High thermal conductivity and flame-retardant phosphorus-free bismaleimide resin composites based on 3D porous boron nitride framework

  • Chenfeng Tian
  • Li Yuan
  • Guozheng LiangEmail author
  • Aijuan GuEmail author


High thermal conductivity and high flame retardancy become necessary properties of thermally resistant thermosetting resins for many cutting-edge fields. However, building a phosphorus-free sustainable strategy is still a challenge; besides, sometimes high thermal conductivity and flame retardancy could not be simultaneously achieved, while sometimes they promote to each other, and no report focuses on explicating their relationship and mechanism. Herein, new resins with high thermal conductivity and greatly improved flame retardancy are developed through building phosphorus-free cross-linked network with three-dimensional porous framework based on boron nitride (BN) skeleton (sBN) and bismaleimide resin (BD). With the same loading of BN, sBN/BD has much higher thermal conductivity than the composite based on BN powders (BN/BD). For composites with 12.53 wt% of fillers (sBN or BN powders), the thermal conductivity of 5sBN/BD reaches 1.53 Wm−1 K−1, about 2.4 and 9.4 times of those of 5BN/BD and BD resin, respectively. The exploring relationship between flame retardancy and thermal conductivity shows that sBN/BD composites are somewhat easier to be ignited, and the flame propagation is faster, but under continuous heating, sBN/BD has much weaker burn strength and fewer smoke releasing compared with BN/BD. 5sBN/BD has about 51.9%, 47.5%, 42.5% and 54.8% lower peak heat release rate, total smoke release, specific extinction area and maximum smoke density than BD resin, respectively. The mechanism behind these interesting results is intensively discussed.



We thank National Natural Science Foundation of China (51873135), Key Major Program of Natural Science Fundamental Research Project of Jiangsu Colleges and Universities (18KJA430013), Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), China, for financially supporting this project.

Compliance with ethical standards

Conflict of interest

The authors declare no conflicts of interest exist.

Supplementary material

10853_2019_3318_MOESM1_ESM.docx (34 kb)
Supplementary material 1 (DOCX 33 kb)


