Polymer Bulletin

, Volume 75, Issue 11, pp 5253–5267 | Cite as

Thermal properties of epoxy–anhydride formulations cured using phosphonium accelerators

  • L. R. Amirova
  • O. L. Khamidullin
  • K. A. Andrianova
  • L. M. Amirova
Original Paper


Influence of structure of epoxy resin and anhydride hardener, as well as type and content of accelerator on thermal properties of epoxy–anhydride networks were investigated by dynamic mechanical analysis (DMA). The experimental values of molecular weight between crosslinks (Mc) in the epoxy polymers were determined. Influence of the catalyst on defect structure of the polymer network was observed. The use of two phosphonium salts as curing accelerators to a greater extent than 2-methylimidazole allows fabricating polymers with a higher crosslink density. The concentration dependence of polymer’s thermal properties was studied and the optimum content of the accelerator giving the network with improved properties was determined.



This work was supported by the Russian Government Program for Competitive Growth of Kazan Federal University.


  1. 1.
    Baker AA (2004) Composite materials for aircraft structures. AIAA, RestonGoogle Scholar
  2. 2.
    White LA, Weber JW, Mathias LJ (2001) Synthesis and thermal characterization of a one component maleimide-epoxy resin. Polym Bull 46(6):463–469CrossRefGoogle Scholar
  3. 3.
    Liang G, Zhang Z, Yang J, Wang X (2007) BMI based composites with low dielectric loss. Polym Bull 59(2):269–278CrossRefGoogle Scholar
  4. 4.
    Chen XM, Ellis B (1993) Chemistry and technology of epoxy resins. Blackie A&P/Chapman & Hall, LondonGoogle Scholar
  5. 5.
    Jin K, Heath WH, Torkelson JM (2015) Kinetics of multifunctional thiol-epoxy click reactions studied by differential scanning calorimetry: effects of catalysis and functionality. Polymer 81:70–78CrossRefGoogle Scholar
  6. 6.
    Konuray AO, Fernández-Francos X, Ramis X (2017) Latent curing of epoxy-thiol thermosets. Polymer 116:191–203CrossRefGoogle Scholar
  7. 7.
    Jin K, Wilmot N, Heath WH, Torkelson JM (2016) Phase-separated thiol–epoxy–acrylate hybrid polymer networks with controlled cross-link density synthesized by simultaneous thiol-acrylate and thiol-epoxy click reactions. Macromolecules 49(11):4115–4123CrossRefGoogle Scholar
  8. 8.
    Lee H, Neville K (1967) Handbook of epoxy resins. Mcgraw-Hill, New YorkGoogle Scholar
  9. 9.
    Zhang JF, Sun X (2004) Mechanical properties of poly (lactic acid)/starch composites compatibilized by maleic anhydride. Biomacromolecules 5(4):1446–1451CrossRefGoogle Scholar
  10. 10.
    Delor-Jestin F, Drouin D, Cheval P-Y, Lacoste J (2006) Thermal and photochemical ageing of epoxy resin–influence of curing agents. Polym Degrad Stabil 91(6):1247–1255CrossRefGoogle Scholar
  11. 11.
    Montserrat S, Flaque C, Calafell M, Andreu G, Malek J (1995) Influence of the accelerator concentration on the curing reaction of an epoxy-anhydride system. Thermochim Acta 269:213–229CrossRefGoogle Scholar
  12. 12.
    Chantarasiri N, Sutivisedsak N, Pouyuan C (2001) Thermally stable metal-containing epoxy polymers from an epoxy resin-schiff base metal complex-maleic anhydride system. Eur Polym J 37(10):2031–2038CrossRefGoogle Scholar
  13. 13.
    Fedoseev MS, Derzhavinskaya LF, Strelnikov VN (2010) Curing of epoxy-anhydride formulations in the presence of imidazoles. Russ J Appl Chem 83:1408–1412CrossRefGoogle Scholar
  14. 14.
    Woo EM, Seferisi JC (1990) Cure kinetics of epoxy/anhydride thermosetting matrix systems. J Appl Polym Sci 40(7–8):1237–1256CrossRefGoogle Scholar
  15. 15.
    Hamerton I, Howlin BJ, Jepson P (2002) Metals and coordination compounds as modifiers for epoxy resins. Coord Chem Rev 224(1–2):67–85CrossRefGoogle Scholar
  16. 16.
    Kurnoskin AV (1996) Metalliferous epoxy-chelate polymers: analytical review. J Macromol Sci Part C Polym Rev 36(3):457–599CrossRefGoogle Scholar
  17. 17.
    Amirova LR, Burilov AR, Amirova LM, Bauer I, Habicher WD (2016) Kinetics and mechanistic investigation of epoxy–anhydride compositions cured with quaternary phosphonium salts as accelerators. J Polym Sci Part A Polym Chem 54(8):1088–1097CrossRefGoogle Scholar
  18. 18.
    Teo JKH, Teo KC, Pan B, Xiao Y, Lu X (2007) Epoxy/polyhedral oligomeric silsesquioxane (POSS) hybrid networks cured with an anhydride: cure kinetics and thermal properties. Polymer 48(19):5671–5680CrossRefGoogle Scholar
  19. 19.
