Izvestiya of Saratov University.

Chemistry. Biology. Ecology

ISSN 1816-9775 (Print)
ISSN 2541-8971 (Online)

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Synthesis and Physicochemical Properties of Grafted Copolymers of Chitosan and Acrylic Monomers

Bayburdov Telman А., Saratov State University
Shmakov Sergei L., Saratov State University

The search and analysis of English-language 2004–2019 scientific literature devoted to the graft polymerization of acrylic monomers (acrylic acid and acrylamide being examples) onto chitosan to obtain novel materials with valuable properties was made. It was revealed that radical copolymerization, with potassium or ammonium persulfate, cerium-ammonium nitrate being initiators was used for grafting. Microwave, UV radiation and gamma rays were also used. To obtain gel, a cross-linking agent (N,N’- methylenebisacrylamide) was introduced. Glutaraldehyde was also used for cross-linking. Along with acrylic acid and acrylamide, other monomers (such as hydroxyethyl methacrylate) were also used. In some cases, chitosan was quaternized (using 2,3-epoxypropyltrimethylammonium chloride) or modified (using maleic anhydride, 2-pyridyl-acetylchitosan chloride), some additives were introduced for functionalization (sodium humate, muscovite, attapulgite, silver nanoparticles, and epidermal growth factor). Hydrogels with a double network, nanocomposites based on grafted chitosan, hydrogel microspheres with tunable macroporous structures were of interest in the study. The prospects of using grafted copolymerization products as (super)absorbents (including heavy metal ions), water absorbers, flocculants, antibacterial agents (including nanocomposites), and materials for biomedical engineering (macroporous scaffolds to model nerve tissue) were assessed.


