Synthesis, Characterization and Metal Ion Adsorption Studies on Novel Aromatic Poly(Azomethine Amide)s Containing Thiourea Groups


A series of novel ladder-type poly(azomethine amide)s (PAMs) were prepared from new azomethine containing carboxylic acid monomer (TCA) with simple aromatic diamines and aromatic diamines with thiourea groups (TDAs) by means of phosphorylation polycondensation reaction. Molecular weights of the polyamides were evaluated viscometrically, and the inherent viscosities were in the range of 0.31 - 0.58 g/dl. These ladder-type polymers were not freely soluble in common organic solvents. Structure of monomers and polymers were confirmed using FT-IR, 1H-NMR and 13C-NMR spectroscopic analysis. Removal of Cu2+ and Cd2+ from aqueous solutions by adsorption onto the polyamides was investigated. The effect of pH, initial metal ion concentrations and contact time were studied in batch experiments. The polyamides were found to be highly effective adsorbents for the removal of Cu2+ and Cd2+ metal ions from aqueous solutions. In a mixture of metal ions, the selectivity order was found to be Pb(II) > Cu(II) > Cr(IV) > Cd(II).

Share and Cite:

L. Ravikumar, S. Kalaivani, T. Vidhyadevi, A. Murugasen, S. Kirupha and S. Sivanesan, "Synthesis, Characterization and Metal Ion Adsorption Studies on Novel Aromatic Poly(Azomethine Amide)s Containing Thiourea Groups," Open Journal of Polymer Chemistry, Vol. 4 No. 1, 2014, pp. 1-11. doi: 10.4236/ojpchem.2014.41001.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] P. E. Cassidy, “Thermally Stable Polymers, Synthesis and Properties,” Marcel Dekker, New York, 1980.
[2] A. Iwan and D. Sek, “Processable Polyazomethines and Polyketanils: From Aerospace to Light-Emitting Diodes and Other Advanced Applications,” Progress in Polymer Science, Vol. 33, No. 3, 2008, pp. 289-345.
[3] M. Grigoras, O. Cataneseu and C. L. Simionesen, “Poly (azomethine)s,” Revue Roumaine de Chimie, Vol. 46, No. 9, 2001, pp. 927-939.
[4] M. Grigoras, C. Otilia and O. Catanescu, “Imino Oligomers and Polymers,” Journal of Macromolecular Science: Part C, Vol. 44, No. 2, 2004, pp. 131-173.
[5] B. Suseela, B. Bhaskar and P. Subhash, “Synthesis and Characterization of New Polyimides and Polyamide-Imides Containing Azomethine Groups in the Polymer Backbone,” Polymer Bulletin, Vol. 22, No. 4, 1989, pp. 371-378.
[6] J. A. Mikroyannidias, “Aromatic Polyisophthalamides with N-Benzylidine Pendant Groups,” Journal of Polymer Science Part A: Polymer Chemistry, Vol. 30, No. 11, 1992, pp. 2371-2377.
[7] L. Ravikumar, R. Saravanan, K. Saravanamani and M. Karunagaran, “Synthesis and Characterization of New Polyamides with Substitutions in the Pendent Benzylidine Rings,” Designed Monomers and Polymers, Vol. 12, No. 4, 2009, pp. 291-303.
[8] K. Yamamoto, M. Higuchi and H. Kanazawa, “Novel Linear Hyperbranched Aromatic Polyamide with Phenylazomethine Units for Chemical Recycling,” Chemistry Letters, Vol. 31, No. 7, 2002, pp. 692-693.
[9] B. J. Vasanthi, L. Ravikumar and A. Selvaraj, “Corrision Control of Phenylthiourea Polymers on Aluminium in Alkaline Medium,” Materials and Corrosion, Vol. 59, No. 1, 2008, pp. 14-20.
[10] M. Sivadhayanithy, L. Ravikumar and C. Rengaswamy, “Desin and Synthesis of New Thermally Stable Polyesters Containing Azo and Phenylthiourea Units,” High Performance Polymers, Vol. 19, No. 1, 2007, pp. 62-75.
[11] B. J. Vasanthi and L. Ravikumar, “Synthesis and Characterization of New Poly(Azomethine Ester)s Having Phenylthiourea Units,” European Polymer Journal, Vol. 43, No. 10, 2007, pp. 4325-4331.
[12] I. Delfanne and G. Levesque, “Polythioamides and Poly (1,3,4-thiadiazole) Synthesis from Dimethyl Tetrathioterephthalate,” Macromolecules, Vol. 22, No. 6, 1989, pp. 2589-2592.
[13] L. Ravikumar, V. Sengodan, M. Balajiprasad, K. Gopalakrishnan and K. Sethupathi, “Synthesis and Characterization of Conductive Blends of Polyaniline with Poly (Azomethine Ester)s,” International Journal of Polymeric Materials and Polymeric Biomaterials, Vol. 56, No. 2, 2007, pp. 197-206.
[14] M. Sivadhayanithy, L. Ravikumar and T. Ramachandran, “Synthesis and Characterization of Thermally Stable Novel Polymers Containing Phenylthiourea, Azo and Sulfone Groups in the Backbone,” Journal of the Chilean Chemical Society, Vol. 52, No. 3, 2007, pp. 1230-1234.
