Environmentally Sensitive Vinylpyrrolidone/Methacrylic Acid Inter-Complex Amphoteric Hydrogel: Preparation, Characterization, and Use in the Binding of Copper Ions

Sepehrianazar, Amir

doi:10.30492/ijcce.2023.555458.5380

Environmentally Sensitive Vinylpyrrolidone/Methacrylic Acid Inter-Complex Amphoteric Hydrogel: Preparation, Characterization, and Use in the Binding of Copper Ions

Document Type : Research Article

Author

Amir Sepehrianazar

Department of Chemistry, Ahar Branch, Islamic Azad University, Ahar, I.R. IRAN

10.30492/ijcce.2023.555458.5380

Abstract

In this study for wastewater remediation, we aimed to prepare Environmentally Sensitive Hydrogels (ESHs) with specific properties to remove copper (Cu²⁺) from wastewater. ESHs were prepared with inter-complex and amphoteric properties by the free radical polymerization method. We prepared two monomers, vinylpyrrolidone (VP) and Methacrylic Acid (MA). N,N'-methylenebisacrylamide was a cross-linker agent to prepare ESHs for binding Cu²⁺ to remove from wastewater. To characterize the structural behavior of synthesized ESHs, we used FT-IR. Thermal properties were investigated by using TGA. We used Scanning Electron Microscopy (SEM) micrographs for morphologic studies. Swelling and diffusion studies were performed at different pH, temperatures, and salt solutions. The amphoteric property and inter-complex formation between VP and MA were monitored by UV spectroscopy. In the Cu²⁺ bindings onto ESH experiments, a Langmuir-type (L) adsorption was observed regarding the Giles classification system. Binding parameters such as equilibrium constant (K_L), monolayer coverage (Q_m), and maximum fractional occupancy (FO%) were calculated as 0.16 L 1/g_ESH, 30 MgCu²⁺1/g_ESH, and 81%, respectively. We found a powerful electrostatic effect between the ionic part of ESH and cationic Cu²⁺. These interactions denote the removal of cationic heavy metals and organic toxic wastes for water treatment.

Keywords

Main Subjects

Polymer Chemistry

References

[1] Saraydın D., Karadağ E., Güven O, Relationship Between the Swelling Process and the Releases of Water-Soluble Agrochemicals from Radiation Crosslinked Acrylamide/Itaconic Acid Copolymers, Polym. Bull., 45(3): 287–294, (2000).

doi:10.1007/s002890070033

[2] Karadağ E., Üzüm Ö. B., Saraydın D., Güven O, Swelling Characterization of Gamma-Radiation Induced Crosslinked Acrylamide/Maleic Acid Hydrogels in Urea Solutions, Mater. Des, 27(7): 576–584 (2006).

doi:10.1016/j.matdes.2004.11.019

[3] Işıkver Y., Saraydın D., Smart Hydrogels: Preparation, Characterization, and Determination of Transition Points of Crosslinked N-isopropyl Acrylamide/ Acrylamide/Carboxylic Acids Polymers, GEL, 7(3):113 (2021).

doi:10.3390/gels7030113

[4] Çaykara T., İnam R., Determination of the Competitive Adsorption of Heavy Metal Ions on Poly(N-Vinyl-2-Pyrrolidone/Acrylic Acid) Hydrogels by Differential Pulse Polarography, J. Appl. Polym. Sci., 89(8): 22 (2003).

https://doi.org/10.1002/app.12328

[5] Yetimoğlu E.K., Kahraman M.V., Ercan Ö., Akdemir Z.S., Apohan N.K., N-Vinylpyrrolidone/Acrylic Acid/ 2-Acrylamido-2-Methylpropane Sulfonic acid Based Hydrogels: Synthesis, Characterization and their Application in the Removal of Heavy Metals, React Funct Polym, 67: 451-460 (2007).

https://doi.org/10.1016/j.reactfunctpolym.2007.02.007

[6] Ali A.E., Shawky H.A., Rehim H.A., Hegazy E., Synthesis and Characterization of PVP/Aac Copolymer Hydrogel and Its Applications in the Removal of Heavy Metals from Aqueous Solution, Eur. Polym. J, 39: 2337-2344 (2003).

https://doi.org/10.1016/S0014-3057(03)00150-2

[7] Lee W.F., Yuan W.Y., Thermoreversible Hydrogels X: Synthesis and Swelling Behavior of the (N‐Isopropylacrylamide‐Co‐Sodium 2‐Acrylamido‐2‐Methyl Propyl Sulfonate) Copolymeric Hydrogels, J Appl Poly Sci, 77(8): 1760-1768 (2000).

