Cationic polymerization of poly(α-methylstyrene-block-isobutyl vinyl ether) using Maghnite-H+ clay (Algerian MMT) as catalyst

  • Moulkheir Ayat
  • Mohammed Belbachir
  • Abdelkader Rahmouni
Original Paper


The synthesis of a new copolymer poly(α-methylstyrene-block-isobutyl vinyl ether) by cationic polymerization is reported. The polymerization was performed in bulk under suitable condition at temperature 0 °C. The copolymer was prepared by the reaction of alpha-methylstyrene (α-MS) with isobutyl vinyl ether (IBVE), in the presence of a natural Algerian montmorillonite clay modified by 0.05–1 M H2SO4, known as Maghnite-H+, as proton source, a non-toxic and an efficient catalyst for cationic polymerization of many vinylic and hetero-cyclic monomers. It was found that H2SO4 concentration allows controlling the chemical composition, the porous structure of the acid-activated clays, and their catalytic performance. The maximal yield of polymer is observed in the presence of Algerian MMT modified by 0.25 M H2SO4. Effects of α-MS/IBVE molar ratio, catalyst concentration, on yield and molecular weight of polymer were revealed in the presence of the most active sample. The structure of the products obtained is confirmed by 1H-NMR, 13C-NMR (nuclear magnetic resonance), Fourier transform infrared spectroscopy, differential scanning calorimetry, and gel-permeation chromatography, finally, a mechanism for the reaction was proposed.


Maghnite-H+ Clay Montmorillonite Catalyst, isobutyl vinyl ether Alpha-methylstyrene Cationic copolymerization Block copolymerization 



All our gratitude to the anonymous referees for their careful reading of the manuscript and valuable comments helped in shaping this paper to the present form. We thank all laboratory staffs of polymer chemistry from the University of Oran 1 Ahmed Benbella (Algeria) for their kind cooperation.


