Skip to main content
Log in

Highly efficient phosphorous-containing flame retardant for transparent epoxy resin with good mechanical properties

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

To develop transparent flame-retardant epoxy resin (EP) having good mechanical properties, a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derived flame retardant (PAHDOPO) was prepared by a neutralization reaction between 10-hydroxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH) and piperazine. When 7% PAHDOPO was added to EP, the obtained flame-retardant EP (EP7) can pass the UL-94 V-0 rating test and exhibit a high limiting oxygen index (LOI) value of 35.8%. Microscale combustion calorimetry investigation results proved that, compared with EP, the peak heat release rate (PHRR) and heat release capacity (HRC) of EP7 decreased by 34.6% and 33.6%, respectively. The observation of the char residue morphology indicated that the addition of PAHDOPO can lead to the formation of the continuous and dense char residue layer, which can improve EP flame retardancy. Meanwhile, compared with EP, EP7 exhibited similar transparency with less than 8% reduction in the average transmittance. Moreover, the mechanical properties of EP7 hardly decreased in comparison with EP. All these results indicated that PAHDOPO can be applied as a high-performance flame retardant of EP with good mechanical properties, transparency, and flame retardancy simultaneously.

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

Access this article

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

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Scheme 2
Fig. 6

Similar content being viewed by others

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

References

  1. Miao XP, Meng Y, Li XY (2015) A novel all-purpose epoxy-terminated hyperbranched polyether sulphone toughener for an epoxy/amine system. Polymer 60:88–95. https://doi.org/10.1016/j.polymer.2015.01.034

    Article  CAS  Google Scholar 

  2. Sharifi M, Jang C, Abrams CF, Palmese GR (2015) Epoxy polymer networks with improved thermal and mechanical properties via controlled dispersion of reactive toughening agents. Macromolecules 48(20):7495–7502. https://doi.org/10.1021/acs.macromol.5b00677

    Article  CAS  Google Scholar 

  3. Jiang J, Cheng YB, Liu Y, Wang Q, He YS, Wang BW (2015) Intergrowth charring for flame-retardant glass fabric-reinforced epoxy resin composites. J Mater Chem A 3(8):4284–4290. https://doi.org/10.1039/c4ta06486k

    Article  CAS  Google Scholar 

  4. Luo WH, Li DS, Chen MF, Su LP, Zhong W, Lan JS, Zheng BT, Zhang HG (2022) A novel polyaromatic ring phosphor-nitrogen imidazole derivative endowing epoxy resin with remarkable flame retardancy and mechanical properties. J Polym Res 29(7):306. https://doi.org/10.1007/s10965-022-03161-9

    Article  CAS  Google Scholar 

  5. Ma TT, Guo CG (2017) Synergistic effect between melamine cyanurate and a novel flame retardant curing agent containing a caged bicyclic phosphate on flame retardancy and thermal behavior of epoxy resins. J Anal Appl Pyrolysis 124:239–246. https://doi.org/10.1016/j.jaap.2017.02.001

    Article  CAS  Google Scholar 

  6. Chen HX, Xia W, Wang S (2022) Biodiesel production from waste cooking oil using a waste diaper derived heterogeneous magnetic catalyst. Braz J Chem Eng. https://doi.org/10.1007/s43153-022-00257-z

    Article  Google Scholar 

  7. Zheng ZH, Xia YR, Liao CC, Liu YH, Chai WH, Niu EC, Hu ZQ (2021) Fabrication of starch-based multi-source integrated halogen-free flame retardant in improving the fire safety of polypropylene. J Polym Res 28(11):445. https://doi.org/10.1007/s10965-021-02804-7

    Article  CAS  Google Scholar 

  8. Tan Y, Shao ZB, Yu LX, Long JW, Qi M, Chen L, Wang YZ (2016) Piperazine-modified ammonium polyphosphate as monocomponent flame-retardant hardener for epoxy resin: flame retardance, curing behavior and mechanical property. Polym Chem 7(17):3003–3012. https://doi.org/10.1039/c6py00434b

    Article  CAS  Google Scholar 

  9. Liu RJ, Xia W, Otitoju TA, Wu WD, Wang S, Li SX, Zhang AL, Chen XC, Tang T, Liu J (2021) Effect of oleic acid on improving flame retardancy of brucite in low-density polyethylene composite. J Appl Polym Sci 139(13):e51862. https://doi.org/10.1002/app.51862

    Article  CAS  Google Scholar 

  10. Chen HX, Xia W, Wang N, Liu Y, Fan PH, Wang S, Liu J, Tang T, Zhang AL (2022) Flame retardancy of biodegradable polylactic acid with piperazine pyrophosphate and melamine cyanurate as flame retardant. J Fire Sci 40(4):254–273. https://doi.org/10.1177/07349041221093546