DOI:10.1002/1097-4628(20000822)77:8<1760::AID-APP13>3.0.CO;2-J

[8] Maskawat Marjub M., Rahman N., Dafader N., Sultana Tuhen F., Sultana S., Tasneem Ahmed F., Acrylic Acid-Chitosan Blend Hydrogel: A Novel Polymer Adsorbent for Adsorption of Lead(Ii) and Copper(Ii) Ions from Wastewater, J. Polym. Eng., 39(10): 883-891 (2019).

https://doi.org/10.1515/polyeng-2019-0139

[9] Zhai S., Xiao H., Shu Y., Zhao Z., Countermeasures of Heavy Metal Pollution, Chin. J. Geochem., 32(4): 446-450 (2013).

https://doi.org/10.1007/s11631-013-0654-y

[10] Seko N., Tamada M., Yoshii F., Current Status of Adsorbent for Metal Ions with Radiation Grafting and Crosslinking Techniques, Nucl Instrum Methods Phys Res B., 236(1-4): 21-29 (2005).

https://doi.org/10.1016/j.nimb.2005.03.244

[11] Hu B., Jia X., Hu J., Xu D., Xia F., Li Y., Assessment of Heavy Metal Pollution and Health Risks in the Soil-Plant-Human System in the Yangtze River Delta, China, Int. J. Environ. Res. Public Health 10, 14(9): 1042 (2017).

doi: 10.3390/ijerph14091042.

[12] Tong S., Schirnding Y.E.V., Prapamontol T., Environmental Lead Exposure: A Public Health Problem of Global Dimensions, Bulletin of the World Health Organization, 78(9): 1068-1077 (2000).

[13] Suberlyak O., Skorokhoda V., “Hydrogels Based on Polyvinylpyrrolidone Copolymers in Hydrogels”. Edited by Haider S. and Haider A. Intech Open, London, UK 23-44, (2017).

doi:10.5772/intechopen.72082

[14] Teodorescu M., Bercea, M., Poly(vinylpyrrolidone) – A Versatile Polymer for Biomedical and Beyond Medical Applications, Polymer-Plastics Technology and Engineering, 54(9): 923–943 (2015).

doi:10.1080/03602559.2014.979506

[15] Ofridam F., Tarhini M., Lebaz N., Gagnière É., Mangin D., Elaissari A., pH-Sensitive Polymers: Classification and Some Fine Potential Applications, Polym. Adv. Technol., 32(4): 1455–1484 (2021).

doi:10.1002/pat.5230

[16] Knipe J.M., Chen F., Peppas N.A., Multiresponsive Polyanionic Microgels with Inverse pH-Responsive Behavior by Encapsulation of Polycationic Nanogels. J. Appl. Polym. Sci., 131(7) (2013).

doi:10.1002/app.40098

[17] Franco P., De Marco I., The Use of Poly(N-vinylpyrrolidone) in the Delivery of Drugs: A Review, Polym. J., 12(5): 1114 (2020).

doi:10.3390/polym12051114

[18] Chen G., Liu J., Yang Y., Zhang L., Wu M., Ni H., Preparation of pH-Sensitive Nanoparticles of Poly (Methacrylic Acid) (PMAA)/Poly (Vinylpyrrolidone) (PVP) by ATRP-Template Miniemulsion Polymerization in the Aqueous Solution, Colloid Polym. Sci, 293(7): 2035–2044 (2015).

doi:10.1007/s00396-015-3554-3

[19] Ponratnam S., Rao S.P., Joshi S.G., Kapur S.L., Copolymerization of Methacrylic Acid and N-vinylpyrrolidone in Aqueous Solution, J. Macromol. Sci. A, 10(6): 1055–1062 (1976).

doi:10.1080/00222337608061236

[20] Devine D.M., Higginbotham C.L., Synthesis and Characterization of Chemically Crosslinked N-Vinyl Pyrrolidinone (NVP) Based Hydrogels, Eur. Polym. J., 41(6): 1272–1279 (2005).

doi:10.1016/j.eurpolymj.2004.12.022

[21] Husain M.S.B., Gupta A., Alashwal B.Y., Sharma S., Synthesis of PVA/PVP Based Hydrogel for Biomedical Applications: A Review, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 40(20): 2388-2393, (2018).

doi:10.1080/15567036.2018.1495786

[22] Jozaghkar M.R., Sepehrian Azar A., Ziaee F., Preparation, Assessment and Swelling Study of Amphiphilic Acrylic Acid/Chitosan Based Semi-Interpenetrating Hydrogels Available online (2022).

