Synthetic sulfonate additives for motor oils Текст научной статьи по специальности «Фундаментальная медицина»

32

AZERBAIJAN CHEMICAL JOURNAL No 1 2020

ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)

UDC 665.7.038.2.665.765

SYNTHETIC SULFONATE ADDITIVES FOR MOTOR OILS

LD.Gulaliyev, S.M.Veliyeva

A.Guliyev Institute of Chemistry of Additives, NAS of Azerbaijan

[email protected]

Received 22.05.2019 Accepted 28.10.2019

Oil-soluble calcium sulfonates on the basis alkylnaphthalene obtained using propylene oligomers of the C18-C30 fraction have been obtained and characterized. The developed synthetic sulfonate additives with different alkalinity possess high physico-chemical and functional properties and are superior in performance to commercial oil sulfonates C-150 and C-300, as well as foreign analogues - additives OLOA-246B and Hightech 6060M. Using the obtained high-alkaline additive, an experimental motor oil M-10G2 was developed, which meets the quality indices required demands.

Keywords: alkylnaphthalene, sulfonate additives, detergent-dispersant additives, motor oils, functional properties.

doi.org/10.32737/0005-2531-2020-1-32-35

Additives providing different functionalities, in particular detergent-dispersant additives of the sulfonate type, are widely used in development of high-performance motor oils complaint with tightened current and future technology regulations [1]. Sulfonate additives may be prepared from either petroleum oils or synthetic al-kylaromatic hydrocarbons. It is becoming important to investigate the production of synthetic sulfonates, which have a number of advantage over petroleum sulfonates: higher content of active substance, relative simplicity of production texnology, and better functional and service prop-

erties [2]. In addition, at the production of petroleum sulfonates, a significant amount of hardly utilizable waste is formed - acid tar (up to 30%).

The aim of the work is to expand the raw material base for the production of synthetic sul-fonate additives and increase the efficiency of their operation. In this regard, we have carried out the synthesis of detergent-dispersant sulfonate type additives on the basis of alkylnaphthalene were obtained using propylene oligomers, and their effect on the properties of lubricating oils has been studied. The additives were obtained by the following scheme:

R

+ R- CH = CH ,

kt

R

R

+ SO

SO 3 |c a + C a (O H ) 2 + C O „ pr0 m 0 te r

H O

SO 3H + Ca (O H ) 2

O 3 ) C a • C a C O 3 • C a (O H) 2

where R = C18-C30

Experimental part

The initial alkylnafhthalene was obtained by alkylation of nafhthalene with propylene oligomers of the C18-C30 fraction in the presence of a zeolite-containing catalyst according to method [3] under conditions that ensure the highest yield of monoalkyl derivative. As a re-

suit alkylnafhthalene with 82% yield was synthesized with following physico-chemical pa-

0 3

rameters: density at 200C - 902.2 kg/m3; index of refraction n22 - 1.5180; molecular mass -525; boiling point, 0C - > 43 00C.

The sulfonation of alkylnafhthalene was carried out with sulfur trioxide gaze at a molar

3

2

2

ratio of 1:1.2 in an octane solution at a temperature of 40-450C for 2 hours. In the product of sulfonation, the mass fraction of oil-soluble sulfonic acids is 79%.

Neutralization of alkylnafhthalenesulfonic acids was carried out with an aqueous suspension of calcium hydroxide at a temperature of 70-750C for 3 hours till the weakly alkaline reaction, after the temperature was raised to 125-1300C for evaporation reaction water. The resulting product was dissolved in octane, mechanical impurities were separated by centrifu-gation and the solvent was distilled off.

Carbonation of neutral sulfonate with carbon dioxide in the presence of excess calcium hydroxide, promoter - methanol, oil diluents M-6, solvent - toluene at a temperature of 40-450C for 1 hour were produced medium-alkaline (C-150 type) and high-alkaline (C-300 type) additives.

Composition and structure of the sul-fonates were confirmed by elemental analysis and IR spectroscopy. The calcium content was determined on a metal analyzer MP-4200 AES, IR spectra were taken from on a spectrometer NICOLET IS-10. Content of active substance in additives was determined by method liquid adsorption microchromotography.

In the IR spectra of the sulfonates there are absorption bands in the regions of 10501070 and 1160-1250 cm-1 resulting from valence symmetric and asymmetric vibrations of the S=O bonds of the SO3 group. The most characteristic of the spectra of alkaline sul-fonates is the presence of bands in the region of 850-880 and 1400-1500 cm-1 related to vibrations of the carbonate of the CO ion.