    Article  CAS  Google Scholar 

  11. Yang G, Wu WH, Wang YH, Jiao YH, Lu LY, Qu HQ, Qin XY (2019) Synthesis of a novel phosphazene-based flame retardant with active amine groups and its application in reducing the fire hazard of Epoxy Resin. J Hazard Mater 366:78–87. https://doi.org/10.1016/j.jhazmat.2018.11.093

    Article  CAS  Google Scholar 

  12. Qian X, Jin J, Lu L, Shao G, Jiang S (2017) Preparation of poly(methyl methacrylate)/silicon particle composites and the study of the properties improvement. J Polym Res 24(3):45. https://doi.org/10.1007/s10965-017-1211-x

    Article  CAS  Google Scholar 

  13. Wang S, Wu WD, Chen Q, Ding Z, Li SX, Zhang AL, Tang T, Liu J, Okoye PU (2022) Preparation of DOPO-derived magnesium phosphate whisker and its synergistic effect with ammonium polyphosphate on the flame retardancy and mechanical property of epoxy resin. J Appl Polym Sci e53430. https://doi.org/10.1002/app.53430

  14. Shen MY, Kuan CF, Kuan HC, Ke CY, Chiang CL (2020) Study on preparation and properties of agricultural waste bagasse eco-type bio-flame-retardant/epoxy composites. J Therm Anal Calorim 144(2):525–538. https://doi.org/10.1007/s10973-020-10368-9

    Article  CAS  Google Scholar 

  15. Gao J, Huang W, He W, Long L, Qin S (2021) Superior flame retardancy of glass fiber-reinforced polyamide 6T composites by synergism between DOPO-based derivative and carbon nanotube. J Therm Anal Calorim 147(2):1265–1274. https://doi.org/10.1007/s10973-020-10500-9

    Article  CAS  Google Scholar 

  16. Zhang JJ, Duan HJ, Cao JF, Zou JH, Ma HR (2020) A high-efficiency DOPO-based reactive flame retardant with bi-hydroxyl for low-flammability epoxy resin. J Appl Polym Sci 138(14):e50165. https://doi.org/10.1002/app.50165

    Article  CAS  Google Scholar 

  17. Peng W, Nie SB, Xu YX, Yang W (2021) A tetra-DOPO derivative as highly efficient flame retardant for epoxy resins. Polym Degrad Stab 193:109715. https://doi.org/10.1016/j.polymdegradstab.2021.109715

    Article  CAS  Google Scholar 

  18. Gangireddy CSR, Wang X, Kan YC, Song L, Hu Y (2019) Synthesis of a novel DOPO-based polyphosphoramide with high char yield and its application in flame-retardant epoxy resins. Polym Int 68(5):936–945. https://doi.org/10.1002/pi.5784

    Article  CAS  Google Scholar 

  19. Yan W, Yu J, Zhang MQ, Wang T, Wen CZ, Qin SH, Huang WJ (2018) Effect of multiwalled carbon nanotubes and phenethyl-bridged DOPO derivative on flame retardancy of epoxy resin. J Polym Res 25(3):72. https://doi.org/10.1007/s10965-018-1472-z

    Article  CAS  Google Scholar 

  20. Chen R, Hu KX, Tang H, Wang JJ, Zhu FS, Zhou H (2019) A novel flame retardant derived from DOPO and piperazine and its application in epoxy resin: flame retardance, thermal stability and pyrolysis behavior. Polym Degrad Stabil 166:334–343. https://doi.org/10.1016/j.polymdegradstab.2019.06.011

    Article  CAS  Google Scholar 

  21. Chen L, Zhao D, Wang XL, Wang YZ (2022) Durable macromolecular firefighting for unsaturated polyester via integrating synergistic charring and hydrogen bond. Chem Eng J 443:136365. https://doi.org/10.1016/j.cej.2022.136365

    Article  CAS  Google Scholar 

  22. Peng C, Wu ZJ, Li JL, Wang Z, Wang HY, Zhao M (2015) Synthesis, thermal and mechanical behavior of a silicon/phosphorus containing epoxy resin. J Appl Polym Sci 132(46):42788. https://doi.org/10.1002/app.42788

    Article  CAS  Google Scholar 

  23. Guo WW, Yu B, Yuan Y, Song L, Hu Y (2017) In situ preparation of reduced graphene oxide/DOPO-based phosphonamidate hybrids towards high-performance epoxy nanocomposites. Compos Pt B-Eng 123:154–164. https://doi.org/10.1016/j.compositesb.2017.05.024

