1. JCCT
  2. All Volumes and Issues
  3. Volume 17, Number 1, 2023
  4. Green Synthesis of Functionalized Poly(3-Glycidoxypropyl-Trimethoxysilane) Using an Eco-Catalyst (Treated Montmorillonite)

Green Synthesis of Functionalized Poly(3-Glycidoxypropyl-Trimethoxysilane) Using an Eco-Catalyst (Treated Montmorillonite)

JCCT.
2023;
Volume 17, Number 1
: pp. 60 - 69
https://doi.org/10.23939/chcht17.01.060
Authors:
  1. Nadia Embarek
  2. Nabahat Sahli
1
Laboratoire de Chimie des Polymères, Département de Chimie Univerité Oran
2
Laboratoire de Chimie des Polymères, Département de Chimie Univerité Oran

Telechelic poly(3-glycidoxypropyltrimethoxysilane) (PGPTMS) with acetate and methacrylate end groups was successfully synthesized by an efficient and solvent-free approach, with anhydrides (acetic anhydride (AA) and methacrylic anhydride (MA)), by cationic ring-opening polymerization of 3 glycidoxypropyltrimetho-xysilane (GPTMS), using an ecologic solid catalyst Maghnite-H+ (Mag-H+), instead of electrophilic catalysts, such as, Bronsted and Lewis acids which are very noxious and corrosive. Mag-H+ is a montmorillonite sheet silicate clay exchanged with protons. The structure of the obtained macromonomers was confirmed by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) and UV-visible spectroscopy. The presence of the methacrylate end groups of bis-macromonomers was determined by UV-visible spectroscopy. In order to find the optimal reaction conditions, effects of reaction time and the amount of anhydrides (AA and MA) on the yield of macromonomers were investigated.

functionalized polymer
3-glycidoxypropyltrimetoxysilane
montmorillonite
eco-catalyst
cationic polymerization
  1. Rempp, P.; Franta, E. Macromonomers: Synthesis, Characterization and Applications. In Advances in Polymer Science; Springer: Berlin, Heidelberg, 1984; Vol 58, pp 1-53. https://doi.org/10.1007/3-540-12793-3_6
  2. Chujo,Y.; Yamashita, Y.: Telechelic Polymers. Synthesis and Applications; CRC Press: Boca Raton, 1989.
  3. DeClercq, R.; Goethals, E.: Polymer Networks Containing Degradable Polyacetal Segments. Macromolecules, 1992, 25, 1109-1113. https://doi.org/10.1021/ma00029a016
  4. Polymeropoulos, G.; Zapsas, G.; Ntetsikas, K.; Bilalis, P.; Gnanou, Y.; Hadjichristidis, N. 50th Anniversary Perspective: Polymers with Complex Architectures. Macromolecules, 2017, 50, 1253-1290. https://doi.org/10.1021/acs.macromol.6b02569
  5. Franta, E.; Lutz, P.; Reibel, L.; Sahli, N.; OuldKada, S.; Belbachir, M. Functionalization of Poly(1,3-Dioxolane). Macromol. Symp. 1994, 85, 167-174. https://doi.org/10.1002/masy.19940850112
  6. Reguieg, F.; Sahli, N.; Belbachir, M.; Lutz, P. One-Step Synthesis of Bis-Macromonomers of Poly(1,3-Dioxolane) Catalyzed by Maghnite-H+. J. Appl.Polym. Sci. 2006, 99, 3147-3152. https://doi.org/10.1002/app.22935
  7. Haoue, S.; Derdar, H.; Belbachir, M.; Harrane, A. Polymerization of Ethylene Glycol Dimethacrylate (EGDM), Using an Algerian Clay as Eco-catalyst (Maghnite-H+ and Maghnite-Na+). Bull. Chem. React. Eng. Catal. 2020, 15, 221-230. https://doi.org/10.9767/bcrec.15.1.6297.221-230
  8. Hydrogels in Medicine and Pharmacy. Fundamentals. Peppas, N., Eds.;CRC Press: Boca Raton, 1987. https://doi.org/10.1201/9780429285097
  9. Peppas,N.; Bures, P.; Leobandung, W.; Ichikawa, H. Hydrogels in Pharmaceutical Formulations. Eur. J. Pharmac. Biopharmac. 2000, 50, 27-46. https://doi.org/10.1016/S0939-6411(00)00090-4
