磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究

陈仕梅; 来方; 李霈; 龚维; 付海; 尹晓刚; 班大明

doi:10.11777/j.issn1000-3304.2017.16350

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磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究

研究论文 | 更新时间：2021-01-26

- 磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究
- Synthesis of Flame Retardant Based on Phosphaphenanthrene and Flame Retardancy Study of Epoxy Resin Modified by Intumescent Flame Retardant System Composed of Ammonium Polyphosphate
- 高分子学报 2017年第8期页码：1358-1365
- 作者机构：
  
  贵州师范大学化学与材料科学学院贵阳 550001
- 作者简介：
  
  班大明, E-mail:bdaming@gznu.edu.cn Da-ming Ban, E-mail:bdaming@gznu.edu.cn
- 基金信息：
  
  国家自然科学基金(51273049);贵州省科技创新人才团队(项目号黔科合人才团队[2014]4006号);贵州省教育厅创新群体重大研究项目(项目号黔科合KY字[2016]025号)
- DOI：10.11777/j.issn1000-3304.2017.16350
  中图分类号：
- 纸质出版日期：2017-8，
  
  收稿日期：2016-12-5，
  
  修回日期：2017-1-15，
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陈仕梅, 来方, 李霈, 龚维, 付海, 尹晓刚, 班大明. 磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究[J]. 高分子学报, 2017,(8):1358-1365.

Chen Shi-mei, Lai Fang, Li Pei, Gong Wei, Fu Hai, Yin Xiao-gang, Ban Da-ming. Synthesis of Flame Retardant Based on Phosphaphenanthrene and Flame Retardancy Study of Epoxy Resin Modified by Intumescent Flame Retardant System Composed of Ammonium Polyphosphate[J]. Acta Polymerica Sinica, 2017,(8):1358-1365.
陈仕梅, 来方, 李霈, 龚维, 付海, 尹晓刚, 班大明. 磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究[J]. 高分子学报, 2017,(8):1358-1365. DOI： 10.11777/j.issn1000-3304.2017.16350.

Chen Shi-mei, Lai Fang, Li Pei, Gong Wei, Fu Hai, Yin Xiao-gang, Ban Da-ming. Synthesis of Flame Retardant Based on Phosphaphenanthrene and Flame Retardancy Study of Epoxy Resin Modified by Intumescent Flame Retardant System Composed of Ammonium Polyphosphate[J]. Acta Polymerica Sinica, 2017,(8):1358-1365. DOI： 10.11777/j.issn1000-3304.2017.16350.

摘要

以9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）、五硫化二磷（P

）为原料合成9，10-二氢-9-氧杂-10-磷杂菲-10-硫化物（DOPS），并将DOPS与聚磷酸铵（APP）组成复合阻燃剂，用于环氧树脂（EP）的阻燃改性.通过氧指数（LOI）、垂直燃烧（UL-94）、热失重（TGA）、锥形量热（CONE）和扫描电镜（SEM）等方法对改性后的环氧树脂的阻燃性能和阻燃机理进行了测试和分析.实验结果表明，DOPS/APP阻燃体系对EP具有很好的阻燃性能，且复配阻燃剂的阻燃效果比单一的阻燃剂阻燃效果好；其中，当阻燃剂的总添加量达到30%时即

DOPS

=10%、

APP

=20%时，阻燃EP复合材料的LOI值可达到29.2%，垂直燃烧等级达到UL-94 V-0级，残炭量可达49.3%.

Abstract

An novel phosphaphenanthrene derivative

6H-dibenzo[c

e] [1

oxaphosphinine-6-sulfide (DOPS)

was synthesized through the reaction of DOPO and phosphorus pentasulfide (P

). The structure of the synthesized compound was characterized and investigated by Fourier transform infrared spectroscopy (FTIR)

nuclear magnetic resonance (NMR)

hot stage melting point determination

and elemental analysis. This flame retardant was aimed at improving the flame retardancy of EP. The intumescent flame retardant (IFR)

composed of DOPS and ammonium polyphosphate (APP) at DOPS/APP ratio of 1:2

was added into EP to form a series of epoxy resin (FR-EP) modified by the flame retardants. The thermal stability was studied by thermal gravimetric analysis (TGA). Flame retardant properties as well as burning behavior of the epoxy resin composites were investigated by limited oxygen index (LOI) and vertical burning test (UL-94). Fire properties of the modified epoxy resin were tested by cone calorimeter. The morphological characteristics of the char residue after cone test were studied by scanning electron microscopy (SEM). DOPS/APP flame retardant increased not only the UL-94 grade but also the LOI value. It was also found that the EP modified by IFR still past UL94 V-0 rating

and its limited oxygen index value reached 29.2% when the flame retardant content was 30 wt%. TGA data indicated that the amount of the char residue at 700℃ was 49.33%. The cone experimental results showed that the values of av-HRR

pk-HRR

and av-EHC of the IFR-EP were lowered to 70%

79%

and 60% of those in the original EP

respectively. When the amount of DOPS was increased to 30 wt%

a high LOI value of 27.6% was obtained

the DOPS-modified EP could still pass UL94 V-0 rating. A series of comprehensive tests showed that DOPS/APP was effective flame retardant on epoxy resin and the flame retardant effect of the compound flame retardant was better than that of the single flame retardant. TGA

DTG

CONE

SEM comprehensive analysis revealed that epoxy resin modified by DOPS/APP was more thermo-stable compared to the pure epoxy. Filled with flame retardant

DOPS/APP-EP formed the continuous

intact and porous foam char layers after burning test. By covering the surface of the polymer

char layer prevented mass and heat exchange from circumstance.

关键词

DOPS合成阻燃性能

Keywords

6H-dibenzo[c e][1 2]oxaphosphinine-6-sulfideSynthesisFlame retardant properties

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