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264 CHEMICAL PROBLEMS 2022 no. 3 (20) ISSN 2221-8688
UDC 661.249; 547.494.254.3
UNSYMMETRICAL DISULPHIDES AS ADDITIVES TO TRANSMISSION OILS
N.N. Novotorzhina, A.R. Sujayev, G.A. Gahramanova, M.R. Safarova, I.P. Ismailov,
M.A. Musayeva, Y.S. Mustafayeva
Institute of Chemistry of Additives, National Academy of Sciences of Azerbaijan, Beyukshor str., kv. 2062, AZ1029, Baku, Azerbaijan e-mail: yegane.434@mail.ru: mob. tel. 051 626 30 25
Received 16.05.2022 Accepted 13.07.2022
Abstract: This paper presents the results of studies of the anti-seize properties of (2,2-dimethyl-4-methylene-1,3-dioxolane-allyl and benzyl)disulfides synthesized on the basis of 2,2-dimethyl-4-chloromethyl-1,3-dioxolane, sodium disulfide and allyl and benzyl chlorides, respectively, in the composition of transmission oils. The synthesized compounds are new compounds not previously described in the literature, the structure of which has been proven by studying their physicochemical properties, elemental composition, and IR spectroscopy. It revealed that the synthesized compounds in terms of extreme pressure efficiency are significantly superior to transmission oil MS-20, as well as bis(2,2-dimethyl-4-methyl-1,3-dioxolane)disulfide, previously synthesized by the authors of this article and a typical extreme pressure additive ethylene-bis-isopropylxanthate (LZ-23k). It found that the replacement of one of the 1,3-diocosolane fragment in bis(2,2-dimethyl-4-methylene-1,3-dioxolane) disulfide with allyl or benzyl radicals leads to an improvement in anti-seize properties due to their better adsorption on metal surfaces of rubbing parts. Keywords: disulfide, 1,3-dioxolane, anti-seize properties, transmission oils, additive. DOI: 10.32737/2221-8688-2022-3-264-2 70
Introduction
The growth trend in the automotive industry causes an increase in demand for effective additives to lubricating oils, which ensure the creation of high-quality lubricating oils that reduce friction and wear of machine parts and mechanisms for their intended purpose.
Transmission oils are used to lubricate gearboxes, steering gears, gears and chains of all types, and in this work, new compounds are proposed as oil additives, on the basis of which high-quality transmission oils can be created.
It should be noted that when creating high-quality oils, the creation of additives from available and cheap raw materials is of no small importance. Such is glycerin, which as a plug product is formed in the production of biodiesel [2].
Based on this cheap raw material, compounds used in numerous areas of the national economy have been synthesized. Of the derivatives of glycerol, 1,3-dioxolanes are especially widely used, which are quite easily obtained by the interaction of glycerol and ketones [3, 4]. And although a large number of compounds used for practical purposes have been obtained on their basis, however, information on their use as additives to lubricating oils is almost absent [5-7].
The main goal of the work was the synthesis of new unsymmetrical disulfides based on 1,3-dioxolanes and the study of the influence of the structure of the fragments that make up the compounds on their anti-seize properties.
CHEMICAL PROBLEMS 2022 no. 3 (20)
www.chemprob.org
Experimental part
Based on 1,3-dioxolane, we synthesized 1,3-dioxolane-benzyl)disulfide. (2,2-dimethyl-4-methylene-1,3-dioxolane- The proposed disulfides were
allyl)disulfide and (2,2-dimethyl-4-methylene- synthesized according to the following scheme:
CH,
ch,
0-CH2
c + Na - s - s - Na+
^0-ch-ch2ci
ch2 = ch - ch|ci ch3 x o . ch2
C6H5CH2CI
ch3 ^ ^o - ch - ch2 - s - s - ch2 = ch - ch2
(I)
ch3v ,o-ch2
ch,
/ N
o - ch - s - s - ch2 c6h5
(II)
At the first stage of the work, saturation of glycerol with dry hydrogen a-chloropropanediol was synthesized by chloride:
CH2OH - CHOH - CH2OH+HC1 —► CH2OH - CHOH - CH2C1
(n£°) - 1.4784; - 1.3146; MRd found. - 22.31; MRd calc. - 22.37
With the subsequent interaction of which chloromethylene-1,3-dioxolane was obtained: with dimethyl ketone, 2,2-dimethyl-4-
ch.