  10. Lutz, P. Free Radical Homopolymerization, in Heterogeneous Medium, of Linear and Star-Shaped Polymerizable Amphiphilic Poly(Ethers): A New Way to Design Hydrogels Well Suited for Biomedical Applications. Macromol. Symp. 2001, 164, 277-292. https://doi.org/10.1002/1521-3900(200102)164:1<277::AID-MASY277>3.0.CO;2-E
  11. Lutolf, M.; Reaber, G.; Zisch, A.; Tirelli, N.; Hubbell, J.A. Cell-Responsive Synthetic Hydrogels. Adv. Mater., 2003, 15, 888-892. https://doi.org/10.1002/adma.200304621
  12. Sahli, N.; Belbachir, M.; Lutz, P. Design and Properties of Degradable Networks Based on Free Radical Copolymerization of Poly(1,3-dioxolane) Macromonomers with Hydrophobic or Hydrophilic Comonomers in Water. Macromol. Chem. Phys. 2005, 206, 1257-1270. https://doi.org/10.1002/macp.200500045
  13. Reguieg, F.; Sahli, N.; Belbachir, M. Nanocomposite Hydrogels Based on Water Soluble Polymer and Montmorillonite-Na+. Orient. J. Chem. [Online] 2015, 31(3). https://doi.org/10.13005/ojc/310343 (accessed July 07, 2021)
  14. Reguieg, F.; Sahli, N.; Belbachir, M. Hydrogel Composite of Poly(Vinylalcohol) with Unmodified Montmorillonite. Curr. Chem. Lett. 2017, 2, 69-76. https://doi.org/10.5267/j.ccl.2016.11.005
  15. Li, L.; He, B.; Chen, X. Epoxylsilane Crosslinking of Rigid Poly(Vinyl Chloride). J. Appl. Polym. Sci. 2007, 106, 3610-3616. https://doi.org/10.1002/app.26890
  16. Tian, M.; Liang, W.; Rao, G.; Zhang, L.; Guo, C.Surface Modification of Fibrillar Silicate and its Reinforcing Mechanism on FS/Rubber Composites. Compos. Sci. Technol. 2005, 65, 1129-1138. https://doi.org/10.1016/j.compscitech.2004.11.008
  17. Zhang, H.; Zhang, Z.; Guo, F.; Liu, W.M. Friction and Wear Behavior of the Hybrid PTFE/Cotton Fabric Composites Filled with TiO2 Nanoparticles and Modified TiO2 Nanoparticles. Polym. Eng. Sci. 2009, 49, 115-122. https://doi.org/10.1002/pen.21228
  18. Gabrielli, L.; Russo, L.; Poveda, A.; Jones, J.R.; Nicotra, F.; Jiménez-Barbero, J.; Cipolla, L. Epoxide Opening versus Silica Condensation during Sol-Gel Hybrid Biomaterial Synthesis. Chem. Eur. J. 2013, 19, 7856-7864. https://doi.org/10.1002/chem.201204326
  19. Innocenzi, P.; Brusatin, G.; Babonneau, F. Competitive Polymerization between Organic and Inorganic Networks in Hybrid Materials. Chem. Mater. 2000, 12, 3726-3732. https://doi.org/10.1021/cm001139b
  20. Innocenzi, P.; Brusatin, G.; Guglielmi, M.; Bertani, R. New Synthetic Route to (3-Glycidoxypropyl)trimethoxysilane-Based Hybrid Organic−Inorganic Materials. Chem. Mater. 1999, 11, 1672-1679. https://doi.org/10.1021/cm980734z
  21. Innocenzi, P.; Esposto, M.; Maddalena, A. Mechanical Properties of 3-Glycidoxypropyltrimethoxysilane Based Hybrid Organic-Inorganic Materials. J. Sol-Gel Sci. Technol. 2001, 20, 293-301. https://doi.org/10.1023/A:1008782203971
  22. Innocenzi, P.; Sassi, A.; Brusatin, G.; Guglielmi, M.; Favretto, D.; Bertani, R.; Venzo, A.; Babonneau, F. A Novel Synthesis of Sol−Gel Hybrid Materials by a Nonhydrolytic/Hydrolytic Reaction of (3-Glycidoxypropyl)trimethoxysilane with TiCl4. Chem. Mater. 2001, 13, 3635-3643. https://doi.org/10.1021/cm011034o
  23. Schmidt, H. New Type of Non-Crystalline Solids between Inorganic and Organic Materials. J. Non-Cryst. Solids, 1985, 73, 681-691. https://doi.org/10.1016/0022-3093(85)90388-6
  24. Schmidt, H. Multifunctional Inorganic-Organic Composite Sol-Gel Coatings for Glass Surfaces. J. Non-Cryst. Solids, 1994, 178, 302-312. https://doi.org/10.1016/0022-3093(94)90299-2
