Interaction of poly(diallyldimethylammonium chloride) with inorganic acids

Objectives. The study set out to investigate the state of poly(N,N-diallyl-N,N-dimethylammonium chloride) (polyDADMAC) in aqueous solutions and the exchange reactions of polyelectrolyte anions with anions of inorganic acids, as well as to assess the effect of the acidity, basicity, and nature of Н_nX_m acids on the state of the polymer-colloidal complex (PCC) in aqueous solutions.

Methods. Potentiometry, dynamic light scattering, infrared spectroscopy, and nuclear magnetic resonance spectroscopy methods were used.

Results. The main factors affecting the state of the polyDADMAC polyelectrolyte in aqueous solutions were determined along with the characteristics of exchange processes involving anions of inorganic acids. The polymer electrolyte polyDADMAC is shown to exist in an aqueous solution in the form of impermeable polymer coils, representing polymer solvent-separated ion pairs. The Cl⁻ anion of the polyelectrolyte is exchanged for the OH⁻ ion of water or the Xⁿ⁻ anions of inorganic acids to form PCCs with polymer chain links and various counteranions. The exchange of the anions takes place mainly on the surface of the polymer coil, which limits the degree of substitution of anions and depends on the strength, nature, and basicity of the Н_nX_m acids. A relationship was found between the degree of substitution of the Xⁿ⁻ anions of the polymer coil and the strength of the resulting PCC with the enthalpy of solvation of inorganic acids Н_nX_m.

Conclusions. The polymer electrolyte polyDADMAC exists in an aqueous solution in the form of impermeable polymer coils, which are represented by polymer solvent-separated ion pairs. The exchange of the Cl⁻ anion of the polyelectrolyte for the OH⁻ ion of water or the Xn⁻ anions of inorganic acids results in the formation of PCCs with polymer chain links and various counteranions. The exchange of the anions, which takes place on the surface of the polymer coil, mainly involves the OH⁻ anion of the polyelectrolyte. A relationship was identified between the state of polymer coils of polyDADMAC, the degree of substitution of anions with different pK_a , and the degree of acid solvation. The degree of substitution of the X^n– anions of acids, which decreases with a decrease in the strength of the НnXm acid and the charge of the resulting anion in the series HClO₄ > HCl > HNO₃ > HBF₄ > HSO₄ ⁻, H2PO₄ ⁻, is characterized by a significant change in the size of the coil of the slow mode of motion of the PCC polyelectrolyte. Here, the increased diffusion coefficient from 3.0·10⁻¹³ to 1.3·10⁻¹⁰ cm²/s corresponds to a decrease in the degree of association of the links of the polymer coil of PCC in the same series. The degree of substitution of the Xn^– anions of the polymer coil and the strength of the forming PCC decrease symbatically with a decrease in the degree of solvation of inorganic acids in water.

1. Golubeva Ya.N., Chebotareva T.A., Tokareva A.A., Krylov A.V., Zheglaty P.V. Prospects the development of urification methods of sludge-lignin deposits of JSC “Baikal Pulp Mill” with polymer electrolytes. Khimicheskaya bezopasnost’ = Chem. Safety Sci. 2023;7(2):55–73 (in Russ.). https://doi.org/10.25514/CHS.2023.2.25004

2. Monney I., Buamah R., Donkor E.A., et al. Treating waste with waste: the potential of synthesized alum from bauxite waste for treating car wash wastewater for reuse. Environ. Sci. Pollut. Res. 2019;26(13):12755–12764. https://doi.org/10.1007/s11356-019-04730-0

3. Xin-Hui Su C., Tow Teng T., Morad N. Optimization of the Coagulation-Flocculation of Reactive Dye Wastewater Using Novel Inorganic-Organic Hybrid Polymer. Iranica J. Energy Environ. 2016;7(1):31–38.

4. Abujazar M., Karaağaç S.U., Bashir M.J.K., et al. Recent advancement in the application of hybrid coagulants in coagulationflocculation of wastewater: A review. J. Cleaner Product. 2022;345:131–133. https://doi.org/10.1016/j.jclepro.2022.131133

5. Kabanov V.A. From synthetic polyelectrolytes to polymersubunit vaccines. Pure Appl. Chem. 2004;76(9):1659–1677. https://doi.org/10.1351/pac200476091659 [Original Russian Text: Kabanov V.A. From synthetic polyelectrolytes to polymer-subunit vaccines. Vysokomolekulyarnye soedineniya. Seriya A. 2004;46(5):759–782 (in Russ.).]

