9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物阻燃聚乳酸的性能研究

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英文篇名：Flame-retardant Properties of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Derivatives in Poly(lactic acid) 作者：张通 ; 龙丽娟 ; 何文涛 ; 何敏 ; 秦舒浩 ; 于杰 英文作者：Tong Zhang;Li-juan Long;Wen-tao He;Min He;Shu-hao Qin;Jie Yu;College of Materials and Metallurgy,Guizhou University;National Engineering Research Center for Compounding and Modification of Polymer Materials; 关键词：阻燃 ; 聚乳酸 ; 9 ; 10-二氢-9-氧杂-10-磷杂菲-10-甲醇10-氧化物(ODOPM) ; 10-(2 ; 5-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ) 英文关键词：Flame retardant;;PLA;;ODOPM;;2-(6-Oxido-6H-dibenz<1,2>oxaphosphorin-6-yl)-methanol 中文刊名：GFXB 英文刊名：Acta Polymerica Sinica 机构：贵州大学材料与冶金学院;国家复合改性聚合物材料工程技术研究中心; 出版日期：2018-10-08 11:56 出版单位：高分子学报 年：2019 期：v.50 基金：黔科合成果(项目号[2018]4210);; 黔科合基础(项目号[2018]1088);; 国家自然科学基金(基金号51463006);; 白云区项目(项目号[2016]11)资助 语种：中文; 页：GFXB201901008 页数：11 CN：01 ISSN：11-1857/O6 分类号：79-89

摘要

通过甲醛与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)反应合成出含羟基的DOPO衍生物9,10-二氢-9-氧杂-10-磷杂菲-10-甲醇10-氧化物(ODOPM).采用傅里叶变换红外光谱(FTIR),核磁共振谱(1HNMR,31P-NMR)以及质谱分析(MS)确定了其结构,同时研究了ODOPM对聚乳酸(PLA)阻燃性能与热性能的影响,并与10-(2,5-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)进行了比较.通过热重分析(TG)、氧指数(LOI)、垂直燃烧(UL-94)和锥形量热(CCT)等研究了2种阻燃剂对PLA阻燃性能及热降解行为的影响,发现2种阻燃剂都能降低材料的热释放峰值(PHRR),提高复合材料的热稳定性和残炭量,然而PLA/ODOPM相对于PLA/DOPO-HQ具有更高的氧指数和燃烧等级. PLA加入5%的ODOPM时就能达到V-0级,加入15%时,氧指数能达到34.4%,而DOPO-HQ加入量为15%时才能达到V-0,LOI值也仅仅28.8%.扫描电镜和拉曼对炭层的分析表明DOPO-HQ复合材料能够形成更加完整致密的炭层,因此具有更好的固相阻燃作用,此外TG-FTIR表明2种阻燃剂都能起到气相阻燃作用. X射线能量色谱(EDS)发现2种复合材料炭层中具有较高的P含量,这可能是炭层中形成了大量的聚磷酸酯.最后流变分析表明ODOPM会降低PLA的复数黏度,且PLA/ODOPM黏度远低于PLA/DOPO-HQ.
        2-(6-Oxido-6H-dibenz<1,2>oxaphosphorin-6-yl)-methanol(ODOPM) was synthesized by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide(DOPO) with methanal,and its structure was characterized by FTIR,~1H-NMR,~(31)P-NMR and MS.The flame-retardant performance of ODOPM in poly(lactic acid)(PLA) was explored and compared with those of 2-(6-oxido-6H-dibenz<1,2>oxaphosphorin-6-yl)-1,4-benzenediol(DOPO-HQ).The flame-retardant properties of PLA-based ODOPM and DOPO-HQ were further investigated by determining the limiting oxygen index(LOI) as well as conducting vertical burning(UL-94) and cone calorimeter tests;their thermal-degradation behavior was studied by thermogravimetric analysis(TG)measurements.The results indicated that both flame retardants could decrease the peak heat release rate(PHRR),improve LOI,and promote the thermal stability and char formation.At flame-retardant content of 15 wt%,PHRR was decreased from 571 kW/m~2 of the neat PLA to ～ 430 kW/m~2 for both PLA/ODOPM and PLA/DOPO-HQ composites,while the former showed a high LOI of 34.4%,72% increase compared with neat PLA(LOI of 20%).Moreover,V-0 rating in UL-94 test was achieved by PLA/ODOPM composite with filler concentration at 5 wt%,but PLA/DOPO-HQ required 15 wt% filler to reach the same rating with only 28.8% for LOI.In addition,all the flame retardant PLA systems decomposed earlier than neat PLA under N2 condition,but the incorporation of ODOPM could increase the maximum degradation temperaeture(T_(max)).Especially,T_(max) of PLA containing 5 wt%ODOPM was 18 °C higher than that of neat PLA.However,PLA/ODOPM had generally lower T_(max) than neat PLA did unless the fill concentration reached 15 wt%.Characterization of char morphology by Raman spectroscopy and scanning electron microscopy(SEM) showed that incorporation of DOPO-HQ was conducive to the formation of a compact cross-linked char layer.TG-FTIR results suggested that both two flame retardants exerted a gas-phase-flame inhibition effect.Energy-dispersive spectroscopy(EDS) demonstrated an increased P content in the carbon layer along with the increasing flame-retardant content,possibly attributed to polyphosphate formation.Rheological analysis indicated that PLA/ODOPM possessed weaker viscoelasticity compared with PLA/DOPO-HQ.Finally,the mechanical measurements on neat PLA and PLA composites,including tensile strength,flexural strength,and notch impact strength,showed that PLA/DOPO-HQ possessed better mechanical properties than PLA/ODOPM did.

引文

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