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Fabrication of halogen-free ammonium phosphate with two components via a simple method and its flame retardancy in polypropylene composites

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Abstract

In this paper, a halogen-free flame retardant with two different functional components was prepared via a simple method. The novelty of this work is the combination of acid source and char-forming agent in one compound simultaneously. And the advantage of this method lies in effectively avoiding the mixture of several components for composites during thermal processing and improving the flame retardancy of polymers. Besides, the chemical structure of modified ammonium phosphate (MAPP) was confirmed by Fourier transform infrared spectra (FTIR) and X-ray diffraction spectra (XRD), respectively. The results indicate that thermal decomposition process of APP after modification is obviously changed. When polypropylene (PP) is composited with 30 phr MAPP, the limiting oxygen index value can reach 28.5 % and pass vertical burning tests (UL-94) V-1 rating. Simultaneously, thermal gravimetric analysis demonstrates that the introduction of diethanolamine can improve the char-forming rate and char residue of PP/APP composites. Except that, the thermal pyrolysis of MAPP detected by FTIR spectra deduces that the char-forming process happens at 350–400 °C. The analysis on char residue after combustion indicates that the cross-linking bonds of P–O–C groups appear. At last, a potential condensed mechanism was primarily proposed.

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References

  1. Xian JM, He ZQ, Li MQ, Lin ZD, Chen JX, Yang QG, Xiao L, Li W. Preparation and properties of coral/β-polypropylene biocomposites. J Therm Anal Calorim. 2015;122:1005–11.

    Article  CAS  Google Scholar 

  2. Marcinčin A, Ujhelyiová A, Marcinčin K, Hricová M. Spinning, mechanical and thermal properties of metallocene polypropylene fibers. J Therm Anal Calorim. 2015;1:1–13.

    Google Scholar 

  3. Papageorgiou DG, Filippousi M, Pavlidou E, Chrissafis K, Tendeloo GV, Bikiaris D. Effect of clay modification on structure–property relationships and thermal degradation kinetics of β-polypropylene/clay composite materials. J Therm Anal Calorim. 2015;122:393–406.

    Article  CAS  Google Scholar 

  4. Alaburdaitė R, Krylova V. Study of thermo-oxidative chemical pre-treatment of isotactic polypropylene. J Therm Anal Calorim. 2014;118:1331–8.

    Article  Google Scholar 

  5. Zheng ZH, Liu SF, Wang BN, Yang T, Cui XJ, Wang HY. Preparation of a novel phosphorus- and nitrogen-containing flame retardant and its synergistic effect in the intumescent flame-retarding polypropylene system. Polym Compos. 2015;36:1606–19.

    Article  CAS  Google Scholar 

  6. Chen XL, Song WK, Liu JB, Jiao CM, Qian Y. Synergistic flame-retardant effects between aluminum hypophosphite and expandable graphite in silicone rubber composites. J Therm Anal Calorim. 2015;120:1819–26.

    Article  CAS  Google Scholar 

  7. Nie SB, Zhou C, Peng C, Liu L, Zhang C, Dong X, Wang DY. Thermal oxidative degradation kinetics of novel intumescent flame-retardant polypropylene composites. J Therm Anal Calorim. 2015;120:1183–91.

    Article  CAS  Google Scholar 

  8. Chen YJ, Guo ZH, Fang ZP. Relationship between the distribution of organo-montmorillonite and the flammability of flame retardant polypropylene. Polym Eng Sci. 2012;52:390–8.

    Article  CAS  Google Scholar 

  9. Zheng ZH, Yang T, Wang BN, Qu BB, Wang HY. Microencapsulated melamine phosphate via the sol–gel method and its application in halogen-free and intumescent flame-retarding acrylonitrile-butadiene-styrene copolymer. Polym Int. 2015;64:1275–88.

    Article  CAS  Google Scholar 

  10. Liu Y, Zhao J, Deng CL, Chen L, Wang DY, Wang YZ. Flame-retardant effect of sepiolite on an intumescent flame-retardant polypropylene system. Ind Eng Chem Res. 2011;50:2047–54.

    Article  CAS  Google Scholar 

  11. Camino G, Costa L, Trossarelli L. Study of the mechanism of intumescence in fire retardant polymers: part I—thermal degradation of ammonium polyphosphate–pentaerythritol mixtures. Polym Degrad Stabil. 1984;6:243–52.

    Article  CAS  Google Scholar 

  12. Camino G, Costa L, Trossarelli L. Study of the mechanism of intumescence in fire retardant polymers: part II—mechanism of action in polypropylene–ammonium polyphosphate–pentaerythritol mixtures. Polym Degrad Stabil. 1984;7:25–31.

    Article  CAS  Google Scholar 

  13. Camino G, Costa L, Trossarelli L. Study of the mechanism of intumescence in fire retardant polymers: part III—effect of urea on the ammonium polyphosphate–pentaerythritol system. Polym Degrad Stabil. 1984;7:221–9.

    Article  CAS  Google Scholar 

  14. Camino G, Costa L, Trossarelli L, Costanzi F, Landoni G. Study of the mechanism of intumescence in fire retardant polymers: part IV—evidence of ester formation in ammonium polyphosphate–pentaerythritol mixtures. Polym Degrad Stabil. 1984;8:13–22.

    Article  CAS  Google Scholar 

  15. Camino G, Costa L, Trossarelli L. Study of the mechanism of intumescence in fire retardant polymers: part V—mechanism of formation of gaseous products in the thermal degradation of ammonium polyphosphate. Polym Degrad Stabil. 1985;12:203–11.