  25. Embarek, N.; Sahli, N. A Novel Green Synthesis Method of Poly(3-Glycidoxypropyltrimethoxysilane) Catalyzed by Treated Bentonite. Bull. Chem. React. Eng. Catal. 2020, 15, 290-303. https://doi.org/10.9767/bcrec.15.2.6568.290-303
  26. Popall, M.; Durand, H. Inorganic-Organic Copolymers as Solid State Li+ Electrolytes. Electrochim. Acta 1992, 37, 1593-1597. https://doi.org/10.1016/0013-4686(92)80118-6
  27. Riegel, B.; Blittersdorf, S.; Kiefer, W.; Hofacker, S.; Müller, M.; Schottner, G. Kinetic Investigations of Hydrolysis and Condensation of the Glycidoxypropyltrimethoxysilane/Aminopropyltriethoxy-Silane System by Means of FT-Raman Spectroscopy I. J. Non-Cryst. Solids 1998, 226, 76-84. https://doi.org/10.1016/S0022-3093(97)00487-0
  28. Sforca, M.; Yoshida, I.; Nunes, S. Organic-Inorganic Membranes Prepared from Polyether Diamine and Epoxy Silane. J. Membr. Sci. 1999, 159, 197-207. https://doi.org/10.1016/S0376-7388(99)00059-9
  29. Sorek, Y.; Zevin, M.; Reisfeld, R.; Hurvits, T.; Ruschin, S. Zirconia and Zirconia−ORMOSIL Planar Waveguides Prepared at Room Temperature. Chem. Mater. 1997, 9, 670-676. https://doi.org/10.1021/cm960135x
  30. Innocenzi, P.; Martucci, A.; Guglielmi, M.; Armelao, L.; Pelli S.; Righini, G.; Battaglin, G. Optical and Surface Properties of Inorganic and Hybrid Organic-Inorganic Silica-Titania Sol-Gel Planar Waveguides. J. Non-Cryst. Solids 1999, 259, 182-190. https://doi.org/10.1016/S0022-3093(99)00534-7
  31. Brusatin, G.; Innocenzi, P.; Guglielmi, M.; Bozio, R.; Meneghetti, M.; Signorini, R.; Maggini, M.;Scorrano, G.;Prato, M. γ(Glicydoxypropyl)-Trymethoxysilane-Based Matrices Tailored for Optical Limiting Applications. In Proc. SPIE 3803, Materials and Devices for Photonic Circuits, Denver, USA, July 18-23, 1999; Armenise, M.N., Pecorella, W., Hubert-Pfalzgraf, L.-G., Najafi S.I., Eds.; Vol. 3803, p 90. https://doi.org/10.1117/12.366748
  32. Innocenzi, P.; Brusatin, G.; Guglielmi, M.; Signorini, R.; Bozio, R.; Maggini, M. 3-(Glycidoxypropyl)-Trimethoxysilane-TiO2 Hybrid Organic-Inorganic Materials for Optical Limiting. J. Non-Cryst. Solids 2002, 65, 68-74. https://doi.org/10.1016/S0022-3093(99)00898-4
  33. Innocenzi, P.; Brusatin, G.; Guglielmi, M.; Signorini, R.; Meneghetti, M.; Bozio, R.; Maggini, M.; Scorrano, G.; Prato M. Optical Limiting Devices Based on C6o Derivatives in Sol-Gel Hybrid Organic-Inorganic Materials. J. Sol-Gel Sci. Technol. 2000, 19, 263-266. https://doi.org/10.1023/A:1008704825802
  34. Signorini, R.; Meneghetti; M.; Bozio, R.; Maggini, M., Scorrano, G.; Prato, M.; Guglielmi, M. Optical Limiting and Non Linear Optical Properties of Fullerene Derivatives Embedded in Hybrid Sol-Gel Glasses. Carbon 2000, 38, 1653-1662. https://doi.org/10.1016/S0008-6223(00)00055-5
  35. Casalboni, M.; De Matteis, F.; Prosposito, P.; Pizzoferrato, R. Optical Investigation of Infrared Dyes in Hybrid Thin Films. Appl. Phys. Lett. 1999, 75, 2172. https://doi.org/10.1063/1.124955
  36. Pomogailo, A.D. Polymer Sol-Gel Synthesis of Hybrid Nanocomposites. Colloid J. 2005, 67, 658-677. https://doi.org/10.1007/s10595-005-0148-7
  37. Inorganic and Organometallic Polymers with Special Properties. Laine, R.M., Eds.; Springer: Netherlands, 2012. https://doi.org/10.1007/978-94-011-2612-0
  38. Harrane, A.; Meghabar, R.; Belbachir, M. A Protons Exchanged Montmorillonite Clay as an Efficient Catalyst for the Reaction of Isobutylene Polymerization. Int. J. Mol. Sci. 2002, 3, 790-800. https://doi.org/10.3390/i3070790
  39. Belbachir, M.;Bensaoula, A. Composition and Method for Catalysis Using Bentonites. US Patent 6274527B1, Aug 14, 2001.
