.