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A Green Synthesis of Polylimonene Using Maghnite-H+, an Exchanged Montmorillonite Clay, as Eco-Catalyst

1Laboratory of Polymer Chemistry, Department of Chemistry, Faculty of Exact and Applied Sciences, Oran 1 University, Algeria

2Department of Chemistry, FSEI, University of Abdelhamid Ibn Badis-Mostaganem, Algeria

Received: 26 May 2018; Revised: 11 Sep 2018; Accepted: 22 Sep 2018; Available online: 25 Jan 2019; Published: 15 Apr 2019.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2019 by Authors, Published by BCREC Group under

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A new green polymerization technique to synthesis polylimonene (PLM) is carried out in this work. This technique consists of using Maghnite-H+ as eco-catalyst to replace Friedel-Crafts catalysts which are toxics. Maghnite-H+ is a montmorillonite silicate sheet clay which is prepared through a simple exchange process. Polymerization experiments are performed in bulk and in solution using CH2Cl2 as solvent. Effect of reaction time, temperature and amount of catalyst is studied, in order to find the optimal reaction conditions. The polymerization in solution leads to the best yield (48.5%) at -5°C for a reaction time of 6 h but the bulk polymerization, that is performed at 25°C, remains preferred even if the yield is lower (40.3%) in order to respect the principles of a green chemistry which recommend syntheses under mild conditions, without solvents and at room temperature. The structure of the obtained polymer (PLM) is confirmed by FT-IR and Nuclear Magnetic Resonance of proton (1H-NMR). The glass transition temperature (Tg) of the polylimonene is defined using Differential Scanning Calorimetry (DSC) and is between 113°C and 116°C. The molecular weight of the obtained polymer is determined by Gel Permeation Chromatography (GPC) analysis and is about 1360 g/mol. Copyright © 2019 BCREC Group. All rights reserved


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Keywords: Polylimonene; Maghnite-H+; eco-catalyst; green polymerization; GPC; 1H-NMR
Funding: Agence Thématique de Recherche en Sciences et Technologie-Algeria (ATRST) for supporting this research (Project Algero-Portugues)

