Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin

Miao-Jun Xu; Si-Yu Xia; Chuan Liu; Bin Li

doi:10.1007/s10118-018-2036-8

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Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin

Articles | Updated：2021-02-18

- Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin
- Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin
- Chinese Journal of Polymer Science 2018年36卷第5期页码：655-664
- Affiliations：
  
  Heilongjiang Key Laboratory of Molecular Design and Preparation of Flame Retarded Materials, College of Science, Northeast Forestry University, Harbin 150040, China
- Author bio：
  
  Bin Li, E-mail libinzh62@163.com
- Funds：
- DOI：10.1007/s10118-018-2036-8
  中图分类号：
- 收稿：2017-08-03，
  
  录用：2017-9-6，
  
  网络首发：2018-01-18，
  
  纸质出版：2018-05-05
- Accepted：
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Miao-Jun Xu, Si-Yu Xia, Chuan Liu, 等. Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin[J]. Chinese Journal of Polymer Science, 2018,36(5):655-664.

Miao-Jun Xu, Si-Yu Xia, Chuan Liu, et al. Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin[J]. Chinese Journal of Polymer Science, 2018, 36(5): 655-664.
Miao-Jun Xu, Si-Yu Xia, Chuan Liu, 等. Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin[J]. Chinese Journal of Polymer Science, 2018,36(5):655-664. DOI： 10.1007/s10118-018-2036-8.

Miao-Jun Xu, Si-Yu Xia, Chuan Liu, et al. Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin[J]. Chinese Journal of Polymer Science, 2018, 36(5): 655-664. DOI： 10.1007/s10118-018-2036-8.

摘要

Abstract

A phosphorus-nitrogen containing flame retardant additive of poly(phosphoric acid piperazine)

defined as PPAP

was synthesized by the salt-forming reaction between anhydrous piperazine and phosphoric acid

and the dehydration polymerization under heating in nitrogen atmosphere. Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy

C and

P solid-state nuclear magnetic resonance measurements. The synthesized PPAP and curing agent

-phenylenediamine were blended into epoxy resin (EP) to prepare flame retardant EP thermosets. The effects of PPAP on the fire retardancy and thermal degradation behavior of cured EP/PPAP composites were investigated by limiting oxygen index (LOI)

vertical burning (UL-94)

thermogravimetric analysis/infrared spectrometry (TG-IR) and cone calorimeter tests. The morphologies and chemical compositions of char residues for cured epoxy resin were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS)

respectively. The results demonstrated that the flame retardant EP thermosets successfully passed UL-94 Ⅴ-0 flammability rating and the LOI value was as high as 30.8% when incorporating 5wt% PPAP into the EP thermosets. The TGA results indicated that the synthesized PPAP flame retardant additive possessed high thermal stability and excellent charring capability. Meanwhile

the incorporation of PPAP stimulated the epoxy resin matrix to decompose and charring ahead of time due to its catalytic decomposition effect

which led to a higher char yield at high temperature. The morphological structures and the analysis results of XPS for char residues of EP thermosets revealed that the introduction of PPAP benefited the formation of a sufficient

more compact and homogeneous char layer containing phosphorus-nitrogen flame retardant elements on the material surface during combustion. The formed char layer with high quality effectively prevented the heat transmission and diffusion

limited the production of combustible gases

and inhibited the emission of smoke

leading to the reduction of heat and smoke release.

关键词

Keywords

references

X. Wang , L. Song , W. Y. Xing , H. D. Lu , Y. Hu . An effective flame retardant for epoxy resins based on poly(DOPO substituted dihydroxyl phenyl pentaerythritol diphosphonate) . Mater. Chem. Phys. , 2011 . 125 ( 3 ): 536 - 541 . DOI: 10.1016/j.matchemphys.2010.10.020 http://doi.org/10.1016/j.matchemphys.2010.10.020 .

Z. K. Chen , G. Yang , J. P. Yang , S. Y. Fu , L. Ye , Y. G. Huang . Simultaneously increasing cryogenic strength, ductility and impact resistance of epoxy resins modified by n -butyl glycidyl ether . Polymer , 2009 . 50 ( 5 ): 1316 - 1323 . DOI: 10.1016/j.polymer.2008.12.048 http://doi.org/10.1016/j.polymer.2008.12.048 .

A. Toldy , A. Szabó , C. Novák , J. Madarász , A. Tóth , G. Marosi . MarosiIntrinsically flame retardant epoxy resin-fire performance and background-Part Ⅱ . Polym. Degrad. Stab. , 2008 . 93 ( 11 ): 2007 - 2013 . DOI: 10.1016/j.polymdegradstab.2008.02.011 http://doi.org/10.1016/j.polymdegradstab.2008.02.011 .

