Advertisement

Cationic Ring Opening Polymerization of Octamethylcyclotetrasiloxane Using a Cost-Effective Solid Acid Catalyst (Maghnite-H+)

  • Djamal Eddine KherroubEmail author
  • Mohammed Belbachir
  • Saad Lamouri
  • Karim Chikh
Research Paper
  • 50 Downloads

Abstract

The polymerization of octamethylcyclotetrasiloxane (D4) catalyzed by Maghnite-H+, a nontoxic and green solid catalyst, is studied. The Maghnite-H+ is a montmorillonite type 2:1 dioctahedral phyllosilicates whose interlayer ions are exchanged by hydronium ions after activation with sulfuric acid which gives it its catalytic appearance. D4 was polymerized cationically by ring opening at 60 °C without solvent using Maghnite-H+ contents less than 5% by weight. The molecular structure of the polymer obtained was identified by IR, 1H NMR and 13C NMR. The DSC was used to study the thermal properties. The operating conditions were optimized so that we can achieve best performance for obtaining a linear polymer with high average molecular mass. The variation of the molecular mass distribution was verified by GPC. Finally, a reaction mechanism was proposed to show the role of the Maghnite-H+ during the different steps of the reaction.

Keywords

Maghnite-H+ Catalyst Montmorillonite Octamethylcyclotetrasiloxane Ring opening polymerization 

