Skip to main content
Springer Nature Link
Log in

High-performance naphthalenediamine-based polybenzoxazine and its cured epoxy resin

  • Polymers & biopolymers
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

To obtain thermosets with high performance, a 1,5-naphthalenediamine (NDA)-based benzoxazine (NB) is successfully synthesized and used as a novel hardener for diglycidyl ether of bisphenol-A (DGEBA). The structure of NB is confirmed by FT-IR and NMR. The curing behaviors of NB and NB/DGEBA are studied by non-isothermal DSC, and the properties of the resulting thermosets are measured by DMA and TGA. The results show that NB’s thermoset has excellent thermal–mechanical property, thermal stability, and flame retardancy, with storage modulus at 30 °C (\( E^{{\prime }} \)) of 2.4 GPa, 10% weight loss temperature (T10%) of 366 °C, glass transition temperature (Tg) of 279 °C, and char yield at 800 °C in nitrogen (CY) of 60.6%. NB-cured DGEBA possesses better stiffness, thermal stability, flame retardancy, and high-temperature resistance than NDA-cured DGEBA, as indicated by the 1.2 GPa higher \( E^{{\prime }} \), 11 °C higher T10%, 21% higher CY, and 50 °C higher Tg.

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Scheme 2
Figure 9

Similar content being viewed by others

Explore related subjects

Discover the latest articles and news from researchers in related subjects, suggested using machine learning.

References

  1. Ghosh NN, Kiskan B, Yagci Y (2007) Polybenzoxazines-New high performance thermosetting resins: synthesis and properties. Prog Polym Sci 32:1344–1391

    Article  CAS  Google Scholar 

  2. Ishida H, Allen DJ (1996) Physical and mechanical characterization of near-zero shrinkage polybenzoxazines. J Polym Sci Part B: Polym Phys 34:1019–1030

    Article  CAS  Google Scholar 

  3. Su YC, Chang FC (2003) Synthesis and characterization of fluorinated polybenzoxazine material with low dielectric constant. Polymer 44:7989–7996

    Article  CAS  Google Scholar 

  4. Li SL, Zhao CX, Wang YA et al (2018) Synthesis and electrochemical properties of electroactive aniline-dimer-based benzoxazines for advanced corrosion-resistant coatings. J Mater Sci 53:7344–7356. https://doi.org/10.1007/s10853-018-2113-y

    Article  CAS  Google Scholar 

  5. Dayo AQ, Zegaoui A, Nizamani AA et al (2018) The influence of different chemical treatments on the hemp fiber/polybenzoxazine based green composites: mechanical, thermal and water absorption properties. Mater Chem Phys 217:270–277

    Article  CAS  Google Scholar 

  6. Zhang K, Shang ZK, Evans CJ et al (2018) Benzoxazine atropisomers: intrinsic atropisomerization mechanism and conversion to high performance thermosets. Macromolecules 217:270–277

    Article  Google Scholar 

  7. Kotzebue LRV, de Oliveira JR, da Silva JB et al (2018) Development of fully biobased high-performance bis-benzoxazine under environmentally friendly conditions. ACS Sustain Chem Eng 6:5485–5494

    Article  CAS  Google Scholar 

  8. Zhang K, Tan XX, Wang YT et al (2019) Unique self-catalyzed cationic ring-opening polymerization of a high performance deoxybenzoin-based 1,3-benzoxazine monomer. Polymer 168:8–15

    Article  CAS  Google Scholar 

  9. Kim HJ, Brunovska Z, Ishida H (1999) Synthesis and thermal characterization of polybenzoxazines based on acetylene-functional monomers. Polymer 40:6565–6573

    Article  CAS  Google Scholar 

  10. Salum ML, Iguchi D, Arza CR et al (2018) Making benzoxazines greener: design, synthesis, and polymerization of a biobased benzoxazine fulfilling two principles of green chemistry. ACS Sustain Chem Eng 6:13096–13106

    Article  CAS  Google Scholar 

  11. Ishida H, Allen DJ (1996) Mechanical characterization of copolymers based on benzoxazine and epoxy. Polymer 37:4487–4495

    Article  CAS  Google Scholar 

  12. Rimdusit S, Ishida H (2000) Development of new class of electronic packaging materials based on ternary systems of benzoxazine, epoxy, and phenolic resins. Polymer 41:7941–7949

    Article  CAS  Google Scholar 

  13. Takeichi T, Guo Y, Agag T (2000) Synthesis and characterization of poly(urethane-benzoxazine) films as novel type of polyurethane/phenolic resin composites. J Polym Sci Part A: Polym Chem 38:4165–4176

    Article  CAS  Google Scholar 

  14. Schafer H, Koschek K (2018) Effect of poly(epsilon-caprolactone) in polybenzoxazine blends and respective copolymers on morphology and mechanical properties. Eur Polym J 108:582–590

    Article  Google Scholar 

  15. Ishida H, Lee YH (2001) Synergism observed in polybenzoxazine and poly(epsilon-caprolactone) blends by dynamic mechanical and thermogravimetric analysis. Polymer 42:6971–6979

    Article  CAS  Google Scholar 

  16. Kimura H, Matsumoto A, Hasegawa K et al (1998) Epoxy resin cured by bisphenol A based benzoxazine. J Appl Polym Sci 68:1903–1910

    Article  CAS  Google Scholar 

  17. Chang SL, Lin CH (2010) Facile, one-pot synthesis of aromatic diamine-based benzoxazines and their advantages over diamines as epoxy hardeners. J Polym Sci Part A: Polym Chem 48:2430–2437