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  1. Finar, I.L. eds. (1985). The terpenoids. vol, 2, Longman, London
  2. Keszler, B., Kennedy, J.P. (1992). Synthesis of high molecular weight poly (β-pinene). Adv. Polym. Sci. 100: 1-9
  3. Ham, G.E. (1964). Penultimate unit effects in terpolymerization. J. Polym. Sci. A Polym. Chem., 2: 4191-4200
  4. Karr, L.L., Coats, J.R. (1988). Insecticidal properties of d-limonene. J. Pesticide Sci. 13: 287-290
  5. Sun, J. (2007). D-Limonene: safety and clinical applications. Alternat. Med. Rev., 12: 259-264
  6. Mathers, T., Damodaran, K. (2007). Renewable chain transfer agents for metallocene polymerizations: The effects of chiral monoterpenes on the polyolefin molecular weight and isotacticity. J. Polym. Sci. A Polym. Chem. 45: 3150-3165
  7. Wilbon, P.A., Fuxiang, C., Chauanbing, T. (2013). Progress in Renewable Polymers from Natural Terpenes, Terpenoids, and Rosin. Macromol. Rapid. Commun. 34: 8-37
  8. Kotaro, S., Masaru, M., Kanji, N., Masami, K. (2010). AAB-Sequence Living Radical Chain Copolymerization of Naturally Occurring Limonene with Maleimide: An End-to-End Sequence-Regulated Copolymer. J. Am. Chem. Soc. 132: 10003-10005
  9. Rukel, E., Wojcik, R., Arlt, H. (1976). Cationic Polymerization of α-Pinene Oxide and β-Pinene Oxide by a Unique Oxonium lon-Carbenium Ion Sequence. J. Macromol. Sci. Part A, 10: 1371-1390
  10. Roberts, W., Day, A. (1950). A Study of the Polymerization of α-and β-Pinene with Friedel-Crafts Type Catalysts. J. Am. Chem. Soc. 72: 1226-1230
  11. Modena, M., Bates, R., Marvel, C. (1965). Some low molecular weight polymers of d‐limonene and related terpenes obtained by Ziegler‐type catalysts. J. Polym. Sci. A Polym. Chem. 3: 949-960
  12. Barros, M.T., Petrova, K.T., Ramos, A.M. (2007). Potentially Biodegradable Polymers Based on α‐or β‐Pinene and Sugar Derivatives or Styrene, Obtained under Normal Conditions and on Microwave Irradiation. Eur. J. Org. Chem. 8: 1357-1363
  13. Sharma, S., Srivastava, K.A. (2004). Synthesis and characterization of copolymers of limonene with styrene initiated by azobisisobutyronitrile. Eur. Polym. J. 40: 2235-2240
  14. Hensen, K., Mahaim, C., Hislderich, W.F. (1997). Alkoxylation of limonene and alpha- pinene over beta zeolite as heterogeneous catalyst, Appl. Catal. A 149: 311-329
  15. Belbachir, M., Bensaoula, A. (2006). US. Patent N° 7,094,823
  16. Baghdadli, M.C., Meghabar, R., Belbachir, M. (2016). Acid-Activated Algerian Montmorillonite as Heterogeneous Catalysts for Cationic Polymerization of Styrene. Asia J. Chem. 28:1197–1204
  17. Yahiaoui, A., Belbachir, M. (2006). Ring‐opening polymerization of styrene oxide with Maghnite‐H+ as ecocatalyst. J. Appl. Polym. Sci. 100: 1681-1687
  18. Ferrahi, M.I., Belbachir, M. (2006). Cyclic polyesters prepared by poly (oxypropylene oxymaloyl) ring-chain reactions. Express Polym. Lett. 1: 24-26
  19. Belbachir, M., Bensaoula, A. (2001). US. Patent No 6,274,527B1
  20. Belbachir, M., Bensaoula, A. (2001). US. Patent 066969.0101
  21. Draoua, Z., Harrane, A., Belbachir, M. (2015). Amphiphilic Biodegradable Poly(ϵ-capro-lactone)-Poly(ethylene glycol) - Poly(ϵ-capro-lactone) Triblock Copolymer Synthesis by Maghnite-H+ as a Green Catalyst. J. Macromol. Sci. Part A, 52: 130-137
  22. Bennabi, S. (2017). New approach for synthesis of poly(ethylglyoxylate) using Maghnite-H+, an Algerian proton exchanged montmorillonite clay, as an eco-catalyst. J. Macromol. Sci. Part A, 54: 1-10
  23. Hennaoui, F., Belbachir, M. (2015). A Green One-pot Synthesis of PDMS Bis-Macromonomers Using an Ecologic Catalyst (Maghnite-H+). J. Macromol. Sci. Part A, 52: 992-1001
  24. Cicel, B. (1992). Mineralogical composition and distribution of Si, Al, Fe, Mg and Ca in the fine fractions of some Czech and Slovak bentonites. Carpath. Ser. Clays, 43: 3-7
  25. Singh, A., Kamal, K. (2012). Synthesis and characterization of polylimonene: Polymer of an optically active terpene. J. Appl. Polym. Sci. 125: 1456-1459
  26. Harrane, A., Meghabar, R., Belbachir, M. (2002). A Protons Exchanged Montmorillonite Clay as an Efficient Catalyst for the Reaction of Isobutylene Polymerization. Int. J. Mol. Sci. 3: 790-800
  27. Harrane, A., Meghabar, R., Belbachir, M. (2006). Kinetics of the ring opening polymerization of ε-caprolactone catalysed by a proton exchanged montmorillonite clay. React. Funct. Polym. 66: 1696-1702
  28. Megherbi, R., Belbachir, M., Meghabar, R. (2006). Maghnite‐H+ as a cationic catalyst in the synthesis of poly(1,3‐dioxolane) and α,ω‐methacryloyloxy‐poly (1,3‐dioxolane) . J. Appl. Polym. Sci. 101: 78-82

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