A Green Synthesis of Polylimonene Using Maghnite-H+, an Exchanged Montmorillonite Clay, as Eco-Catalyst
This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.
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
- Finar, I.L. eds. (1985). The terpenoids. vol, 2, Longman, London.
- Keszler, B., Kennedy, J.P. (1992). Synthesis of high molecular weight poly (β-pinene). Adv. Polym. Sci. 100: 1-9.
- Ham, G.E. (1964). Penultimate unit effects in terpolymerization. J. Polym. Sci. A Polym. Chem., 2: 4191-4200.
- Karr, L.L., Coats, J.R. (1988). Insecticidal properties of d-limonene. J. Pesticide Sci. 13: 287-290.
- Sun, J. (2007). D-Limonene: safety and clinical applications. Alternat. Med. Rev., 12: 259-264.
- 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.
- Wilbon, P.A., Fuxiang, C., Chauanbing, T. (2013). Progress in Renewable Polymers from Natural Terpenes, Terpenoids, and Rosin. Macromol. Rapid. Commun. 34: 8-37.
- 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.
- 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.
- 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.
- 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.
- 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.
- Sharma, S., Srivastava, K.A. (2004). Synthesis and characterization of copolymers of limonene with styrene initiated by azobisisobutyronitrile. Eur. Polym. J. 40: 2235-2240.
- 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.
- Belbachir, M., Bensaoula, A. (2006). US. Patent N° 7,094,823.
- 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.
- Yahiaoui, A., Belbachir, M. (2006). Ring‐opening polymerization of styrene oxide with Maghnite‐H+ as ecocatalyst. J. Appl. Polym. Sci. 100: 1681-1687.
- Ferrahi, M.I., Belbachir, M. (2006). Cyclic polyesters prepared by poly (oxypropylene oxymaloyl) ring-chain reactions. Express Polym. Lett. 1: 24-26.
- Belbachir, M., Bensaoula, A. (2001). US. Patent No 6,274,527B1
- Belbachir, M., Bensaoula, A. (2001). US. Patent 066969.0101
- 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
- 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.
- 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.
- 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.
- Singh, A., Kamal, K. (2012). Synthesis and characterization of polylimonene: Polymer of an optically active terpene. J. Appl. Polym. Sci. 125: 1456-1459.
- 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.
- 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.
- 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.
This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.
As a journal Author, you have rights for a large range of uses of your article, including use by your employing institute or company. These Author rights can be exercised without the need to obtain specific permission.
Authors publishing in BCREC journals have wide rights to use their works for teaching and scholarly purposes without needing to seek permission, including: use for classroom teaching by Author or Author's institutionand presentation at a meeting or conference and distributing copies to attendees; use for internal training by author's company; distribution to colleagues for their reseearch use; use in a subsequent compilation of the author's works; inclusion in a thesis or dissertation; reuse of portions or extrcats from the article in other works (with full acknowledgement of final article); preparation of derivative works (other than commercial purposes) (with full acknowledgement of final article); voluntary posting on open web sites operated by author or author’s institution for scholarly purposes (follow CC by SA License).
Authors and readers can copy and redistribute the material in any medium or format, as well as remix, transform, and build upon the material for any purpose, even commercially, but they must give appropriate credit (cite to the article or content), provide a link to the license, and indicate if changes were made. If you remix, transform, or build upon the material, you must distribute your contributions under the same license as the original.
Copyright Transfer Agreement
The Authors submitting a manuscript do so on the understanding that if accepted for publication, copyright publishing of the article shall be assigned to Bulletin of Chemical Reaction Engineering & Catalysis journal and Department of Chemical Engineering Diponegoro University as publisher of the journal.
Copyright encompasses exclusive rights to reproduce and deliver the article in all form and media, including reprints, photographs, microfilms and any other similar reproductions, as well as translations. The reproduction of any part of this journal, its storage in databases and its transmission by any form or media, such as electronic, electrostatic and mechanical copies, photocopies, recordings, magnetic media, etc., will be allowed only with a written permission from Bulletin of Chemical Reaction Engineering & Catalysis journal and Department of Chemical Engineering Diponegoro University.
Bulletin of Chemical Reaction Engineering & Catalysis journal and Department of Chemical Engineering Diponegoro University, the Editors and the Advisory International Editorial Board make every effort to ensure that no wrong or misleading data, opinions or statements be published in the journal. In any way, the contents of the articles and advertisements published in the Bulletin of Chemical Reaction Engineering & Catalysis are sole and exclusive responsibility of their respective authors and advertisers.
Remember, even though we ask for a transfer of copyright, our journal authors retain (or are granted back) significant scholarly rights.
The Copyright Transfer Form can be downloaded here: [Copyright Transfer Form BCREC 2016]
The copyright form should be signed originally and send to the Editorial Office in the form of original mail, scanned document or fax :
Prof. Dr. I. Istadi (Editor-in-Chief)
Editorial Office of Bulletin of Chemical Reaction Engineering and Catalysis
Department of Chemical Engineering, Diponegoro University
Jl. Prof. Soedarto, Kampus Undip Tembalang, Semarang, Central Java, Indonesia 50275
Telp.: +62-24-7460058, Fax.: +62-24-76480675