SYNTHESIS OF POLYMETHYLENE ANTHRACENE SULFOXY ACID BASED ON PYROLYSIS SECONDARY PRODUCT

ABSTRACT

Based on the secondary product of the pyrolysis process: the anthracene fraction isolated from the tar product, 1-anthracenesulfoacid was synthesized with 82% yield, and the physicochemical properties of the obtained compounds were studied. A number of process factors were determined and optimized. The structure of substances was proved by IR-spectroscopy and X-ray analysis.

Polymethylene Anthracene Sulfo acid was synthesized by polycondensation of the obtained anthracene sulfo acid with formaldehyde.

АННОТАЦИЯ

На основе вторичного продукта процесса пиролиза: антраценовой фракции, выделенной из смолистого продукта, синтезирована 1-антраценсульфокислота с выходом 82% и изучены физико-химические свойства. Определено и оптимизировано влияние различных факторов на ход процесса. Строение веществ доказано методами ИК-спектроскопии и рентгеноструктурного анализа.

Полиметилен антрацен сульфокислоту синтезировали поликонденсацией полученной антрацен сульфокислоты с формальдегидом.

Ключевые слова: пиролиз, тар-продукт, вакуумная и простое перегонка, сульфирование, электрофильный замещения, антраценсульфокислота, поликонденсация.

Keywords: pyrolysis, tar-product, vacuum and simple driving, sulfonation, electrophilic exchange, anthracene sulfo acid, polycondensation.

Introduction. The range of chemical products is expanding through the modernization of chemical industry enterprises, the launch of new enterprises and the deep processing of hydrocarbon raw materials and mineral resources. Ustyurt gas-chemical complex, one of the largest enterprises in our country, has produced 387,000 tons of polyethylene; 83,000 tons of polypropylene and 102,000 tons of pyrolysis distillate, 8,000 tons of pyrolysis oil and 10,000 tons of tar products as secondary products. Secondary products are currently not processed at the enterprise and are sold as low-quality fuel at low prices [1]. It should be noted that many import-substituting products can be obtained as a result of the processing of these secondary products.

In order to study the composition of the tar product the anthracene fraction was separated and purified at 340-360⁰C as a result of driving under vacuum and atmospheric pressure [3].

Anthracene sulfonation reactions have been in insufficient degree in according to studied in the literature. Anthracenesulfoacids is a solid product with a certain range of melting point; well soluble in water and poorly soluble in organic solution [4]. Unlike halogenation and nitration, anthracenesulfonation produces α and β-anthracenesulfoacids.

In comparation with naphthalene the interaction of anthracene with electrophilic substances mainly goes to the 9^th and 10^th states, that is, the meso-state. Quantum-chemical calculations show that the meso-states have high electron density and allow the electrophilic exchange reaction to proceed [5]. At treatment of anthracene with oleum in acetic acid equal amounts of 1- and 2-sulfonic acids are obtained. Sulfonation with 75% H₂SO₄ at 100⁰C produces the 2-sulfoacid, while addition of mercury shifts the sulfo group to the 1-state [6,7].

The reaction initially produces 9-anthracenesulfoacid as a primary product and then leads to the formation of thermodynamically more stable 1- and 2-anthracenesulfoacids due to ease of desulfation [8].

When using concentrated sulfuric acid, a mixture of 1,5- and 1,8-anthracenesulfonic acids is formed at 25^oC. At temperatures above 100°C, the 2nd isomer yield is high. When the reaction is carried out in the presence of mercury salt, the direction of the process changes and 1-sulfoanthracene is synthesized [9]. As the temperature and duration of the reaction increase, the formation of a mixture of 2-sulfoacids and disulfoacids from 1-sulfoacid increases. The oxidation reaction of anthracene sulfoacids is used to obtain the corresponding anthraquinone sulfoacids [10,11].