  1. 1.
    Matyjaszewski K (ed) (1996) Cationic polymerization: mechanism, synthesis and application. Marcel & Dekker, New YorkGoogle Scholar
  2. 2.
    Sawamoto M (1991) Modern cationic vinyl polymerization. Prog Polym Sci 16:111CrossRefGoogle Scholar
  3. 3.
    Kamigaito M, Sawamoto M, Higashimura T (1991) Living cationic polymerization of vinyl ethers by electrophile lewis acid initiating systems. 7. Living cationic polymerization of isobutyl vinyl ether by trimethylsilyl halide zinc halide initiating systems in the presence of paramethoxybenzaldehyde-effects of halide anions and zinc halides. J Polym Sci A Polym Chem 29:1909Google Scholar
  4. 4.
    Faust R (2000) Cationic macromolecular engineering via furan derivatives. Macromol Symp 157:101–108.;2-T CrossRefGoogle Scholar
  5. 5.
    Hadjikyriacou S, Faust R (2000) Living coupling reaction in living cationic polymerization. 3. Coupling reaction of living polyisobutylene using bis (furanyl) derivatives. Macromolecules 33:730CrossRefGoogle Scholar
  6. 6.
    Kamigaito M, Yamaoka K, Sawamoto M, Higashimura T (1992) Living cationic polymerization of isobutyl vinyl ether by benzoic-acid derivatives zinc chloride initiating systems—slow interconversion between dormant and activated growing species. Macromolecules 25:6400CrossRefGoogle Scholar
  7. 7.
    Hadjichristidis N, Pispas S, Floudas G (2003) Block copolymers by cationic polymerization. In: Block copolymers: synthetic strategies, physical properties, and applications. Wiley, Hoboken, NJ, pp 28--46. ISBN: 0-471-39436-X
  8. 8.
    Hayashi K, Hayashi K, Okamura S (1973) Copolymerization of styrene with isobutyl vinyl ether by radiation. Polym J 4:495–501. CrossRefGoogle Scholar
  9. 9.
    Brown DR, Carpathica G (1994) Review: clays as catalyst and reagent support. Ser Clays 45:45–56Google Scholar
  10. 10.
    Laszlo P (1987) Preparative chemistry using supported reagents. Academic Press, San DiegoGoogle Scholar
  11. 11.
    Belbachir M, Bensaoula A (2006) US Patent No. 0069446 A1Google Scholar
  12. 12.
    Ayat M, Bensaada N, Belbachir M, Harrane A, Meghabar R (2015) Synthesis and characterization of poly(α-methylstyrene) by cationic polymerization using a new solid ecological catalyst. Orient J Chem 31:2115–2123. CrossRefGoogle Scholar
  13. 13.
    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. CrossRefGoogle Scholar
  14. 14.
    Ayat M, Rahmouni A, Belbachir M (2016) Selective synthesis, characterization, and kinetics studies of poly(α-methyl styrene) induced by Maghnite-Na+ Clay (Algerian MMT). Bull Chem React Eng Catal 11:376–388. CrossRefGoogle Scholar
  15. 15.
    Ayat M, Rahmouni A, Belbachir M (2016) Methyl methacrylate and alpha-methylstyrene: new strategy for synthesis of bloc copolymers for use in potential biomedical applications generated by an ecologic catalyst called maghnite (Algerian MMT). Bull Chem React Eng Catal 11:316–329. CrossRefGoogle Scholar
  16. 16.
    Bensaada N, Ayat M, Meghabar R, Belbachir M (2015) The synthesis of polystyrene with a new chemical approach. Curr Chem Lett 4:55–60. CrossRefGoogle Scholar
  17. 17.
    Ayat M, Belbachir M, Rahmouni A (2017) Synthesis of block copolymers consists on vinylidene chloride and α-methylstyrene by cationic polymerization using an acid exchanged motmorillonite clay as heterogeneous catalyst (Algerian MMT). J Mol Struct 1139:381–389. CrossRefGoogle Scholar
  18. 18.
    Benadda M, Ferrahi MI, Belbachir M (2014) Synthesis of poly(N-vinyl-2-pyrrolidone-co-methyl methacrylate) by Maghnite-H+ a non-toxic catalyst. Bull Chem React Eng Catal 11:201–206. Google Scholar
  19. 19.
    Medjdoub L, Rahmouni A, Belbachir M (2016) New method for nucleophilic substitution on hexachlorocyclotriphosphazene by allylamine using an Algerian proton exchanged montmorillonite clay (Maghnite-H+) as a green solid catalyst. Bull Chem React Eng Catal 11:151–160. CrossRefGoogle Scholar
  20. 20.
    Hamam N, Ferrahi MI, Belbachir M (2016) Cationic ring opening copolymerization of 1,3-dioxolane with styrene by montmorillonite maghnite-H+ catalyst. Orient J Chem 32:1313–1317. CrossRefGoogle Scholar
  21. 21.
    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. Bull Chem React Eng Catal 11:170–175. CrossRefGoogle Scholar
  22. 22.
    El-Kebir A, Harrane A, Belbachir M (2016) Polymerization of DL-lactide induced by protonated montmorillonite clay as a solid catalyst: mechanism study. Mat Res 107:1–7. Google Scholar
  23. 23.
    El-Kebir A, Harrane A, Belbachir M (2015) Protonated montmorillonite clay used as green non-toxic catalyst for the synthesis of biocompatible polyglycidol. Arab J Sci Eng 40:1–6. CrossRefGoogle Scholar
  24. 24.
    Kherroub DE, Belbachir M, Lamouri S (2015) Study and optimization of the polymerization parameter of furfuryl alcohol by Algerian modified clay. Arab J Sci Eng 40:143–150. CrossRefGoogle Scholar
