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Thermal degradation mechanism and flame retardancy of epoxy systems containing tris(3-nitrophenyl) phosphine

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Abstract

The aim of this work was to study the effect of tris(3-nitrophenyl) phosphine (NPPh3), which showed a good thermal stability and carbon-forming ability, on the flame retardancy and thermal degradation mechanism of epoxy resins. A series of diglycidyl ether of bisphenol A (DGEBA) loaded with tris(3-nitrophenyl) phosphine (NPPh3) were prepared. It was found that NPPh3 can effectively improve the flame retardancy and thermal stability of the composites. When the loading amount of NPPh3 was 14%, the LOI value of the DGEBA composites was 29.2% (about 1.53 times the corresponding value of the original DGEBA resin). Thermal stability was studied by thermogravimetric analysis, and the results showed that the addition of NPPh3 can improve char formation of this system both in nitrogen and in air atmosphere. Specifically, its combustion residue at 800 °C in nitrogen atmosphere was about 4.26 times of the original resin. Differential scanning calorimetry indicated that NPPh3 slightly decreased the glass transition temperature of epoxy resins. Additionally, the gaseous degradation products were analyzed by thermogravimetric analysis/infrared spectrometry, providing insight into the thermal degradation mechanism. Scanning electron microscopy and Fourier transform infrared were brought together to evaluate the morphology and structure of the residual char obtained after combustion.

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References

  1. Hu J, Shan J, Zhao J, Tong Z. Isothermal curing kinetics of a flame retardant epoxy resin containing DOPO investigated by DSC and rheology. Thermochim Acta. 2016;632:56–63.

    Article  CAS  Google Scholar 

  2. Zhao W, Liu J, Peng H, Liao J, Wang X. Synthesis of a novel PEPA-substituted polyphosphoramide with high char residues and its performance as an intumescent flame retardant for epoxy resins. Polym Degrad Stab. 2015;118:120–9.

    Article  CAS  Google Scholar 

  3. Yang S, Wang J, Huo S, Wang J, Tang Y. Synthesis of a phosphorus/nitrogen-containing compound based on maleimide and cyclotriphosphazene and its flame-retardant mechanism on epoxy resin. Polym Degrad Stab. 2016;126:9–16.

    Article  CAS  Google Scholar 

  4. Zhang T, Liu W, Wang M, Liu P, Pan Y, Liu D. Synergistic effect of an aromatic boronic acid derivative and magnesium hydroxide on the flame retardancy of epoxy resin. Polym Degrad Stab. 2016;130:257–63.

    Article  CAS  Google Scholar 

  5. Zhang W, Fina A, Cuttica F, Camino G, Yang R. Blowing-out effect in flame retarding epoxy resins: insight by temperature measurements during forced combustion. Polym Degrad Stab. 2016;131:82–90.

    Article  CAS  Google Scholar 

  6. Liu S, Fang Z, Yan H, Chevali VS, Wang H. Synergistic flame retardancy effect of graphene nanosheets and traditional retardants on epoxy resin. Compos A Appl Sci Manuf. 2016;89:26–32.

    Article  CAS  Google Scholar 

  7. Huo S, Wang J, Yang S, Wang J, Zhang B, Zhang B, Chen X, Tang Y. Synthesis of a novel phosphorus-nitrogen type flame retardant composed of maleimide, triazine-trione, and phosphaphenanthrene and its flame retardant effect on epoxy resin. Polym Degrad Stab. 2016;131:106–13.

    Article  CAS  Google Scholar 

  8. Tan Y, Shao ZB, Yu LX, Xu YJ, Rao WH, Chen L, Wang YZ. Polyethyleneimine modified ammonium polyphosphate toward polyamine-hardener for epoxy resin: thermal stability, flame retardance and smoke suppression. Polym Degrad Stab. 2016;131:62–70.

    Article  CAS  Google Scholar 

  9. Wang S, Xin F, Chen Y, Qian L, Chen Y. Phosphorus-nitrogen containing polymer wrapped carbon nanotubes and their flame-retardant effect on epoxy resin. Polym Degrad Stab. 2016;129:133–41.

    Article  CAS  Google Scholar 

  10. Zhang M, Luo Z, Zhang J, Chen S, Zhou Y. Effects of a novel phosphorus–nitrogen flame retardant on rosin-based rigid polyurethane foams. Polym Degrad Stab. 2015;120:427–34.

    Article  CAS  Google Scholar 

  11. Xu GR, Xu MJ, Li B. Synthesis and characterization of a novel epoxy resin based on cyclotriphosphazene and its thermal degradation and flammability performance. Polym Degrad Stab. 2014;109(109):240–8.

    Article  CAS  Google Scholar 

  12. Ding J, Tao Z, Fan L, Yang S. Preparation and characterization of flame retardant epoxy resins based on phosphorus-containing biphenyl-type phenolic resin. e-Polymers. 2010;10(1):1372–84.

    Article  Google Scholar 

  13. Sun S, He Y, Wang X, Wu D. Flammability characteristics and performance of halogen-free flame-retarded polyoxymethylene based on phosphorus–nitrogen synergistic effects. J Appl Polym Sci. 2010;118(1):611–22.

