SYNTHESIS OF ACRYLIC COPOLYMER CONTAINING NICKEL IONS

ABSTRACT

This article describes the results of the synthesis of an acrylic copolymer containing nickel ions and the study of its fundamental physicochemical properties. During the research, a copolymer was synthesized based on acrylic monomers in the presence of nickel ions, and the structure and functional groups of the resulting product were analyzed using FT-IR spectroscopy. The spectral results revealed the presence of characteristic carboxyl, acrylic, and metal-complex groups within the polymer chain, confirming the successful formation of the copolymer. Furthermore, the physicochemical properties of the synthesized copolymer, including its solubility in various solvents and its stability under thermal influence, were investigated. The findings established that the material possesses a high degree of thermal and chemical stability.

АННОТАЦИЯ

В данной статье изложены результаты синтеза акрилового сополимера, содержащего ионы никеля, и исследования его основных физико-химических свойств. В процессе исследования на основе акриловых мономеров в присутствии ионов никеля был синтезирован сополимер, структура и функциональные группы которого проанализированы методом ИК-спектроскопии. Результаты спектрального анализа подтвердили успешное образование сополимера, указав на наличие в полимерной цепи характерных карбоксильных, акриловых и металлокомплексных групп. Также были изучены физико-химические свойства синтезированного сополимера, включая его растворимость в различных растворителях и термическую устойчивость; установлено, что полученный продукт обладает высокой степенью термической и химической стабильности.

Keywords: Acrylic copolymer, nickel ions, copolymerization, FT-IR spectroscopy, polymer synthesis, physicochemical properties.

Ключевые слова: акриловый сополимер, ионы никеля, сополимеризация, ИК-спектроскопия, синтез полимеров, физико-химические свойства.

Introduction.

In this research, copolymers based on Ni and Sn acrylate monomers were compared to identify the differences between their synthesis, structure, and properties. Through this method, the influence of their structure and size on the formation of the copolymer compound and its solubility characteristics was determined. Furthermore, the possibilities for their application in developing temperature-resistant, adhesive coatings in the form of hydrogels were established. (1). In this research, metal-containing polymer compounds are classified among compounds possessing important functional groups due to their unique structures and combined properties. They integrate the specific physicochemical properties of metals with the strength and processing ease of polymers. In recent years, advanced polymerization techniques have expanded the possibilities for obtaining such materials under constant control. Specifically, metal-ion-containing polymer compounds with the desired structure and properties can be synthesized through controlled processes such as ATRP (Atom Transfer Radical Polymerization), RAFT (Reversible Addition-Fragmentation Chain-Transfer), and other controlled radical polymerization methods. (2). In this research, PIM-MMA, bis-AMP-MMA, and AMP-MMA monomers were synthesized. Due to its high reactivity, PIM-MMA was not utilized for obtaining complex compounds; however, it was found to possess specific adsorption properties for Ni(II) ions. While complex compounds of bis-AMP-MMA and AMP-MMA were obtained with both Co(II) and Ni(II), AMP-MMA formed a particularly strong bond with Ni(II). Consequently, among the synthesized polymers, the AMP-MMA monomer stood out for its high selectivity toward Ni(II) ions. (3). In this research, a dinickel complex compound was synthesized, which showed effective results in the copolymerization process of ethylene and acrylate. Recent studies indicate that the dinickel complex possesses two nickel centers, leading to various types of acrylate bonding patterns. When the dinickel complex is mixed with, a 1:1 bonding occurs, which enhances the catalytic rate. This interaction alters the incorporation of acrylate with the MW (molecular weight) copolymer and induces cationic bonding. (4). In this research, previously non-existent, highly stable, and regenerable copolymer compounds were synthesized using Co(II), Ni(II), and Cu(II) complexes based on acrylamide, acrylic acid, and terpyridine monomers. Their composition and properties were extensively studied using various physicochemical methods. The results demonstrate that all metal-containing polymer compounds exhibited regenerative properties while maintaining high durability. The best recovery performance was observed in the nickel-containing sample, which is attributed to the excellent mobility of the coordination bonds. (5). In this research, metal-polymer materials based on the copolymers of polypropylene glycol maleate phthalate with acrylic acid, utilizing nickel and silver ions as metals, were obtained for the first time. The synthesized copolymer compounds were analyzed using various physicochemical methods. Due to their excellent performance in pyridine electroreduction reactions, the catalytic activity of these previously unobtained metal-polymer compounds was observed. It was determined that the components of the metal-nanoparticle polymer compounds are equivalent. (6). In this research, nickel complex compounds based on 2-(diarylphosphino)-N-phenylbenzenamine were synthesized and utilized as pre-catalysts in the catalysis of bicyclic hydrocarbon (co)polymerization. When activated with MAO (methylaluminoxane), the nickel compounds acted as catalysts with high activity, inducing bicyclic hydrocarbon polymerization and reaching a maximum number-average molecular weight (Mn) of 27,4 times 10,5 g/mol. Additionally, they accelerate the copolymerization of bicyclic hydrocarbons and MA (maleic anhydride), resulting in the formation of NB/MA copolymer compounds with maximum molecular weight. (7).

Materials and methods.