\ TsOH ch2oh - choh - ch2ci + c = o-»
ch,
ch,
ch,
/ \
,0 - ch2 o - ch - ch2ci
(4°) - 1.4350; (d|°) - 1.0937; MRD found. - 35.80; MRD calc. - 35.86
Sodium disulfide was obtained by dissolving sulfur in sodium sulfide nonahydrate:
70°C
Na2S • 9H20 + S
Na - S - S - Na
Fig. 1. Infrared spectrum (2,2-dimethyl-4-methylene-1,3-dioxolane-allyl)disulfide
The individuality of the obtained compounds was proved through determining their elemental composition (C, S, N, H, Cl) by the TruSpec-Micro (LECO) analyzer, refractive indices specific gravity (efj0) with
calculations of MRD found. and MRD calc., as well as IR spectroscopy. IR spectra were taken on a SPECORD-75IR IR spectrophotometer, Carl-Zeiss (Germany) using KBr prisms in the region - 4000-400 cm1.
In the IR spectrum of (2,2-dimethyl-4-methylene-1,3-dioxolane-allyl)disulfide (Fig.1) -S-S- absorption bands in the region of 483+10 cm-1 were identified, characterizing the -C=S-bond 1634 cm-1, absorption bands =C-H bonds
are observed in the region of 3081 cm-1, bands above 3000 indicate the presence of an unsaturated bond, bending vibrations of 5C-H correspond to 920-859 cm-1 [8].
In the IR spectrum of (2,2-dimethyl-4-methylene-1,3-dioxolane-benzyl)disulfide (Fig.2) absorption bands of the C-H bond are observed in the aromatic 3093,89-1634 cm-1, 3060,80-1634 cm-1, 3027-1634 cm-1, absorption bands correspond to the aromatic ring 1300,731634 cm-1, 1583-1634 cm-1, 1538-1634 cm-1, 1494-1634 cm-1, 1453-1634 cm-1, bending vibrations 5C-H correspond to 697 cm-1, 763 cm" 1, 862 cm-1, 913 cm-1.
Fig. 2. Infrared spectrum (2,2-dimethyl-4-methylene-1,3-dioxolane-benzyl)disulfide
Anti-seize properties were determined by the ASTM D2596 test method, the estimated indices were the load wear index, the critical load, the welding load.
Syntheses of disulfides were carried out as follows:
The installation used in the production of
disulfides consists of a glass three-necked flask equipped with a thermometer and a dropping funnel and a mechanical stirrer heated by an electric mantle heater.
(2,2-Dimethyl-4-methylene-1,3-dioxolane-allyl)disulfide (I) is as follows:
ch.
CH
4/
/ N
.0 - ch2
о - ch - ch2 - s - s - ch2 - ch = сн2
24 g (0.1 mol nanohydrate) of sodium sulfide (Na2S 9H2O), 3.2 g (0.1 mol) of sulfur (S) and 50 ml of water were placed in a reaction flask, stirred at 70°C for 1 hour, then in the flask
was fed with 15 g (0.1 mol) of 2,2-dimethyl-4-chloromethyl-1,3-dioxolane and 0.6 g of tetrabutylammonium bromide [(C4H9)4N]Br as a catalyst, 50 ml of benzene and stirred for 30
minutes, allylchloride was added to the flask, stirring was continued for 4 hours at 60-65°C.
The resulting product was washed with water; benzene was distilled off and dried under vacuum. The yield of the obtained product is 17
g (77.3%).
Physical and chemical characteristics and elemental composition of the product are as follows:
(п£°) - 1.4990; (d|°) - 1.1190; MRD found - 58.65; MRD calc. - 58.09
C8H16O2S2: found, %: C - 48.95; H - 7.00; S - 29.1
Calculated, %: C - 49.06; H - 7.32; S - 28.92
(2,2-Dimethyl-4-methylene-1,3-dioxolane-allyl)disulfide, brown liquid, soluble in solvents and mineral oils.
