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Poly(urethane-benzoxazine)s

Abstract

New poly(urethane-benzoxazine)s (PUB) were prepared by the Diels-Alder reaction of bisfuranic benzoxazine monomers, containing additional polymerizable allyl groups (2,2′-bis(8-allyl-3-furfuryl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane), to bisma-leimides having urethane structure. The thermal behaviour of intermediate cycloadducts was evaluated by TGA, DMA and DSC measurements and their curing behaviour was investigated by DSC, 1H-NMR and ATR-FTIR analysis. Introduction of urethane bismaleimide in the networks structure leads to an increase of flexibility and thermal stability of resulted films, in comparison with polyurethanes, but mechanical properties has not been optimized, probable due to the large amount of soft segments (47–79.98 %) that leads to a phase separation.

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References

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

    CAS  Article  Google Scholar 

  2. Holly FW, Cope AC (1944) Condensation products of aldehydes and ketones with o-aminobenzyl alcohol and o-hydroxybenzylamine. J Am Chem Soc 66:1875–1879

    CAS  Article  Google Scholar 

  3. Burke WJ (1949) 3,4-Dihydro-1,3,2H-Benzoxazines. Reaction of p-substituted phenols with N, N-dimethylolamines. J Am Chem Soc 71:609–612

    CAS  Article  Google Scholar 

  4. Yagci Y, Kiskan B, Ghosh NN (2009) Recent advancement on polybenzoxazine-a newly developed high performance thermoset. J Polym Sci A Polym Chem 47:5565–5576

    CAS  Article  Google Scholar 

  5. Demir KD, Kiskan B, Aydogan B, Yagci Y (2013) Thermally curable main-chain benzoxazine prepolymers via polycondensation route. React Funct Polym 73:346–359

    CAS  Article  Google Scholar 

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

    CAS  Article  Google Scholar 

  7. Reghunadhan Nair CP (2004) Advances in addition-cure phenolic resins. Prog Polym Sci 29:401–498

    Article  Google Scholar 

  8. Shen BS, Ishida H (1996) Development and characterization of high-performance polybenzoxazine composites. Polym Compos 17:710–719

    CAS  Article  Google Scholar 

  9. Chandramohan A, Devaraju S, Vengatesan MR, Alagar M (2012) Octakis(dimethylsiloxypropylglycidylether)silsesquioxane (OG-POSS) reinforced 1,1-bis(3-methyl-4-hydroxymethyl)cyclohexane based polybenzoxazine nanocomposites. J Polym Res 19:9903

    Article  Google Scholar 

  10. Chernykh A, Agag T, Ishida H (2009) Synthesis of linear polymers containing benzoxazine moieties in the main chain with high molecular design versatility via click reaction. Polymer 50:382–390

    CAS  Article  Google Scholar 

  11. Kiskan B, Aydogan B, Yagci Y (2009) Synthesis, characterization, and thermally activated curing of oligosiloxanes containing benzoxazine moieties in the main chain. J Polym Sci A Polym Chem 47:804–811

    CAS  Article  Google Scholar 

  12. Andreu R, Reina JA, Ronda JC (2008) Carboxylic acid-containing benzoxazines as efficient catalysts in the thermal polymerization of benzoxazines. J Polym Sci A Polym Chem 46:6091–6101

    CAS  Article  Google Scholar 

  13. Yang P, Wang X, Gu Y (2012) Copolymers of phenolphthalein-aniline-based benzoxazine and biphenyl epoxy: curing behavior and thermal and mechanical properties. J Polym Res 19:9901

    Article  Google Scholar 

  14. Ardhyananta H, Wahid MH, Sasaki M, Agag T, Kawauchi T, Ismail H, Takeichi T (2008) Performance enhancement of polybenzoxazine by hybridization with polysiloxane. Polymer 49:4585–4591

    CAS  Article  Google Scholar 

  15. 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 A Polym Chem 38:4165–4176

    CAS  Article  Google Scholar 

  16. Yeganeh H, Razavi-Nouri M, Ghaffari M (2008) Investigation of thermal, mechanical, and electrical properties of novel polyurethanes/high molecular weight polybenzoxazine blends. Polym Adv Technol 19:1024–1032

    CAS  Article  Google Scholar 

  17. Rimdusit S, Pirstpindvong S, Tanthapanichakoon W, Damrongsakkul S (2005) Toughening of polybenzoxazine by alloying with urethane prepolymer and flexible epoxy: A comparative study. Polym Eng Sci 45:288–296

    CAS  Article  Google Scholar 

  18. Jamshidi S, Yeganeh H, Mehdipour-Ataei S (2011) Preparation and properties of one-pack polybenzoxazine-modified polyurethanes with improved thermal stability and electrical insulating properties. Polym Int 60:126–135

