SYNTHESIS OF TIN-CONTAINING ACRYLIC OLIGOMERS

ABSTRACT

This article presents the synthesis process of tin-containing acrylic oligomers, utilizing various conditions for the synthesis. The obtained samples were studied through various spectroscopic methods. X-ray fluorescence analysis was used to determine the amount of tin in the compound. IR spectroscopy was employed to examine the functional groups within the tin-containing acrylate oligomers. The results indicate that the tin content in the oligomer is high, reaching 86%, and according to the IR spectrum, the organic compounds in the mixture formed coordination bonds with the metal. The following physical properties of the samples were studied under laboratory conditions: thermal stability, resistance to aqueous environments, and elasticity.

АННОТАЦИЯ

В данной статье представлен процесс синтеза оловосодержащего акрилового олигомера, при котором для синтеза использовались различные условия. Полученные образцы были изучены с помощью различных спектроскопических методов. Для определения содержания олова в соединении был использован метод рентгенофлуоресцентного анализа. Для изучения функциональных групп в составе оловосодержащих акрилатных олигомеров применялся метод ИК-спектроскопии. Полученные результаты показывают, что содержание олова в олигомере является высоким и составляет 86%, а согласно данным ИК-спектра, органические соединения в составе смеси образовали координационную связь с металлом. В лабораторных условиях были изучены следующие физические свойства образцов: термостойкость, устойчивость к водной среде и эластичность.

Keywords: Tin salt, acrylic acid, styrene, oligomer, IR spectrum, X-ray fluorescence analysis, physicochemical properties, thermal stability.

Ключевые слова: Соль олова, акриловая кислота, стирол, олигомер, ИК-спектр, Рентгенофлуоресцентный анализ, физико-химические свойства, термостойкость.

Introduction.

In this article states that crystalline catalysts synthesized based on n-alkyl acrylate and dibutyltin maleate for polyurethanes slow down the reaction at 30 °C, thereby extending the shelf life of the system. At temperatures above the melting point, they become activated and accelerate the process; in this regard, particle size and molecular mass play a key role. As a result, the obtained adhesives demonstrate higher initial strength and excellent final properties compared to traditional samples. [1, 4531-4540-pages].

This scientific article examines the toxicity aspects of tin catalysts actively used in the synthesis of polymer materials, as well as the safety of tin (IV) compounds as PVC stabilizers. It analyzes the differences between divalent and tetravalent tin compounds, the effects of canned products on human health, and historical sources related to iron ions. Furthermore, small-scale trials, the practical application of tin-based medical implants, and the characteristic properties of alkyl/aryl and tin (IV) compounds are briefly described. [2, 677-689-pages].

In this study, the performance dynamics of a composite electrode consisting of ultrafine tin powder in a PVDF-based gel-polymer electrolyte medium were analyzed. The insertion of lithium into the electrode structure causes a restructuring of the initial configuration, which in turn accelerates ion movement and ensures an increase in the lithium diffusion coefficient from 10^-14 to 10^-10 cm²/s. The preservation of electrode integrity depends on the binding properties of the gel-polymer film, and the loss of capacity is directly explained by the degradation of this film and the failure of the active electrode surface. [3, 311-316-pages].

In this research work, using a complex method, honeycomb-structured films were synthesized in a single step based on a polymer solution and Eu and Sn complexes. During the experiments, the influence of ambient humidity and solution concentration on the size of micropores was studied, and the resulting samples were examined using physicochemical analysis methods such as SEM, AFM, and XRD. The results showed that Eu-based composites possess high optical properties, while it was determined that Sn-containing samples, when thermally treated at 600 °C, transform into unique bowl-shaped SnO2 microparticles. [4, 2068-2074-pages].

A new composite filler based on rice husk silica integrated with SeNPs and PHMG was obtained. When added to EP-PDMS polymer coatings, this substance increased surface hydrophobicity and improved anti-biofouling resistance by up to 5 times. As a result of 7-month trials, the 5 wt % SiO₂-SeNPs-PHMG sample exhibited the lowest adhesion strength and high biocidal activity. [5, 1467-1482-pages].