10.12.2021 DOI: 10.3906/kim-2109-50

[23] Jozaghkar M.R., Sepehrian Azar A., Ziaee F., Synthesis and Characterization of Semi-Interpenetrating Polymer Network Hydrogel Based on Polyacrylic Acid/Polyallylamine and its Application in Wastewater Remediation. Polym. Bull. (2022).

https://doi.org/10.1007/s00289-022-04162-w

[25] a) Jozaghkar M.R., Sepehrian Azar A., Ziaee F., Preparation, Characterization, and Swelling Study of N,N’-Dimethylacrylamide/Acrylic Acid Amphiphilic Hydrogels in Different Conditions, Polymer Bulletin, 79: 5183–5195 (2021).

https://doi.org/10.1007/s00289-021-03760-4

b) Jiang X., Li C., Han Q., Modulation of Swelling of PVA Hydrogel by Polymer and Crosslinking Agent Concentration, Bull., 80: 1303–1320 (2023).

https://doi.org/10.1007/s00289-022-04116-2

c) Ji S., Li X., Wang S., Li H., Duan H., Yang X., Lv P., Physically Entangled Antiswelling Hydrogels with High Stiffness. Rapid Commun, 43(19): 2200272 (2022)

https://doi.org/10.1002/marc.202200272

[25] Gorshkov N.I., Murko A.Y., Gavrilova I.I., Bezrukova M.A., Kipper A.I., Krasikov V.D., Panarin, E.F., Synthesis of Water-Soluble Copolymers of N-Vinylpyrrolidone with N-Vinyldithiocarbamate as Multidentate Polymeric Chelation Systems and Their Complexes with Indium and Gallium. Molecules, 25(20): 4681 (2020).

doi:10.3390/molecules25204681

[26] a) Sonmez B., Celikkol A.N., Pullulan Based Hydrogels for the Removal of Various Metal Ions from Aqueous Solutions, J. Environ. Chem. Eng., 9(5): 106188, (2021).

https://doi.org/10.1016/j.jece.2021.106188

b) Shen B., Guo Z., Huang B., Zhang G., Fei P., Hu S., Preparation of Hydrogels Based on Pectin with Different Esterification Degrees and Evaluation of their Structure and Adsorption Properties, J. Biol. Macromol., 202: 397-406 (2022).

https://doi.org/10.1016/j.ijbiomac.2021.12.160

c) Jamnongkan T., Mongkholrattanasit R., Wattanakornsiri A., Wachirawongsakorn P., Takatsuka Y., Hara T., Green Adsorbents for Copper (II) Biosorption from Waste Aqueous Solution Based on Hydrogel-Beads of Biomaterials, Afr. J. Chem. Eng., 35: 14-22 (2021).

https://doi.org/10.1016/j.sajce.2020.10.005

d) Tirtom V.N., Dinçer A., Effective Removal of Heavy Metals from an Aqueous Solution with Poly(N-Vinylimidazole-Acrylamide) Hydrogels, Sci. Technol., 56(5): 912-924 (2021).

https://doi.org/10.1080/01496395.2020.1735434

[27] Torun M., Şolpan D., The Removal of Cationic Dyes from Aqueous Solutions by Using Poly(N-Vinylpyrrolidone-Co-Methacrylic Acid) Hydrogel Adsorbents: Effects of pH and Composition on Adsorption. Fibers Polym., 16(4): 735–743 (2015).

doi:10.1007/s12221-015-0735-0

[28] Sharpe L.A., Vela Ramirez J.E., Haddadin O.M., Ross K.A., Narasimhan B., Nicholas A. Peppas, pH-Responsive Microencapsulation Systems for the Oral Delivery of Polyanhydride Nanoparticles, Biomacromolecules, 19(3): 793-802 (2018).

https://doi.org/10.1021/acs.biomac.7b01590

[29] Saraydin D., Işıkver Y., Karadağ E., A Study on the Correlation Between Adsorption and Swelling for Poly(Hydroxamic Acid) Hydrogels-Triarylmethane Dyes Systems, J Polym Environ, 26(9): 3924–3936 (2018).

doi:10.1007/s10924-018-1257-9

[30] Knipe J.M., Chen F., Peppas N.A., Multiresponsive Polyanionic Microgels with Inverse pH Responsive Behavior by Encapsulation of Polycationic Nanogels, J. Appl. Polym. Sci., 131(7): 40098(1-8) (2013).

[31] Chongyang Zhu, Ning Tang, Jing Gan, Xiaojun Zhang, Yang Li, Xin Jia, Yongqiang Cheng, A pH-sensitive Semi-Interpenetrating Polymer Network Hydrogels Constructed by Konjac Glucomannan and Poly (Γ-Glutamic Acid): Synthesis, Characterization and Swelling Behavior, Int. J. Biol. Macromol., 185: 229-239 (2021).

https://doi.org/10.1016/j.ijbiomac.2021.06.046.