6. Tokareva A.A., Krylov A.V., Bondareva A.M., Chebotareva T.A., Zheglaty P.V. Integrated approaches to the treatment of highly polluted wastewater. Khimicheskaya bezopasnost’ = Chem. Safety Sci. 2023;7(1):81–92 (in Russ.). https://doi.org/10.25514/CHS.2023.1.24006

7. ZheglatyP.V., BobrovaI.V., KrylovA.V., NosikN.N., NosikD.N. New Virucidal Agents Containing Complex Based on Polypyrrolidinium Polymers: RF Pat. 2782065. Publ. 21.10.2022 (in Russ.).

8. Kristianto H., Rahman H., Prasetyo S., et al. Removal of Congo red aqueous solution using Leucaena leucocephala seed’s extract as natural coagulant. Appl. Water Sci. 2019;9:88. https://doi.org/10.1007/s13201-019-0972-2

9. ZhaoY.X., GaoB.Y., Shon H., et al. Coagulation characteristics of titanium (Ti) salt coagulant compared with aluminum (Al) and iron (Fe) salts. J. Hazardous Mater. 2011;185(2–3): 1536–1542. https://doi.org/10.1016/j.jhazmat.2010.10.084

10. NesterovYu.V. Ionity iionoobmen. Sorbtsionnaya tekhnologiya pri dobyche urana i drugikh metallov metodom podzemnogo vyshchelachivaniya (Ionites and Ion Exchange. Sorption Technology in the Extraction of Uranium and Other Metals by Underground Leaching). Moscow: Atomredmetzoloto; 2007. 480 p. (in Russ.).

11. Matveichuk Yu.V., Stanishevskii D.V. Anion-Exchange Extraction of Doubly Charged Anions by Higher Quaternary Ammonium Salts with Different Steric Accessibility of the Exchange Center. J. Anal. Chem. 2020;75(6):711–716. https://doi.org/10.1134/S1061934820040097 [Original Russian Text: Matveichuk Yu.V., Stanishevskii D.V. Anion-Exchange Extraction of Doubly Charged Anions by Higher Quaternary Ammonium Salts with Different Steric Accessibility of the Exchange Center. Zhurnal analiticheskoi khimii. 2020;75(6):496–501 (in Russ.). https://doi.org/10.31857/S0044450220040106 ]

12. Kuzmin V.I. , Gudkova N.V. , Kuzmin D.V., et al. Effect of solvation-dehydration of quaternary ammonium base salts in the organic phase on the selectivity of anion-exchange extraction. Sep. Sci. Technol. 2023;58(7):1283–1294. https://doi.org/10.2139/ssrn.3967023

13. Egorov V.V., Rakhman’ko E.M., Pomelenok E.V., et al. Effect of the steric accessibility of the exchange site in long-chain quaternary ammonium salts on the anion-exchange extraction of divalent ions. Russ. J. Phys. Chem. 2006;80(6):969–973. https://doi.org/10.1134/S0036024406060239 [Original Russian Text: Egorov V.V., Rakhman’ko E.M., Pomelenok E.V., Okaev E.B. Effect of the steric accessibility of the exchange site in long-chain quaternary ammonium salts on the anion-exchange extraction of divalent ions. Zhurnal fizicheskoi khimii. 2006;80(6):1104–1109 (in Russ.).]

14. Merenbloom S.I., Flick T.G., Daly M.P., et al. Effects of select anions from the Hofmeister series on the gas-phase conformations of protein ions measured with travelingwave ion mobility spectrometry/mass spectrometry. J. Am. Soc. Mass Spectrom. 2011;22(11):1978–1990. https://doi.org/10.1007/s13361-011-0238-1

15. Xie W.J., Liu C.W., Yang L.J., et al. On the molecular mechanism of ion specific Hofmeister series. Sci. China Chem. 2014;57(1):36–47. https://doi.org/10.1007/s11426-013-5019-1

16. Tsyganov A.R., Rakhman’ko E.M., Starobinets G.L. Anion exchange extraction of acid dyes with trinonyloctadecylammonium salts. Izvestiya AN BSSR. Seriya khimicheskikh nauk = Proceedings of Academy of Sciences of BSSR. Chemical Series. 1980;2:61–66 (in Russ.).