(2,2-dimethyl-4-methylene-1,3-dioxolane-benzyl)disulfide (II) is as follows:
CH3
ch.
/ \
,0 - CH2
О - CH - CH2 - S - S - CH2C6H5
In a reaction flask at 70V, 24 g (0.1 mol) of sodium sulfide nonahydrate (Na2S-9H2O), 3.2 g (0.1 mol) of sulfur and 50 ml of water were stirred for 1 hour, then 15 g (0.1 mol) of 2,2-dimethyl-4-chloromethylene-1,3-dioxolane was added, 50 ml of benzene and 0.6 g of tetrabutylammonium bromide [(C4H9)4N]Br as a catalyst were stirred for 40 minutes. Then, 8.7 g (0.1 mol) of benzylchloride
was added to the flask and stirring was continued for 5 hours. The product was washed with water; benzene was distilled off and dried under vacuum. The yield of the obtained product is 14 g (72%).
Physical and chemical characteristics and elemental composition of the product are as follows:
(4°) - 1.5290; (dla) - 1.0954; MRD found. - 76.1; MRD calc. - 75.52 C13H18O2S2: found, %: С - 57.84; H - 6.81; S - 23.49
Calculated, %: C - 57.9; H - 6.69; S - 23.63
The synthesized compounds were tested at 5% concentration as anti-seize additives in MC-20 gear oil.
To determine the effectiveness of the synthesized disulfides, Table also provides data on the anti-seize properties of bis(2,2-dimethyl-
4-methylene-1,3-dioxolane) disulfide previously synthesized by the authors, as well as the well-known typical anti-seize pressure additive LZ-23к (ethylene-bis-isopropylxanthate) (ГОСТ 11883-77).
Table 1. Tribological characteristics of the synthesized compounds in MC-20 gear oil
Compounds Concentration of samples in oil, % Extreme pressure properties ass. to ASTM D2596
Load wear index, N Critical load, N Welding load, N
ch3 о - ch2 c' ch3 // ^o - ch - ch2 - s - s - ch2 = ch - ch2 (I) 5 720 1098 3920
ch3 ^ o - ch2 cr ch3 ^o - ch - ch2 - s - s - ch2c6h5 (II) 5 731 980 4381
CH»\ o-CH2 CH2-o>^ ch3 1 1 \ 5 528 980 3980
iC3H7OCS - CH2 - CH2 - SCOC3H7-i S S 5 528 980 3980
MC-20 oil - 330 794 1568
Results and discussion
It should be noted that, in general, all disulfides are characterized by high extreme pressure properties caused by the fact that the -S-S- bond is relatively easily broken and a protective layer consisting of iron sulfides (FeS, Fe2S3) is formed on the metal surface [9, 10].
The test results showed that the disulfides synthesized by the authors of this work also have high anti-seize properties, and disulfides containing allyl and benzyl fragments, in these properties, are somewhat superior to the known bis (2,2-dimethyl-4-methylene-1,3-dioxolane) disulfide and a typical anti-seize additive LZ-23k.
The higher anti-seize properties of the proposed disulfides compared with the structure of bis(2,2-dimethyl-4-methylene-1,3-dioxolane) disulfide can be explained by the presence in the bis(2,2-dimethyl-4-methylene-1,3-dioxolane) disulfide of 2 dioxolane fragments, which are somewhat more difficult to adsorb on the metal surface due to their branched structure. And the replacement of one of the dioxolane fragments with allylic or benzyl radicals significantly increases the adsorption of the compound on the metal surface, which leads to accelerated formation of a protective layer that reduces the surface destruction of rubbing parts [11].
■ i /
2 J
2 ? a { : § \ ; 1 g 1 i 3 g î 1 1
AlUI load
Fig. 3. "Wear-load"graph in lagorithmic coordinates: 1) (2,2-Dimethyl-4-methylene-1,3-dioxolane-allyl)disulfide; 2) (2,2-dimethyl-4-methylene-1,3-dioxolane-benzyl)disulfide
A comparison of the anti-seize properties of the synthesized disulfides with each other showed that the critical loads of both compounds are very close in their values, however, in terms of the welding load and the load wear index, (2,2-dimethyl-4-methylene-1,3-dioxolane-benzyl)disulfide is somewhat superior according to this parameter (2,2-dimethyl-4-methylene-1,3-dioxolane-allyl)disulfide, which can be clearly seen in the figure 3.
