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Synthesis of Polytetrahydrofuran Using Protonated Kaolin as A Solid Acid Catalyst

1Laboratory of Water Treatment and Valorization of Industrial Waste, Department of Chemistry, Faculty of Sciences, Badji-Mokhtar University, BP12, 23000, Annaba, Algeria

2Department of Petrochemical and Process Engineering, Faculty of Technology, University of 20 Août 1955 Skikda, Algeria

Received: 2 May 2018; Revised: 28 Nov 2018; Accepted: 12 Dec 2018; Available online: 30 Apr 2019; Published: 1 Aug 2019.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2019 by Authors, Published by BCREC Group under

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In this work, a non-toxic protonated kaolin clay exchanged with protons, was successfully applied as a solid acid catalyst for the polymerization of tetrahydrofuran (poly(THF)) at room temperature in the presence of acetic anhydride. Prior to using the kaolin as a catalyst, it was treated with HCl (0.1 M) and characterized using various analytical techniques. The amounts of catalyst and reaction time on the conversion of THF were investigated. Characterizations of nuclear magnetic Resonance of proton (1H-NMR), Fourier Transform Infrared spectroscopy (FT-IR), X-ray Diffraction (XRD), Optical Microscopy (OM), and Differential Scanning Calorimetry (DSC) techniques were used to examine the resulting polymer. X-ray characterization and DSC data indicated that the obtained poly(THF) is a highly crystalline substance. The results showed that protonated kaolin (kaolin–H+) has a high catalytic activity for the polymerization of THF with a conversion rate of 50.02% after 20 hours. 

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Keywords: polymer synthesis; cationic polymerization; protonated kaolin clay; polytetrahydrofuran
Funding: University of Annaba