References

  1. Narayana PL et al (2011) US Patent. 20110237740 A1Google Scholar
  2. Belbachir M, Bensaoula A (2001) US Patent. No 6, 274,527B1Google Scholar
  3. Bouchama A, Ferrahi MI, Belbachir M (2015) Copolymerization of ε-caprolactone with tetrahydrofuran by a solid acid, in the presence of acetic anhydride. J Mater Environ Sci 6:977–982Google Scholar
  4. Chen B, Zhan X, Yi L, Chen F (2007) Cationic ring opening polymerization of octamethylcyclotetrasiloxane initiated by acid treated bentonite. Chin J Chem Eng 15:661–665CrossRefGoogle Scholar
  5. Chojnowski J, Cypryk M (2000) Silicon-containing polymers. Kluwer, DordrechtGoogle Scholar
  6. Chojnowski J, Cypryk M, Kazmierski K (2002) Cationic polymerization of a model cyclotrisiloxane with mixed siloxane units initiated by a protic acid. Mechanism of polymer chain formation. Macromolecules 36:9904–9912CrossRefGoogle Scholar
  7. Chojnowski J, Rubinsztajn S, Fortuniak W, Kurjata J (2007) Oligomer and polymer formation in hexamethylcyclotrisiloxane (D3)—hydrosilane systems under catalysis by tris(pentafluorophenyl)borane. J Inorg Orgamet Polym Mater 17:173–187CrossRefGoogle Scholar
  8. Clark JH, Rhodes CN (2000) Clean synthesis using porous inorganic solid catalysts and supported reagents. Royal Society of Chemistry, CambridgeGoogle Scholar
  9. Conan JT, William PW, Guoping C (2003) Acid and base catalyzed ring-opening polymerization of 2,2,4,4,6,6-hexamethyl-8,8-diphenylcyclotetrasiloxane. Polymer 44:4149–4155CrossRefGoogle Scholar
  10. Crafts JM (1900) Friedel memorial lecture. J Chem Soc Trans 77:993–1000CrossRefGoogle Scholar
  11. DeGroot JV et al (2004) Highly transparent silicone materials. In: Norwood R, Eich M, Kuzyk M (eds) Linear and nonlinear optics of organic materials, 2nd edn. Proc SPIE IV, Midland, pp 116–123CrossRefGoogle Scholar
  12. Dollase T, Spiess HW, Gottlieb M, Yerushalmi-Rozen R (2002) Crystallization of PDMS: the effect of physical and chemical crosslinks. Europhys Lett 60:390–396CrossRefGoogle Scholar
  13. Dumitriu S (2002) Polymeric biomaterials. Marcel Dekker, New YorkGoogle Scholar
  14. Friedel C, Crafts JM (1877) Comprehensive organic name reactions and reagents. Comptes Rendus 84:1392–1450Google Scholar
  15. Gee RP (2015) Emulsion polymerization of dimethylcyclosiloxane in cationic emulsion: mechanism study utilizing two phase liquid–liquid reaction kinetics. Colloids Surf A Physicochem Eng Asp 481:297–306CrossRefGoogle Scholar
  16. Jian W, Xueming C, Panjin J, Qing H, Mingtao R (2015) Synthesis and characterization of the copolymers containing blocks of polydimethylsiloxane in low boiling point mixtures. Mater Chem Phys 149:216–223Google Scholar
  17. Jiang S, Qiu T, Li X (2010) Kinetic study on the ring-opening polymerization of octamethylcyclotetrasiloxane (D4) in miniemulsion. Polymer 51:4087–4094CrossRefGoogle Scholar
  18. Kendrick TC, Parbhoo B, White JW (1991) The silicon–heteroatom bond. Wiley, ChichesterGoogle Scholar
  19. Kherroub DE, Belbachir M, Lamouri S, Bouhadjar L, Chikh K (2013) Synthesis of polyamide-6/montmorillonite nanocomposites by direct in situ polymerization catalysed by exchanged clay. Orient J Chem 29:1429–1436CrossRefGoogle Scholar
  20. Kherroub DE, Belbachir M, Lamouri S (2014a) Cationic ring opening polymerization of ε-caprolactam by a montmorillonite clay catalyst. BCREC 9:74–80CrossRefGoogle Scholar
  21. Kherroub DE, Belbachir M, Lamouri S (2014b) Preparation and characterization of organophilic montmorillonite (12-Maghnite) using Algerian clay. Orient J Chem 30:1647–1651CrossRefGoogle Scholar
  22. Kherroub DE, Belbachir M, Lamouri S (2015a) Nylon 6/clay nanocomposites prepared with Algerian modified clay (12-Maghnite). Res Chem Intermed 41:5217–5228CrossRefGoogle Scholar
  23. Kherroub DE, Belbachir M, Lamouri S (2015b) Study and optimization of the polymerization parameter of furfuryl alcohol by Algerian modified clay. Arab J Sci Eng 40:143–150CrossRefGoogle Scholar
  24. Kherroub DE, Belbachir M, Lamouri S (2015c) Synthesis of poly(furfuryl alcohol)/montmorillonite nanocomposites by direct in situ polymerization. Bull Mater Sci 38:57–63CrossRefGoogle Scholar
  25. Meghabar R, Megherbi A, Belbachir M (2003) Maghnite-H+, an ecocatalyst for cationic polymerization of N-vinyl-2-pyrrolidone. Polymer 44:4097–4100CrossRefGoogle Scholar
  26. Molenberg A, Möller M (1995) A fast catalyst system for the ring-opening polymerization of cyclosiloxanes. Macromol Rapid Commun 16:449–453CrossRefGoogle Scholar
  27. Namrata ST, Florence DJ, Lawrence F, Jacques L (2012) Oxidation, chain scission and cross-linking studies of polysiloxanes upon ageings. OJOPM 2:13–22CrossRefGoogle Scholar
  28. Narins RS, Beer K (2006) Liquid injectable silicone: a review of its history, immunology, technical considerations, complications, and potential. Plast Reconstr Surg 118:77–84CrossRefGoogle Scholar
  29. Pibre G, Chaumont P, Fleury E, Cassagnau P (2008) Ring-opening polymerization of decamethylcyclopentasiloxane initiated by a superbase: kinetics and rheology. Polymer 49:234–240CrossRefGoogle Scholar
  30. Rodriquez F (1989) Principles of polymer systems. Hemisphere Publishing Corp, New YorkGoogle Scholar
  31. Sigwalt P (1987) New developments in cationic polymerization of cyclosiloxanes. Polym J 19:567–580CrossRefGoogle Scholar
  32. Sun CN, Shen MM, Deng LL, Mo JQ, Zhou BW (2014) Kinetics of ring-opening polymerization of octamethylcyclotetrasiloxane in microemulsion. Chin Chem Lett 25:621–626CrossRefGoogle Scholar
  33. Wilczek L, Rubinsztajn S, Chojnowski J (1986) Comparison of the cationic polymerization of octamethylcyclotetrasiloxane and hexamethylcyclotrisiloxane. Makromol Chem 187:39–51CrossRefGoogle Scholar
  34. Ya-Qing Z, Xiang K, Xiao-Li Z, Zheng-Hong L (2010) Particle kinetics and physical mechanism of microemulsion polymerization of octamethylcyclotetrasiloxane. Powder Technol 201:146–152CrossRefGoogle Scholar

Copyright information

© Shiraz University 2017

Authors and Affiliations

  • Djamal Eddine Kherroub
    • 1
    • 2
    Email author
  • Mohammed Belbachir
    • 1
  • Saad Lamouri
    • 3
  • Karim Chikh
    • 1
  1. 1.Laboratory of Polymer Chemistry, Department of Chemistry, Faculty of Exact and Applied SciencesUniversity of Oran 1 Ahmed Ben BellaEl’Menouer OranAlgeria
  2. 2.Institute of Sciences and TechnologyUniversity Centre of Relizane Ahmed ZabanaRelizaneAlgeria
  3. 3.Laboratory of Macromolecular ChemistryPolytechnic Military School (EMP)AlgiersAlgeria

Personalised recommendations