SYNTHESIS AND PROPERTIES OF FURAN-CONTAINING OLIGOMERS

ABSTRACT

In recent years, furan derivatives have become increasingly important in the creation of materials and compositions with the desired properties. The traditional direction of furfural processing is the extraction of furfuryl alcohol obtained as a result of its condensation and resins with various specified properties. Taking into account the above, divinyl ether copolymers of furfuryl alcohol and vinylacetylene are synthesized in the article. Based on the method of furfuryl alcohol, divinyl ether was obtained with vinylacetylene in a highly basic system. The obtained oligomer molecular mass was determined cryoscopically and viscosimetrically. To purify the obtained oligomer, it was carried out by the extraction method in the presence of various solvents. The identification of the synthesized oligomer was carried out by a modern inspection method. The obtained substance was examined in the IQ spectrum and found to be consistent with the composition of the obtained substance.

АННОТАЦИЯ

В последние годы производные фурана приобретают все большее значение в создании материалов и композиций с заданными свойствами. Традиционным направлением переработки фурфурола является извлечение фурфурилового спирта, получаемого в результате его конденсации, и смол с различными заданными свойствами. С учетом вышеизложенного в статье синтезированы дивинилэфирные сополимеры фурфурилового спирта и винилацетилена. На основе метода фурфурилового спирта получен дивиниловый эфир с винилацетиленом в высокоосновной системе. Молекулярную массу полученного олигомера определяли криоскопически и вискозиметрически. Очистку полученного олигомера проводили методом экстракции в присутствии различных растворителей. Идентификацию синтезированного олигомера проводили современным методом контроля. Полученное вещество исследовали в ИК-спектре и установили, что оно соответствует составу полученного вещества.

Keywords: vinylfurfuryl ether, acrylic acid, colloid silica sol, dinitrile azobisimoic acid (DAA), cryoscopically and viscosimetrically method, furan, divinylfurfuryl acrylate.

Ключевые слова: винилфурфуриловый эфир, акриловая кислота, коллоидный кремнизол, динитрилазобисимоевая кислота (ДАК), криоскопический и вискозиметрический метод, фуран, дивинилфурфурилакрилат.

Introduction. Currently, the scope of industrial organic synthesis is so large that the problem of limited natural resources of oil and gas necessary to meet its needs remains urgent. In this regard, the direction of obtaining basic compounds based on natural renewable raw materials is a prospect[1-4]. The processing of plant carbohydrates, which make up 2/3 of the annual renewable biomass, opens a direct way to obtain furan compounds, which are genetically closely related to the simplest sugars. In recent years, furan derivatives have become increasingly important in the creation of materials and compositions with the desired properties. The traditional direction of furfural processing is the extraction of furfuryl alcohol obtained as a result of its condensation and resins with various specified properties[5-8]. Tetrahydrofurfuryl alcohol is generally recognized as a "green" solvent for industrial use in the production of acrylates and epoxy resins, and is also included in environmentally friendly diesel fuel and technical cleaning compounds. Due to its low toxicity, the ability to destroy microorganisms, and its high solubility in organic and aqueous media, 2-hydroxymethyltetrahydrofuran and its derivatives are successfully used in the pharmaceutical industry and cosmetology, in particular, as synthetic fragrances[9-12]. Vinyl esters of furfuryl alcohol have high reactive activity. Taking into account the above, divinyl ether copolymers of furfuryl alcohol and vinylacetylene are synthesized in the article. Based on the method of furfuryl alcohol, divinyl ether was obtained with vinylacetylene in a highly basic system[13; 14].

Materials and methods. 50 mg of vinyl furfuryl ether, 50 mg of acrylic acid, 50 mg of colloidal creminisol and dinitrile azobisimoic acid (DAA) were used as an initiator (1% by mass of monomers) in a reaction flask. The flask was equipped with a thermometer, placed on a magnetic stirrer and heated at 85-120℃for 2 hours. At the end of the reaction, the viscous, black and hardenable polymer - divinylfurfuryl acrylate formed in the flask was purified by precipitation three times and dried until it reached a constant mass. The molecular mass of the obtained polymer was determined by cryoscopic and viscometric methods and was around 2700-4200 depending on the synthesis method and the influencing factors. The highest molecular mass was formed in the presence of an initiator at 120℃ and 2 hours. As the temperature decreases and mixing in the reaction mixture decreases, the formation of oligomers occurs due to clarification. To purify the obtained oligomer, it was carried out by the extraction method in the presence of various solvents. The extraction results are tabulated below. (Table 1).

Table 1.

Solubility of reactants and products in solvents

As can be seen in table 1, the initial reagents were dissolved in ethyl, amyl alcohol, dimethylformamide, toluene, isobutyl, using the fact that the product is insoluble in decane, octane, hexane, the oligomer was separated cleanly in the presence of heptane  and its physical properties were studied, the refractive index of divinylfurfuryl acrylate measured in a refractometer is shown in the following table.

Table 2.

Values

The granules of the synthesized copolymer obtained in the colloidal silica matrix are distinguished by their high ion exchange capacity. The overall process can be represented by the following reaction scheme.

Results and discussion. Identification of the synthesized oligomer was carried out by a modern inspection method. The obtained substance was examined in the IR spectrum and found to be consistent with the composition of the obtained substance (Fig. 1).

