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Synthesis of high-molecular-weight benzoxazines from various combinations of bisphenols and diamines via Mannich condensation and properties of their thermosets


High-molecular-weight (HMW) benzoxazines were synthesized by Mannich condensation with various combinations of bisphenols and diamines, and the mechanical and thermal properties of the polybenzoxazines derived from the HMW benzoxazines were measured by tensile tests and thermogravimetric analysis (TGA) to investigate the structure-property relationship. Free-standing precursor films were easily obtained from the solutions of HMW benzoxazines by a cast method on glass plates, and transparent and very tough polybenzoxazine films were obtained by thermally curing the precursor films at a temperature up to 240 °C. The polybenzoxazine films showed higher tensile strength and larger elongation at break than typical polybenzoxazine, i.e., PB-a obtained from low-molecular weight benzoxazine synthesized from bisphenol-A and aniline. In particular, among the HMW polybenzoxazines presented in this work, the PODP-oda film derived from 4,4′-oxydiphenol and 4,4′-oxydianiline showed remarkably good mechanical properties (E = 3.7 GPa, sb = 125 MPa, and eb = 4.5%). Moreover, the PODP-oda film revealed a higher 5 wt% weight loss temperature (Td5 = 332 °C) and char yield at 850 °C (CY850 = 58%) than PB-a (Td5 = 301 °C and CY850 = 42%), as evidenced by TGA, suggesting good thermal stability.

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  1. 1.

    Ishida H, Froimowicz P. Advanced and emerging polybenzoxazine science and technology. Amsterdam: Elsevier; 2017.

    Google Scholar 

  2. 2.

    Ishida H, Agag T. Handbook of benzoxazine resins. Amsterdam: Elsevier; 2011.

    Google Scholar 

  3. 3.

    Ning H, Ishida H. Phenolic materials via ring-opening polymerization: synthesis and characterization of bisphenol-A based benzoxazines and their polymers. J Polym Sci Part A Polym Chem. 1994;32:1121–9.

    CAS  Article  Google Scholar 

  4. 4.

    Ishida H, Allen DJ. Physical and mechanical characterization of near-zero shrinkage polybenzoxazines. J Polym Sci Part B Polym Phys. 1996;34:1019–30.

    CAS  Article  Google Scholar 

  5. 5.

    Shen SB, Ishida H. Synthesis and characterization of polyfunctional naphthoxazines and related polymers. J Appl Polym Sci. 1996;34:1595–605.

    Article  Google Scholar 

  6. 6.

    Takeichi T, Agag T, Yong G. Synthesis and properties of polybenzoxazine based composites. Recent Res Devel Polym Sci. 2000;4:85–105.

    CAS  Google Scholar 

  7. 7.

    Su Y-C, Chang F-C. Synthesis and characterization of fluorinated polybenzoxazine material with low dielectric constant. Polymer 2003;44:7989–96.

    CAS  Article  Google Scholar 

  8. 8.

    Ardhyananta H, Wahid MH, Sasaki M, Agag T, Kawauchi T, Ismail H, et al. Performance enhancement of polybenzoxazine by hybridization with polysiloxane. Polymer 2008;49:4585–91.

    CAS  Article  Google Scholar 

  9. 9.

    Ardhyananta H, Kawauchi T, Ismail H, Takeichi T. Effect of pendant group of polysiloxanes on the thermal and mechanical properties of polybenzoxazine hybrids. Polymer 2009;50:5959–69.

    CAS  Article  Google Scholar 

  10. 10.

    Ardhyananta H, Kawauchi T, Takeichi T, Ismail H. Preparation and properties of polybenzoxazine/poly(dimethylsiloxane-co-diphenylsiloxane) hybrids as high performance polymers. High Perform Polym. 2010;22:609.

    CAS  Article  Google Scholar 

  11. 11.

    Takeichi T, Agag T, Zeidam R. Preparation and properties of polybenzoxazine/poly(imide-siloxane) alloys: In situ ring-opening polymerization of benzoxazine in the presence of soluble poly(imide-siloxane)s. J Polym Sci Part A Polym Chem. 2001;39:2633–41.

    CAS  Article  Google Scholar 

  12. 12.

    Jang J, Seo D. Performance improvement of rubber-modified polybenzoxazine. J Appl Polym Sci. 1998;67:1–10.

    CAS  Article  Google Scholar 

  13. 13.

    Suwitaningsih DN, Katsuta S, Kawauchi T, Furukawa N, Takeichi T. Preparation and characterization of liquid rubber-modified polybenzoxazine. J Photopolym Sci Technol. 2015;28:137–43.

    CAS  Article  Google Scholar 

  14. 14.

    Allen DJ, Ishida H. Physical and mechanical properties of flexible polybenzoxazine resins: effect of aliphatic diamine chain length. J Appl Polym Sci. 2006;101:2798–809.

    CAS  Article  Google Scholar 

  15. 15.