    Article  CAS  Google Scholar 

  24. Gu LQ, Qiu JH, Yao YW, Sakai E, Yang LT (2018) Functionalized MWCNTs modified flame retardant PLA nanocomposites and cold rolling process for improving mechanical properties. Compos Sci Technol 161:39–49. https://doi.org/10.1016/j.compscitech.2018.03.033

    Article  CAS  Google Scholar 

  25. Dai SS, Yu XJ, Chen R, Zhou H, Pan ZQ (2020) Transparent epoxy resin material with excellent fire retardancy enabled by a P/N/S containing flame retardant. J Appl Polym Sci 138(16):e50263. https://doi.org/10.1002/app.50263

    Article  CAS  Google Scholar 

  26. Luo QQ, Yuan YC, Dong CL, Liu SM, Zhao JQ (2015) Intumescent flame retardancy of a DGEBA epoxy resin based on 5,10-dihydro-phenophosphazine-10-oxide. RSC Adv 5(84):68476–68484. https://doi.org/10.1039/c5ra11847f

    Article  CAS  Google Scholar 

  27. Zhong L, Zhao Y, Tang QL, Zhang KX, Deng WH, Zhang LW, Wang R, Chen J, Deng JJ, Liao W, Wang QW, Chen MJ, Liu ZG (2021) Highly efficient flame-retardant and transparent epoxy resin. Polym Adv Technol 32(8):2940–2952. https://doi.org/10.1002/pat.5306

    Article  CAS  Google Scholar 

  28. Li L, Cai ZS (2020) Flame-retardant performance of transparent and tensile-strength-enhanced epoxy resins. Polymers 12(2):317. https://doi.org/10.3390/polym12020317

    Article  CAS  Google Scholar 

  29. Wang PL, Fu XL, Kan YC, Wang X, Hu Y (2019) Two high-efficient DOPO-based phosphonamidate flame retardants for transparent epoxy resin. High Perform Polym 31(3):249–260. https://doi.org/10.1177/0954008318762037

    Article  CAS  Google Scholar 

  30. Shen D, Xu YJ, Long JW, Shi XH, Chen L, Wang YZ (2017) Epoxy resin flame-retarded via a novel melamine-organophosphinic acid salt: thermal stability, flame retardance and pyrolysis behavior. J Anal Appl Pyrolysis 128:54–63. https://doi.org/10.1016/j.jaap.2017.10.025

    Article  CAS  Google Scholar 

  31. Xu MJ, Xia SY, Liu C, Li B (2018) Preparation of poly(phosphoric acid piperazine) and its application as an effective flame retardant for epoxy resin. Chin J Polym Sci 36(5):655–664. https://doi.org/10.1007/s10118-018-2036-8

    Article  CAS  Google Scholar 

  32. Li DS, Zhang ZY, Wang SQ, Xu MJ, Li B (2022) A monomolecular intumescent flame retardant for improvement simultaneously of fire safety, smoke suppression, and mechanical properties of epoxy resin. J Appl Polym Sci 139(19):e52104. https://doi.org/10.1002/app.52104

    Article  CAS  Google Scholar 

  33. Lee WL, Liu LC, Chen CM, Lin JS (2014) Syntheses and flame retarding properties of DOPO polymers, melamine polymers, and DOPO-melamine copolymers. Polym Adv Technol 25(1):36–40. https://doi.org/10.1002/pat.3201

    Article  CAS  Google Scholar 

  34. Goedderz D, Schafer T, Klitsch J, Weber L, Weber B, Fuhr O, Buntkowsky G, Schonberger F (2020) Doring M (2022) Coordination compounds of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-Oxide (DOPO) ligands: extremely high thermostability and ligand oxidation in the solid state. Eur J Inorg Chem 25:2444–2456. https://doi.org/10.1002/ejic.202000269

    Article  CAS  Google Scholar 

  35. Yan H, Zhao ZL, Wang YH, Jin Q, Zhang XY (2017) Structural modification of ammonium polyphosphate by DOPO to achieve high water resistance and hydrophobicity. Powder Technol 320:14–21. https://doi.org/10.1016/j.powtec.2017.07.029

    Article  CAS  Google Scholar 

  36. Wang QZ, Liu C, Xu YJ, Liu Y, Zhu P, Wang YZ (2021) Highly efficient flame retardation of polyester fabrics via novel DOPO-modified sol-gel coatings. Polymer 226:123761. https://doi.org/10.1016/j.polymer.2021.123761

