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材料导报  2022, Vol. 36 Issue (19): 21090131-6    https://doi.org/10.11896/cldb.21090131
  高分子与聚合物基复合材料 |
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
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
贵州民族大学化学工程学院,贵阳 550025
Non-isothermal Thermal Degradation Kinetics of Polylactic Acid/DOPS Derivatives Flame Retardant Composites
YE Xiaolin, XU Zhiyan, HOU Zeming, WANG Jianhang, TAN Fang, ZHANG Daohai, CAI Xiaodong, ZHOU Guoyong, WU Zhongli, BAO Dongmei
School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China
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摘要 近年来,磷杂菲类阻燃剂因其良好的阻燃性和相容性等特点而被阻燃界学者们广泛研究。本工作以一种新型磷杂菲衍生物马来酸酐-9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(MAH-DOPS)为阻燃剂,将其添加到聚乳酸(PLA)中制备PLA/MAH-DOPS阻燃复合材料;再通过TG/DTG方法研究其热降解过程;最后采用Kissinger法、Flynn-Wall-Ozawa法和Coats-Redfern法对PLA和PLA/MAH-DOPS的非等温热降解动力学数据进行分析,求出热降解活化能(E)和指前因子(A),并推测出可能的热降解机理及其动力学方程。实验结果表明:与纯PLA相比,PLA/MAH-DOPS的初始分解温度(T5%)、最大热失重速率(Rmax)和峰温(TP)均降低,残炭量升高。热降解动力学参数分别为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,lnAK(PLA/MAH-DOPS)= 24.43;PLA和PLA/MAH-DOPS的热降解机理函数均为g(α)=[-ln(1-α)]3/4,反应级数n=3/4,热降解机理属于随机成核和随后生长反应。
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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
关键词:  磷杂菲衍生物  MAH-DOPS  聚乳酸  热降解动力学    
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.
Key words:  phosphaphenanthrene derivatives    MAH-DOPS    polylactic acid    thermal degradation kinetic
出版日期:  2022-10-10      发布日期:  2022-10-12
ZTFLH:  O631  
基金资助: 国家自然科学基金(51863004);贵州省省级科技计划项目(黔科合基础〔2020〕1Y211; 黔科合基础-ZK〔2021〕一般248);贵州省2018年度高层次创新型人才培养-千层次人才项目
通讯作者:  dongtian1314521@163.com   
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.
链接本文:  
http://www.mater-rep.com/CN/10.11896/cldb.21090131  或          http://www.mater-rep.com/CN/Y2022/V36/I19/21090131
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