DOI: https://doi.org/10.9767/bcrec.11.3.578.376-388

Selective Synthesis, Characterization and Kinetics Studies of poly(α-Methyl styrene) induced by Maghnite-Na+ Clay (Algerian MMT)

Laboratory of Polymer Chemistry, Department of Chemistry, Faculty of Science, University of Oran 1. Ahmed Benbella. BP N ° 1524 El M'Naouar, 31000 Oran, Algeria

Received: 30 Jun 2016; Published: 11 Oct 2016.
Editor(s): Istadi Istadi
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
A new and efficient catalyst of Na-Montmorillonite (Na+-MMT) was employed in this paper for α-methylstyrene (AMS) cationic polymerization. Maghnite clay, obtained from Tlemcen Algeria, was investigated to remove heavy metal ion from wastewater. “Maghnite-Na” is a Montmorillonite sheet silicate clay, exchanged with sodium as an efficient catalyst for cationic polymerization of many vinylic and heterocyclic monomers. The various techniques, including 1H-NMR, 13C-NMR, IR, DSC and Ubbelohde viscometer, were used to elucidate structural characteristics and thermal properties of the resulting polymers. The structure compositions of “MMT”, “H+-MMT” and “Na+-MMT” have been developed. It was found that the cationic polymerization of AMS is initiated by Na+-MMT at 0 °C in bulk and in solution. The influences of reaction temperature, solvent, weight ratio of initiator/monomer and reaction time on the yield of monomer and the molecular weight are investigated. The kinetics indicated that the polymerization rate is first order with respect to the monomer concentration. A possible mechanism of this cationic polymerization is discussed based on the results of the 1H-NMR Spectroscopic analysis of these model reactions. A cationic mechanism for the reaction was proposed. From the mechanism studies, it was showed that monomer was inserted into the growing chains.
Keywords: synthesis; cationic polymerization; catalysts; montmorillonite; Na+-MMT; poly(α-methylstyrene); mechanism; thermal properties