    Baranek AD, Kendrick LL, Narayanan J, Tyson GE, Wand S, Patton DL. Flexible aliphatic-bridged bisphenol-based polybenzoxazines. Polym Chem. 2012;3:2892–900.

    CAS  Article  Google Scholar 

  16. 16.

    Takeichi T, Kano T, Agag T. Synthesis and thermal cure of high molecular weight polybenzoxazine precursors and the properties of the thermosets. Polymer. 2005;46:12172–80.

    CAS  Article  Google Scholar 

  17. 17.

    Takeichi T, Kano T, Agag T, Kawauchi T, Furukawa N. Preparation of high molecular weight polybenzoxazine prepolymers containing siloxane unites and properties of their thermosets. J Polym Sci Part A Polym Chem. 2010;48:5945–52.

    CAS  Article  Google Scholar 

  18. 18.

    Chernykh A, Liu J-P, Ishida H. Synthesis and properties of a new crosslinkable polymer containing benzoxazine moiety in the main chain. Polymer. 2006;47:7664–9.

    CAS  Article  Google Scholar 

  19. 19.

    Takeichi T, Uchida S, Inoue Y, Kawauchi T, Furukawa N. Preparation and properties of polymer alloys consisting of high-molecular-weight benzoxazine and bismaleimide. High Perform Polym. 2013;26:265–73.

    Article  Google Scholar 

  20. 20.

    Uchida S, Kawauchi T, Furukawa N, Takeichi T. Polymer alloys of high-molecular-weight benzoxazine and epoxy resin. High Perform Polym. 2014;26:846–55.

    Article  Google Scholar 

  21. 21.

    Ohara M, Yoshimoto K, Kawauchi T, Takeichi T. Synthesis of high-molecular-weight benzoxazines having azomethine linkages in the main-chain and the properties of their thermosetting resins. Polymer. 2020;202:122668.

    CAS  Article  Google Scholar 

  22. 22.

    Nagai A, Kamei Y, Wang X-S, Omura M, Sudo A, Nishida H, et al. Synthesis and crosslinking behavior of a novel linear polymer bearing 1,2,3-triazol the main chain by and benzoxazine groups in a step-growth click-coupling reaction. J Polym Sci Part A Polym Chem. 2008;46:2316–25.

    CAS  Article  Google Scholar 

  23. 23.

    Chernykh A, Agag T, Ishida H. Synthesis of linear polymers containing benzoxazine moieties in the main chain with high molecular design versatility via click reaction. Polymer. 2009;50:382–90.

    CAS  Article  Google Scholar 

  24. 24.

    Liu Y-L, Chou C-I. High performance benzoxazine monomers and polymers containing furan groups. J Polym Sci Part A Polym Chem. 2005;43:5267–82.

    CAS  Article  Google Scholar 

  25. 25.

    Chou C-I, Liu Y-L. High performance thermosets from a curable Diels-Alder polymer possessing benzoxazine group in the main chain. J Polym Sci Part A Polym Chem. 2008;46:6509–17.

    CAS  Article  Google Scholar 

  26. 26.

    Kiskan B, Aydogan B, Yagci Y. Synthesis, characterization, and thermally activated curing of oligosiloxanes containing benzoxazine moieties in the main chain. J Polym Sci Part A Polym Chem. 2009;47:804–11.

    CAS  Article  Google Scholar 

  27. 27.

    Takeichi T, Endo Y, Kaburagi Y, Hishiyama Y, Inagaki M. Carbonization and graphitization of polyimide films: effect of size of leaving group at imidization. J Appl Polym Sci. 1998;68:1613–20.

    CAS  Article  Google Scholar 

  28. 28.

    Shirai Y, Takahashi K, Kawauchi T, Takeichi T. Preparation and properties of polyimide-polysiloxane hybrids using sol-gel method. J Photopolym Sci Technol. 2013;26:333–40.

    CAS  Article  Google Scholar 

  29. 29.

    Low H-Y, Ishida H. Mechanistic study on the thermal decomposition of polybenzoxazines: effects of aliphatic amines. J Polym Sci Part B Polym Phys. 1998;36:1935–46.

    CAS  Article  Google Scholar 

  30. 30.

    Low H-Y, Ishida H. Structural effects of phenols on the thermal and thermo-oxidative degradation of polybenzoxazines. Polymer 1999;40:4365–76.

    CAS  Article  Google Scholar 

  31. 31.

    van Krevelen DW. Some basic aspects of flame resistance of polymeric materials. Polymer. 1975;16:615–20.

    Article  Google Scholar 

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TK acknowledges financial support from the Ryukoku University Science and Technology Fund.

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Correspondence to Takehiro Kawauchi or Tsutomu Takeichi.

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Murai, Y., Uemura, T., Chen, Y. et al. Synthesis of high-molecular-weight benzoxazines from various combinations of bisphenols and diamines via Mannich condensation and properties of their thermosets. Polym J 53, 439–447 (2021).

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