    Article  CAS  Google Scholar 

  14. Xiao L, Sun D, Niu T, Yao Y. Syntheses and characterization of two novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-based flame retardants for epoxy resin. Appl Phys A. 2014;118(4):1365–70.

    Google Scholar 

  15. Zhang X, Zhong Y, Mao ZP. The flame retardancy and thermal stability properties of poly (ethylene terephthalate)/hexakis (4-nitrophenoxy) cyclotriphosphazene systems. Polym Degrad Stab. 2012;97(8):1504–10.

    Article  CAS  Google Scholar 

  16. Wang SB, Wang LS. Synthesis and application of triphenylphosphine and its derivates. Mod Chem Ind. 2006;26(6):66–9.

    Google Scholar 

  17. Agrawal S, Narula AK. Synthesis and characterization of phosphorus containing aromatic poly(amide-imide)s copolymers for high temperature applications. Polym Bull. 2013;70(12):3241–60.

    Article  CAS  Google Scholar 

  18. Bai CY, Tang XD, Chen XT, Zhang JH. Synthesis and characterization of bis(3-aminophenyl)phenyl phosphine oxide. Chem Reag. 2010;32(5):470–2.

    CAS  Google Scholar 

  19. Chen X, Ma C, Jiao C. Enhancement of flame-retardant performance of thermoplastic polyurethane with the incorporation of aluminum hypophosphite and iron-graphene. Polym Degrad Stab. 2016;129:275–85.

    Article  CAS  Google Scholar 

  20. Yang Y, Liu J, Cai X. Antagonistic flame retardancy between hexakis(4-nitrophenoxy) cyclotriphosphazene and potassium diphenylsulfone sulfonate in the PC system. J Therm Anal Calorim. 2016;126(2):571–83.

    Article  CAS  Google Scholar 

  21. Xu MJ, Ma Y, Hou MJ, Li B. Synthesis of a cross-linked triazine phosphine polymer and its effect on fire retardancy, thermal degradation and moisture resistance of epoxy resins. Polym Degrad Stab. 2015;119:14–22.

    Article  CAS  Google Scholar 

  22. Bao X, Cai X. Synergistic effect of methyl phenyl silicone resin and DOPO on the flame retardancy of epoxy resins. J Therm Anal Calorim. 2014;118(1):369–75.

    Article  CAS  Google Scholar 

  23. Xu MJ, Xu GR, Leng Y, Li B. Synthesis of a novel flame retardant based on cyclotriphosphazene and DOPO groups and its application in epoxy resins. Polym Degrad Stab. 2016;123:105–14.

    Article  CAS  Google Scholar 

  24. Zhang L, Wang Y, Liu Q, Cai X. Synergistic effects between silicon-containing flame retardant and DOPO on flame retardancy of epoxy resins. J Therm Anal Calorim. 2016;123(2):1–8.

    CAS  Google Scholar 

  25. Yang S, Wang J, Huo S, Cheng L, Wang M. Preparation and flame retardancy of an intumescent flame-retardant epoxy resin system constructed by multiple flame-retardant compositions containing phosphorus and nitrogen heterocycle. Polym Degrad Stab. 2015;119:251–9.

    Article  CAS  Google Scholar 

  26. Ding H, Wang J, Wang C, Chu F. Synthesis of a novel phosphorus and nitrogen-containing bio-based polyols and its application in flame retardant polyurethane sealant. Polym Degrad Stab. 2016;124:43–50.

    Article  CAS  Google Scholar 

  27. Zhang T, Liu W, Wang M, Liu P, Pan Y, Liu D. Synthesis of a boron/nitrogen-containing compound based on triazine and boronic acid and its flame retardant effect on epoxy resin. High Perform Polym. 2016;29(5):513–23.

    Article  CAS  Google Scholar 

  28. Zhang L, Wang Y, Cai X. Effect of a novel polysiloxane-containing nitrogen on the thermal stability and flame retardancy of epoxy resins. J Therm Anal Calorim. 2016;124(2):791–8.

    Article  CAS  Google Scholar 

  29. Xu W, Wirasaputra A, Liu S, Yuan Y, Zhao J. Highly effective flame retarded epoxy resin cured by DOPO-based co-curing agent. Polym Degrad Stab. 2015;122:44–51.

    Article  CAS  Google Scholar 

  30. Wang P, Yang F, Li L, Cai Z. Flame retardancy and mechanical properties of epoxy thermosets modified with a novel DOPO-based oligomer. Polym Degrad Stab. 2016;129:156–67.

    Article  CAS  Google Scholar 

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Correspondence to Xufu Cai.

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Luo, H., Yang, Y., Cao, X. et al. Thermal degradation mechanism and flame retardancy of epoxy systems containing tris(3-nitrophenyl) phosphine. J Therm Anal Calorim 132, 1629–1637 (2018). https://doi.org/10.1007/s10973-018-7081-6

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  • DOI: https://doi.org/10.1007/s10973-018-7081-6

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