DOI: https://doi.org/10.9767/bcrec.11.2.541.151-160

New Method for Nucleophilic Substitution on Hexachlorocyclotriphosphazene by Allylamine Using an Algerian Proton Exchanged Montmorillonite Clay (Maghnite-H+) as a Green Solid Catalyst

Laboratory of Polymer Chemistry, Department of Chemistry, Faculty of Exact and Applied Sciences, University of Oran1 Ahmed BenBella, BP 1524 El M'Naouar, 31000 Oran, Algeria

Received: 28 Sep 2015; Revised: 5 Dec 2015; Accepted: 4 Jan 2016; Available online: 30 Jun 2016; Published: 20 Aug 2016.
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Open Access Copyright (c) 2016 by Authors, Published by BCREC Group under http://creativecommons.org/licenses/by-sa/4.0.

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Abstract

Nucleophilic substitution on hexachlorocyclotriphosphazene (HCCTP) with allylamine in order to give hexa(allylamino)cyclotriphosphazene (HACTP)  is performed for the first time under mild conditions by using diethylether as solvent to replace benzene which is very toxic. The reaction time is reduced to half and also performed at room temperature but especially in the presence of an eco-catalyst called Maghnite-H+. This catalyst has a significant role in the industrial scale. In fact, the use of Maghnite is preferred for its many advantages: a very low purchase price compared to other catalysts, the easy removal of the reaction mixture. Then, Maghnite-H+ is became an excellent catalyst for many chemical reactions. The structure of HACTP synthesized in the presence of Maghnite-H+ to 5% by weight is confirmed by 1H-NMR, 13C-NMR, 31P-NMR (Nuclear magnetic resonance) and FTIR (Fourier Transform Infrared spectroscopy). MALDI-TOF (Matrix-Assisted Laser Desorption/Ionisation-time-of-flight mass spectrometry) is used to establish the molecular weight of HACTP which is 471 g/mol. DSC (Differential Scanning Calorimetery) and TGA (Thermogravimetric Analysis) show that HACTP is a crystalline product with a melting point of 88 °C. It is reactive after melting but is degraded from 230 °C. 

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Keywords: Hexachlorocyclotriphosphazene; Allylamine; Nucleophilic substitution; Maghnite-H+; NMR spectroscopy; Thermal properties

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Section: Original Research Articles
Language : EN
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  12. Allcock, H.R. (2006). Recent developments in polyphosphazene materials science. Current Opinion in Solid State Materials Science, 10: 231-240
  13. Gleria, M., Jaeger, R.D. (2004). Phosphazenes a worldwide insight. Nova Science Publishers Incorporation, Hauppauge, New York
  14. Allcock, H.R., Napierala, M.E., Cameron, C.G., O’Connor, S.J.M. (1996). Synthesis and Characterization of Ionically Conducting Alkoxy Ether/Alkoxy Mixed-Substituent Poly(organophosphazenes) and Their Use as Solid Solvents for Ionic Conduction. Macromolecules, 29: 1951-1956
  15. Xu, G., Lu, Q., Yu, B., Wen, L. (2006). Inorganic polymer phosphazene disulfide as cathode material for rechargeable lithium batteries. Solid State Ionics, 177: 305-309
  16. Allcock, H.R., Wood, R.M. (2006). Design and synthesis of ion-conductive polyphosphazenes for fuel cell applications: Review. Journal of Polymer Science, Part B. Polymer Physics, 44: 2358-2368
  17. Li, Z., Qin, J., Li, S., Ye, C., Luo, J., Cao, Y. (2002). Polyphophazene Containing Indole-Based Dual Chromophores: Synthesis and Nonlinear Optical Characterization. Macromolecules, 35: 9232-9235
  18. Christova, D., Ivanova, S. D., Velichkova, R. S., Tzvetkova, P., Mihailova, P., Uzunov, I., Lakov, L., Peshev, O. (2003). Organic–inorganic composites based on cyclotriphosphazene-cross-linked PHEMA networks. Designed Monomers and Polymers, 6: 11-21
  19. Belbachir, M. (2001). US Patent. 066969.0101
  20. Belbachir, M., Bensaoula, A. (2001). Composition and method for catalysis using bentonites. US Patent. US6274527
  21. Kuan, J. F., Lin, K. F. (2004). Synthesis of Hexa(allylamino)cyclotriphosphazene as a reactive fire retardant for unsaturated polyesters. Journal of Applied Polymer Science, 91: 697-702

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