The studies of the physico-chemical and functional properties of additives were carried out by standard laboratory methods [4]. The detergent properties were determined on a PZV unit accordance with GOST 5726-2013, dispersion properties at 2500C, according to the technique described in [5]. The anticorrosive properties were evaluated on a DK-NAMI device at 1400C for 25 hours, according to GOST 2050275, the oxidation stability was measured on a DK-NAMI device for 30 hours at 2000C according to GOST 11063-77.

Colloidal stability of the dispersions was evaluated by decomposing the additive with 15% of distilled water at 1100C for 4 hours and precipitating with benzene followed by centrifuging [6]. Stability of colloidal dispersion was established on a decrease of alkalinity of the additive expressed in percentage of the initial one.

Results and discussion

The obtained additives NSKan (neutral), CC-150an (medium-alkaline) and CC-300an (high alkaline) are viscous liquids of dark brown color, the characteristics of which are shown in Table 1 and 2. In the same place for comparison are presented similar indicators of commercial petroleum sulfonates C-150 and C-300, as well as foreign analogues - additives OLOA 246B and Hightech 6060M.

Synthesized additives have a micellar structure characteristic for sulfonates. They have high physico-chemical and functional properties. With the introduction of the developed additives in the oil M-11 at a concentration of 5%, its detergent, dispersant, neutralizing, anticorrosive properties and stability against oxidation are significantly improved.

Table 1. Characteristics of neutral sulfonate additives

Indicators Neutral sulfonates

NSKan OLOA 246 B

Alkaline number, mg KOH/g 26 23

Mass fraction, %, of

calcium sulfonate 75.3 41.1

calcium 5.9 -

mechanical impurities 0.07 0.1

Sulfat ash, mass. % 10.9 8.6

Detergent properties on installation PZV, points* 0 0.5

Dispersant ability at 2500C, %* 50 40

*M-11 oil with 5% additive

34

I.D.GULALIYEV, S.M.VELIYEVA

Neutral alkylnaphthalene sulfonate has a higher content of the active substance, a lower content of mechanical impurities and better dispersant properties as compared to the OLOA 246B additive.

By their detergent properties the synthesized medium- and high-alkaline additives are on the same level with product additives such as C-150 and C-300 additives, and surpass them in dispersant, anticorrosion properties and stability against oxidation. Thus, the dispersant properties of the additives CC-150an and CC-300an are 70 and 80%, respectively, while for the additives C-150 and C-300, these indices are equal to 60 and 75%. In addition, experimental additives have a higher stability of the colloidal dispersion to the action of water than theiranalogs.

The alkaline sulfonates developed by a

number of indicators are superior to their foreig-nanalogs. Thus, the growth in viscosity of the oxidized oil in the presence of additives CC-150an, CC-300an and Hightech 6060M is 62, 54 and 78%, respectively.

Using the most effective high-alkaline additive CC-300an, has been studied as a deter-gent-dispersant component in combination with antioxidant and anticorrosion additives in the lubricating composition of M-10G2 motor oil intended for automotive diesel engines.

The results of laboratory tests (Table 3) showed that the use of the synthesized sulfonate ensures the production of test oil M-10G2 with nigh physico-chemical and functional (detergent-dispersant, antioxidant, anticorrosive) properties corresponding to the requirements imposed on these oils.

Table 2. Characteristics of medium- and high-alkaline sulfonate additives

Indicators Medium- and high-alkaline sulfonate additives

CC-150an C-150 CC-300an C-300 Hightech 6060M

Alkaline number, mg KOH/g 154 150 305 303 142

Mass fraction of calcium sulfonate, % 32.5 31.5 32.1 30.0 32.0

Mass fraction of calcium, % 13.7 13.4 27.6 26.9 -

Sulfate ash, mass. % 23.9 23.0 44.3 42.9 23.1

Mass fraction of mechanical impurities, % 0.04 0.08 0.05 0.09 0.05

Temperature of flashes in open in crucible, 0C 190 180 210 200 185

Detergent properties on installation PZV, points * 0 0 0 0 0.5

Dispersant ability at 2500C, % * 70 60 80 75 60

Corrosion of lead plates, g/m2 * 76 85 64 90 85

Stability over the induction period of precipitation: sludge, % 0.6 0.7 0.5 0.8 0,9