M. Gao , W. H. Wu , Z. Q. Xu . Thermal degradation behaviors and flame retardancy of epoxy resins with novel silicon-containing flame retardant . J. Appl. Polym. Sci. , 2013 . 127 ( 3 ): 1842 - 1847 . DOI: 10.1002/app.37909 http://doi.org/10.1002/app.37909 .

B. K. Kandola , B. Biswas , D. Price , A. R. Horrocks . Studies on the effect of different levels of toughener and flame retardants on thermal stability of epoxy resin . Polym. Degrad. Stab. , 2010 . 95 ( 2 ): 144 - 153 . DOI: 10.1016/j.polymdegradstab.2009.11.040 http://doi.org/10.1016/j.polymdegradstab.2009.11.040 .

S. V. Levchik , E. D. Weil . A review of recent progress in phosphorus-based flame retardants . J. Fire Sci. , 2006 . 24 ( 5 ): 345 - 364 . DOI: 10.1177/0734904106068426 http://doi.org/10.1177/0734904106068426 .

H. T. Lin , C. H. Lin , Y. M. Hu , W. C. Su . An approach to develop high- T g epoxy resins for halogen-freecopper clad laminates . Polymer , 2009 . 50 ( 24 ): 5685 - 5692 . DOI: 10.1016/j.polymer.2009.09.075 http://doi.org/10.1016/j.polymer.2009.09.075 .

U. Braun , A. I. Balabanovich , B. Schartel , U. Knoll , J. Artner , M. Ciesielski , T. Hoffmann . Influence of the oxidation state of phosphorus on the decomposition and fire behaviour of flame-retarded epoxy resin composites . Polymer , 2006 . 47 8495 - 8508 . DOI: 10.1016/j.polymer.2006.10.022 http://doi.org/10.1016/j.polymer.2006.10.022 .

H. Ren , J. Z. Sun , B. J. Wu , Q. Y. Zhou . Synthesis and properties of a phosphorus-containing flame retardant epoxy resin based on bis-phenoxy(3-hydroxy) phenyl phosphine oxide . Polym. Degrad. Stab. , 2007 . 92 ( 6 ): 956 - 961 . DOI: 10.1016/j.polymdegradstab.2007.03.006 http://doi.org/10.1016/j.polymdegradstab.2007.03.006 .

Y. Li , H. B. Zheng , M. J. Xu , B. Li , T. Lai . Synthesis of a novel phosphonate flame retardant and its application in epoxy resins . J. Appl. Polym. Sci. , 2015 . 132 ( 45 ): 13085 - 13094 . http://onlinelibrary.wiley.com/doi/10.1002/app.42765/pdf http://onlinelibrary.wiley.com/doi/10.1002/app.42765/pdf , .

M. J. Xu , G. R. Xu , Y. Leng , B. Li . Synthesis of a novel flame retardant based on cyclotriphosphazene and DOPO groups and its application in epoxy resins . Polym. Degrad. Stab. , 2016 . 123 105 - 114 . DOI: 10.1016/j.polymdegradstab.2015.11.018 http://doi.org/10.1016/j.polymdegradstab.2015.11.018 .

M. J. Xu , W. Zhao , B. Li . Synthesis of a novel curing agent containing organophosphorus and its application in flame-retarded epoxy resins . J. Appl. Polym. Sci. , 2014 . 131 ( 23 ): 12406 - 12417 . http://onlinelibrary.wiley.com/doi/10.1002/app.41159/pdf http://onlinelibrary.wiley.com/doi/10.1002/app.41159/pdf , .

C. Martin , G. Lligadas , J. C. Ronda , M. Galia , V. Cadiz . Synthesis of novel boron-containing epoxy-novolac resins and properties of cured products . J. Polym. Sci., Part A:Polym. Chem. , 2006 . 44 ( 21 ): 6332 - 6344 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .

M. Dogan , S. M. Unlu . Flame retardant effect of boron compounds on red phosphorus containing epoxy resins . Polym. Degrad. Stab. , 2014 . 99 12 - 17 . DOI: 10.1016/j.polymdegradstab.2013.12.017 http://doi.org/10.1016/j.polymdegradstab.2013.12.017 .

T. Zhang , W. Liu , M. Wang , P. Liu , Y. Pan , D. Liu . 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 . DOI: 10.1177/0954008316650929 http://doi.org/10.1177/0954008316650929 .

