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

张通; 龙丽娟; 何文涛; 何敏; 秦舒浩; 于杰

doi:10.11777/j.issn1000-3304.2018.18148

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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

研究论文 | 更新时间：2021-01-26

- 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
  增强出版
- Flame-retardant Properties of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Derivatives in Poly(lactic acid)
- 高分子学报 2019年50卷第1期页码：71-81
- 作者机构：
  
  1.贵州大学材料与冶金学院　贵阳 550025
  2.国家复合改性聚合物材料工程技术研究中心　贵阳 550014
- 作者简介：
  
  E-mail: longlijuan.2006@aliyun.com Li-juan Long, E-mails:longlijuan.2006@aliyun.com
  E-mail: yujiegz@126.com Jie Yu,E-mail: yujiegz@126.com
- 基金信息：
  
  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)和白云区项目(项目号 [2016]11)资助()
- DOI：10.11777/j.issn1000-3304.2018.18148
  中图分类号：
- 纸质出版日期：2019-1，
  
  网络出版日期：2018-10-8，
  
  收稿日期：2018-6-27，
  
  修回日期：2018-8-13，
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张通, 龙丽娟, 何文涛, 何敏, 秦舒浩, 于杰. 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[J]. 高分子学报, 2019,50(1):71-81.

Tong Zhang, Li-juan Long, Wen-tao He, Min He, Shu-hao Qin, Jie Yu. Flame-retardant Properties of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Derivatives in Poly(lactic acid)[J]. Acta Polymerica Sinica, 2019,50(1):71-81.
张通, 龙丽娟, 何文涛, 何敏, 秦舒浩, 于杰. 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[J]. 高分子学报, 2019,50(1):71-81. DOI： 10.11777/j.issn1000-3304.2018.18148.

Tong Zhang, Li-juan Long, Wen-tao He, Min He, Shu-hao Qin, Jie Yu. Flame-retardant Properties of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Derivatives in Poly(lactic acid)[J]. Acta Polymerica Sinica, 2019,50(1):71-81. DOI： 10.11777/j.issn1000-3304.2018.18148.

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(

H-NMR，

P-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.

Abstract

2-(6-Oxido-6

-dibenz

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

H-NMR

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-6

-dibenz

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

of the neat PLA to ~ 430 kW/m

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 N

condition

but the incorporation of ODOPM could increase the maximum degradation temperaeture (

max

). Especially

max

of PLA containing 5 wt% ODOPM was 18 °C higher than that of neat PLA. However

PLA/ODOPM had generally lower

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.

关键词

阻燃聚乳酸910-二氢-9-氧杂-10-磷杂菲-10-甲醇10-氧化物(ODOPM)10-(25-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)

Keywords

Flame retardantPLAODOPM2-(6-Oxido-6H-dibenz<ce><12>oxaphosphorin-6-yl)-methanol

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