The curves clearly show changes in wear scar diameters (Wd) of joints 1 and 2 with load.
The higher anti-seize properties of (2,2-dimethyl-4-methylene- 1,3-dioxolane-benzyl)disulfide can be explained as being due to its low thermal stability, as is known that the lower the thermal stability of the compounds, the higher their anti-seize properties.
Thus, the synthesized disulfides obtained on the basis of readily available and cheap raw materials - glycerol, have sufficiently high extreme pressure properties, following which these compounds may be of interest as extreme pressure additives for transmission oils used in gearboxes and other mechanisms.
References
1. Mustafayev N.P., Novotorzhina N.N., Ismayilova G.G., Musayeva B.I., Ramazanova Yu.B., Gahramanova G.A., Ismayilov I.P. Synthesis of new bis(2,2-dialkyl-1,3-dioxolan-4-yl-methyl)sulfides based on glycerol derivatives and studies of them as additives to gear oils. Journal of Oil Refining and Petrochemistry. 2019, no. 10, pp. 39-42.
2. Fangxia Yang, Milford A.Hanna, Runcang Sun. Value-added uses for crude glycerol-a byproduct of biodiesel production. Journal Biotechnology for Biofuels. 2012, no. 5, p. 13.
3. Ramazanov D.N., Jumbe, A., Nekhaev, A.I., Samoylov, V.O., Maximov, A.L., Yegorova, Y.B. Interaction of glycerin with acetone in the presence of ethylene glycol. Journal Petrochemistry. 2015, vol. 55, no. 2, p. 148.
4. Rubtsov M.V., Baichikov A G. Synthetic and pharmaceutical preparations. M.: Medicine, 1971, p. 11.
5. Hatice Bashpinar., Kuchuk, Ayshe., Yusufoglu, Emel., Mataraci, Sibel Doslar. Synthesis and Biological Activity of New 1,3-Dioxolanes as Potential Antibacterial and Antifungal Compounds. Journal molecules. 2011, vol. 16, no. 8, pp. 68066815.
6. Matthias Schmidt, Johannes Ungvari, Julia Glode, Bodo Dobner, Andreas Langner. New 1,3-dioxolane and 1,3-dioxane derivatives as effective modulators to overcome multidrug resistance. Journal Bioorganic & Medicinal Chemistry. 2007, vol. 15, no. 6, pp. 2283-2297.
7. Voitkevich, S.A. 865 aromatic substances for perfumery and household chemicals. Moscow: Food industry. 1997, 596 p.
8. Bellamy L. J. The infra-red spectra of complex molecules, Moscov: Mir Publ., 1991, 592 p.
9. Xue-Ye Wang, Xin-Fang Li, Xiao-Hong Wen, Yuan-Qiang Tan. DFT Method Mtudy on Lubricant Properties of Disulfide Compounds as Extreme pressure Additive. Journal of Theoretical and Computational Chemistry. 2006, vol. 5, no. 1, pp. 1-10.
10. Kirichenko G.N., Khanov V.Kh., Ibragimov A.G., Glazunova V.I., Kirichenko V.Yu., Dzhemilev U. M. Synthesis of unsymmetrical dialkyl disulfides and their use as extreme pressure additives for oils. Journal Petrochemistry. 2003, vol 43, no 6, pp. 468-470.