    Article  CAS  Google Scholar 

  16. Camino G, Costa L, Trossarelli L. Study of the mechanism of intumescence in fire retardant polymers: part VI—mechanism of ester formation in ammonium polyphosphate-pentaerythritol mixtures. Polym Degrad Stabil. 1985;13:213–28.

    Article  Google Scholar 

  17. Gao M, Wu W, Yan Y. Thermal degradation and flame retardancy of epoxy resins containing intumescent flame retardant. J Therm Anal Calorim. 2009;95:605–8.

    Article  CAS  Google Scholar 

  18. Ribeiro SPS, Estevão LRM, Nascimento RSV. Brazilian clays as synergistic agents in an ethylenic polymer matrix containing an intumescent formulation. J Therm Anal Calorim. 2007;87:661–5.

    Article  CAS  Google Scholar 

  19. Han ZD, Fina A, Malucelli G. Thermal shielding performances of nano-structured intumescent coatings containing organo-modified layered double hydroxides. Prog Org Coat. 2015;78:504–10.

    Article  CAS  Google Scholar 

  20. Zheng ZH, Sun HM, Li WJ, Zhong SL, Yan JT, Cui XJ, Wang HY. Co-microencapsulation of ammonium polyphosphate and aluminum hydroxide in halogen-free and intumescent flame retarding polypropylene. Polym Compos. 2014;35:715–29.

    Article  CAS  Google Scholar 

  21. Zheng ZH, Yan JT, Sun HM, Cheng ZQ, Li WJ, Wang HY, Cui XY. Preparation and characterization of microencapsulated ammonium polyphosphate and its synergistic flame-retarded polyurethane rigid foams with expandable graphite. Polym Int. 2014;63:84–92.

    Article  CAS  Google Scholar 

  22. Wu K, Song L, Wang ZZ, Hu Y. Preparation and characterization of double shell microencapsulated ammonium polyphosphate and its flame retardance in polypropylene. J Polym Res. 2009;16:283–94.

    Article  CAS  Google Scholar 

  23. Chen XL, Jiao CM, Zhang J. Microencapsulation of ammonium polyphosphate with hydroxyl silicone oil and its flame retardance in thermoplastic polyurethane. J Therm Anal Calorim. 2011;104:1037–43.

    Article  CAS  Google Scholar 

  24. Lei ZQ, Cao YM, Xie F. Study on surface modification and flame retardants properties of ammonium polyphosphate for polypropylene. J Appl Polym Sci. 2012;124:781–8.

    Article  CAS  Google Scholar 

  25. Zheng ZH, Qiang LH, Yang T, Wang BN, Cui XJ, Wang HY. Preparation of microencapsulated ammonium polyphosphate with carbon source- and blowing agent-containing shell and its flame retardance in polypropylene. J Polym Res. 2014;21:443–57.

    Article  Google Scholar 

  26. Jiang WZ, Hao JW, Han ZD. Study on the thermal degradation of mixtures of ammonium polyphosphate and a novel caged bicyclic phosphate and their flame retardant effect in polypropylene. Polym Degrad Stabil. 2012;97:632–7.

    Article  CAS  Google Scholar 

  27. Teoh MM, Liu SL, Chung TS. Effect of pyridazine structure on thin-film polymerization and phase behavior of thermotropic liquid crystalline copolyesters. J Polym Sci B Polym Phys. 2005;43:2230–42.

    Article  CAS  Google Scholar 

  28. Li J, Ke CH, Xu L, Wang YZ. Synergistic effect between a hyperbranched charring agent and ammonium polyphosphate on the intumescent flame retardance of acrylonitrile-butadiene-styrene polymer. Polym Degrad Stabil. 2012;97:1107–13.

    Article  CAS  Google Scholar 

  29. Mahapatra SS, Karak N. s-Triazine containing flame retardant hyperbranched polyamines: synthesis, characterization and properties evaluation. Polym Degrad Stabil. 2007;92:947–55.

    Article  CAS  Google Scholar 

  30. Huang GB, Liang HD, Wang Y, Wang X, Gao JR, Fei ZD. Combination effect of melamine polyphosphate and graphene on flame retardant properties of poly(vinyl alcohol). Mater Chem Phys. 2012;132:520–8.

    Article  CAS  Google Scholar 

  31. Wang X, Li Y, Liao W, Gu J, Li D. A new intumescent flame-retardant: preparation, surface modification, and its application in polypropylene. Polym Adv Technol. 2008;19:1055–61.

    Article  CAS  Google Scholar 

  32. Wang ZY, Han EH, Ke W. Influence of nano-LDHs on char formation and fire-resistant properties of flame-retardant coating. Prog Org Coat. 2005;53:29–37.

    Article  CAS  Google Scholar 

  33. Qu BJ, Xie RC. Intumescent char structures and flame-retardant mechanism of expandable graphite-based halogen-free flame-retardant linear low density polyethylene blends. Polym Int. 2003;52:1415–22.

    Article  CAS  Google Scholar 

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Correspondence to Zaihang Zheng.

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Zheng, Z., Liu, Y., Zhang, L. et al. Fabrication of halogen-free ammonium phosphate with two components via a simple method and its flame retardancy in polypropylene composites. J Therm Anal Calorim 127, 2013–2023 (2017). https://doi.org/10.1007/s10973-016-5779-x

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  • DOI: https://doi.org/10.1007/s10973-016-5779-x

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