Study of the formation of structures in solutions of chitosan – polyvinyl alcohol polymer blends
Abstract
The aim of this work was the investigation of the formation of structures in solutions of individual polymers, as well as their blends with each other in buffer solvents with different values of pH. In this study we used a sample of chitosan (degree of deacetylation ~ 84 %, M = 130,000), which is a polycation when dissolved, and polyvinyl alcohol (r = 1.25 g/cm3, M = 5000). Buffer systems based on acetic acid and sodium acetate with pH = 3.8, 4.25, and 4.75 were used as solvents. Viscosimetry was used to determine the intrinsic viscosity, the degree of structuring, and the Huggins constant. The Kriegbaum method was used to determine the nature of the aggregates formed by the blend of the studied polymers. In the course of the research, it was shown that an increase in the pH of the acetate buffer used as a solvent was accompanied by a compression of the macromolecular coil (a decrease in intrinsic viscosity values), a deterioration in the quality of the
solvent (an increase in Huggins constant values), and an increase in the degree of polymer aggregation in a solution for chitosan polyelectrolyte. At the same time for a solution of polyvinyl alcohol the pH of the buffer practically did not affect the nature of the polymer-solvent interaction. It has been proved that polymer blends are characterized by an increase in aggregation processes and a decrease in the thermodynamic quality of the solvent in comparison with solutions of individual polymers. The size of the “combined” macromolecular coil, characterized by the intrinsic viscosity value for the polymer blend, which can be both above (buffer solvent with pH = 3.80) and below (buffer solvent with pH = 4.25 and 4.75) additive
values, changed depending on the type of formed polymer-polymer aggregates (homo- or hetero-). It was established that the type of aggregates (homo- or hetero-) formed in solutions of polymer blends was determined not only by the thermodynamic quality of the used solvents, but also by the concentration of the polymers in the initial solutions
Downloads
References
Matevosyan M. S., Askadskii A. A., Slonimskii G. L. Mechanical relaxational properties of polymer films as a function of the prehistory of their preparation from solutions. Polymer Science U.S.S.R. 1987;29(4): 843–850. https://doi.org/10.1016/0032-3950(87)90457-6
Kulish E. I., Chernova V. V., Vildanova R. F., Volodina V. P., Kolesov S. V. The influence of the prehistory of the formation of film samples of chitosan on the process of their enzymatic decomposition. Bulletin of the Bashkir University. 2011;16(2): 339–340. Available at: https://elibrary.ru/item.asp?id=16461557 (In Russ., abstract in Eng.)
Kulish E. I., Lazdina R. Yu., Shurshina A. S., Kolesov S. V., Zakharova E. M., Zakharov V. P. Structure formation as a method of forming physicomechanical characteristics of films obtained from aqueous solutions of certain polysaccharides. Polymer Science, Series A. 2021;63 (1): 54–62. https://doi.org/10.1134/s0965545x21010053
Alig I., Lellinger D., Skipa T. Influence of thermorheological history on electrical and rheological properties of polymer–carbon nanotube composites. In: Polymer–Carbon Nanotube Composites. 2011; 295–328. https://doi.org/10.1533/9780857091390.2.295
Mazinov A. S., Tyutyunik A. S., Gurchenko V. S. Changes in the spectral characteristics and conductivity of fullerene films depending on the type of solvent. Applied Physics = Prikladnaya Fizika. 2020;2: 64–70. Available at: https://elibrary.ru/item.asp?id=43064333 (In Russ., abstract in Eng.)
Gorodnyakova I. S., Shcherbina L. A., Budkute I. A. Influence of the composition of the precipitation bath on the structure and properties of the fiber obtained by the wet method from solutions of poly [acrylonitrileco- methyl acrylate-co-2-acrylamide-2-methylpropane sulfonic acid] in aprotic and hydrotropic solvents. Polimernye materialy i tekhnologii. 2020;6(4): 42–57. https://doi.org/10.32864/polymmattech-2020-6-4-42-57 (In Russ., abstract in Eng.)
Liu B., Zhang H., Ren J., Ma T., Yu M., Xie L., Lu D. Effect of solvent aromaticity on poly(9,9- dioctylfluorene) (PFO) chain solution behavior and film condensed state structure. Polymer. 2019;185(17): 121986. https://doi.org/10.1016/j.polymer.2019.121986
Rafikov S. R., Budtov V. P., Monakov Yu. B. Vvedeniye v f iziko-khimiyu rastvorov polimerov [Introduction to the physicochemistry of polymer solutions]. Мoscow: Khimiya Publ.; 1978. 320 p. (in Russ.)
Plate N. A., Vasilyev A. Ye. Fiziologicheski aktivnyye polimery [Physiologically active polymers]. Мoscow: himiya Publ., 1986. 296 p. (in Russ.)
Anwar H., Ahmad M., Minhas, M. U., Rehmani S. Alginate-polyvinyl alcohol based interpenetrating polymer network for prolonged drug therapy, Optimization and in-vitro characterization. Carbohydrate Polymers. 2017;166: 183–194. https://doi.org/10.1016/j.carbpol.2017.02.080
Timofejeva A., D’Este M., Dagnija L. Calcium phosphate/polyvinyl alcohol composite hydrogels: A review on the freeze-thawing synthesis approach and applications in regenerative medicine. European Polymer Journal. 2017;95: 547–565. https://doi.org/10.1016/j.eurpolymj.2017.08.048
Matyjaszewski K., Möller M. Copper-mediated atom transfer radical polymerization. In: Polymer Science: A Comprehensive Reference. Elsevier Science; 2012;3: 377–428.
https://doi.org/10.1016/b978-0-444-53349-4.00071-6
Schmitz C., Auza L. G., Koberidze D., Rasche S., Fischer R., Bortesi L. Conversion of chitin to defined chitosan oligomers: current status and future prospects. Marine Drugs. 2019;17(8): 452. https://doi.org/10.3390/md17080452
Crini G. Historical review on chitin and chitosan biopolymers. Environmental Chemistry Letters. 2019;17: 1623-1643. https://doi.org/10.1007/s10311-019-00901-0
Shukla S. K., Mishra A. K., Arotiba O. A., Mamba B. B. Chitosan-based nanomaterials: a state-of-theart review. International Journal of Biological Macromolecules. 2013;59: 46–58. https://doi.org/10.1016/j.ijbiomac.2013.04.043
Keong L. C., Halim A. S. In Vitro models in biocompatibility assessment for biomedical-grade chitosan derivatives in wound management. International Journal of Molecular Sciences. 2009;10(3): 1300–1313. https://doi.org/10.3390/ijms10031300
Li J., Wu Y., Zhao L. Antibacterial activity and mechanism of chitosan with ultra high molecular weight. Carbohydrate Polymers. 2016;148: 200–205. https://doi.org/10.1016/j.carbpol.2016.04.025
Arinshtein A. E. Effect of aggregation processes on the viscosity of suspensions. Sov. Phys. JETP. 1992;74(4): 646–648. Available at: http://jetp.ac.ru/cgi-bin/dn/e_074_04_0646.pdf
Doi M., Edwards S. F. The theory of polymer dynamics. New York: The Clarendon Press, Oxford University Press; 1986. 391 p.
Gennes P. G. de Scaling concepts in polymer physics. Ithaca, N.Y.: Cornell University Press; 1979. 324 p.
Copyright (c) 2021 Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases
This work is licensed under a Creative Commons Attribution 4.0 International License.