We synthesized a nickel-containing acrylic copolymer using liquid-state acrylic acid, methyl methacrylate monomer, ammonium persulfate, and nickel nitrate salt. For the synthesis process, we utilized a magnetic stirrer with a hotplate, a thermostat to monitor the temperature, and a custom-made mold fashioned from aluminum foil to pour the resulting gel-like viscous substance. To identify the functional groups present within the nickel-ion-containing acrylic copolymer, IR spectroscopy (FTIR) was employed. Initially, the nickel salt and the initiator were accurately weighed. Then, 100 ml of distilled water was poured into a heat-resistant, flat-bottomed flask, to which the pre-measured nickel salt was added. The flask was placed on a magnetic stirrer, and the acrylic acid and methyl methacrylate monomers were added. The mixture was heated at 110⁰C for one and a half hours. The magnetic stirrer was set to a speed of 1500–2000 rpm to prevent phase separation of the mixture. Subsequently, 0.5 grams of ammonium persulfate was added to the resulting mixture, followed by further heating on the magnetic stirrer. A small additional amount of initiator was then introduced, and the heating continued for another half hour. As a result, a blue-green, viscous, gel-like liquid was formed. The obtained polymer compound was washed with distilled water and dried at room temperature.

Results and Discussion

Hydrogen bonds and Hydroxyl (OH) or Amine (NH) groups (3200–3500 cm^-1 region): These broad and intense peaks are formed as a result of the stretching vibrations of hydroxyl (OH) and amine (NH) groups. Carbonyl (C=O) group (peaks around 1699–1710 cm^-1): This represents the stretching vibration of the carbonyl (C=O) group belonging to acrylic acid or its esters (MMA). CH, CH₂, and CH₃ groups (2929–2945 cm^-1): Characteristic aliphatic stretching vibrations. S=O groups (1161–1211 cm^-1): Stretching vibrations of the sulfonic groups (due to the presence of AMPS). Metal-ligand (Ni-O or Ni-N) bonds (1010–1040 cm^-1): Peaks in this region are often attributed to the vibrations of metal-ligand bonds. Coordination bonding (600–800 cm^-1): Changes and new minor peaks in this region directly indicate the coordination bonding of nickel with oxygen or nitrogen (Ni-O / Ni-N).

Figure 1. FT-IR Spectrum of Nickel-Containing Acrylic Copolymer

The structure of the synthesized nickel acrylate-based copolymer was analyzed using FT-IR spectroscopy, and the characteristic functional groups observed in the spectrum confirmed the successful synthesis of the polymer. The physicochemical properties of the obtained polymer, including its solubility in various solvents and its thermal stability, were studied in detail, revealing its high level of thermal and chemical resistance. Throughout the research, the copolymer was synthesized using a new and efficient method, which stands out not only for increasing the economic efficiency of the process but also for its technological convenience.

Conclusion.

In this research, a nickel acrylate-based copolymer was synthesized using an efficient method, and its structure and properties were comprehensively investigated. The results of the FT-IR spectroscopy analysis demonstrated the presence of characteristic functional groups within the polymer composition, confirming the successful synthesis of the copolymer. The physicochemical properties of the obtained polymer, including its solubility and thermal stability, were examined, and it was found to possess a high degree of stability. The research findings indicate that, due to its structural and functional characteristics, the nickel acrylate-based copolymer is a promising material for the production of hydrogels, heat-resistant coatings, and polymer films. Furthermore, the developed synthesis method is technologically simple and economically efficient, enabling the large-scale production of such copolymers. Consequently, the conducted research establishes an important scientific and practical foundation for creating nickel-based acrylic copolymers as new functional materials and for their application across various industrial sectors.

References:

1. Nurmuminovich E. K. et al. THE STUDYING SYNTHESIS AND RESEARCH OF NICKEL AND TIN ACRYLATE ON THE BASIS OF THE COPOLYMERS //Journal of Pharmaceutical Negative Results. – 2022. – Т. 13.
2. Liu, X., et al. (2024). Recent advances in controlled polymerization for functional metallopolymers. Polymer Reviews, 64(1), 306-370.
3. Giove, A. Preparation of ion-imprinted polymers for the hydrometallurgical separation of Co (II) and Ni (II) ions: influence of metal-chelator complexes on selectivity. – 2024.
4. Xiong, S., et al. Switchable Synthesis of Ethylene/Acrylate Copolymers Using a Dinickel Catalyst: Evidence for Chain Growth at Nickel Centers and Cation Exchange Polymerization Concepts // ACS Catalysis. – 2024. – Vol. 14. – No. 7. – pp. 5260–5268.
5. Sorin E. S. et al. High-strength, self-healing copolymers of acrylamide and acrylic acid with Co (II), Ni (II), and Cu (II) complexes of 4′-phenyl-2, 2′: 6′, 2 ″-terpyridine: preparation, structure, properties, and autonomous and pH-triggered healing //Polymers. – 2024. – Т. 16. – №. 22. – С. 3127
6. Burkeev M. Z. et al. Synthesis and catalytic properties of new polymeric monometallic composites based on copolymers of polypropylene glycol maleate phthalate with acrylic acid //Polymers. – 2021. – Т. 13. – №. 24. – С. 4369.
7. Cao L., Li M., Cai Z. Copolymerization of Norbornene and Methyl Acrylate by Nickel Catalyst Bearing 2-(Diarylphosphino)-N-phenylbenzenamine Ligands //Catalysts. – 2023. – Т. 13. – №. 2. – С. 311.