    CAS  Article  Google Scholar 

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

    CAS  Article  Google Scholar 

  20. Baqar M, Agag T, Ishida H, Qutubuddin S (2011) Poly(benzoxazine-co-urethane)s: a new concept for phenolic/urethane copolymers via one-pot method. Polymer 52:307–317

    CAS  Article  Google Scholar 

  21. Jamshidi S, Yeganeh H, Mehdipour-Ataei S (2011) Poly(urethane-co-benzoxazine)s via reaction of phenol terminated urethane prepolymers and benzoxazine monomer and investigation of their properties. Polym Adv Technol 22:1502–1512

    CAS  Article  Google Scholar 

  22. Gaina V, Gaina C (2007) Bismaleimides and biscitraconimides with bisallyl groups. High Perform Polym 19:160–174

    CAS  Article  Google Scholar 

  23. Gaina C, Ursache O, Gaina V, Musteata VE (2013) High performance thermosets based on multifunctional intermediates containing allyl, maleimide and benzoxazine groups. J Polym Res 20:263

    Article  Google Scholar 

  24. Gaina V, Gaina C, Sava M, Stoleriu A, Rusu M (1997) Bismaleimide resins containing urethanic moieties. J Macromol Sci Pure Appl Chem 34:2435–2449

    Article  Google Scholar 

  25. Gaina C, Ursache O, Gaina V, Buruiana E (2012) Novel thermally reversible epoxy-urethane networks. Des Monom Polym 15:63–73

    CAS  Article  Google Scholar 

  26. Gaina C, Ursache O, Gaina V, Buruiana E, Ionita D (2012) Investigation on the thermal properties of new thermo-reversible networks based on poly(vinyl furfural) and multifunctional maleimide compounds. Expr Polym Lett 6:129–141

    CAS  Article  Google Scholar 

  27. Feng JL, Yue CY, Chian KS (2006) Synthesis and characterization of the bismaleimides containing aliphatic-ether chain for microelectronics application. e-Polym 6:580–590

    Google Scholar 

  28. Okhawilai M, Pudhom K, Rimdusit S (2014) Synthesis and characterization of sequential interpenetrating polymer networks of polyurethane acrylate and polybenzoxazine. Polym Eng Sci 54:1151–1161

    CAS  Article  Google Scholar 

  29. Chou CI, Liu YL (2008) High performance thermosets from a curable Diels-Alder polymer possessing benzoxazine groups in the main chain. J Polym Sci A Polym Chem 46:6509–6517

    CAS  Article  Google Scholar 

  30. Liu YL, Chou CI (2005) High performance benzoxazine monomers and polymers containing furan groups. J Polym Sci A Polym Chem 43:5267–5282

    CAS  Article  Google Scholar 

  31. Wang Z, Zhao J, Ran Q, Zhu R, Gu Y (2013) Research on curing mechanism and thermal property of bis-allyl benzoxazine and N, N’-(2,2,4-trimethylhexane-1,6-diyl) dimaleimide blend. React Funct Polym 73:668–673

    CAS  Article  Google Scholar 

  32. Chaisuwan T, Ishida H (2010) Higly processible maleimide and nitrile functionalized benzoxazines for advanced composites applications. J Appl Polym Sci 117:2559–2565

    CAS  Google Scholar 

  33. Liu YL, Yu YM (2006) Cocuring behaviors of benzoxazine and maleimide derivatives and the thermal properties of the cured products. J Polym Sci A Polym Chem 44:1890–1899

    CAS  Article  Google Scholar 

  34. Samson N, Mechin F, Pascault JP (1998) New segmented polyurethane ureas based on 4,4′-dicyclohexylmethane diisocyanate and on various soft segments. J Appl Polym Sci 70:2331–2342

    CAS  Article  Google Scholar 

Download references

Acknowledgments

Paper dedicated to the 65th anniversary of “Petru Poni” Institute of Macromolecular Chemistry of Romanian Academy, Iasi, Romania.

One of the authors (C-D.V.) acknowledges the financial support of a grant of the Romanian National Authority for Scientific Research, CNCS–UEFISCDI, project number PN-II-ID-PCE-2011-3-0187.

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Correspondence to V. Gaina.

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Gaina, C., Ursache, O., Gaina, V. et al. Poly(urethane-benzoxazine)s. J Polym Res 21, 586 (2014). https://doi.org/10.1007/s10965-014-0586-1

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  • DOI: https://doi.org/10.1007/s10965-014-0586-1

Keywords

  • Polybenzoxazine
  • Diels-Alder reaction
  • Curing reaction
  • Bismaleimides