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  1. Dale, J. (1993). The Contrasting Behaviour of Oxirane and Oxetane in Cationic Cyclooligomerization and Polymerization. Tetrahedron, 49: 8707-8725
  2. Won Kang, J., Kyoo Han, Y. (1997). Polymerization of Tetrahydrofuran with New Transition Metal Catalyst and its Mechanism:(p-Metylbenzyl)-O-Cyanopyridinium Hexafluoroantimonate. Bulletin of the Korean Chemical Society,18: 433-438
  3. Clark, J.S., Elustondo F., Trevitt, G.P., Boyall, D., Robortson, J., Blake, A.J., Wilson, C., Stammen, B. (2002). Preparation of Cyclic Ethers for Polyether Synthesis by Catalytic Ring-Closing Enyne Metathesis of Alkynylethers. Tetrahedron, 58: 1973-1982
  4. Javakannan, M., Ramakrishnan, S. (2001). Recent Developments in Polyether Synthesis. Macromolecular Rapid Communications, 22: 1463-1473
  5. Shibayama, M., Takahashi, H., Nomura, S., Imai, M. (1998). Isothermal Crystallization offend-Linkedpoly(Tetrahydrofuran) Networks. 3. Small-Angle Neutron Scattering. Polymer, 39: 3759-3766
  6. Aouissi, A., AL-Deyab, S.S., AL-Shehri, H. (2010). The Cationic Ring–Opening Polymerization of Tetrahydrofuran with 12-tungstophosphoric Acid. Molecules, 15: 1398-1407
  7. Niyomthai, T., Jongsomjit, B., Praserthdam, P. (2018). Impact of AlCl3 and FeCl2 Addition on Catalytic Behaviors of TiCl4/MgCl2/THF Catalysts for Ethylene Polymerization and Ethylene/1-Hexene Copolymerization. Bulletin of Chemical Reaction Engineering & Catalysis, 13(3): 393-404
  8. doi: 10.9767/bcrec.13.3.2116.393-404
  9. Kušan, J., Keul, H., Höcker, H. (2013). Block Copolymers Comprising a Polytetrahydrofuran Block and One or Two [5]-polyurethane Block(s): Synthesis and Characterization. e-Polymers, 1: 94-102
  10. doi: 10.1515/epoly.2001.1.1.94
  11. Aouissi, A., AL-Deyab, S.S., AL-Shehri, H. (2010). Cationic Ring–Opening Polymerization of Tetrahydrofuran with Keggin-Type Heteropolycompounds as Solid Acid Catalysts. Chinese Journal of Polymer Science, 28: 305-310
  12. Yahiaoui, A., Belbachir, M., Soutif, J.C., Fontaine, L. (2005). Synthesis and Structural Analyses of poly (1,2-Cyclohexene Oxide) over Solid Catalyst. Materials Letters, 59: 759-767
  13. Kadokawa, J., Lwasaki, Y., Taqaya, H. (2002). Ring-Opening Polymerization of Lactones Catalysed by Ion–Exchanged Clay Montmorillonite. Green Chemistry, 4: 14-16
  14. Chandramohan, A., Mandhakini, M., Dinakaran, K., Alagar, M. (2012). Preparation and Characterization of Vinyl Ester Monomer–Toughened Epoxy-Clay Hybrid Nanocomposites: Thermal and Morphological Properties. International Journal of Polymer Analysis and Characterization,17: 477-484
  15. Aslya, A., Harrane, A., Belbachir, M. (2016). Polymerization of DL–Lactide induced by Protonated Montmorillonite Clays as a Solid Catalyst: Mechanism Study. Materials Research, 19: 132-–137
  16. Harrane, A., Meghabar, R., Belbachir, M. (2002). A Protons Exchanged Montmorillonite Clays as an Efficient Catalyst for the Reaction of Isobutylene Polymerization. International Journal of Molecular Sciences, 3: 790-800
  17. Yahiaoui, A., Belbachir, M. (2006). Ring–Opening Polymerization of Styrene Oxide with Maghnite –H+ as Ecocatalyst. Journal of Applied Polymer Science, 100: 1681-1687
  18. Kherroub, D., Belbachir, M., Lamouri, S. (2018). Green Polymerization of Hexadecamethylcyclooctasiloxane Using an Algerian Proton Exchanged Clay Called Maghnite-H+. Bulletin of Chemical Reaction Engineering & Catalysis, 13: 36-46
  19. Ayat, M., Belbachir, M., Rahmouni, A. (2016). Selective Synthesis, Characterization and Kinetics Studies of poly(α-Methyl styrene) induced by Maghnite-Na+ Clay (Algerian MMT). Bulletin of Chemical Reaction Engineering & Catalysis, 11: 376-388
  20. Meghabar, R., Megherbi, A., Belbachir, M. (2003). Ecocatalyst for Cationic Polymerization of N-vinyl-2-pyrrolidone. Polymer, 44: 4097-4100
  21. Belmokhtar, A., Sahli, N., Yahiaoui, A., Belbachir, M. (2007). Polycondensation of Pyrrole and Benzaldehyde Catalyzed by Maghnite-H+. eXPRESS Polymer Letters, 1: 443-449
  22. Rahmouni, A., Belbachir, M. (2016). Green Synthesis of Cationic Polyacrylamide Composite Catalyzed by an Ecologically Catalyst Clay Called Maghnite-H+ (Algerian MMT) Under Microwave Irradiation. Bulletin of Chemical Reaction Engineering & Catalysis, 11: 170-175
  23. Harrane, A., Naar, N., Belbachir, M. (2007). Ring–Opening Polymerization of Oxetane by the Use of a Montmorillonite Clay as Catalyst. Materials Letters, 61: 3555-3558
  24. Ouis, N., Benharrats, N., Belbachir, M. (2004). Synthèses de Polytétrahydrofurane Catalysées par le kaolin de tamazert. Comptes Rendus Chimie, 7: 955-962
  25. Kherroub, D., Belbachir, M. Lamouri, S. (2017). Synthesis and Characterization of Polyvinylmethylsiloxanes by Cationic Polymerization Using a Solid Green Catalyst. e-Polymers, 17: 439-448
  26. Hartati, H., Widati, A., Dewi, T., Prasetyoko, D. (2017). Direct Synthesis of Highly Crystalline ZSM-5 from Indonesian Kaolin. Bulletin of Chemical Reaction Engineering & Catalysis, 12: 251-255
  27. Dang, T.H., Chen, B.H., Lee, D.J. (2013). Application of Kaolin-based Catalysts in Biodiesel Production via Transesterification of Vegetable Oils in Excess Methanol. Bioresource Technology, 145: 175-181
  28. Benkenfoud, K., Harrane, A., Belbachir, M. (2012). Ring Opening Polymerization of Tetrahydrofuran Catalysed by Maghnite–H+. Chinese Journal of Polymer Science, 30: 56-62
  29. Kumar, S., Panda, A. K., Singh, R.K. (2013). Preparation and characterization of acids and alkali treated Kaolin clay. Bulletin of Chemical Reaction Engineering & Catalysis, 8: 61-69
  30. Ferrahi, M.I., Belbachir, M. (2003). Polycondensation of Tetrahydrofuran with Phthalic Anhydride induced by a Proton Exchanged Montmorillonite Clay. International Journal of Molecular Sciences, 4: 312-325
  31. Boulmokh, A., Berrejem, Y., Guerfi, K., Gheid A. (2007). Kaolin from Djebel Debbagh Mine, Guelma, Algeria. Research Journal of Applied Sciences, 2:435-440
  32. Fan, W.W., Fan, X.D., Tian, W., Liao, X.Q., Zhang, W.B., Mu, C.G.; Kong, J. (2013). Poly (ethyleneglycol)-poly(tetrahydrofuran)-poly(ethyleneglycol) triblock copolymer: synthesis, crystallization behavior and novel morphology. eXPRESS Polymer Letters, 7: 416-430
  33. Reguieg, F., Sahli, N., Belbachir, M., Lutz, P.J. (2006). One-step Synthesis of bis–Macromonomers of poly(1,3–dioxolane) catalyzed by Maghnite–H+. Journal of Applied Polymer Science, 99: 3147-3152

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