Advertisement

Journal of Thermal Analysis and Calorimetry

, Volume 114, Issue 3, pp 1207–1215 | Cite as

The structure and thermal properties of novel DOPO-containing 1,3-benzoxazines

  • Haixiao Su
  • Zhiguo Liu
Article

Abstract

Three DOPO (9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide)-containing benzoxazin (3a3c) were successfully prepared from 2-hydroxybenzaldehyde, p-substituted aniline, and DOPO by a three-step procedure. Since the phosphorus and the adjacent aliphatic carbon are both chiral centers, two pairs of enantiomers exist in 3a, 3b, or 3c. Compound 3a′, which is a pair of enantiomers existing in 3a, was isolated using recrystallization in ethyl acetate solvent. All the structures were confirmed by FT-IR, NMR, and MS spectra. The X-ray analysis indicated that the 3a′ is the RR/SS enantiomers and belongs to the monoclinic crystal system, its space group being P21/c. The thermal properties were investigated by DSC and TG. It has been found that the peak temperature of thermally induced ring-opening reaction was around 260–270 °C. Compounds (3a3c, 3a′, and 3c′) had two similar thermal processes from 50 to 600 °C in TG, whereas the compound 3b′ had three thermal processes. The char yields of 3a3c were 18.10, 16.84, and 16.34 %, respectively, while those of 3a′–3c′ were 26.00, 31.80, and 19.21 %, respectively. The results indicated that compounds 3a′–3c′ had better char properties than 3a3c.

Keywords

DOPO-containing benzoxazine Synthesis Enantiomers XRD Char property 

Notes

Acknowledgments

The authors acknowledge the financial support for this study from the Education Department of Sichuan Province, Xihua University, open laboratory of State Key Laboratory of Polymer Materials and Engineering(Sichuan University).

References

  1. 1.
    Holly FW, Cope AC. Condensation compounds of aldehydes and ketones with o-aminobenzyl alcohol and o-hydroxybenzylamine. J Am Chem Soc. 1944;66:1875–9.CrossRefGoogle Scholar
  2. 2.
    Schreiber H, Gurrit E, Betamide patents. 1973; DE 2255504; DE 2323936.Google Scholar
  3. 3.
    Peng CR. Study on synthesis of novel benzoxazine based on polyamine and application in PCB. Master’s thesis. Sichuan University, Chengdu, 2006.Google Scholar
  4. 4.
    Gu Y, Xie ML, Liu XH. Progress in the study of phenolic resin using ring-opening polymerization of benzoxazines. Chem Ind Eng Prog. 1998;2:43–7.Google Scholar
  5. 5.
    He YL, Li L, Dong FY. Advance in the research of benzoxazines of high property. Insul Mater. 2009;39(4):5–8.Google Scholar
  6. 6.
    Ghosh NN, Kiskan B, Yagci Y. Polybenzoxazines-new high performance thermosetting resins: synthesis and properties. Prog Polym Sci. 2007;32:1344–91.CrossRefGoogle Scholar
  7. 7.
    Ishida H. US Patent 5543516, 1996.Google Scholar
  8. 8.
    Shen SB, Ishida H. Dynamic mechanical and thermal characterization of high-performance polybenzoxazines. J Polym Sci Part B. 1999;37:3257–68.CrossRefGoogle Scholar
  9. 9.
    Bimlesh L, Indra KV, Jayashree B. Thermal behaviour of cardanol-based benzoxazines. J Therm Anal Calorim. 2010;102:769–74.CrossRefGoogle Scholar
  10. 10.
    Bimlesh L, Indra KV, Jayashree B. Cardanol-based bisbenzoxazines effect of structure on thermal behavior. J Therm Anal Calorim. 2012;107:661–8.CrossRefGoogle Scholar
  11. 11.
    Men WW, Lu ZJ. High performance polybenzoxazines. Prog Chem. 2007;19(5):779–86.Google Scholar
  12. 12.
    Wolfgang M. Method for producing organic compounds containing poly-DOPO and the use of the same. P US20060247344A1. 2006;11:2.Google Scholar
  13. 13.
    Wang Y, Luo Y, Zhang Z. Study on epoxy resin modified with flame retardant DOPO-MA. Insul Mater. 2010;43(3):20–3.Google Scholar
  14. 14.
    Satio T, Shi K. Cyclic organophosphorus compounds and process for making same. US Patent 3702878. 1972-11-24.Google Scholar
  15. 15.
    Schartel B, Braun U, Balabanovich AI, Artner J. Pyrolysis and fire behaviour of epoxy systems containing a novel 9,10-dihydro-9-oxa-10-phosphaphenant hrene-10-oxide-(DOPO)-based diamino hardener. J Eur Polym. 2008;44(3):704–15.CrossRefGoogle Scholar
  16. 16.
    Sun YM, Wang CS. Synthesis and luminescent characteristics of novel phosphorus containing light-emitting polymers. Polymer. 2001;42:1035–45.CrossRefGoogle Scholar
  17. 17.
    Qian LJ, Ye Lj, Xu GZ, Guo JQ. Preparation and characterization of hexa-(DOPO-hydroxymethyl phenoxy)-cyclotriphosphazene. New Chem Mater. 2010;38(8):48–50.Google Scholar
  18. 18.
    Levchik S, Piot rowski A, Weil E, Yao Q. New developments in flame retardancy of epoxy resins. J Polym Degrad Stab. 2005;88(1):57–62.CrossRefGoogle Scholar
  19. 19.
    Lin CH, Cai SX, Leu TS, Hwang TY, Lee HH. Synthesis and properties of flame retardant benzoxazines by three approaches. J Polym Sci Part A. 2006;44:3454–68.CrossRefGoogle Scholar
  20. 20.
    Lin CH, Chang SL, Hsieh CW, Lee HH. Aromatic diamine-based benzoxazines and their high performance thermoset. Polymer. 2008;49:1220–9.CrossRefGoogle Scholar
  21. 21.
    Chang SL, Lin CH, Lin HT, Huang HJ, Hwang KY. Development of an aromatic triamine-based flame-retardant benzoxazine and its high-performance copolybenzoxazines. J Eur Polym. 2009;45:680–9.CrossRefGoogle Scholar
  22. 22.
    Lin CH, Lin HT, Chang SL, Hwang HJ. Benzoxazines with tolyl, p-hydroxyphenyl or p-carboxyphenyl linkage and the structure–property relationship of resulting thermosets. Polymer. 2009;50:2264–72.CrossRefGoogle Scholar
  23. 23.
    Sponton M, Lligadas JG. Development of a DOPO-containing benzoxazine and its high performance flame retardant copolybenzoxazines. Polym Degrad Stab. 2009;94:1693–9.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2013

Authors and Affiliations

  • Haixiao Su
    • 1
  • Zhiguo Liu
    • 2
  1. 1.School of Materials Science and EngineeringXihua UniversityChengduPeople’s Republic of China
  2. 2.School of Physics and ChemistryXihua UniversityChengduPeople’s Republic of China

Personalised recommendations