    He Y, Zhang L, Chen G, Li X, Yao D, Lee JH, Zhang Y (2014) Surface functionalized carbon nanotubes and its effects on the mechanical properties of epoxy based composites at cryogenic temperature. Polym Bull 71(10):2465–2485CrossRefGoogle Scholar
  20. 20.
    Miyagawa H, Rich MJ, Drzal LT (2006) Thermo-physical properties of epoxy nanocomposites reinforced by carbon nanotubes and vapor grown carbon fibers. Thermochim Acta 442(1–2):67–73CrossRefGoogle Scholar
  21. 21.
    Sun Y, Zhang Z, Moon KS, Wong CP (2004) Glass transition and relaxation behavior of epoxy nanocomposites. J Polym Sci Part B Polym Phys 42(21):3849–3858CrossRefGoogle Scholar
  22. 22.
    Morimune S, Kotera M, Nishino T, Goto K, Hata K (2011) Poly (vinyl alcohol) nanocomposites with nanodiamond. Macromolecules 44(11):4415–4421CrossRefGoogle Scholar
  23. 23.
    Musto P, Abbate M, Ragosta G, Scarinzi G (2007) A study by Raman, near-infrared and dynamic-mechanical spectroscopies on the curing behaviour, molecular structure and viscoelastic properties of epoxy/anhydride networks. Polymer 48(13):3703–3716CrossRefGoogle Scholar
  24. 24.
    Uzay C, Boztepe MH, Bayramoğlu M, Geren N (2017) Effect of post-curing heat treatment on mechanical properties of fiber reinforced polymer (FRP) composites. Mater Test 59(4):366–372CrossRefGoogle Scholar
  25. 25.
    Guerrero P, De la Caba K, Valea A, Corcuera M, Mondragon I (1996) Influence of cure schedule and stoichiometry on the dynamic mechanical behaviour of tetrafunctional epoxy resins cured with anhydrides. Polymer 37(11):2195–2200CrossRefGoogle Scholar
  26. 26.
    Worzakowska M (2008) Synthesis, characterization, thermal, and viscoelastic properties of an unsaturated epoxy polyester cured with different hardeners. J Appl Polym Sci 110(6):3582–3589CrossRefGoogle Scholar
  27. 27.
    Park SJ, Jin FL (2004) Thermal stabilities and dynamic mechanical properties of sulfone-containing epoxy resin cured with anhydride. Polym Degrad Stabil 86(3):515–520CrossRefGoogle Scholar
  28. 28.
    Corcuera MA, Andres MA, Sarasua R, Mondragon I (1992) Rheological and mechanical behaviour of tetraglycidyldiaminodiphenylmethane (TGDDM)/anhydride epoxy systems. Polym Int 29(2):97–102CrossRefGoogle Scholar
  29. 29.
    Patel SR, Patel RG (1992) Effect of the anhydride structure on the curing kinetics and thermal stability of tetrafunctional epoxy resin. Thermochim Acta 202:97–104CrossRefGoogle Scholar
  30. 30.
    Boquillon N, Fringant C (2000) Polymer networks derived from curing of epoxidised linseed oil: influence of different catalysts and anhydride hardeners. Polymer 41(24):8603–8613CrossRefGoogle Scholar
  31. 31.
    Grenier-Loustalot MF, Larroque S, Grande D, Grenier P, Bedel D (1996) Phenolic resins: 2. Influence of catalyst type on reaction mechanisms and kinetics. Polymer 37(8):1363–1369CrossRefGoogle Scholar
  32. 32.
    Carter JT, Emmerson GT, Faro CL, McGrail PT, Moore DR (2003) The development of a low temperature cure modified epoxy resin system for aerospace composites. Compos Part A Appl Sci Manuf 34(1):83–91CrossRefGoogle Scholar
  33. 33.
    Amirova LR, Khamidullin OL, Zalyalova GM, Amirova LM (2017) Estimation of kinetic parameters for curing of epoxy-anhydride compositions by DSC. Russ Chem Bull 66(3):483–487CrossRefGoogle Scholar
  34. 34.
    Tobolski AV (1960) Properties and structure of polymers. Wiley, New YorkGoogle Scholar
  35. 35.
    Fedoseev MS, Derzhavinskaya LF, Noskova OA (2015) Influence of the nature of polymer epoxy matrix on heat-treatment, thermomechanical, physico-mechanical properties of polymeric materials. Materialovedenie 5:11–16Google Scholar
  36. 36.
    Shan L, Robertson CG, Verghese KNE, Burts E, Riffle JS, Ward TC, Reifsnider KL (2001) Influence of vinyl ester/styrene network structure on thermal and mechanical behavior. J Appl Polym Sci 80(7):917–927CrossRefGoogle Scholar
  37. 37.
    Chan LC, Nae HN, Gillham JK (1984) Time-temperature–transformation (TTT) diagrams of high Tg epoxy systems: competition between cure and thermal degradation. J Appl Polym Sci 29(11):3307–3327CrossRefGoogle Scholar
  38. 38.
    Farkas A, Strohm PF (1968) Imidazole catalysis in the curing of epoxy resins. J Appl Polym Sci 12(1):159–168CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Kazan Federal UniversityKazanRussia
  2. 2.Kazan National Research Technical UniversityKazanRussia

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