    Article  CAS  Google Scholar 

  37. Yang SJ, Zhang B, Liu MR, Yang YD, Liu XL, Chen DP, Wang BB, Tang G, Liu XY (2021) Fire performance of piperazine phytate modified rigid polyurethane foam composites. Polym Adv Technol 32(11):4531–4546. https://doi.org/10.1002/pat.5454

    Article  CAS  Google Scholar 

  38. Zhu ZM, Wang LX, Dong LP (2019) Influence of a novel P/N-containing oligomer on flame retardancy and thermal degradation of intumescent flame-retardant epoxy resin. Polym Degrad Stabil 162:129–137. https://doi.org/10.1016/j.polymdegradstab.2019.02.021

    Article  CAS  Google Scholar 

  39. Gao YY, Deng C, Du YY, Huang SC, Wang YZ (2019) A novel bio-based flame retardant for polypropylene from phytic acid. Polym Degrad Stabil 161:298–308. https://doi.org/10.1016/j.polymdegradstab.2019.02.005

    Article  CAS  Google Scholar 

  40. Lee S, Morgan AB, Schiraldi DA, Maia J (2019) Improving the flame retardancy of polypropylene foam with piperazine pyrophosphate via multilayering coextrusion of film/foam composites. J Appl Polym Sci 137(15):48552. https://doi.org/10.1002/app.48552

    Article  CAS  Google Scholar 

  41. He XD, Zhang WC, Yang RJ (2017) The characterization of DOPO/MMT nanocompound and its effect on flame retardancy of epoxy resin. Compos Pt A-Appl Sci Manuf 98:124–135. https://doi.org/10.1016/j.compositesa.2017.03.020

    Article  CAS  Google Scholar 

  42. Liu L, Wang ZZ, Xu XY (2017) Melamine amino trimethylene phosphate as a novel flame retardant for rigid polyurethane foams with improved flame retardant, mechanical and thermal properties. J Appl Polym Sci 134(39):45234. https://doi.org/10.1002/app.45234

    Article  CAS  Google Scholar 

  43. Zhou LS, Zhang GC, Yang SS, Yang LB, Cao JP, Yang KW (2019) The synthesis, curing kinetics, thermal properties and flame rertardancy of cyclotriphosphazene-containing multifunctional epoxy resin. Thermochim Acta 680:178348. https://doi.org/10.1016/j.tca.2019.178348

    Article  CAS  Google Scholar 

  44. Huang ZY, Wang ZZ (2021) Synthesis of a bio-based piperazine phytate flame retardant for epoxy resin with improved flame retardancy and smoke suppression. Polymer Adv Technol 32(11):4282–4295. https://doi.org/10.1002/pat.5429

    Article  CAS  Google Scholar 

  45. Zhao B, Liu PW, Xiong KK, Liu HH, Zhao PH, Liu YQ (2019) Impacts of multi-element flame retardants on flame retardancy, thermal stability, and pyrolysis behavior of epoxy resin. Polym Degrad Stabil 167:217–227. https://doi.org/10.1016/j.polymdegradstab.2019.07.004

    Article  CAS  Google Scholar 

  46. Schartel B, Pawlowski KH, Lyon RE (2007) Pyrolysis combustion flow calorimeter: A tool to assess flame retarded PC/ABS materials? Thermochim Acta 462:1–14. https://doi.org/10.1016/j.tca.2007.05.021

    Article  CAS  Google Scholar 

  47. Bai ZM, Jiang SD, Tang G, Hu Y, Song L, Yuen RKK (2014) Enhanced thermal properties and flame retardancy of unsaturated polyester-based hybrid materials containing phosphorus and silicon. Polym Adv Technol 25(2):223–232. https://doi.org/10.1002/pat.3227

    Article  CAS  Google Scholar 

  48. Wang X, Hu Y, Song L, Xing WY, Lu HD (2012) Preparation, flame retardancy, and thermal degradation of epoxy thermosets modified with phosphorous/nitrogen-containing glycidyl derivative. Polym Adv Technol 23(2):190–197. https://doi.org/10.1002/pat.1851

    Article  CAS  Google Scholar 

  49. Liu DY, Cui YH, Zhang TL, Zhao WH, Ji PF (2021) Improving the flame retardancy and smoke suppression of epoxy resins by introducing of DOPO derivative functionalized ZIF-8. Polym Degrad Stabil 194:109749. https://doi.org/10.1016/j.polymdegradstab.2021.109749

    Article  CAS  Google Scholar 

  50. Yang S, Wang J, Huo SQ, Wang M, Wang JP (2015) Preparation and flame retardancy of a compounded epoxy resin system composed of phosphorus/nitrogen-containing active compounds. Polym Degrad Stabil 121:398–406. https://doi.org/10.1016/j.polymdegradstab.2015.10.006

