Evaluation of hydrophilic properties of acrylonitrile/acrylic acid copolymer films dendrigrafted with citric acid

Document Type : Original research


1 Department of Textile Engineering, Amirkabir University of Technology, Tehran, Iran

2 Department of Textile Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran


The present study investigates the hydrophilic properties of acrylonitrile/acrylic acid P(AN/AA) copolymer films with various acrylic acid (AA) contents dendrigrafted with citric acid from zero to fourth generation numbers. It was found that the hydrophilicity of the dendrigrafted films was a complicated phenomenon. Various parameters such as intermolecular hydrogen bonding, roughness and active functional groups affected the wettability of the film samples measured via static contact angle. The results revealed that the hydrophilicity decreased with increasing the generation number owing to the steric hindrance of terminal groups. However, active functional group increased by rising generation numbers which was confirmed using zeta potential measurement. Furthermore, the percentage conversion of the reactions showed a reduction with increasing generation number and AA content which was in agreement with the reduction in wettability corresponding to the higher contact angle. On the other hand, zeta potential as well as roughness of the films increased with successive generations.


Main Subjects



    1. Sen K, Bahrami SH, Bajaj P (1996) High-performance acrylic fibers. J Macromol Sci Poylm Rev 36: 1-76
    2. Abdouss M, Mousavi Shoushtari A, Majidi Simakani A, Akbari S, Haji A (2013) Citric acid-modified acrylic micro and nanofibers for removal of heavy metal ions from aqueous media. Desalin Water Treat 52: 7133-7142
    3. Jia Z, Du S, Tian G (2007) Surface modification of acrylic fiber by grafting of casein. J Macromol Sci Pure 44: 299-304
    4. Matama T, VazF, Gubitz GM, Cavaco-Paulo A (2006) The effect of additives and mechanical agitation in surface modification of acrylic fibres by cutinase and esterase. Biotechnol J 1: 842-9
    5. Abdolahifard M, Bahrami SH, Malek RMA (2011) Surface modification of PET fabric by graft copolymerization with acrylic acid and its antibacterial properties. ISRN Org Chem 2011: 1-8
    6. Bajaj P, Sreekumar T, Sen K (2001) Effect of reaction medium on radical copolymerization of acrylonitrile with vinyl acids. J Appl Polym Sci 79: 1640-1652
    7. Akbari S, Kish MH, Entezami AA (2008) Copolymer of acrylonitrile/acrylic acid solid surface film dendrigrafted with citric acid. Polym Int 57: 846-853
    8. Akbari S (2013) The application of dendritic materialin textile engineering. Sci Bull Escorena 7: 11-28
    9. Klaykruayat B, Siralertmukul K, Srikulkit K (2010) Chemical modification of chitosan with cationic hyperbranched dendritic polyamidoamine and its antimicrobial activity on cotton fabric. Carbohyd Polym 80: 197-207
    10. Bashar MM, Khan MA (2013) An overview on surface modification of cotton fiber for apparel use. J Polym Environ 21: 181-190
    11. Barzegar RR, Akbari S, Kish MH (2013) Dendrigraft with citric acidon acrylonitrile/acrylic acid copolymer electrospun fibres. Polym Int 62: 1767-1776
    12. Caminade A-M, Laurent R, Majoral J-P (2005) Characterization of dendrimers. Adv Drug Deliv Rev 57: 2130-2146
    13. Kresge C, Leonowicz M, Roth W (2001) Dendrimers and dendrons. Concepts, Syntheses, Applications. VCH: Weinheim.
    14. Voit B (2000) New developments in hyperbranched polymers. J Polym Sci Pol Chem 38: 2505-2525
    15. Njikang GN, Gauthier M, Li J (2008) Sustained release properties of arborescent polystyrene-graft-poly (2-vinylpyridine) copolymers. Polymer 49: 5474-5481
    16. Gauthier M, Moeller M (1991) Uniform highly branched polymers by anionic grafting: Arborescent graft polymers. Macromolecules 24: 4548-4553
    17. Gauthier M (2007) Arborescent polymers and other dendrigraft polymers: A journey into structural diversity. J Polym Sci Pol Chem 45: 3803-3810
    18. Teertstra SJ, Gauthier M (2004) Dendrigraft polymers: Macromolecular engineering on a mesoscopic scale. Prog Polym Sci 29: 277-327
    19. Akbari S, Kish MH, Entezami AA (2011) Copolymer of acrylonitrile/acrylic acid film dendrigrafted with citric acid: Host/guest properties of dendrigraft/dye complexes in relation to acrylic acid content. Iran Polym J 20: 539-549