[15] A. Kausar, S. Zulfiqar, Z. Ahmad and M. I. Sarwar, “Novel Processable and Heat Resistance Poly(Phenylthiourea Azomethine Imide)s: Synthesis and Characterization,” Polymer Degradation and Stability, Vol. 95, No. 9, 2010, pp. 1826-1833.
[16] N. Kabay, M. Demiccioglu, H. Elcinci, M. Yuksel, M. Saglam, M. Akcay and M. Streat, “Removal of Metal Pollutants Cd(II) and Cr(III) from Phosphoric Acid Solutions by Chelating Resins Containing Phosphoric or Diphosphoric Groups,” Industrial & Engineering Chemistry Research, Vol. 37, No. 6, 1998, pp. 2541-2547.
[17] S. Y. Chen, W. Shen, F. Yu and H. P. Wang, “Kinetic and Thermodynamic Studies of Adsorption of Cu2+ and Pb2+ onto Amidoximated Bacterial Cellulose,” Polymer Bulletin, Vol. 63, No. 2, 2009, pp. 283-297.
[18] H. L. Vasconcelous, V. T. Favere, N. S. Gonealves and M. C. M. Laranjeira, “Chitoson Modified with Reactive Blue 2 Dye on Adsorption Equilibrium of Cu(II) and Ni(II) Ions,” Reactive and Functional Polymers, Vol. 67, No. 10, 2007, pp. 1052-1060.
[19] S. S. Gupta and K. G. Bhattacharyya, “Removal of Cd(II) from Aquous Solutions by Kaolinite Montmorillonite and Their Poly(Oxo Zirconium) and Tetrabutylammonium Derivatives,” Journal of Hazardous Materials, Vol. 128, No. 2-3, 2006, pp. 247-257.
[20] G. Zuo and M. Muhammed, “Thiourea-Based Coordinating Polymers: Synthesis and Binding to Noble Metals,” Reactive Polymers, Vol. 24, No. 3, 1995, pp. 165-181.
[21] A. Lezzi and S. Cbianco, “Chelating Resins Supporting Dithiocarbamate and Methyl Thiourea Groups in Adsorption of Heavy Metal Ions,” Journal of Applied Polymer Science, Vol. 54, No. 7, 1994, pp. 889-897.
[22] M. Monier, D. M. Ayad and A. A. Sarhan, “Adsorption of Cu(II), Co(II) and Ni(II) Ions by Modified Magnetic Chitosan Chelating Resin,” Journal of Hazardous Materials, Vol. 177, No. 1-3, 2010, pp. 962-970.
[23] R. A. Ravikumar and R. K. Hussian, “Synthesis of Functionalized Phenolformaldehyde Polymer Resins by the Reaction of 2,4-Dihydroxyacetophenone Formaldehyde Resins with Various Amines and Their Metal Uptake Properties,” Journal of Applied Polymer Science, Vol. 92, No. 3, 2004, pp. 1501-1509.
[24] A. M. Donia, A. A. Atia and A. M. Henish, “Efficient Removal of Hg(II) Using Magnetic Chelating Resin Derived from Copolymerization of Bisthiourea/Thiourea/ Glutaraldehyde,” Separation and Purification Technology, Vol. 60, No. 1, 2008, pp. 46-53.
[25] L. Ravikumar, S. S. Kalaivani, A. Murugesan, T. Vidhyadevi, G. Karthik, S. D. Kirupha and S. Sivanesan, “Synthesis, Characterization, and Heavy Metal Ion Adsorption Studies of Polyamides, Polythioamides Having Pendent Chlorobenzylidine Rings,” Journal of Applied Polymer Science, Vol. 122, No. 3, 2011, pp. 1634-1642.
[26] A. Murugesan, L. Ravikumar, V. SathyaSelvaBala, V. SenthilKumar, T. Vidhyadevi, S. D. Kirupha, S. S. Kalaivani, S. Krithiga and S. Sivanesan, “Removal of Pb(II), Cu(II) and Cd(II) Ions from Aqueous Solution Using Polyazomethineamides: Equilibrium and Kinetic Approach,” Desalination, Vol. 271, No. 1-3, 2011, pp. 199-208.
[27] A. Murugesan, T. Vidhyadevi, S. S. Kalaivani, M. P. Premkumar, L. Ravikumar and S. Sivanesan, “Kinetic and Thermodynamic Studies on the Removal of Zn2+ and Ni2+ from Their Aqueous Solution Using Poly(Phenylthiourea)Imine,” Chemical Engineering Journal, Vol. 197, 2012, pp. 368-378.
[28] S. D. Kirupha, A. Murugesan, T. Vidhyadevi, P. Baskaralingam, S. Sivanesan and L. Ravikumar, “Novel Polymeric Adsorbents Bearing Amide, Pyridyl, Azomethine and Thiourea Binding Sites for the Removal of Cu(II) and Pb(II) Ions from Aqueous Solution,” Separation Science and Technology, Vol. 48, No. 2, 2013, pp. 254-262.
[29] J. Tan, C. Wang, W. Peng, G. Li and J. M. Jiang, “Synthesis, Characterization, and Properties of Novel Aromatic Polyamides Containing Phthalazinone Moiety,” Polymer Bulletin, Vol. 62, No. 2, 2009, pp. 195-207.
[30] A. K. Mohanty, D. Das, A. K. Panigrahi and M. Mishra, “Synthesis and Characterization of a Novel Polyamide: Polycondensation of 2,5-Diaminothiazole with Terephthalic Acid,” European Polymer Journal, Vol. 34, No. 12, 1998, pp. 1889-1898.
[31] A. Denizil, N. Sanli, B. Gavipean, S. Patir and G. Alsanck, “Methacryloylamidoglutamic Acid Incorporated Poros Poly(Methyl Methacrylate) Beads for Heavy-Metal Removal,” Industrial & Engineering Chemistry Research, Vol. 43, No. 19, 2004, pp. 6095-6010.

Copyright © 2022 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.