S. M. Unlu , S. D. Dogan , M. Dogan . Comparative study of boron compounds and aluminum trihydroxide as flame retardant additives in epoxy resin . Polym. Adv. Technol. , 2014 . 25 ( 8 ): 769 - 776 . DOI: 10.1002/pat.3274 http://doi.org/10.1002/pat.3274 .

J. Canadell , A. Mantecon , V. Cadiz . Copolymerization of a silicon-containing spiroorthoester with a phosphorus-containing diglycidyl compound:influence on flame retardancy and shrinkage . Polym. Degrad. Stab. , 2007 . 92 ( 10 ): 1934 - 1941 . DOI: 10.1016/j.polymdegradstab.2007.06.019 http://doi.org/10.1016/j.polymdegradstab.2007.06.019 .

L. A. Mercado , M. Galia , J. A. Reina . Silicon-containing flame retardant epoxy resins:synthesis, characterization and properties . Polym. Degrad. Stab. , 2006 . 91 ( 11 ): 2588 - 2594 . DOI: 10.1016/j.polymdegradstab.2006.05.007 http://doi.org/10.1016/j.polymdegradstab.2006.05.007 .

S. Song , J. Ma , K. Cao , G. Chang , Y. Huang , J. Yang . Synthesis of a novel dicyclic silicon-/phosphorus hybrid and its performance on flame retardancy of epoxy resin . Polym. Degrad. Stab. , 2014 . 99 43 - 52 . DOI: 10.1016/j.polymdegradstab.2013.12.013 http://doi.org/10.1016/j.polymdegradstab.2013.12.013 .

X. Qian , L. Song , Y. Bihe , B. Yu , Y. Shi , Y. Hu , R. K. Yuen . Organic/inorganic flame retardants containing phosphorus, nitrogen and silicon:preparation and their performance on the flame retardancy of epoxy resins as a novel intumescent flame retardant system . Mater. Chem. Phys. , 2014 . 143 ( 3 ): 1243 - 1252 . DOI: 10.1016/j.matchemphys.2013.11.029 http://doi.org/10.1016/j.matchemphys.2013.11.029 .

S. Wang , F. Xin , Y. Chen , L. Qian , Y. Chen . Phosphorus-nitrogen containing polymer wrapped carbon nanotubes and their flame-retardant effect on epoxy resin . Polym. Degrad. Stab. , 2016 . 129 133 - 141 . DOI: 10.1016/j.polymdegradstab.2016.04.011 http://doi.org/10.1016/j.polymdegradstab.2016.04.011 .

X. H. Zhang , F. Liu , S. Chen , G. R. Qi . Novel flame retardant thermosets from nitrogen-containing and phosphorus-containing epoxy resins cured with dicyandiamide . J. Appl. Polym. Sci. , 2007 . 106 ( 4 ): 2391 - 2397 . DOI: 10.1002/(ISSN)1097-4628 http://doi.org/10.1002/(ISSN)1097-4628 .

L. Gu , G. Chen , Y. Yao . Two novel phosphorus-nitrogen-containing halogen-free flame retardants of high performance for epoxy resin . Polym. Degrad. Stab. , 2014 . 108 68 - 75 . DOI: 10.1016/j.polymdegradstab.2014.05.030 http://doi.org/10.1016/j.polymdegradstab.2014.05.030 .

J. Artner , M. Ciesielski , O. Walter , M. Doring , R. M. Perez , J. K. W. Sandler , V. Altstadt , B. Schartel . A novel DOPO-based diamine as hardener and flame retardant for epoxy resin systems . Macromol. Mater. Eng. , 2008 . 293 ( 6 ): 503 - 514 . DOI: 10.1002/(ISSN)1439-2054 http://doi.org/10.1002/(ISSN)1439-2054 .

M. J. Alcon , G. Ribera , M. Galia , V. Cadiz . Advanced flame retardant epoxy resins from phosphorus-containing diol . J. Polym. Sci., Part A:Polym. Chem. , 2005 . 43 3510 - 3515 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .

S. Y. Lu , I. Hamerton . Recent developments in the chemistry of halogen-free flame retardant polymers . Prog. Polym. Sci. , 2002 . 27 1661 - 1712 . DOI: 10.1016/S0079-6700(02)00018-7 http://doi.org/10.1016/S0079-6700(02)00018-7 .

S. Duquesne , J. Lefebvre , G. Seeley , G. Camino , R. Delobel , M. Lebras . Vinyl acetate/butyl acrylate copolymers:Part 2:fire retardancy using phosphorus-containing additives and monomers . Polym. Degrad. Stab. , 2004 . 85 ( 2 ): 883 - 892 . DOI: 10.1016/j.polymdegradstab.2004.04.004 http://doi.org/10.1016/j.polymdegradstab.2004.04.004 .