  1. 1.
    Iredale RJ, Ward C, Hamerton I (2017) Modern advances in bismaleimide resin technology: a 21st century perspective on the chemistry of addition polyimides. Prog Polym Sci 69:1–21CrossRefGoogle Scholar
  2. 2.
    Carolan D, Ivankovic A, Kinloch AJ et al (2017) Toughened carbon fibre-reinforced polymer composites with nanoparticle-modified epoxy matrices. J Mater Sci 52:1767–1788. CrossRefGoogle Scholar
  3. 3.
    Fan X, Miao J, Yuan L, Guan Q, Gu A, Liang G (2018) Preparation and origin of thermally resistant biobased epoxy resin with low internal stress and good UV resistance based on SiO2 hybridized cellulose for light emitting diode encapsulation. Appl Surf Sci 447:315–324CrossRefGoogle Scholar
  4. 4.
    Wang Z, Cheng Y, Wang H et al (2017) Sandwiched epoxy–alumina composites with synergistically enhanced thermal conductivity and breakdown strength. J Mater Sci 52:4299–4308. CrossRefGoogle Scholar
  5. 5.
    Zhang Z, Yuan L, Guan Q et al (2017) Synergistically building flame retarding thermosetting composites with high toughness and thermal stability through unique phosphorus and silicone hybridized graphene oxide. Compos Part A Appl Sci Manuf 98:174–183CrossRefGoogle Scholar
  6. 6.
    Guan Q, Yuan L, Zhang Y et al (2017) Improving the mechanical, thermal, dielectric and flame retardancy properties of cyanate ester with the encapsulated epoxy resin-penetrated aligned carbon nanotube bundle. Compos Part B Eng 123:81–91CrossRefGoogle Scholar
  7. 7.
    Zhang Z, Xu W, Yuan L et al (2018) Flame retardant cyanate ester resin with suppressed toxic volatiles based on environmentally friendly halloysite nanotube/graphene oxide hybrid. J Appl Polym Sci 135:46587–46600CrossRefGoogle Scholar
  8. 8.
    Guan Q, Yuan L, Zhang Y et al (2018) Tailoring the structure of aligned carbon nanotube bundle by reactive polymer for strengthening its surface interaction with thermosets and the excellent properties of the hybrid thermosets. Appl Surf Sci 439:638–648CrossRefGoogle Scholar
  9. 9.
    Hull TR, Stec AA (2009) Polymer and fire. Royal Society of Chemistry, CambridgeGoogle Scholar
  10. 10.
    Blasi CD (1996) Modeling of solid- and gas-phase processes during thermal degradation of composite materials. Polym Degrad Stab 54:241–248CrossRefGoogle Scholar
  11. 11.
    Nelson GL (1995) Fire and polymers: an overview. ACS Publication, Washington, DCCrossRefGoogle Scholar
  12. 12.
    Shi Y, Qian X, Zhou K et al (2013) CuO/graphene nanohybrids: preparation and enhancement on thermal stability and smoke suppression of polypropylene. Ind Eng Chem Res 52:13654–13660CrossRefGoogle Scholar
  13. 13.
    Bao C, Song L, Xing W et al (2012) Preparation of graphene by pressurized oxidation and multiplex reduction and its polymer nanocomposites by masterbatch-based melt blending. J Mater Chem 22:6088–6096CrossRefGoogle Scholar
  14. 14.
    Gu J, Liang C, Zhao X et al (2017) Highly thermally conductive flame-retardant epoxy nanocomposites with reduced ignitability and excellent electrical conductivities. Compos Sci Technol 139:83–89CrossRefGoogle Scholar
  15. 15.
    Yang D, Huang S, Ruan M et al (2018) Mussel inspired modification for aluminum oxide/silicone elastomer composites with largely improved thermal conductivity and low dielectric constant. Ind Eng Chem Res 57:3255–3262CrossRefGoogle Scholar
  16. 16.
    Tian L, Wang Y, Jin E, Li Y, Wang R, Shang Y (2017) Aluminum nitride-filled elastic silicone rubber composites for drag reduction. Adv Mech Eng 9:1–9Google Scholar
  17. 17.
    Tanaka S, Hojo F, Kagawa H, Takezawa Y (2014) Fabrication of highly water-resistant AlN particles with hybrid α-Al2O3/organic layers. J Ceram Soc Jpn 122:211–215CrossRefGoogle Scholar
  18. 18.
    Wereszczak AA, Morrissey TG, Volante CN, Farris PJ, Groele RJ, Wiles RH, Wang H (2013) Thermally conductive MgO-filled epoxy molding compounds. IEEE Trans Compon Packag Manuf Technol 3:1994–2005CrossRefGoogle Scholar
  19. 19.
    Chen J, Huang X, Zhu Y, Jiang P (2017) Cellulose nanofiber supported 3D interconnected BN nanosheets for epoxy nanocomposites with ultrahigh thermal management capability. Adv Funct Mater 27:1604754CrossRefGoogle Scholar
  20. 20.
    Jiang Y, Liu Y, Min P, Sui G (2017) BN@PPS core-shell structure particles and their 3D segregated architecture composites with high thermal conductivities. Compos Sci Technol 144:63–69CrossRefGoogle Scholar
  21. 21.
    Wang Z, Huang Y, Zhang G et al (2018) Enhanced thermal conductivity of segregated poly(vinylidene fluoride) composites via forming hybrid conductive network of boron nitride and carbon nanotubes. Ind Eng Chem Res 57:10391–10397CrossRefGoogle Scholar
  22. 22.
    Golberg D, Bando Y, Huang Y, Terao T, Mitome M, Tang C, Zhi C (2010) Boron nitride nanotubes and nanosheets. ACS Nano 4:2979–2993CrossRefGoogle Scholar
  23. 23.
    Singh B, Kaur G, Singh P et al (2016) Nanostructured boron nitride with high water dispersibility for boron neutron capture therapy. Sci Rep 6:35535CrossRefGoogle Scholar