    Article  CAS  Google Scholar 

  51. Li SN, Zhao XJ, Liu XH, Yang X, Yu R, Zhang Y, Huang W, Deng KW (2019) Cage-ladder-structure, phosphorus-containing polyhedral oligomeric silsesquinoxanes as promising reactive-type flame retardants for epoxy resin. J Appl Polym Sci 136(23):47607. https://doi.org/10.1002/app.47607

    Article  CAS  Google Scholar 

  52. Yang S, Hu YF, Zhang QX (2018) Synthesis of a phosphorus–nitrogen-containing flame retardant and its application in epoxy resin. High Perform Polym 31(2):186–196. https://doi.org/10.1177/0954008318756496

    Article  CAS  Google Scholar 

  53. Zhao PF, Zeng W, Yang ZW, Yang YX, Li J, Shi JP, Wen N, Li HT, Guan J, Lei ZQ, Chen DL (2021) Preparation of a novel functionalized magnesium-based curing agent as an intrinsic flame retardant for epoxy resin. Chemosphere 273:129658. https://doi.org/10.1016/j.chemosphere.2021.129658

    Article  CAS  Google Scholar 

  54. Zhang Z, Dong CH, Liu J, Kong DZ, Sun L, Lu Z (2019) Preparation of a synergistic reactive flame retardant based on silicon, phosphorus and nitrogen and its application to cotton fabrics. Cellulose 27(3):1799–1815. https://doi.org/10.1007/s10570-019-02900-4

    Article  CAS  Google Scholar 

  55. Chen YS, Duan HJ, Ji S, Ma HR (2020) Novel phosphorus/nitrogen/boron-containing carboxylic acid as co-curing agent for fire safety of epoxy resin with enhanced mechanical properties. J Hazard Mater 402:123769. https://doi.org/10.1016/j.jhazmat.2020.123769

    Article  CAS  Google Scholar 

  56. Pang FQ, Liu XD, Zheng XT, Lin YC, Jian RK (2021) An intrinsic flame retardant epoxy resin with high transparency and strengthened mechanical property. J Appl Polym Sci 138(42):e51230. https://doi.org/10.1002/app.51230

    Article  CAS  Google Scholar 

  57. Ai YF, Xia L, Pang FQ, Xu YL, Zhao HB, Jian RK (2020) Mechanically strong and flame-retardant epoxy resins with anti-corrosion performance. Compos Pt B-Eng 193:108019. https://doi.org/10.1016/j.compositesb.2020.108019

    Article  CAS  Google Scholar 

  58. Zeng BR, Zhou RR, Zheng XH, Ye JY, Chen JM, Xu YT, Yuan CH, Dai LZ (2021) Polyhedral oligomeric silsesquioxane hybrided with DOPO and phenylboronic acid for flame-retarded epoxy resin. Polym Adv Technol 32(6):2339–2351. https://doi.org/10.1002/pat.5262

    Article  CAS  Google Scholar 

  59. Yang YX, Xiao D (2022) Fabrication of two multifunctional phosphorus-nitrogen flame retardants toward improving the fire safety of epoxy resin. e-Polymers 22(1):430–444. https://doi.org/10.1515/epoly-2022-0042

    Article  CAS  Google Scholar 

  60. He L, Chen T, Zhang Y, Hu LR, Wang T, Han R, He JL, Luo W, Liu ZG, Deng JN, Chen MJ (2021) Imide-DOPO derivative endows epoxy resin with excellent flame retardancy and fluorescence without losing glass transition temperature. Compos Pt B-Eng 230:109553. https://doi.org/10.1016/j.compositesb.2021.109553

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge financial support from the General Project Fund of the Liaoning Education Department (No. LJGD2019014).

Author information

Authors and Affiliations

Authors

Contributions

Conceptualization: Song Wang; Methodology: Song Wang, Sanxi Li; Formal analysis and investigation: Qi Chen; Writing—original draft preparation: Qi Chen, Song Wang; Writing—review and editing: Qi Chen, Song Wang; Funding acquisition: Sanxi Li; Resources: Song Wang, Ailing Zhang; Supervision: Song Wang.

Corresponding author

Correspondence to Song Wang.

Ethics declarations

All authors certify that they have no affiliations with or involvement in any organization or entity with any financial interest or non-financial interest in the subject matter or materials discussed in this manuscript.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, Q., Wang, S., Li, S. et al. Highly efficient phosphorous-containing flame retardant for transparent epoxy resin with good mechanical properties. J Polym Res 30, 32 (2023). https://doi.org/10.1007/s10965-022-03398-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-022-03398-4

Keywords

Navigation