1. Tizzotti M., Charlot A., Fleury E., Stenzel M., Bernard J. Modification of Polysaccharides Through Controlled/ Living Radical Polymerization Grafting-Towards the Generation of High Performance Hybrids // Macromol. Rapid Commun. 2010. Vol. 31. P. 1751–1772.
2. Rong Q., Feng F., Ma Z. Metal ions doped chitosanpoly(acrylic acid) nanospheres: synthesis and their application in simultaneously electrochemical detection of four markers of pancreatic cancer // Biosensors & Bioelectronics. 2016. Vol. 75. P. 148–154.
3. Lin Y., Hong Y., Song Q., Zhang Z., Gao J., Tao T. Highly effi cient removal of copper ions from water using poly(acrylic acid)-grafted chitosan adsorbent // Colloid Polym. Sci. 2017. Vol. 295, № 4. P. 627–635. 4. Fang S., Wang G., Li P., Xing R., Liu S., Qin Y., Yu H., Chen X., Li K. Synthesis of chitosan derivative graft acrylic acid superabsorbent polymers and its application as water retaining agent // Intern. J. of Biol. Macromol. 2018. Vol. 115. P. 754–761.
5. Fang S., Wang G., Xing R., Chen X., Liu S., Qin Y., Li K., Wang X., Li R., Li P. Synthesis of superabsorbent polymers based on chitosan derivative graft acrylic acid-coacrylamide and its property testing // Intern. J. of Biol. Macromol. 2019. Vol. 132. P. 575–584.
6. He G., Ke W., Chen X., Kong Y., Zheng H., Yin Y., Cai W. Preparation and properties of quaternary ammonium chitosan-g-poly(acrylic acid-co-acrylamide) superabsorbent hydrogels // React. Funct. Polym. 2017. Vol. 111. P. 14–21.
7. Liu J., Wang Q., Wang A. Synthesis and characterization of chitosan-g-poly(acrylic acid)/sodium humate superabsorbent // Carbohydrate Polymers. 2007. Vol. 70. P. 166–173.
8. Zheng Y., Zhang J., Wang A. Fast removal of ammonium nitrogen from aqueous solution using chitosang-poly(acrylic acid)/attapulgite composite // Chem. Engin. J. 2009. Vol. 155. P. 215–222.
9. Xie Y. T., Wang A.Q. Preparation and Swelling Behaviour of Chitosan-g-poly(acrylic acid)/Muscovite Superabsorbent Composites // Iran. Polym. J. 2010. Vol. 19, № 2. P. 131–141.
10. Metzler M., Chylinska M., Kaczmarek H. Preparation and characteristics of nanosilver composite based on chitosan-g-acrylic acid copolymer // J. Polym. Res. 2015. Vol. 22. P. 146–155.
11. Santos dos K. S. C. R., Coelho J. F. J., Ferreira P., Pinto I., Lorenzetti S. G., Ferreira E. I., Higa O. Z., Gil M. H. Synthesis and characterization of membranes obtained by graft copolymerization of 2-hydroxyethyl methacrylate and acrylic acid onto chitosan // Intern. J. of Pharm. 2006. Vol. 310. P. 37–45.
12. Yao H.-Y., Lin H.-R., Sue G.-P., Lin Y.-J. Chitosan-based hydrogels prepared by UV polymerization for wound dressing // Polymers and Polymer Composites. 2018. Vol. 27, № 3. P. 1–13.
13. Ge H., Pang W., Luo D. Graft copolymerization of chitosan with acrylic acid under microwave irradiation and its water absorbency // Carbohydrate Polymers. 2006. Vol. 66. P. 372–378.
14. Al-Karawi A. J. M., Al-Qaisi Z. H. J., Abdullaha H. I., Al-Mokarama A. M. A., Al-Heetimi D. T. A. Synthesis, characterization of acrylamide grafted chitosan and its use in removal of copper(II) ions from water // Carbohydrate Polymers. 2011. Vol. 83. P. 495–500.
15. Kumar P., Choonara Y. E., du Toit L. C., Modi G., Naidoo D., Pillay V. Novel High-Viscosity Polyacrylamidated Chi tosan for Neural Tissue Engineering : Fabrication of Anisotropic Neurodurable Scaffold via Molecular Disposition of Persulfate-Mediated Polymer Slicing and Complexation // Intern. J. Mol. Sci. 2012. Vol. 13. P. 13966–13984.
16. Pourjavadi A., Mahdavinia G. R. Superabsorbency, pHsensitivity and swelling kinetics of partially hydrolyzed chitosan-g-poly(acrylamide) hydrogels // Turk. J. Chem. 2006. Vol. 30. P. 595–608.
17. Molatlhegi O., Alagha L. Adsorption characteristics of chitosan grafted copolymer on kaolin // Appl. Clay Sci. 2017. Vol. 150. P. 342–353.
18. Ali Z. A., Venkatesan J., Kim S. K., Sudha P. N. Benefi cial effect of chitosan g polyacrylamide copolymer in removal of heavy metals from industrial dye effl uents // Intern. J. of Environ. Sci. 2011. Vol. 1, № 5. P. 820–833.
19. Jung S., Abel J. H., Starger J. L., Yi H. Porosity-Tuned Chitosan-Polyacrylamide Hydrogel Microspheres for Improved Protein Conjugation // Biomacromolecules. 2016. Vol. 17, № 7. P. 2427–2436.
20. Bulut E. Controlled delivery of the popular nonsteroidal anti-infl ammatory drug, paracetamol, from chitosan-gpolyacrylamide microspheres prepared by the emulsion crosslinking technique // Artifi cial Cells, Nanomedicine, and Biotechnology. 2016. Vol. 44, № 6. P. 1482– 1490.
21. Singh V., Tiwari A., Tripathi D. N., Sanghi R. Microwave enhanced synthesis of chitosan-graft-polyacrylamide // Polymer. 2006. Vol. 47. P. 254–260.
22. Sokker H. H., El-Sawy N. M., Hassan M. A., El-Anadouli B. E. Adsorption of crude oil from aqueous solution by hydrogel of chitosan based polyacrylamide prepared by radiation induced graft polymerization // J. of Hazardous Materials. 2011. Vol. 190. P. 359–365.
23. Tang H., Guo J., Shan B., Lu J. Synthesis and Applications of a Novel Copolymer of Chitosan as Heavy Metal Removal Agent // Advanced Materials Research. 2011. Vols. 233–235. P. 741–746.
24. Zeng M., Feng Z., Huang Y., Liu J., Ren J., Xu Q., Fan L. Chemical structure and remarkably enhanced mechanical properties of chitosan-graft-poly(acrylic acid)/polyacrylamide double-network hydrogels // Polym. Bull. 2016. Vol. 74, № 1. P. 55–74.
25. Lalita, Singh A. P., Sharma R. K. Selective sorption of Fe(II) ions over Cu(II) and Cr(VI) ions by cross-linked graft copolymers of chitosan with acrylic acid and binary vinyl monomer mixtures // Intern. J. of Biol. Macromolecules. 2017. Vol. 105, part 1. P. 1202–1212.
26. Said M., Atassi Y., Tally M., Khatib H. Environmentally Friendly Chitosan-g-poly(acrylic acid-co-acrylamide)/ Ground Basalt Superabsorbent Composite for Agricultural Applications // J. of Polymers and Environment. 2018. Vol. 26, iss. 9. P. 3937–3948.