Polycondensation refers to the formation of high-molecular substances as a result of the interaction of monomers with two or more functional groups. In order to form macromolecules as a result of polycondensation, condensation or coupling reactions known in organic chemistry can be used, but in such reactions monomers must have at least two different functional groups. Usually, as a result of polycondensation reactions polymer and submolecular substances (water, alcohol, ammonia, hydrogen chloride, etc.) are separated. Many polymers were synthesized by condensation of polycyclic aromatic hydrocarbons with formaldehyde in the presence of sulfuric acid catalyst [12-14].

Experimental part. Anthracene was isolated by recrystallization from the anthracene fraction obtained by the extraction of ‘tar-product,’ a secondary product of the Ustyurt gas chemical complex belonging to ‘Uz-KorGaz Chemikal’ LLC, and this structure was determined using IR-spectrum (Fig.1) analysis [15 ].

Figure 1. IR spectrum of anthracene

Table 1.

Anthracene IR spectrum analysis

The spectrum analysis shows that the valence and deformation vibrations characteristic of the С-H group in the aromatic ring in the ranges 3049,15 and 720,79 cm^-1, the valence vibrations characteristical for the aromatic ring doublet in the 1532,79 cm^-1 region and region the 880,28 cm^-1 a signal of valence vibrations characteristical for the aromatic ring were observed.

1. Synthesis of sodium anthracene sulfonate

The procedure was carried out in a three-necked flask equipped with Libix cooler, stirrer and thermometer lowered to the bottom of the flask. 0,1 mol (17,8 g) of anthracene was heated at 50⁰C and 0,12 mol (ρ=1,84 g/ml, 98% strength) of concentrated sulfuric acid was added. After the sulfuric acid was completely added, the temperature of the mixture was increased to 160⁰C and heating was continued for 6 h. The resulting sulfo-mass was cooled and shaken with 500 ml of distilled water and transferred to a 1000 ml beaker. Then 6,55 g of calcium hydroxide was slowly added to the mixture at stirring. The calcium sulfate in the mixture was then vacuum filtered through Büchner funnel and 16 g of Na₂CO₃ was added to the filtrate at stirring until a basic medium was formed. Calcium carbonate was filtered under vacuum through a Buehner funnel and the obtained yellow precipitate was dried in a vacuum evaporator at of 60-70⁰C. The resulting white crystalline substance was dried in open air for 3 h. 1-anthracenesulfonate sodium salt with mass 22,96 g was obtained. The reaction yield was 82%.

The investigated process can be described is as follows:

Reaction mechanism [13]:

In order to extract anthracene sulfo acids from the mixture, the sulfo-mass diluted with water was heated to 60-70°C and neutralized by adding crushed limestone. The following reaction has occurred:

2Аr-SО₃H + H₂SО₄ + 2CаCО₃ = (АrSО₃)₂Cа + CаSО₄ + 2H₂О + 2CО₂

During of which the reaction, calcium sulfate dihydrate precipitated. The precipitate was filtered and sodium carbonate was added to the filtrate, whereby the calcium salt of the sulphonic acid was converted into the sodium salt and the calcium carbonate precipitated:

(АrSО₃)₂Cа + Nа₂CО₃ = 2АrSО₃Nа + CаCО₃

The calcium carbonate was filtered and the filtrate was concentrated. Pure sulfonic acids were isolated by recrystallization.

Anthracene sulfonic acids are colorless, mostly crystalline substances, soluble in water, hygroscopic and acidic. Aromatic sulfoacids are similar to mineral acids, the pKa values (-5,0) vary in the same range and the same as the pKa values ​​of strong mineral acids, they dissociate well in dilute solutions, the heat of neutralization of aromatic sulfoacids is 58,1 kJ/g-eq.1- The structure of sodium anthracenesulfonate was determined using the IR spectrum (Fig. 2).

Figure 2. IR-spectrum of 1-anthracenesulfonatesodium

Table 2.