11. Handbook of Chemist-21. Chemistry and technology. p. 137.
ASÍMMETRÍK DÍSULFÍDL9R TRANSMÍSSÍYA YAGLARINA A§QAR KÍMÍ
N.N. Novotorjina, A.R. Sucayev, Q.A. Qahramanova, M.R. Safarova, Í.P. ísmayilov,
М.Э. Musayeva, Y.S. Mustafayeva
AMEA-nin akad. Э. Quliyev adina A^qarlar Kimyasi institutu AZ1029, Boyük^or §osesi, 2062-ci kvartal; e-mail: yegane.434@mail.ru
Xülasa: Bu i§da müvafiq olaraq 2,2-dimetil-4-xlorometil-1,3-dioksolan, natriium disulfidva allil-, benzilxloridlar asasinda sintez edilan (2,2-dimetil-4-metilen-1,3-dioksolan-alil va benzil)disulfidlarin transmissiya yaglari tarkibinda siyrilmaya qar§i xüsusiyyatlarinin tadqiqat naticalari taqdim olunur. Sintez edilmi§ birla§malar avvallar adabiyyatda tasvir olunmayan, strukturu fiziki -kimyavi xassalari, element tarkibi va IQ-spektroskopiyasinin oyranilmasi ila sübut edilmi§ yeni birla§malardir. Sintez edilmi§ birla§malarin siyrilmaya qar§i xassalari ЧМТ-1 dord kürali sürtünma ma§ininda tayin edilmi§dir. Müayyan edilmi§dir ki, sintez edilmi§ birla§malarin siyrilmaya qar§i xassalari MS-20 transmissiya yagindan, ham?inin avvallar bu maqalanin müalliflari tarafindan sintez edilmi§ bis(2,2 -dimetil-4-metil-1,3-dioksolan)disulfid va müqayisa ü?ün gotürülmü? tipik etilen-bis -izopropil ksantogenatdan ^3-23k) xeyli üstündür. Taqdim olunmu§ i§da asas triboloji xassalarin oyranilmasi zamani, 4 -kürali sürtünma ma§ininda §arlarin yeyilma izinin diametrinin neca dayi§ildiyi aydin gorünür (§akil 3). Müayyan edilmi§dir ki, bis(2,2 -dimetil-4-metilen-1,3-dioksolan) disulfidin tarkibindaki 1,3-diokosolandan birinin allil va ya benzil radikallari ila avaz edilmasi onlarin siyrilma xassalarini yax§ila§dirir, bunu onunla izah etmak olar ki, metal sathlarda daha yax§i adsorbsiya olunur.
A^ar sozlar: disulfid, 1,3-dioksolan, siyrilma xassalari, transmissiya yaglari, a§qar
НЕСИММЕТРИЧНЫЕ ДИСУЛЬФИДЫ В КАЧЕСТВЕ ПРИСАДОК К ТРАНСМИССИОННЫМ МАСЛАМ
Н.Н. Новоторжина, А.Р. Суджаев, Г.А. Гахраманова, М.Р. Сафарова, И.П. Исмаилов,
МА. Мусаева, Е.С. Мустафаева
Институт химии присадок им. акад. А. Кулиева Национальной АН Азербайджана Аз 1029, Боюкшорское шоссе, 2062-й квартал: e-mail: yegane.434@,mailru
Аннотация: В работе представлены результаты исследований противозадирных свойств (2,2-диметил-4-метилен-1,3-диоксолан-аллил и бензил)дисульфидов, синтезированных на основе 2,2 -диметил-4-хлорметил-1,3-диоксолана, дисульфида натрия и аллил- и бензилхлоридов, в составе трансмиссионных масел. Синтезированные соединения представляют собой новые ранее неописанные в литературе соединения, структура которых доказана исследованием их физико -химических свойств, элементного состава и ИК-спектроскопией. Установлено, что синтезированные соединения по противозадирной эффективности значительно превосходят трансмиссионное масло МС-20, а также бис(2,2-диметил-4-метил-1,3-диоксолан)дисульфид, ранее синтезированный авторами настоящей статьи и типичную противозадирную присадку этилен-бис-изопропилксантогенат (ЛЗ-23к). Показано, что замена одного из 2-х диоксолановых фрагментов в бис(2,2-диметил-4-метилен-1,3-диоксолан)дисульфиде на аллильный или бензильный радикалы приводит к улучшению противозадирных свойств, ввиду их лучшей адсорбции на металлической поверхности трущихся деталей.
Ключевые слова: дисульфид, 1,3-диоксолан, противозадирные свойства, трансмиссионные масла, присадка.
