DOPO衍生物改性碳纳米管的制备及对聚乳酸阻燃性能的影响  

Preparation of DOPO Derivative Modified Carbon Nanotubes and Their Effect on Flame Retardancy of Polylactic Acid

作　　者：高京 何文涛 王欣欣 向宇姝[2] 龙丽娟[2] 秦舒浩[2] GAO Jing;HE Wentao;WANG Xinxin;XIANG Yushu;LONG Lijuan;QIN Shuhao(Hubei Key Laboratory for Processing and Application of Catalytic Materials,Huanggang Normal University,Huanggang 438000,China;National Engineering Research Center for Compounding and Modifcation of Polymeric Materials,Guiyang 550014,China)

机构地区：[1]黄冈师范学院催化材料制备及应用湖北省重点实验室,黄冈438000 [2]国家复合改性聚合物材料工程技术研究中心,贵阳550014

出　　处：《高等学校化学学报》2022年第3期165-174,共10页Chemical Journal of Chinese Universities

基　　金：黄冈师范学院博士基金(批准号:2042019029);国家自然科学基金(批准号:22065008)资助。

摘　　要：以含羧基的碳纳米管(CNT-COOH)和9,10-二氢-9-氧-10-磷杂菲-10-氧化物(DOPO)衍生物DOPO-NH;为原料,通过酰氯化反应、缩合反应等制备了一种新型无机-有机杂化阻燃剂—DOPO衍生物改性碳纳米管(CNT-DOPO),利用傅里叶变换红外光谱、透射电子显微镜、X射线光电子能谱及热重分析等对其结构进行表征并对有机物接枝率进行了定量测试.结果表明,DOPO-NH;成功接枝到碳纳米管上,接枝率约为50%.将CNT-COOH,DOPO-NH;和CNT-DOPO以质量分数5%添加到聚乳酸(PLA)中制备阻燃PLA复合材料.锥形量热测试结果表明,与纯PLA相比,PLA/5CNT-COOH,PLA/5DOPO-NH;和PLA/5CNT-DOPO 3种复合材料的热释放速率峰值分别下降46%,3.4%和39.8%;炭层形貌和结构分析表明,PLA/5CNT-DOPO的炭层石墨化程度最高,CNT-DOPO;在凝聚相阻燃方面有明显的促进作用.流变结果表明,碳纳米管对黏弹转变影响很明显,PLA/5CNT-COOH和PLA/5CNT-DOPO基本上表现为弹性行为.正是由于碳纳米管的存在,使得PLA复合材料在低频区黏度增大,并且在燃烧后期形成了连续致密的炭层,有效降低了材料的热释放速率和烟释放.Using carboxyl carbon nanotubes(CNT-COOH)and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)derivative DOPO-NH;as raw materials,a new type of inorganic-organic hybrid flame retardant(CNT-DOPO)was prepared through acid chlorination and condensation reactions.The structure was characterized by Fourier transform infrared spectroscopy,transmission electron microscopy,X-ray photoelectron spectroscopy and thermogravimetric analysis,and the grafting rate was quantitatively tested.CNT-COOH,DOPO-NH;and CNT-DOPO were added to polylactic acid(PLA)in the same mass fraction of 5%to prepare flame-retardant PLA composites.The results showed that DOPO-NH;was successfully grafted onto carbon nanotubes with a grafting rate of about 50%.The cone calorimetric test results showed that the peak heat release rate of PLA/5CNT-COOH,PLA/5DOPO-NH;and PLA/5CNT-DOPO was 46%,3.4%,39.8%lower than that of pure PLA,respectively.The morphology and structure analysis of the char residues showed that the char layer of PLA/5CNT-DOPO had the highest degree of graphitization,and carbon nanotubes and DOPO-NH;had a certain promoting effect on the condensed phase flame retardancy.The rheological results showed that the addition of carbon nanotube had a great effect on the viscoelastic transition of PLA composites.PLA/5CNT-COOH and PLA/5CNT-DOPO basically exhibited elastic behavior.The addition of carbon nanotube or modified carbon nanotube increased the viscosity of PLA composites at low frequency,and promoted the formation of consistent and compact char layer in the later stage of combustion,Accordingly,the heat release rate and the smoke production of PLA composites decreased significantly.

关 键 词：聚乳酸 9 10-二氢-9-氧-10-磷杂菲-10-氧化物衍生物 碳纳米管 阻燃性能 

分 类 号：O631[理学—高分子化学]