  24. 24.
    Liu D, Lei W, Qin S, Chen Y (2014) Template-free synthesis of functional 3D BN architecture for removal of dyes from water. Sci Rep 4:4453CrossRefGoogle Scholar
  25. 25.
    Zeng X, Yao Y, Gong Z, Wang F, Sun R, Xu J, Wong CP (2015) Ice-templated assembly strategy to construct 3D boron nitride nanosheet networks in polymer composites for thermal conductivity improvement. Small 11:6205–6213CrossRefGoogle Scholar
  26. 26.
    Zeng X, Ye L, Yu S, Li H, Sun R, Xu J, Wong CP (2015) Artificial nacre-like papers based on noncovalent functionalized boron nitride nanosheets with excellent mechanical and thermally conductive properties. Nanoscale 7:6774–6781CrossRefGoogle Scholar
  27. 27.
    Wang D, Mu X, Cai W, Song L, Ma C, Hu Y (2018) Constructing phosphorus, nitrogen, silicon-co-contained boron nitride nanosheets to reinforce flame retardant properties of unsaturated polyester resin. Compos Part A Appl Sci Manuf 109:546–554CrossRefGoogle Scholar
  28. 28.
    Qiu S, Hou Y, Xing W et al (2018) Self-assembled supermolecular aggregate supported on boron nitride nanoplatelets for flame retardant and friction application. Chem Eng J 349:223–234CrossRefGoogle Scholar
  29. 29.
    Qu T, Yang N, Hou J et al (2017) Flame retarding epoxy composites with poly(phosphazene-co-bisphenol A)-coated boron nitride to improve thermal conductivity and thermal stability. RSC Adv 7:6140–6151CrossRefGoogle Scholar
  30. 30.
    Jin W, Yuan L, Liang G, Gu A (2014) Multifunctional cyclotriphosphazene/hexagonal boron nitride hybrids and their flame retarding bismaleimide resins with high thermal conductivity and thermal stability. ACS Appl Mater Interfaces 6:14931–14944CrossRefGoogle Scholar
  31. 31.
    Xu W, Li A, Liu Y, Chen R, Li W (2018) CuMoO4@hexagonal boron nitride hybrid: an ecofriendly flame retardant for polyurethane elastomer. J Mater Sci 53:11265–11279. CrossRefGoogle Scholar
  32. 32.
    Cai W, Guo W, Pan Y et al (2018) Polydopamine-bridged synthesis of ternary h-BN@PDA@SnO2 as nanoenhancers for flame retardant and smoke suppression of epoxy composites. Compos Part A Appl Sci Manuf 111:94–105.CrossRefGoogle Scholar
  33. 33.
    Yu B, Xing W, Guo W, Qiu S, Wang X, Lo S, Hu Y (2016) Thermal exfoliation of hexagonal boron nitride for effective enhancements on thermal stability, flame retardancy and smoke suppression of epoxy resin nanocomposites via sol–gel process. J Mater Chem A 4:7330–7340CrossRefGoogle Scholar
  34. 34.
    Cai W, Hong N, Feng X et al (2017) A facile strategy to simultaneously exfoliate and functionalize boron nitride nanosheets via Lewis acid-base interaction. Chem Eng J 330:309–321CrossRefGoogle Scholar
  35. 35.
    Kozlowski G, Vallelian S (2009) Eutrophication and endangered aquatic plants: an experimental study on Baldellia ranunculoides (L.) Parl. (Alismataceae). Hydrobiologia 635:181–187CrossRefGoogle Scholar
  36. 36.
    Li W, Zhou B, Wang M et al (2015) Silane functionalization of graphene oxide and its use as a reinforcement in bismaleimide composites. J Mater Sci 50:5402–5410. CrossRefGoogle Scholar
  37. 37.
    Wang Y, Al-Biloushi M, Schiraldi DA (2012) Polymer/clay aerogel-based glass fabric laminates. J Appl Polym Sci 124:2945–2953CrossRefGoogle Scholar
  38. 38.
    Ye S, Feng J, Wu P (2013) Highly elastic graphene oxide–epoxy composite aerogels via simple freeze-drying and subsequent routine curing. J Mater Chem A 1:3495–3503CrossRefGoogle Scholar
  39. 39.
    Jiang S, Bai Z, Tang G et al (2014) Fabrication of Ce-doped MnO2 decorated graphene sheets for fire safety applications of epoxy composites: flame retardancy, smoke suppression and mechanism. J Mater Chem A 2:17341–17351CrossRefGoogle Scholar
  40. 40.
    Morgan AB, Charles A (2007) Flame retardant polymer nanocomposites. Wiley, HobokenCrossRefGoogle Scholar
  41. 41.
    Hu Y (2008) Flame retardant polymer nanocomposites. Chemical Industry Press, BeijingGoogle Scholar
  42. 42.
    Li J (2013) Flame retardant theory. Science Press, BeijingGoogle Scholar
  43. 43.
    Shao Z, Zhang M, Li Y, Han Y, Ren L, Deng C (2018) A novel multi-functional polymeric curing agent: synthesis, characterization, and its epoxy resin with simultaneous excellent flame retardance and transparency. Chem Eng J 345:471–482CrossRefGoogle Scholar
  44. 44.
    Wang J, Qian L, Huang Z, Fang Y, Qiu Y (2016) Synergistic flame-retardant behavior and mechanisms of aluminum poly-hexamethylenephosphinate and phosphaphenanthrene in epoxy resin. Polym Degrad Stab 130:173–181CrossRefGoogle Scholar
  45. 45.
    Brehme S, Schartel B, Goebbels J, Fischer O, Pospiech D, Bykov Y, Döring M (2011) Phosphorus polyester versus aluminium phosphinate in poly(butylene terephthalate) (PBT): flame retardancy performance and mechanisms. Polym Degrad Stab 96:875–884CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Materials Science and Engineering, College of Chemistry, Chemical Engineering and Materials ScienceSoochow UniversitySuzhouPeople’s Republic of China

Personalised recommendations