Flame-retardant Properties of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Derivatives in Poly(lactic acid)

Tong Zhang; Li-juan Long; Wen-tao He; Min He; Shu-hao Qin; Jie Yu

doi:10.11777/j.issn1000-3304.2018.18148

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Flame-retardant Properties of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Derivatives in Poly(lactic acid)

Research Article | 更新时间：2021-01-26

- Flame-retardant Properties of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Derivatives in Poly(lactic acid)
  增强出版
- Acta Polymerica Sinica Vol. 50, Issue 1, Pages: 71-81(2019)
- 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：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2018.18148
  CLC：
- Published：2019-1，
  
  Published Online：8 October 2018，
  
  Received：27 June 2018，
  
  Revised：13 August 2018，
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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 50(1):71-81(2019)
DOI：

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 50(1):71-81(2019) 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

references

Liu T, Jing J, Zhang Y, Fang Z P . RSC Adv , 2018 . 8 ( 8 ): 4483 - 4493 . DOI:10.1039/C7RA12582Hhttp://doi.org/10.1039/C7RA12582H .

Wen X, Gong J, Yu H O, Liu Z, Wan D, Liu J, Jiang Z W, Tang T . J Mater Chem , 2012 . 2 ( 37 ): 19974 - 19980.

Li S M, Ren J, Yuan H, Yu T, Yuan W Z . Polym Int , 2009 . 59 ( 2 ): 242 - 248.

Shi X W, Liao F H, Ju Y Q, Dai X, Cao Y, Li J W, Wang X L . Fire Mater , 2017 . 41 ( 4 ): 362 - 374 . DOI:10.1002/fam.v41.4http://doi.org/10.1002/fam.v41.4 .

Reddy M M, Vivekanandhan S, Misra M, Bhatia S K, Mohanty A K . Prog Polym Sci , 2013 . 38 1653 - 1689 . DOI:10.1016/j.progpolymsci.2013.05.006http://doi.org/10.1016/j.progpolymsci.2013.05.006 .

Xiong Y Q, Zhang X Y, Liu J, Li M M, Guo F, Xia X N, Xu W J . J Appl Polym Sci , 2012 . 125 ( 2 ): 1219 - 1225 . DOI:10.1002/app.v125.2http://doi.org/10.1002/app.v125.2 .

Shi Y Q, Yu B, Zheng Y Y, Yang J, Duan Z P, Hu Y . J Colloid Interface Sci , 2018 . 521 160 - 171 . DOI:10.1016/j.jcis.2018.02.054http://doi.org/10.1016/j.jcis.2018.02.054 .

Luo H, Zhou F, Yang Y Y, Cao X L, Cai X F . J Therm Analy Calorim , 2018 . 132 ( 1 ): 483 - 491 . DOI:10.1007/s10973-017-6898-8http://doi.org/10.1007/s10973-017-6898-8 .

Zhao Chunxia(赵春霞), Deng Limin(邓利民), Huang Zhiyu (黄志宇) . 高分子学报 , Acta Polymerica Sinica , 2015 . ( 4 ): 382 - 389.

Chen Shimei(陈仕梅), Lai Fang(来方), Li Pei(李霈), Gong Wei(龚维), Fu Hai(付海), Yin Xiaogang(尹晓刚), Ban Daming(班大明) . 高分子学报 , Acta Polymerica Sinica , 2017 . ( 8 ): 1358 - 1365.

Buczko A, Stelzig T, Bommer L, Rentsch D, Heneczkowski M, Gaan S . Polym Degrad Stab , 2014 . 107 158 - 165 . DOI:10.1016/j.polymdegradstab.2014.05.017http://doi.org/10.1016/j.polymdegradstab.2014.05.017 .

Butnaru I, Fernándezronco M P, Czechpolak J, Heneczkowski M, Bruma M, Gaan S . Polymers , 2015 . 7 ( 8 ): 1541 - 1563 . DOI:10.3390/polym7081469http://doi.org/10.3390/polym7081469 .

Liu C, Yao Q . Ind Eng Chem Res , 2017 . 53 ( 31 ): 8789 - 8796.

Ni P, Fang Y Y, Qian L J, Qiu Y . J Appl Polym Sci , 2018 . 135 ( 6 ): 45815 DOI:10.1002/app.45815http://doi.org/10.1002/app.45815 .

Schäfer A, Seibold S, Lohstroh W, Walter O, Döring M . J Appl Polym Sci , 2007 . 105 ( 2 ): 685 - 696 . DOI:10.1002/(ISSN)1097-4628http://doi.org/10.1002/(ISSN)1097-4628 .

Jing J, Zhang Y, Fang Z P . Polymer , 2017 . 108 29 - 37 . DOI:10.1016/j.polymer.2016.11.036http://doi.org/10.1016/j.polymer.2016.11.036 .

Zhao B, Chen L, Long J W, Chen H B, Wang Y Z . Ind Eng Chem Res , 2013 . 52 ( 8 ): 2875 - 2886 . DOI:10.1021/ie303446shttp://doi.org/10.1021/ie303446s .

Chang Q F, Long L J, He W T, Qin S H, Yu J . Thermochim Acta , 2016 . 639 84 - 90 . DOI:10.1016/j.tca.2016.07.006http://doi.org/10.1016/j.tca.2016.07.006 .

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Related Institution

College of Chemistry, Sichuan University

Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education and Xinjiang Uygur Autonomous Region, Xinjiang University

Xinjiang Institute of Light Industry Technology

College of Polymer Science and Engineering of Sichuan University, State Key Laboratory of Polymer Materials Engineering

Key Laboratory for Advanced Polymer Materials of Shanghai, School of Materials Science and Engineering, East China University of Science and Technology

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