    20. Gao B, Du W, Ma Q, Zhang R, Wang C, Zhang J (2016) Effects of grafting low-generation poly (amido amine) onto carbon fiber surface by in situ polymerization on the mechanical properties offiber composites. High Perform Polym: https:// doi.org/10.1177/0954008316658534
    21. Akbari S, Kish MH, Entezami AA (2010) Modification of acrylonitrile/acrylic acid copolymer films and fibers by dendrigraft formation. Polym Int 59: 1550-1557
    22. Abdouss M, Mousavi Shoushtari A, Majidi Simakani A, Akbari S, Haji A (2014) Citric acid-modified acrylic micro and nanofibers for removal of heavy metal ions from aqueous media. Desalin Water Treat 52: 7133-7142
    23. Akbari S (2016) Thermal analysis of acrylonitrile/ acrylic acid copolymer dendrigrafted with citric acid. J Text Polym 4: 27-36
    24. Chami Khazraji A, Robert S (2013) Self-assembly and intermolecular forces when cellulose and water interact using molecular modeling. J Nanomater 2013: 10.1155/2013/745979
    25. Miwa M, Nakajima A, Fujishima A, Hashimoto K, Watanabe T (2000) Effects of the surface roughness on sliding angles of water droplets on superhydrophobic surfaces. Langmuir 16: 5754- 5760
    26. Fürstner R, Barthlott W, Neinhuis C, Walzel P (2005) Wetting and self-cleaning properties of artificial superhydrophobic surfaces. Langmuir 21: 956-961
    27. Li S, Huang J, Ge M, Cao C, Deng S, Zhang S, Chen G, Zhang K, Al-Deyab SS, Lai Y (2015) Self-cleaning cotton: Robust flower-like TiO2@cotton fabrics with special wettability for effective self-cleaning and versatile oil/water separation (Adv. Mater. Interfaces 14/2015). Adv Mater Interfaces 2: 10.1002/admi.201570068
    28. Sadeghi P, Tavanai H, Khoddami A (2017) Hydrophobicity of fluorocarbon-finished electrospun poly (acrylonitrile) nanofibrous webs. J Text Inst 108: 189-195
    29. Zhang M, Feng S, Wang L, Zheng Y Lotus effect in wetting and self-cleaning. Biotribology 5: 31- 43
    30. Yuan Y, Lee TR (2013) Contact angle and wetting properties. In: Surface science techniques. Bracco G, Holst B (Eds), Springer, 3-34
    31. Kubiak K, Wilson M, Mathia T, Carval P (2011) Wettability versus roughness of engineering surfaces. Wear 271: 523-528
    32. Krumpfer JW, McCarthy TJ (2010) Contact angle hysteresis: A different view and a trivial recipe for low hysteresis hydrophobic surfaces. Faraday Discuss 146: 103-111
    33. Gao L,McCarthy TJ (2006) Contact angle hysteresis explained. Langmuir 22: 6234-6237
    34. Xu QF, Liu Y, Lin F-J, Mondal B, Lyons AM (2013) Superhydrophobic TiO2–polymer nanocomposite surface with UV-induced reversible wettability and self-cleaning properties. ACS Appl Mater Interfac 5: 8915-8924
    35. Pawlak Z, Urbaniak W, Oloyede A (2011) The relationship between friction and wettability in aqueous environment. Wear 271: 1745-1749
    36. Bajaj P, Paliwal D, Gupta A (1993) Acrylonitrile– acrylic acids copolymers. I. Synthesis and characterization. J Appl Polym Sci 49: 823-833
    37. Wu J, Lin J, Li G, Wei C (2001) Influence of the COOH and COONa groups and crosslink density of poly(acrylic acid)/montmorillonite superabsorbent composite on water absorbency. Polym Int 50: 1050-1053
    38. Yang CQ (1991) Characterizing ester crosslinkages in cotton cellulose with FT-IR photoacoustic spectroscopy 1. Text Res J 61: 298-305
    39. Janorkar AV, Luo N, Hirt DE (2004) Surface modification of an ethylene-acrylic acid copolymer film: Grafting amine-terminated linear and branched architectures. Langmuir 20: 7151- 7158
    40. Walters KB, Hirt DE (2007) Synthesis and characterization of a tertiary amine polymer series from surface-grafted poly (tert-butyl acrylate) via diamine reactions. Macromolecules 40: 4829- 4838
    41. de Gennes P-G, Hervet H (1983) Statistics of "starburst" polymers. J Phys Let 44: 351-360
    42. Zhang J, Han Y (2008) A topography/chemical composition gradient polystyrene surface: Toward the investigation of the relationship between surface wettability and surface structure and chemical composition. Langmuir 24: 796-801
    43. Wenzel RN (1949) Surface roughness and contact angle. J Phys Chem 53: 1466-1467
    44. Tsai P-S, Yang Y-M, Lee Y-L (2006) Fabrication of hydrophobic surfaces by coupling of Langmuir- Blodgett deposition and a self-assembled monolayer. Langmuir 22: 5660-5665
  • Receive Date: 01 November 2016
  • Revise Date: 11 January 2017
  • Accept Date: 12 February 2017
  • First Publish Date: 01 June 2017