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  1. Sigwalt, P. (1985). Recent Results in Proton-Initiated and Non Proton-Initiated Cationic Polymerizations. Polym. J. 17: 57-71
  2. Ribeiro, R.M., Portela, M.F., Deffieux, A., Cramail, H., Rocha, M. (1996). Isoespecific homo and copolymerization of styrene with ethylene in the presence of VCl3, AlCl3 as catalyst. Macromol. Rapid. Commun. 17: 461-469
  3. Satoh, K., Nakashima, J., Kamigaito, I., Sawamoto, M. (2001). Novel BF3OEt2/R-OH initiating system for controlled cationic polymerization of styrene in the presence of water. Macromolecules. 34: 396-401
  4. Higashimura, T., Ishihama, Y., Sawamoto, M. (1993). Living cationic polymerization of styrene: new initiating systems based on added halide salts and the nature of the growing species. Macromolecules. 26: 744-751
  5. Hasebe, T., Kamigaito, M., Sawamoto, M. (1996). Living cationic polymerization of Styrene with TiCl3 (OiPR) as a lewis-acid Activator. Macromolecules. 29: 6100-6103
  6. Clark, J.H., Monks, G.L., Nightingale, D.J., Price, P.M., White, J.F. (2000). A new solid acid-based route to linear alkybenzenesy. J. Catal. 193: 348-350
  7. Clark, J.H., Macquarrie, D.J. (1998). Catalysis of liquid phase organic reactions using chemically modified mesoporous inorganic solids. Chem. Commun. 8: 853-860
  8. Köppl, A., Alt, H.G., Phillips, M.D. (2001). Partially hydrolyzed trimethylaluminum (PHT) as heterogeneous cocatalyst for the polymerization of olefins with metallocene complexes. J. Appl. Polym. Sci. 80: 454-466
  9. Jung, H.K., Dong, R.K. (2006). US. Patent 7, 115, 683
  10. Banerjee, S., Paira, T.K., Mandal, T.K. (2013). Control of molecular weight and tacticity in stereospecific living cationic polymerization of α-methylstyrene at 0 °C using FeCl3-based initiators: Effect of tacticity on thermal properties. Macromol. Chem. Phys. 214: 1332-1344
  11. Li, D., Hadjikyriacous, S., Faust, R. (1996). Living carbocationic polymerization of α-Methylstyrene using tin halides as coinitiators. Macromolecules 29: 6061-6067
  12. Worsfold, D.J., Bywater, S. (1957). Cationic Polymerization of α-Methylstyrene. J. Am. Chem. Soc. 79: 4917-4920
  13. Matsuguma, Y., Kunitake, T. (1971). The effect of conteranions on the polymer steric structure in the cationic polymerization of α-Methylstyrene. Polym. J. 2: 353-358
  14. Villesange, M., Sauvet, G., Vairon, J.P., Sigwalt, P. (1977). Kinetic study of cationic polymerization of α-Methylstyrene initiated by BuOTiCl3 in dichloromethane solution. J. Macromol. Sci. Part A: Chem. 11: 391-410
  15. Toman, L., Pokorný, S., Spěváček, J. (1989). Cationic polymerization of α-methylstyrene in dichloromethane initiated with system 2,5-dichloro-2,5-dimethylhexane-BCl3. I. Molecular weight distribution and stereoregularity of poly (α-methylstyrene). J. Polym. Sci. Part A: Polym. Chem. 27: 2217-2228
  16. Li, B.T., Liu, W.H., Wu, Y.X. (2012). Synthesis of long-chain branched isotactic-rich polystyrene via cationic polymerization. Polymer 53: 3194-3202
  17. Bompart, M., Vergnaud, J., Strub, H., Carpentier, J.F. (2011). Indium(III) halides as exceptionally active water-tolerant catalysts for cationic polymerization of styrenics. Polym. Chem. 2: 1638-1640
  18. Chen, D., Xue, Z., Su, Z. (2003). A new catalyst of 1,2-molybdophosphoric acid for cationic polymerization of styrene: activity and mechanism studies. J. Mol. Catal. A: Chem. 203: 307-312
  19. Sage, V., Clark, J.H., Macquarrie, D.J. (2003). Cationic polymerization of styrene using mesoporous silica supported aluminum chloride. J. Mol. Catal. A: Chem. 198: 349-358
  20. Kostjuk, S.V., Dubovik, A.Y., Vasilenko, I.V., Frolov, A.N., Kaputsky, F.N. (2007). Kinetic and mechanistic study of the quasiliving cationic polymerization of styrene with the 2-phenyl-2-propanol/AlCl3.OBu2 Initiating System. Eur. Polym. J. 43: 968-979
  21. Belbachir, M., Bensaoula, A. (2006). Composition and method for using bentonites. US. Patent 7, 094, 823 B2
  22. Belbachir, M., Harrane, A., Megharbi, R. (2006). Maghnite, a green catalyst for cationic polymerization of vinylic and cyclic monomers. Macromol. Symp. 245-246: 1-4
  23. Harrane, A., Meghabar, R., Belbachir, M. (2006). Kinetics of the ring opening polymerization of e-caprolactone catalysed by a proton exchanged montmorillonite clay. Reactive & Functional Polymers. 66: 1696-1702
  24. Harrane, A., Naar, N., Belbachir, M. (2007). Ring opening polymerization of oxetane by the use of a montmorillonite clay as catalyst. Mater. Lett. 61: 3555-3558