17. Egorov V.V., Rakhman’ko E.M., Okaev E.B., Pomelenok E.V., NazarovV.A. Effects of ion association of lipophilic quaternary ammonium salts in ion-exchange and potentiometric selectivity. Talanta. 2004;63(1):119–130. https://doi.org/10.1016/j.talanta.2003.11.019

18. Tager A.A. Fiziko-khimiya polimerov (Physico-Chemistry of Polymers). Moscow: Nauchnyi mir; 2007. 573 p. (in Russ.).

19. Anouti M., Caillon-Caravanier M., Le Floch C. Alkylammonium-Based Protic Ionic Liquids. II. Ionic Transport and Heat-Transfer Properties: Fragility and Ionicity Rule. J. Phys. Chem. B. 2008;112(31):9412–9416. https://doi.org/10.1021/jp803489n

20. Wilkes J.S. A short history of ionic liquids-from molten salts to neoteric solvents. Green Chem. 2002;4(2):73–80. https://doi.org/10.1039/B110838G

21. Pernak J., Legosz B., Walkiewicz F., Klejdysz T., Borkowsky A., Chrzanowski L. Ammonium ionic liquids with anion of natural oriqin. RSC Adv. 2015;5(80):65471–65480. https://doi.org/10.1039/C5RA11710K

22. Eneh C.L, Nixon K., Lalwani S.M., et al. Solid-LiquidSolution Phases in Poly(diallyldimethylammonium) / Poly(actylic acid) Polyelectrolyte Complexes at Varying Temperatures. Macromolecules. 2024;57(5):2363–2375. https://doi.org/10.1021/acs.macromol.4c00258

23. Esakova A.S., Laptinskaya T.V., Litmanovich E.A. Diffusion of polydiallyldimethylammonium chloride in aqueous solutions with added salt. Moscow University Physics Bulletin. 2010;65(2):119–125. https://doi.org/10.3103/S0027134910020098 [Original Russian Text: Esakova A.S., Laptinskaya T.V., Litmanovich E.A. Diffusion of polydiallyldimethylammonium chloride in aqueous solutions with added salt. Vestnik Moskovskogo universiteta. Seriya 3. Fizika. Astronomiya. 2010;2:50–56 (in Russ.).]

24. Litmanovich E.A., Orleneva A.P., Korolev B.A., Kasaikin V.A., Kulichikhin V.G. Dynamics of the polymer chain in aqueous and salt-containing aqueous solutions of poly(dimethyl diallylammonium chloride). Polym. Sci. Ser. A. 2000;42(6):689–693. [Original Russian Text: Litmanovich E.A., Orleneva A.P., Korolev B.A., Kasaikin V.A., Kulichikhin V.G. Dynamics of the polymer chain in aqueous and salt-containing aqueous solutions of poly(dimethyl diallylammonium chloride). Vysokomolekulyarnye soedineniya. Seriya A. 2000;42(6):1035–1041 (in Russ.).]

25. Marcelo G., Tarazona M. P., Saiz E. Solution properties of poly(diallyldimethylammonium chloride) (PDDA). Polymer. 2005;46(8):2584–2594. https://doi.org/10.1016/j.polymer.2005.01.078

26. Litmanovich E.A., Kasaikin V.A, Zezin A.B., Kabanov V.A. Effect of the concentration of poly-(N,N’- diallyldimethylammonium chloride) in a solution on the self-organization in its mixtures with sodium dodecyl sulfate. Doklady Physical Chemistry. 2000;373(1–3):121–124. [Original Russian Text: Litmanovich E.A., Kasaikin V.A, Zezin A.B., Kabanov V.A. Effect of the concentration of poly- (N,N’-diallyldimethylammonium chloride) in a solution on the self-organization in its mixtures with sodium dodecyl sulfate. Doklady Akademii nauk. 2000;373(3):350–354 (in Russ.).]

27. Jia X., Zhan X., Gong X., et al. Thermal decomposition mechanism of poly(dimethyldiallylammonium chloride). Therm. Anal. Calorim. 2022;147(7):4589–4596. https://doi.org/10.1007/s10973-021-10860-w

28. Krylov A.V., Tokareva A. A., Syromyatnikov P.А, Novichkova P.M., Zheglatiy P.V. Abnormal behavior of supramolecular systems based on quaternary ammonium salts and hydroxides in aqueous solutions. AIP Conf. Proc. 2022;2390(1):020040. https://doi.org/10.1063/5.0070097