increase in viscosity, % 62 71 54 77 78

Colloidal dispersion stability, % 89 75 98 90 76

*M-11 oil with 5% additive

Table 3. Characteristics of experimental motor oil M-10G2

Indicators M-10G2 motor oil

norm experimental

Kinematic viscosity at 1000C, mm2/s 11 ± 0.5 11.2

Viscosity index, not less than 85 90

Sulphate ash, %, no more than 1.65 1.43

Alkaline number, mg KOH to 1g oil, no less than 6.0 8.4

Temperature, 0C, of: flashes in open crucible, no less than 205 205

hardening, no higher than - 15 - 15

Detergent properties on installation PZV, points, no more than 1.0 0

Stability over the induction period of precipitation, h, no less than 40 40

Corrosion of lead plates, g/m2, no more than 20 none

Conclusions

Based on the product of nafhthalene al-kylation, propylene oligomers of the C18-C30 fraction were used to synthesize neutral, medium- and high alkaline oil-soluble calcium sul-fonates, which significantly improve the functional properties of lubricating oils, and also have a high stability of colloidal dispersion to water action.

High efficiency of the developed additives allows them to be used as a detergent-dispersant component in the composition of additive packages for modern motor oils.

References

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2. Sadyhov K.I. Neftianye i sinteticheskie sulfo-natnye prisadki k motornym maslam. Baku: Elm, 2006. 180 c.

3. Magerramov A.M., Sadyhov K.I., Agaev A.N., Magerramov M.N. Tceolitsoderzhashchie kataliza-tory v ekologicheski chistom proizvodstve sulfo-natnykh prisadok k smazochnym maslam. Materialy azerbaidzhano-rossiiskogo simpoziuma s mezhdunarodnym uchastiem "Kataliz v reshenii problem neftehimii i neftepe-rerabotki". Baku, 2830 sentiabria 2010. S. 216-217.

4. Nefteprodukty: Masla. Smazki. Prisadki. 1987. M.: Standarty. Ch. 3. S. 144-147.

5. Glavati O.L. Fiziko-himiia dispergiruiushchikh prisadok k maslam. Kiev: Nauk. dumka, 1989. 183 s.

6. Velieva S.M., Zeinalova N.N., Kulaliev I.D., Agaev A.N. Issledovanie kolloidnoi stabilnosti gidrok-sialkilbenzilsulfonatnykh prisadok. Azerb. neftianoe hoz-vo. 2011. № 2. S. 60-63.

MOTOR YAGLARINA SiNTETiK SULFONAT A§QARLARI LC.Gutoliyev, S.M.Valiyeva

Oliqomer propilenin Ci8-C30 fraksiyasindan istifada etmakla alinan alkilnaftalin asasinda yagda hall olan kalsium sulfonatlari alinmi§ va xarakteriza edilmi§dir. Yaradilmi§ muxtalif qalavili sintetik sulfonat a§qarlari yuksak fiziki -kimyavi va funksional xassalara malik olub, gostaricilara gora amtaa neft man§ali C-150 va C-300 sulfonatlardan, hamginin xarici analoq olan OLOA -246 B va Xaytek 6060M a§qarlarindan ustundurlar. Alinmi§ yuksak qalavili a§qarin i§tiraki ila keyfiyyat gostaricilarina gora irali surulan talablara cavab veran M-10 Г2 tipli tacrubi motor yagi i§lanilmi§dir.

Agar sozlar: alkilnaftalin, sulfonat a§qarlari, yuyucu-dispersedici a§qarlar, motor yaglari, funksional xassalar.

СИНТЕТИЧЕСКИЕ СУЛЬФОНАТНЫЕ ПРИСАДКИ К МОТОРНЫМ МАСЛАМ

И.Д.Гулалиев, С.М.Велиева

Получены и охарактеризованы маслорастворимые сульфонаты кальция на основе алкилнафталина, полученного с использованием олигомеров пропилена фракции С18-С30. Разработанные синтетические сульфонатные присадки с различной щелочностью обладают высокими физико-химическими и функциональными свойствами и по показателям превосходят товарные нефтяные сульфонаты С-150 и С-300, а также зарубежные аналоги - присадки ОЛОА-246В и Хайтек 6060М. С использованием полученной высокощелочной присадки разработано опытное моторное масло М-10Г2, которое по показателям качества отвечает предъявляемым требованиям.

Ключевые слова: алкилнафталин, сульфонатные присадки, моюще-диспергирующие присадки, моторные масла, функциональные свойства.