Skip to main content
SpringerLink
Log in

Synthesis of epoxy resins using phosphorus-based precursors for flame-retardant coating

  • Published:
Journal of Coatings Technology and Research Aims and scope Submit manuscript

Abstract

Materials imparting flame retardancy play a pivotal role in the development of advanced materials due to their ability to reduce the annihilating effect of fire on man and environment. Realizing the commercial significance of epoxy resins, an attempt has been made to enhance their flame retardancy even under demanding conditions. Among the various flame-retardant materials, phosphorus-containing compounds are gaining interest both in academic and industrial areas due to their simple mechanism of action which involves char formation, a barrier between the substrate and the fire which protects the substrate from being burnt. In the present research work, unconventional starting material—diethanolamine—was used to synthesize phosphorus-based flame-retardant precursors. Intermediates formed in first step were reacted with epichlorohydrin to form epoxy resins. Structure of the compounds was confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, hydroxyl, and epoxy values. Resins were cured with commercial polyamide, and properties were compared with commercial epoxy resin. Coating films were characterized by various physical, mechanical, and thermal properties like impact resistance, pencil hardness, gloss, solvent resistance, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The TGA and DSC results showed that the char yield value has increased from 3.36 to 8.53%, and the glass transition temperature (Tg) has increased from 72.86 to 82.05°C while the initial degradation temperature decreased. Coatings showed excellent flame retardancy with maximum Limiting Oxygen Index value of 35 and a self-extinguishing behavior as confirmed by the UL-94 test.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

References

  1. Dewprashad, B, “Fundamentals of Epoxy Formulation.” J. Chem. Educ., 71 290–294 (1946)

    Article  Google Scholar 

  2. Ashcroft, WR, “Curing Agents for Epoxy Resins.” In: Ellis, B (ed.) Chemistry and Technology of Epoxy Resins, pp. 37–71. Springer, Dordrecht (1993)

    Chapter  Google Scholar 

  3. Gibson, G, “Epoxy Resins.” In: Brydson, JA (ed.) Brydson’s Plastics Materials, pp. 773–797. Elsevier, Amsterdam (2017) https://doi.org/10.1016/b978-0-323-35824-8.00027-x

    Chapter  Google Scholar 

  4. Ramos, D, Helson, M, Soares, V, Nascimento, R, “Modification of Epoxy Resin: A Comparison of Different Types of Elastomer.” Polym. Test., 24 387–394 (2005). https://doi.org/10.1016/j.polymertesting.2004.09.010

    Article  Google Scholar 

  5. Chikhi, N, Fellahi, S, Bakar, M, “Modification of Epoxy Resin Using Reactive Liquid (ATBN) Rubber.” Eur. Polym. J., 38 251–264 (2002). https://doi.org/10.1016/S0014-3057(01)00194-X

    Article  Google Scholar 

  6. Cheng, X, Chen, Y, Du, Z, Zhu, P, Wu, D, “Effect of the Structure of Curing Agents Modified by Epoxidized Oleic Esters on the Toughness of Cured Epoxy Resins.” J. Appl. Polym. Sci., 119 3504–3510 (2010). https://doi.org/10.1002/app.32998

    Article  Google Scholar 

  7. Ross, H, Coscia, T, “Some Reactions of Epichlorohydrin with Amines.” J. Org. Chem., 29 824–826 (1964). https://doi.org/10.1021/jo01027a012

    Article  Google Scholar 

  8. Cross, RP, Fugassi, P, Branch, K, Calvin, M, “The Reaction of Epichlorohydrin with Secondary Amines.” J. Am. Chem. Soc. , 80 (5) 1257–1259 (1964). https://doi.org/10.1021/ja01538a057

    Google Scholar 

  9. Christopher, M, Dobinson, B, Rolfe, M, Michael, R, “Glycidyl Ether from Alcohol and Epichlorohydrin.” US Patent 5,420,312, 1995

  10. Bukowska, A, Bukowski, W, “Reactivity of Some Carboxylic Acids in Reactions with Some Epoxides in the Presence Chromium (III) Ethanoate.” Org. Process Res. Dev., 6 (3) 234–237 (2002). https://doi.org/10.1021/op010112q

    Article  Google Scholar 

  11. Bukowski, W, “The Solvent Effects in the Reactions of Carboxylic Acids with Oxiranes 1 Kinetics of the Reaction of Acetic Acid with Epichlorohydrin in Butan-1-ol.” Int. J. Chem. Kinet., 32 (6) 378–387 (2000). https://doi.org/10.1002/(sici)1097-4601(2000)32:6<378::aid-kin4>3.0.co;2-3

    Article  Google Scholar 

  12. Saurabh, T, Patnaik, M, Bhagt, SL, Renge, VC, “Epoxidation of Vegetable Oils: A Review.” Int. J. Adv. Eng. Technol., 2 (4) 491–501 (2011)

    Google Scholar 

  13. Jian, X, Hay, AS, “Epoxidation of Unsaturated Polymers with Hydrogen Peroxide.” J. Polym. Sci. C, 28 285–288 (1990). https://doi.org/10.1002/pol.1990.140280903

    Article  Google Scholar 

  14. Caillol, S, David, G, Boutevin, B, Pascault, JP, “Biobased Thermosetting Epoxy: Present and Future.” Chem. Rev., 114 1082–1115 (2014). https://doi.org/10.1021/cr3001274