In the research, the protective properties of experimental varnishes containing 5% SnCl₂ and 20% nHAP against dentin erosion were investigated. According to the results obtained, the SnG and nHSnG containing coatings significantly reduced the wear of tooth tissues while providing effective hermetization (sealing) of the dentin tubules. This confirms that these varnishes are highly effective and promising tools for reducing tooth sensitivity and combating erosion. [6, 94-100-pages].

Materials and Methods.

In the experiment, instruments for IR spectroscopy and elemental analysis methods were utilized. To determine the quantity of elements, an X-ray Fluorescence elemental analysis instrument manufactured by the Analytik Jena company in Germany was used. To examine the composition of the compound, the ICPE-9800 instrument manufactured by the Shimadzu company in Japan was utilized. First, safety regulations were strictly followed. The fume hood was turned on, and a magnetic stirrer heater was placed inside. Then, the necessary reagents were measured. To begin, 100 ml of distilled water was poured into a heat-resistant flask, and 1.5 grams of tin salt were added and mixed thoroughly. The flask was placed on the magnetic stirrer and set to rotate at a speed of 400-600 rpm. 0.5 grams of alkali were added to the resulting white solution, and the process was observed until the alkali was completely dissolved. To the resulting sample, 10 ml of acrylic acid and 10 ml of methyl methacrylate were added, and to obtain the oligomer compound, it was heated at a temperature of 110-130°C for one and a half hours. The following figure shows the polymerization reaction of the tin acrylate oligomer. Reaction of tin with acrylic acid and alkali
(figure 1).

Figure 1. Polymerization reaction of tin acrylate oligomer

Ammonium persulfate was added to the resulting mixture as an initiator in the amount of 0.5 grams, and after 5 minutes, the mixture turned into a white thick mass. The resulting mixture was filtered and poured onto aluminum foil, then dried in an oven at a low temperature; as a result, a white substance was formed that was sticky to the touch and, upon further drying, became insoluble in water.

Results and discussion.

The peaks in the 1699 cm^-1 and 1715 cm^-1 regions correspond to carbonyl and carboxyl groups, which belong to free or hydrogen-bonded carboxyl (C=O) groups in the acrylic acid. The peak at 1622 cm^-1 is a very important one, as coordination-bonded carboxylate groups (COO) typically manifest in this region. This indicates that the tin (Sn) atom has formed a complex with the carboxyl groups in the polymer chain. The hydrocarbon chain signals at 3024 cm^-1 represent CH vibrations that overlap with the broad absorption region of hydroxyl (OH) groups. The 2926 cm^-1 signals are valence vibrations of saturated CH₂ and CH₃ groups (characteristic of acrylic and styrene compounds). The peak at 1451 cm^-1 is formed due to the deformation vibrations of CH₂ groups. The peaks at 1163 cm^-1 and 1099 cm^-1 are valence vibrations in ester bonds (C-O-C). The signals at 759 cm^-1 and 698 cm^-1 represent out-of-plane C-H vibrations in the aromatic ring, if styrene is present in the oligomer composition. Changes around 600 - 500 cm^-1 at the far right of the spectrum directly indicate the formation of the Sn-O bond. Here is the IR of nickel acrylate as shown in (Figure 2).

Figure 2. IR spectrum of the tin-containing acrylic oligomer

In the 3.4 - 4.0 keV region, the L_alpha and L_beta series lines of tin are located. The height of these peaks indicates a high content of tin in the sample. In the 25 - 28 keV region (on the upper graph), the K_alpha and K_beta lines of tin are also clearly visible. In particular, the strong peak around 25.2 keV serves as the primary identifier for tin. Besides tin, the spectrum also contains traces or signals of other metals. Small peaks are observed in the 6.4 keV and 7.0 keV regions for Fe (Iron), and small peaks for other elements are also present. Here is the elemental analysis of nickel acrylate as shown in (Figure 3).

Figure 3. X-ray fluorescence spectrum of tin acrylate oligomer

Conclusion

Special instruments and methods were used during the synthesis process. The chain length of the synthesized tin oligomers was studied, and the required functional groups were introduced. In this process, appropriate synthesis methods were selected, and the applications of the obtained products were investigated. Today, the production of organotin oligomers that are environmentally safe and characterized by low toxicity remains one of the priority directions of synthetic chemistry. These compounds are considered promising because the tin within their composition also serves as a catalyst.

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