IR-spectral analysis of sodium 1-anthracenesulfonate

Aromatic sulfo-acids are very important for industry. Because they beside with using as a cationites also are widely used in the production of organic dyes, as raw materials for organic synthesis, as intermediates in obtaining surfactants, sulfo-drugs and physiologically active compounds.

Synthesized anthracene sulfoacid was polycondensed with 37% formalin at 110-120⁰C and pressure 35-40 atm. As a result oligomers with linear structure, polymethyleneanthracene sulfoacid polymer with spatial structure were synthesized.

The properties of obtained polymethyleneanthracenesulfoacid as a cationite were investigated.

Conclusion

Based on the secondary product of the pyrolysis process: the anthracene fraction from the tar product. As a result of sulfonation of the obtained anthracene, the synthesis of sulfo-antharcene was carried out. Polymethylene Anthracene sulfo-acid was synthesized by polycondensation of sulfo-anthracene with formalin under high pressure. Due to the presence of an active sulfo- group in this spatial polymer, its properties as a cationites were studied.

References:

1. Kenjaev A.Q., Nurmonov S.E., Qodirov O.Sh. Piroliz jarayoni maxsuloti ‘piroliz moyi’ tarkibini aniqlash. // Kopozitsion materiallar jurnali. 2021. №2. 15-17 pp. [In Uzbek]
2. Kodirov O.Sh., Mirzakulov X.Ch., Berdiev X.U., Sharipova V.V., Issledovanie ximicheskogo sostava pirokondensata piroliznogo proizvodstvayu.// Universum: Texnicheskie nauki: elektron. Nauchn. Jurn. 2018. № 9(54). URL: http://7universum.com/ru/tech/archive/item/6383 [In Uzbek]
3. Habiev F., Nurmonov S. Uglevodorodlar pirolizi ikkilamchi mahsuloti tarkibi tahlili. // O'zMU xabarlari: ilmiy jurnal. 2022. №3/2. 468-473 pp. [In Uzbek]
4. Sokolov V.Z. Proizvodstvo i ispol`zovanie aromaticheskix uglevodorodov. 1980. Moskva: ‘Ximiya,’ 336 p. [In Russian].
5. Knunyants I.L. Kratkaya ximicheskaya entsiklopediya. 2019. Book on Demand Ltd. Tom 1. 638 p. [In Russian].
6. Agronomov A.YE. Izbrannie glavi organicheskoy ximii. 1990. M: Izd.2. 560 p. [In Russian].
7. S`yuter CH.N. Ximiya organicheskix soedineniy seri. 1950. Chast` 2. 219 p. [In Russian].
8. Vorojtsov N.N. Osnovi sinteza promejutochnix produktov i krasiteley. 1934. Moskva: Gos.Tex.Xim.Izdat. 534 p. [In Russian].
9. Gorelik M.V. Osnovi ximii i texnologii aromaticheskix soedineniy. Moskva-1992., Ximiya. 192 p. [In Russian].
10. Efros L.S. Ximiya i texnologiya promejutochnix produktov. Moskva, 1987., Ximiya 420 p. [In Russian].
11. Kriven`ko A.P., Astaxova L.N. Reaktsii elektrofil`nogo zamesheniya v arenax: Ucheb.posobie dlya studentov ximicheskix spetsial`nostey universitetov. Saratov: Nauchnaya kniga, 2008. 54 p. [In Russian].
12. Moshinskaya N.K. Polimernie materiali na osnove aromaticheskix uglevodorodov i formaldegida. Kiev. Izdatel`stvo Texnika, 1969. 226 p. [In Russian].
13. Morgan P.U. Polikondensatsionnie protsessi sinteza polimerov. – L.: Ximiya, 1970. 448 p. [In Russian].
14. Sokolov L.B.  Osnovi  sinteza  polimerov  metodom  polikondensasii. – M.: Ximiya, 1979. 264 p. [In Russian].
15. Tarasevich B.N. IK spektri osnovnix klassov organicheskix soedineniy. Spravochnie materiali. Moskva, 2012. 55 p. [In Russian].