    Article  Google Scholar 

  15. Baiker, JJ, Cofer, KB, Leonard, H, Sheets, DM, “Synthesis of glycidyl ethers of polyhydric phenols.” US Patent 3,121,727 (1964)

  16. Saxena, NK, Gupta, DR, “Development and Evaluation of Fire Retardant Coatings.” Fire Technol., 26 (4) 329–341 (1990). https://doi.org/10.1007/BF01293077

    Article  Google Scholar 

  17. Weil, ED, “Flame-Retardant Coatings—A State-of-the-Art Review.” J. Fire Sci. (2011). https://doi.org/10.1177/0734904110395469

  18. Weil, ED, Levchik, SV, “Flame Retardants in Commercial Use or Development for Textiles.” J. Fire Sci., 26 243–281 (2011). https://doi.org/10.1177/0734904108089485

    Article  Google Scholar 

  19. Szolnoki, B, Toldy, A, Konrád, P, Szebényi, G, Marosi, G, “Comparison of Additive and Reactive Phosphorus-Based Flame Retardants in Epoxy Resins.” Period. Polytech. Chem. Eng., 2 85–91 (2013). https://doi.org/10.3311/ppch.2175

    Article  Google Scholar 

  20. Reistad, T, Mariussen, E, Fonnum, F, “The Effect of a Brominated Flame Retardant, Tetrabromobisphenol-A, on Free Radical Formation in Human Neutrophil Granulocytes: The Involvement of the MAP Kinase Pathway and Protein Kinase C.” Toxicol. Sci., 83 89–100 (2005). https://doi.org/10.1093/toxsci/kfh298

    Article  Google Scholar 

  21. Tirri, T, Aubert, M, Pawelec, W, Holappa, A, Wilén, C, “Structure–Property Studies on a New Family of Halogen Free Flame Retardants Based on Sulfenamide and Related Structures.” Polymers, 8 (10) 360 (2016). https://doi.org/10.3390/polym8100360

    Article  Google Scholar 

  22. Schartel, B, “Phosphorus-Based Flame Retardancy Mechanisms—Old Hat.” Materials, 3 4710–4745 (2010). https://doi.org/10.3390/ma3104710

    Article  Google Scholar 

  23. Jeng, R, Shau, S, Lin, J, Su, W, Chiu, Y, “Flame Retardant Epoxy Polymers Based on All Phosphorus-Containing Components.” Eur. Polym. J., 38 683–693 (2002). https://doi.org/10.1016/S0014-3057(01)00246-4

    Article  Google Scholar 

  24. Gu, J-W, Zhang, G-C, Dong, S-L, Zhang, Q-U, Kong, J, “Study on Preparation and Fire-Retardant Mechanism Analysis of Intumescent Flame-Retardant Coatings.” Surf. Coat. Technol., 201 7835–7841 (2007). https://doi.org/10.1016/j.surfcoat.2007.03.020

    Article  Google Scholar 

  25. Yanga, X, Guoa, Y, Luob, X, Zhenga, N, Maa, T, Tana, J, Lia, C, Zhanga, Q, Gu, J, “Self-Healing, Recoverable Epoxy Elastomers and Their Composites with Desirable Thermal Conductivities by Incorporating BN Fillers Via In-Situ Polymerization.” Compos. Sci. Technol., 164 59–64 (2018). https://doi.org/10.1016/j.compscitech.2018.05.038

    Article  Google Scholar 

  26. Nygaard, D, Diguilio, M, Rock, R, “Production of Diethanolamine.” US Patent 6,063,965 (2000)

  27. Frauenkron, M, Melder, J, Ruider, G, Rossbacher, R, Hoke, H, “Ethanolamines and Propanolamines.” In: Elvers, B (ed.) Ullmann’s Encyclopedia of Industrial Chemistry, vol. 13, p. 405. https://doi.org/10.1002/14356007.a10 (2012)

  28. Patil, DM, Phalak, GA, Mhaske, ST, “Synthesis of Bio-Based Epoxy Resin from Gallic Acid with Various Epoxy Equivalent Weights and Its Effects on Coating Properties.” J. Coat. Technol. Res., 14 (2) 355–365 (2017). https://doi.org/10.1007/s11998-016-9853-x

    Article  Google Scholar 

  29. Chen, X, Jiao, C, “Thermal Degradation Characteristics of a Novel Flame Retardant Coating Using TG-IR Technique.” Polym. Degrad. Stab., 93 2222–2225 (2008). https://doi.org/10.1016/j.polymdegradstab.2008.09.005

    Article  Google Scholar 

  30. Vlad-bubulac, T, Hamciuc, C, Petreus, O, “Synthesis and Properties of Some Phosphorus-Containing Polyesters.” High Perform. Polym., 18 255–264 (2005). https://doi.org/10.1177/0954008306059504

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Polymer and Surface Engineering, Institute of Chemical Technology, Mumbai, 400019, India

    Siddhesh Mestry & S. T. Mhaske

Authors
  1. Siddhesh Mestry
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. S. T. Mhaske
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to S. T. Mhaske.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mestry, S., Mhaske, S.T. Synthesis of epoxy resins using phosphorus-based precursors for flame-retardant coating. J Coat Technol Res 16, 807–818 (2019). https://doi.org/10.1007/s11998-018-00157-3

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11998-018-00157-3

Keywords

Search

Navigation