B. Perret , B. Schartel , K. Stöß , M. Ciesielski , J. Diederichs , M. Döring , J. Krämer , V. Altstädt . A new halogen-free flame retardant based on 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide for epoxy resins and their carbon fiber composites for the automotive and aviation industries . Macromol. Mater. Eng. , 2011 . 296 14 - 30 . DOI: 10.1002/mame.v296.1 http://doi.org/10.1002/mame.v296.1 .

S. Yang , J. Wang , S. Huo , M. Wang , Y. Tang . 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 . DOI: 10.1016/j.polymdegradstab.2016.01.011 http://doi.org/10.1016/j.polymdegradstab.2016.01.011 .

S. Yang , J. Wang , S. Huo , M. Wang . Preparation and flame retardancy of a compounded epoxy resin system composed of phosphorus/nitrogen-containing active compounds . Polym. Degrad. Stab. , 2015 . 121 398 - 406 . DOI: 10.1016/j.polymdegradstab.2015.10.006 http://doi.org/10.1016/j.polymdegradstab.2015.10.006 .

M. Gao , S. S. Yang . A novel intumescent flame-retardant epoxy resins system . J. Appl. Polym. Sci. , 2010 . 113 ( 4 ): 2346 - 2351 . https://www.researchgate.net/publication/243894937_A_Novel_Intumescent_Flame-Retardant_Epoxy_Resins_System https://www.researchgate.net/publication/243894937_A_Novel_Intumescent_Flame-Retardant_Epoxy_Resins_System , .

M. J. Xu , Y. Ma , M. J. Hou , B. Li . 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 . DOI: 10.1016/j.polymdegradstab.2015.04.027 http://doi.org/10.1016/j.polymdegradstab.2015.04.027 .

K. Yang , M. J. Xu , B. Li . Synthesis of N-ethyl triazine-piperazine copolymer and flame retardancy and water resistance of intumescent flame retardant polypropylene . Polym. Degrad. Stab. , 2013 . 98 ( 7 ): 1397 - 1406 . DOI: 10.1016/j.polymdegradstab.2013.03.023 http://doi.org/10.1016/j.polymdegradstab.2013.03.023 .

Y. Tan , Z. B. Shao , L. X. Yu , J. W. Long , M. Qi , L. Chen , Y. Z. Wang . Piperazine-modified ammonium polyphosphate as monocomponent flame-retardant hardener for epoxy resin:flame retardance, curing behavior and mechanical property . Polym. Chem. , 2016 . 7 ( 17 ): 3003 - 3012 . DOI: 10.1039/C6PY00434B http://doi.org/10.1039/C6PY00434B .

T. M. Nguyen , S. C. Chang , B. Condon , T. P. Thomas , P. Azadi . Thermal decomposition reactions of cotton fabric treated with piperazine-phosphonates derivatives as a flame retardant . J. Anal. Appl. Pyrolysis. , 2014 . 110 122 - 129 . DOI: 10.1016/j.jaap.2014.08.006 http://doi.org/10.1016/j.jaap.2014.08.006 .

M. Gao , Y. Q. Wo , W. H. Wu . Microencapsulation of intumescent flame-retardant agent and application to epoxy resins . J. Appl. Polym. Sci. , 2011 . 119 2025 - 2030 . DOI: 10.1002/app.32930 http://doi.org/10.1002/app.32930 .

L. P. Gao , D. Y. Wang , Y. Z. Wang . A flame-retardant epoxy resin based on a reactive phosphorus-containing monomer of DODPP and its thermal and flame-retardant properties . Polym. Degrad. Stab. , 2008 . 93 ( 7 ): 1308 - 1315 . DOI: 10.1016/j.polymdegradstab.2008.04.004 http://doi.org/10.1016/j.polymdegradstab.2008.04.004 .

W. Zhang , X. Li , R. J. Yang . Pyrolysis and fire behaviour of epoxy resin composites based on a phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS) . Polym. Degrad. Stab. , 2011 . 96 ( 10 ): 1821 - 1832 . DOI: 10.1016/j.polymdegradstab.2011.07.014 http://doi.org/10.1016/j.polymdegradstab.2011.07.014 .

S. Yang , J. Wang , S. Q. Huo , M. Wang , B. Zhang . Synergistic flame-retardant effect of expandable graphite and phosphorus-containing compounds for epoxy resin:strong bonding of different carbon residues . Polym. Degrad. Stab. , 2016 . 128 89 - 98 . DOI: 10.1016/j.polymdegradstab.2016.03.017 http://doi.org/10.1016/j.polymdegradstab.2016.03.017 .

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