    Article  CAS  Google Scholar 

  18. Burke WJ, Kolbezen MJ, Stephens CW (1952) Condensation of naphthols with formaldehyde and primary amines. J Am Chem Soc 74:3601–3605

    Article  CAS  Google Scholar 

  19. Burke WJ, Reynolds RJ (1954) Condensation of 2-naphthol with acetaldehyde ammonia. J Am Chem Soc 76:1291–1293

    Article  CAS  Google Scholar 

  20. Shen SB, Ishida H (1996) Synthesis and characterization of polyfunctional naphthoxazines and related polymers. J Appl Polym Sci 61:1595–1605

    Article  CAS  Google Scholar 

  21. Uyar T, Hacaloglu J, Ishida H (2013) Synthesis, characterization, and thermal properties of alkyl-functional naphthoxazines. J Appl Polym Sci 127:3114–3123

    Article  CAS  Google Scholar 

  22. Zhang WF, Froimowicz P, Arza CR et al (2016) Latent catalyst-containing naphthoxazine: synthesis and effects on ring-opening polymerization. Macromolecules 49:7129–7140

    Article  CAS  Google Scholar 

  23. Kaya G, Kiskan B, Yagci Y (2018) Phenolic naphthoxazines as curing promoters for benzoxazines. Macromolecules 51:1688–1695

    Article  CAS  Google Scholar 

  24. Arza CR, Froimowicz P, Han L et al (2017) Design, synthesis, characterization, and polymerization of fused-ring naphthoxazine resins. Macromolecules 50:9249–9256

    Article  CAS  Google Scholar 

  25. Kiskan B, Yagci Y (2005) Synthesis and characterization of naphthoxazine functional poly(epsilon-caprolactone). Polymer 46:11690–11697

    Article  CAS  Google Scholar 

  26. Yildirim A, Kiskan B, Demirel AL et al (2006) Synthesis, characterization and properties of naphthoxazine-functional poly(propyleneoxide)s. Eur Polym J 42:3006–3014

    Article  CAS  Google Scholar 

  27. Yeganeh H, Jangi A (2010) Thermally curable polyurethanes containing naphthoxazine groups in the main chain. Polym Inter 59:1375–1383

    Article  CAS  Google Scholar 

  28. Uyar T, Koyuncu Z, Ishida H et al (2008) Polymerisation and degradation of an aromatic amine-based naphthoxazine. Polym Degrad Stabil 93:2096–2103

    Article  CAS  Google Scholar 

  29. Agag T (2006) Preparation and properties of some thermosets derived from allyl-functional naphthoxazines. J Appl Polym Sci 100:3769–3777

    Article  CAS  Google Scholar 

  30. Ohashi S, Pandey V, Arza CR et al (2016) Simple and low energy consuming synthesis of cyanate ester functional naphthoxazines and their properties. Polym Chem 7:2245–2252

    Article  CAS  Google Scholar 

  31. Lin CH, Chang SL, Hsieh CW et al (2008) Aromatic diamine-based benzoxazines and their high performance thermosets. Polymer 49:1220–1229

    Article  CAS  Google Scholar 

  32. Agag T, Jin L, Ishida H et al (2009) A new synthetic approach for difficult benzoxazines: preparation and polymerization of 4,4’-diaminodiphenyl sulfone-based benzoxazine monomer. Polymer 50:5940–5944

    Article  CAS  Google Scholar 

  33. Jubsilp C, Punson K, Takeichi T et al (2010) Curing kinetics of benzoxazine-epoxy copolymer investigated by non-isothermal differential scanning calorimetry. Polym Degrad Stabil 95:918–924

    Article  CAS  Google Scholar 

  34. Ren ST, Yang X, Zhao XJ et al (2015) Kinetics and properties of diethyltoluenediamine typebenzoxazine-cured diglycidyl ether of bisphenol-A. Thermochim Acta 616:33–41

    Article  CAS  Google Scholar 

  35. Jubsilp C, Damrongsakkul S, Takeichi T et al (2006) Curing kinetics of arylamine-based polyfunctional benzoxazine resins by dynamic differential scanning calorimetry. Thermochim Acta 447:131–140

    Article  CAS  Google Scholar 

  36. Sini NK, Bijwe J, Varma IK (2014) Thermal behaviour of bis-benzoxazines derived from renewable feed stock ‘vanillin’. Polym Degrad Stabil 109:270–277

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This study is financially supported by the Natural Science Foundation of Hebei Province (E2018210079). The authors gratefully thank Professor Huang Wei and Yang Xin of the Institute of Chemistry Chinese Academy of Sciences for their help.

Author information

Authors and Affiliations

  1. School of Materials Science and Engineering, Shijiazhuang Tiedao University, 17 Northeast, Second Inner Ring, Shijiazhuang, 050043, Hebei, People’s Republic of China

    Shitong Ren, Shaoyue Zhang, Weibo Zhao & Wei Wang

Authors
  1. Shitong Ren
    View author publications

    Search author on:PubMed Google Scholar

  2. Shaoyue Zhang
    View author publications

    Search author on:PubMed Google Scholar

  3. Weibo Zhao
    View author publications

    Search author on:PubMed Google Scholar

  4. Wei Wang
    View author publications

    Search author on:PubMed Google Scholar

Corresponding author

Correspondence to Shitong Ren.

Ethics declarations

Conflict of interest

There author declares that they have no conflict of interest.

Additional information

Publisher's Note

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

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 317 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ren, S., Zhang, S., Zhao, W. et al. High-performance naphthalenediamine-based polybenzoxazine and its cured epoxy resin. J Mater Sci 55, 806–816 (2020). https://doi.org/10.1007/s10853-019-04051-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-019-04051-0