  25. Harrane, A., Oussadi, K., Belaouedj, M.A., Belbachir, M., Meghabar, R. (2005). Cationic ring opening polymerization of glycolide catalysed by amontmorillonite clay catalyst. J. Polym. Res. 12: 361–365
  26. Yahiaoui, A., Hachemaoui, A., Belbachir, M. (2007). Synthesis of hydrosoluble polymers of oxazoline using Maghnite-H as catalyst. J. Appl. Polym. Sci. 104: 1792–1800
  27. Harrane, A., Oussadi, K., Belaouedj, M.A., Meghabar, R., Belbachir, M. (2005). Synthesis of Biodegradable Diblock Copolymers of Glycolide and Poly(oxyethylene) Using a Montmorillonite Clay as Catalyst. J. Polym. Res. 12: 367-371
  28. Yahiaoui, A., Belbachir, M., Soutif, J.C., Fontaine, L. (2005). Synthesis and structural analyses of poly (1,2-cyclohexene oxide) over solid acid catalyst. Mater. Lett. 59: 759-767
  29. Kwon, O.Y., Park, K.W., Jeong, S. (2001). Preparation of Porous Silica-Pillared Montmorillonite: Simultaneous Intercalation of Amine-Tetraethylorthosilicate into H-Montmorillonite and Intra-Gallery Amine-Catalyzed Hydrolysis of Tetraethylorthosilicate. Bull. Korean Chem. Soc. 22: 678-686
  30. Kwon, OY., Shin, HS., Choi, S.W. (2000). Preparation of porous silica-pillared layered phase: Simultaneous intercalation of amine-tetraethylorthosilicate into the H+-magadiite and intragallery amine-catalyzed hydrolysis of tetraethylorthosilicate. Chem. Mater. 12(5): 1273-1278
  31. Harrane, A., Belbachir, M. (2007). Synthesis of Biodegradable Polycaprolactone/ Montmorillonite Nanocomposites by Direct In‐situ Polymerization Catalysed by Exchanged Clay. Macromol. Symp. 247: 379-384
  32. Meghabar, R., Megherbi, A., Belbachir, M. (2003). Maghnite-H+, an ecocatalyst for cationic polymerization of N-vinyl-2- pyrrolidone. Polymer 44: 4097-4100
  33. Ayat, M., Harrane, A. Belbachir, M. (2008). Maghnite‐H+ a solid catalyst for the cationic polymerization of α‐methylstyrene. J. Appl. Polym. Sci. 109: 1476-1479
  34. Haous, M., Harrane, A., Belbachir, M., Taulelle, F. (2007). Solid State NMR Characterization of formation of Poly (Ԑ-caprolactone)/Maghnite Nanocomposites by In‐situ Polymerization. J. Polym. Sci. Part B: Polym. Phys. 45: 3060-3068
  35. Burge, D.E., Bruss, D.B. (1963). Preparation and properties of some poly-α-methylstyrenes. J. Polym. Sci. Part A: 1: 1927-1935
  36. Kerr, P.F., Hamilton, P.K., Pill, R.J. (1950). Analytical data on reference, Clay Minerals: American Petroleum Institute Project 49. Clay Minerals Standards, preliminary report, 7: 92-98
  37. Damour, A., Salvetat, D. (1993). Analyses sur un hydrosilicate d’alumine trouvé à Montmorillon. Ann. Chim. Phys. 3: 376–383
  38. Jianzhong, M., Dangge, G., Xinjiang, C., Yun, C. (2006). Synthesis and Characterization of VP/O-MMT Macromolecule Nanocomposite Material via Polymer Exfoliation–Adsorption Method. J. Compos. Mater. 40: 2279-2286
  39. Kwon, O.Y., Park, K.W., Jeong, S. (2001). Preparation of Porous Silica-Pillared Montmorillonite: Simultaneous Intercalation of Amine-Tetraethylorthosilicate into H-Montmorillonite and Intra-Gallery Amine-Catalyzed Hydrolysis of Tetraethylorthosilicate. Bull. Korean Chem. Soc. 22: 678-686
  40. Ayat, M., Harrane, A. Belbachir, M. (2008). Maghnite‐H+ a solid catalyst for the cationic polymerization of α‐methylstyrene. J. Appl. Polym. Sci. 109: 1476-1479
  41. Chabani, M., Yahiaoui, A., Hachemaoui, A., Belbachir, M. (2011). New Approach for the Polymerization of 2-Chloroethyl Vinyl Ether Using a Maghnite Clay as Eco-Catalyst. J. Appl. Polym. Sci. 122, 1800-1806
  42. Ferrahi, M.I., Belbachir, M. (2003). Polycondensation of Tetrahydrofuran with Phthalic Anhydride Induced By a Proton Exchanged Montmorillonite Clay. Int. J. Mol. Sci. 4: 312-325
  43. Yahiaoui, A., Belbachir, M. (2006). Ring-opening polymerization of styrene oxide with maghnite-H+ as ecocatalyst. J. Appl. Polym. Sci. 100: 1681-1687
  44. Rahmouni, A., Harrane, A., Belbachir, M. (2012). Kinetics Study of Catio-Radically Polymerization of Aniline Catalyzed by Maghnite- Na+ Clay Catalyst Layered (Western Algeria). World Journal of Nano Science & Technology 1: 26-32
  45. Breen, C., Madejová, J., Komadel, P. (1995). Characterization of moderately acid-treated, size-fractionated montmorillonites using IR and MAS NMR spectroscopy and thermal analysis. J. Mater. Chem. 5: 469-474
  46. Kim, B.T., Min, Y.K., Asami, T., Park., N.K., Kwon, O.Y., hoky., Yoshida, S. (1997). Synthesis of 2-fluoroabscisic acid - a potentential photo-stable abscisic-acid. Tetrahydron Letter. 38(10): 1797-1800

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