Figure 1. IR spectrum of synthesized compound

950.91 cm^-1 all OH groups,  a broad band of non-planar bending vibrations for intermediate OH, vibration of the hydroxyl group and C – O bonds, 1014.56 cm^-1 furans ring vibration is strong, 1176.58 cm^-1 ketals and acetals – C – O – C – O – C –, ring vibration is strong, 1276.88 cm^-1 aromatic and vinyl group = C – O – C - , ring vibration is strong, 1674.21 cm^-1 C=C represents asymmetric vibrations in uncoordinated macromolecules, corresponding to the composition of the synthesized substance. The area of 3734.19 cm^-1 was caused by the fact that the purity level of the substance did not meet the requirements.

Conclusion. Currently, the scope of industrial organic synthesis is so large that the problem of limited natural resources of oil and gas necessary to meet its needs remains urgent. In recent years, furan derivatives have become increasingly important in the creation of materials and compositions with the desired properties. The traditional direction of furfural processing is the extraction of furfuryl alcohol obtained as a result of its condensation and resins with various specified properties. Vinyl esters of furfuryl alcohol have high reactive activity. Taking into account the above, divinyl ether copolymers of furfuryl alcohol and vinylacetylene are synthesized in the article. Based on the method of furfuryl alcohol, divinyl ether was obtained with vinylacetylene in a highly basic system. The flask was equipped with a thermometer, placed on a magnetic stirrer and heated at 85-120℃ for 2 hours. At the end of the reaction, the viscous, black and hardenable polymer - divinylfurfuryl acrylate formed in the flask was purified by precipitation three times and dried until it reached a constant mass. To purify the obtained oligomer, it was carried out by the extraction method in the presence of various solvents. The extraction results were tabulated. Identification of the synthesized oligomer was carried out by a modern inspection method. The obtained substance was examined in the IR spectrum and found to be consistent with the composition of the obtained substance.

References:

1. Firuz O., Vohid A. Synthesis of ionites based on cremnisole //Universum: технические науки. – 2022. – №. 4-13 (97). – С. 19-21.
2. Abror o’g’li, A. A. (2023). IMPROVING THE PHYSICO-CHEMICAL PROPERTIES OF UREA FURFURAL RESIN. American Journal of Pedagogical and Educational Research, 12, 268-271.
3. Davron o’g’li, N. D. (2023). APPLICATION OF UREA-FORMALDEHYDE AND UREA-FURFURAL RESINS IN DIFFERENT SOLVENTS. American Journal of Pedagogical and Educational Research, 12, 265-267.
4. Firuz O., Vokhid A. SYNTHESIS AND PROPERTIES OF COMPLEX FORMING IONITES //Universum: технические науки. – 2023. – №. 2-6 (107). – С. 38-40.
5. Ostonov F., Akhmedov V., Olimov B. PREPARATION OF HYBRID COMPOSITES BY SOL-GEL METHOD AND ANALYSIS OF ITS PROPERTIES //Scientific Collection «InterConf». – 2022. – №. 123. – С. 256-259.
6. Zuhriddin, R., & Niginabonu, J. (2022). Production of polyethylene terephthalate. Universum: технические науки, (5-11 (98)), 58-62.
7. O’G’Li, R. Z. K., & Qizi, J. N. Q. (2022). Analysis of importance and methods of production of block sopolymers based on polyetylenterephtalate. International Journal of Advanced Technology and Natural Sciences, 3(1), 51-55.
8. Zuhriddin, R., Niginabonu, J., Aminjon, V., & Temurbek, D. (2022). Mechanisms of eterification of tereftalic acid with etylenglycol. Universum: технические науки, (5-11 (98)), 63-67.
9. Nigina J., Mizrob Z. PRODUCTION OF VINYL ETHERS OF FURFURYL ALCOHOL //Universum: химия и биология. – 2023. – №. 9-2 (111). – С. 57-62.
10. Bobir, O., Vokhid, A., Gulnoz, G., & Sherzod, R. (2022). SYNTHESIS AND PROPERTIES OF NITROGEN-RETAINING CORROSION INHIBITORS. Universum: химия и биология, (4-2 (94)), 43-46.
11. Ostonov F. КРЕМНИЙОРГАНИК БИРИКМАЛАР БИЛАН МОДИФИКАЦИЯЛАНГАН АКРИЛ БИРИКМАЛАРИНИНГ ОЛИНИШИ //ЦЕНТР НАУЧНЫХ ПУБЛИКАЦИЙ (buxdu. uz). – 2020. – Т. 1. – №. 1.
12. Olimov, B. B., & Rakhmatov, S. (2022). SYNTHESIS AND USE OF CORROSION INHIBITORS ON THE BASIS OF DIATOMIC PHENOLS IN THE OIL AND GAS INDUSTRY. In Kimyo va tibbiyot: nazariyadan amaliyotgacha (pp. 141-143).
13. Шодиев С. В., Остонов Ф. И., Ахмедов В. Н. ГEТEРОЦИКЛИК БИРИКМАЛАРНИНГ ВИНИЛ ЭФИРЛАРИ АСОСИДА ГИБРИД КОМПОЗИТЛАР СИНТEЗИ //Journal of Universal Science Research. – 2023. – Т. 1. – №. 9. – С. 362-366.