  40. Belbachir, M.; Bensaoula, A. Composition and Method for Catalysis Using Bentonites. US Patent 0069446A1, Oct 04, 2003.
  41. Beloufa, K.; Sahli, N.; Belbachir, M. Synthesis of Copolymer from 1,3,5-Trioxane and 1,3-Dioxolane Catalyzed by Maghnite-H+. J. Appl. Polym. Sci. 2010, 115, 2820-2827. https://doi.org/10.1002/app.30901
  42. Bennabi, S.; Sahli, N.; Belbachir, M.; Brachais, C.-H.; Boni, G.; Couvercelle, J.-P. New Approach for Synthesis of Poly(Ethylglyoxylate) Using Maghnite-H+, an Algerian Proton Exchanged Montmorillonite Clay, as an Eco-Catalyst. J. Macromol. Sci. A 2017, 54, 843-852. https://doi.org/10.1080/10601325.2017.1339558
  43. Derdar, H.; Belbachir, M.; Harrane, A. A Green Synthesis of Polylimonene Using Maghnite-H+, an Exchanged Montmorillonite Clay, as Eco-Catalyst. Bull. Chem. React. Eng. Catal. 2019, 14, 69-78. https://doi.org/10.9767/bcrec.14.1.2692.69-78
  44. Seghier, S.;Belbachir, M. Degradation of Poly(3-(Oxiran-2-ylmethyl)Oxazolidin-2-one) in the Presence of an Algerian Activated Clay. Iran J. Sci. Technol. Trans. A Sci. 2019, 43, 1545-1550. https://doi.org/10.1007/s40995-018-0629-2
  45. Hennaoui, F.; Belbachir, M. A Green One-pot Synthesis of PDMS Bis-Macromonomers Using an Ecologic Catalyst (Maghnite-H+). J. Macromol. Sci. A 2015, 52, 992-1001. https://doi.org/10.1080/10601325.2015.1095602
  46. Breen, C.; Madejová, J.; Komadel, P. Characterisation of Moderately Acid-Treated, Size-Fractionated Montmorillonites Using IR and MAS NMR Spectroscopy and Thermal Analysis. J. Mater. Chem. 1995, 5, 469-474. https://doi.org/10.1039/JM9950500469
  47. Číčel, B.; Komadel, P.; Bednáriková, E.; Madejová, J. Mineralogical Composition and Distribution of Si, Al, Fe, Mg, and Ca in the Fine Fractions of Some Czech and Slovak Bentonites. Geol. Carpath. Clays 1992, 1, 3-7.
  48. Farmer, V.C. The Infrared Spectra of Minerals. Mineralogical society: London, 1974. https://doi.org/10.1180/mono-4
  49. CRC Atlas of Spectral Data and Physical Constants for Organic Compounds; Grasselli, J.G.; Ritchey, W.M., Eds.; CRC Press: Cleveland, 1973.
  50. Wang, J.; Fan, X.; Tian, W.; Wang, Y.; Li, J. Ring-Opening Polymerization of γ-Glycidoxypropyltrimethoxysilane Catalyzed by Multi-Metal Cyanide Catalyst. J. Polym. Res. 2011, 18, 2133-2139. https://doi.org/10.1007/s10965-011-9623-5