  25. 25.
    Seghier S, Belbachir M (2015) Green polymerization of 4-(oxiran-2-ylmethyl) morpholine. Arab J Sci Eng 40:1–7. CrossRefGoogle Scholar
  26. 26.
    Draoua Z, Harrane A, Belbachir M (2015) Amphiphilic biodegradable poly(e-caprolactone)- poly(ethylene glycol) – poly(e-caprolactone) triblock copolymer synthesis by Maghnite-H+ as a green catalyst. J Macromol Sci Part A 52:130–137CrossRefGoogle Scholar
  27. 27.
    Hennaoui F, Belbachir M (2015) Green one-pot synthesis of PDMS bis-macromonomers using an ecologic catalyst (Maghnite-H+). J Macromol Sci Part A 52:992–1001A. CrossRefGoogle Scholar
  28. 28.
    Bennabi S, Belbachir M (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 54:843–852. CrossRefGoogle Scholar
  29. 29.
    Zeggai FZ, Belbachir M, Hachemaoui A (2017) In-situ preparation of conducting polymers/copper (II)-maghnite clay nanocomposites. Mater Sci Res India 14:204–211.
  30. 30.
    Chikh K, Bouhadjar L, Kherroub DE, Meghabar R, Belbachir M (2017) Synthesis and characterization of polyvinyl alcohol/Na+-MMt nanocomposite: effect of charge content and CO2 adsorption properties. Der Pharma Chemica 9:90–94. Google Scholar
  31. 31.
    Wu P, Ming C (2006) The relationship between acidic activation and microstructural changes in montmorillonite from heping, China. Spectrochim Acta A Mol Biomol Spectrosc 63:85–90CrossRefGoogle Scholar
  32. 32.
    Christidis GE, Scott PW, Dunham AC (1997) Acid activation and bleaching capacity of bentonites from the islands of Milos and Chios, Aegean, Greece. Appl Clay Sci 12:329–347CrossRefGoogle Scholar
  33. 33.
    Plancton A, Giese RFJ, Snyder R, Drits VA, Bukin AS (1989) Stacking faults in the kaolin-group minerals: defect structure of kaolinite. Clays Clay Miner 37:203–210CrossRefGoogle Scholar
  34. 34.
    Galan E (2006) Genesis of clay minerals. In: Bergaya F, Theng BKG, Lagaly G (eds) Handbook of clay science. Elsevier, Amsterdam, pp 1129–1162CrossRefGoogle Scholar
  35. 35.
    Komadel P, Madejova J, Bergaya F, Theng BKG, Lagaly G (2006) Acid activation of clay minerals. In: Handbook of clay science. Elsevier, UK, pp 263–287Google Scholar
  36. 36.
    Rhodes CN, Brown DR (1993) Surface properties and porosities of silica and acid-treated montmorillonite catalyst supports: influence on activities of supported ZnCl2 alkylation catalysts. J Chem Soc Faraday Trans 89:1387–1391. CrossRefGoogle Scholar
  37. 37.
    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 5:469–474CrossRefGoogle Scholar
  38. 38.
    Macht F, Eusterhues K, Pronk GJ, Totsche KU (2011) Specific surface area of clay minerals: comparison between atomic force microscopy measurements and bulk-gas (N2) and -liquid (EGME) adsorption methods. Appl Clay Sci 53:20–26CrossRefGoogle Scholar
  39. 39.
    Beloufa K, Sahli N, Belbachir M (2010) Synthesis of copolymer from 1,3,5-trioxane and 1,3-dioxolane catalyzed by Maghnite-H+. J Appl Polym Sci 115:2820–2827. CrossRefGoogle Scholar
  40. 40.
    Timofeeva MN, Panchenko VN, Volcho KP, Zakusin SV, Krupskaya VV, Gil A, Mikhalchenko OS, Vicente MA (2016) Effect of acid modification of kaolin and metakaolin on Brønsted acidity and catalytic properties in the synthesis of octahydro-2H-chromen-4-ol from vanillin and isopulegol. J Mol Catal A Chem 414:160–166CrossRefGoogle Scholar
  41. 41.
    Timofeeva MN, Panchenko VN, Gil A, Zakusin SV, Krupskaya VV, Volcho KP, Vicente MA (2015) Effect of structure and acidity of acid modified clay materials on synthesis of octahydro-2H-chromen-4-ol from vanillin and isopulegol. Catal Commun 69:234–238Google Scholar
  42. 42.
    Cai Q, Li J, Bao F, Shan Y (2005) Tunable dimerization of a-methylstyrene catalyzed by acidic ionic liquids. Appl Catal A Gen 279:139–143. CrossRefGoogle Scholar
  43. 43.
    Tsubokawa N (1980) Cationic polymerization of α‐methylstyrene initiated by channel black surface. J Polym Sci Part C Polym Lett 18:461–464.
  44. 44.
    Belbekiri H, Meghabar R, Belbachir M (2015) Cationic ring-opening copolymerization of propylene oxide with tetrahydrofuran by acid exchanged montmorillonite clay. Der Pharma Chemica 7:201–209. Google Scholar
  45. 45.
    Baghdadli MC, Meghabar R, Belbachir M (2016) Acid-activated Algerian montmorillonite as heterogeneous catalysts for cationic polymerization of styrene. Asian J Chem 28:1197–1204. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Moulkheir Ayat
    • 1
    • 2
  • Mohammed Belbachir
    • 2
  • Abdelkader Rahmouni
    • 2
  1. 1.Department of Chemistry, Faculty of SciencesDr Moulay Taher UniversityNasr SaidaAlgeria
  2. 2.Laboratory of Polymer Chemistry, Department of Chemistry, Faculty of ScienceUniversity of Oran 1 Ahmed BenbellaOranAlgeria

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