[32] Nurkeeva Z.S., Mun G.A., Khutoryanskiy V.V., Bitekenova A.B., Dubolazov A.V., Esirkegenova S.Z., pH Effects in the Formation of Interpolymer Complexes Between Poly(N-Vinylpyrrolidone) and Poly(Acrylic Acid) in Aqueous Solutions, EPJ E, 10(1): 65–68 (2003).

doi:10.1140/epje/e2003-00003-4

[33] Kozlovskaya V., Kharlampieva E., Mansfield M.L., Sukhishvili S.A., Poly(methacrylic acid) Hydrogel Films and Capsules: Response to pH and Ionic Strength, and Encapsulation of Macromolecules, Chem. Mater., 18(2): 328–336 (2005).

https://doi.org/10.1021/cm0517364

[34] Atta A.M., Arndt K.-F., Swelling Behavior of pH- and Temperature-Sensitive Copolymers Containing 2-Hydroxy-Ethyl Methacrylate and N-Vinyl-2-Pyrrolidone Crosslinked with New Crosslinkers, Polym. Int., 53(11): 1870–1881 (2004).

doi:10.1002/pi.1606

[35] Jin S., Liu M., Zhang F., Chen S., Niu A., Synthesis and Characterization of Ph-Sensitivity Semi-IPN Hydrogel Based on Hydrogen Bond Between Poly(N-Vinylpyrrolidone) and Poly(Acrylic Acid). Polym. J., 47(5): 1526–1532 (2006).

doi:10.1016/j.polymer.2006.01.009

[36] Behera M., Ram S., Inquiring The Mechanism of Formation, Encapsulation, and Stabilization of Gold Nanoparticles by Poly(Vinyl Pyrrolidone) Molecules in 1-Butanol, Appl. Nanosci., 4(2): 247–254 (2013).

doi:10.1007/s13204-013-0198-9

[37] Wang J., Tsuzuki T., Tang B., Cizek P., Sun L., Wang X., Synthesis of Silica-Coated Zno Nanocomposite: The Resonance Structure of Polyvinyl Pyrrolidone (PVP) as a Coupling Agent. Colloid Polym. Sci., 288(18): 1705–1711 (2010).

doi:10.1007/s00396-010-2313-8

[38] Das J.K., Das N., Bandyopadhyay S., Effect of PVP Intermediate Layer on the Properties of SAPO 34 Membrane, Adv. Mater. Sci. Eng., 1–7 (2012).

doi: 10.1155/2012/650217

[39] Zhunuspayev D.E., Mun G.A., Hole P., Khutoryanskiy V.V., Solvent Effects on the Formation of Nanoparticles and Multilayered Coatings Based on Hydrogen-Bonded Interpolymer Complexes of Poly(acrylic acid) with Homo- and Copolymers of N-Vinyl Pyrrolidone, Langmuir, 24(23):13742–13747 (2008).

doi:10.1021/la802852h

[40] Kharlampieva E., Erel-Unal I., Sukhishvili S.A., Amphoteric Surface Hydrogels Derived from Hydrogen-Bonded Multilayers: Reversible Loading of Dyes and Macromolecules. Langmuir, 23(1): 175–181 (2006).

doi:10.1021/la061652p

[41] Muta H., Miwa M., Satoh M., Ion-Specific Swelling of Hydrophilic Polymer Gels. Polym. J., 42(14): 6313–6316 (2001).

doi:10.1016/s0032-3861(01)00098-2

[42] Kemik Ö.F., Ngwabebhoh F.A., Yildiz U., A Response Surface Modelling Study for Sorption of Cu²⁺, Ni²⁺, Zn^2+, and Cd²⁺ Using Chemically Modified Poly(Vinylpyrrolidone) and Poly(Vinylpyrrolidone-Co-Methylacrylate) Hydrogels, Adsorp. Sci. Technol., 35(3-4): 263–283 (2016).

doi:10.1177/0263617416674950

[43] Ekici S., Işıkver Y., Şahiner N., Saraydın D., Adsorption of Some Textile Dyes onto Crosslinked Poly(N-vinylpyrrolidone), Adsorption Science and Technology, 21(7): 651–659 (2003).

doi:10.1260/026361703772776439

[44] William Kajjumba G., Emik S., Öngen A., Kurtulus Özcan H., Aydın S., Modeling of Adsorption Kinetic Processes—Errors, Theory, and Application, “Advanced Sorption Process Applications”, Edited by Edebali, S., IntechOpen, London, UK (2018).

doi:10.5772/intechopen.80495

[45] Tran H.N., You S.J., Hosseini Bandegharaei A., Chao H.P., Mistakes and Inconsistencies Regarding Adsorption of Contaminants from Aqueous Solutions: A Critical Review.Water Res., 120: 88-116 (2017).

https://doi.org/10.1016/j.watres.2017.04.014