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AZ9RBAYCAN KIMYA JURNALI № 3 2017
UDC 665.7.038.2.665.765
STRONTIUM CONTAINING SULPHONATES ON THE BASIS OF ALKYLPHENOL AS MULTIFUNCTIONAL ADDITIVES FOR LUBRICATING OILS
A.N.Agayev, S.M.Veliyeva, I.D.Gulaliyev, M.N.Aliyeva, S.A.Hasanova
A.Quliyev Institute of Chemistry of Additives, NAS of Azerbaijan
aki05@mail.ru Received 08.07.2016
Based on sulphomethylated alkyl(C25-C30)phenol new modifications of sulphonate type additives-strontium hydroxyalkylbenzylsulphonate have been synthesized and studied. Developed base and medium alkaline sulphonates are characterized by their high physico-chemical and functional properties and exceed foreign analogue - Hightech 6060M additive. Being the additives of a broad spectrum they significantly improve the detergent-dispersant, anti-corrosion properties, stability against oxidation of base oil and also possess high thermal stability. Using given medium alkaline additive the test M-10 r2k motor oil have been developed which in term of quality meets the requirements.
Keywords: alkylphenol, sulphomethylation, multifunctional additives, motor oils, functional properties.
Presently in the refining industry of the developed countries of the world the most important place is given to increasing the production of high-quality motor oils that meet the requirements of modern and advanced equipment at the expense of the wider application of effective additives for various purposes, including sul-phonates. High alkaline sulphonates derived on the basis of petrol oils and synthetic alkyl aromatic carbohydrates in relatively small concentrations provides motor oils with high dispersant-detergent properties [1]. On the effectiveness of these additives significantly affect the nature of
the cation present in their structure [2]. Moreover, the use of alkyl phenol materials to get sulphonates provides for multifunctionality in oils [3].
Given the urgency of the problem, the synthesis of new multifunctional additives of sulphonate type with improved environmental properties - hydroxyalkylbenzylsulphonate strontium with various alkali has been made using method [4] and their effect on lubricating oils properties have been researched.
The additives were obtained by the following scheme:
Ö
H
kt
+ R-CH=CH
MR
+ HOCH2SO3Na
-H о
OH
CH2SO3Na + Sr(OH)
OH
-NaOH
Л
CH2SO3
M
4.
Sr
J
Г OH
+ (CH3O)2Sr + CO2
-CH3OH
л
CH2SO3
^R
Sr- SrCO • Sr(OH)2
J2
where R=C25-C30.
STRONTIUM CONTAINING SULPHONATES ON THE BASIS OF ALKYLPHENOL
61
Experimental part
Starting alkylphenol prepared by alkylation of phenol with industrial chloroparaffins C25-C30 (molecular mass - 400; chlorinity - 12%) in the presence of catalyst using the method [5]. As a result alkylphenol with 73% yield was synthesized with following physico-chemical parameters: density with 20 C - 881.9 kg/m3; index of refraction - n ^ - 1.4810; molecular mass - 540.
In order to get alkylphenol sulphacids instead of economically unprofitable and environmentally dangerous method of sulphonation with gaseous trioxide sulphur the promising method is used - sulphomethylation with hydroxymethane-sulphonate [4], which excludes the formation of hard recyclable acid sludge waste.
The sulphomethylation reaction of alkyl-phenol with sodium hydroxymethanesulphonate was carried out at a molar ratio 1:1, temperature 70-800C in the duration of 10 hours in nonane solution. Then by the reaction of the resulting sodium hydroxysulphonates with strontium hydroxide with 75-800C for 5 hours the basic sulphonate is synthesized.
With carbonation of the basic sulphonate carbon dioxide in the presence of the promotermethanol, strontium methylate, solvent - toluene, oil breaker M-6 at, the temperature of 40-450C, a medium alkaline additive was obtained [6].
Composition and structure of the sul-phonates were confirmed by elemental analysis and IR spectroscopy. The sulphur content was determined according to GOST 1431-81, strontium content on metal analyzer MP-4200 AES, IR-spectra were taken from spectrometer NICOLET IS-10. Content of active substance in additives was determined through liquid adsorption microchromotography.
In IR spectra of sulphonates absorption bands in the 1050-1070 and 1160-1250 cm are taking place arising from the valence symmetric and asymmetric vibrations of the S=O of SO3 group, bands at the 3100-3500 cm-1 are conditioned by stretching vibrations of OH-group. Absorption bands 1420-1440 cm-1 is characteristic for CH2Ar group deformation vibrations.
The studies of the physico-chemical and functional properties of derived additives were carried out by standard laboratory methods. Thermal stability of additives were studied on
derivatograph of OD-102T type Paulic (Hungary) system in dynamic heating mode with rate of 50C/min on air. Standard served calcined alumina.
Cleaning properties were determined on ELVs, dispersant properties - using method [7] with 2500C.
Anticorrosion properties were evaluated on DK-NAMI with 1400C in 254 hours, stability against oxidation on DK-NAMI for 30 hours at 2000C. The effect of additives on the oil properties was evaluated on the device "slip ring" at 3300C for 30 min [8].
Results and discussion
Obtained additives OCCsr (basic sulpho-nate strontium) and CC-150sr (medium alkaline sulphonate) are viscous dark-brown liquids, which characteristics are shown in Table 1. For comparison the corresponding figures for the indications for known sulphonate additive hightech 6060M, derived on the basis of synthetic alkylbenzoles. As it follows from the data cited above the new synthesized modifications on alkylphenolsulphonate type additives are completely soluble in the base oils and are characterized with high physico-chemical and functional properties. Being the additives of a broad spectrum they significantly improve detergent, dispersant, anti-corrosion properties and stability against oxidation of M-11 oil. According to some data (active matter content, mechanical impurity, purity) developed strontium hydroxyl-alkylbenzylsulphonates excel Hightech 6060M additive. For their detergent properties these additives are at a level of a foreign counterpart, and for stability against oxidation, dispersant and anticorrosion properties surpass the said additive. Thus, adding derived base and medium alkalines to M-11 oil in concentration of 5% the corrosion in lead constitutes 46 and 22 g/m2 accordingly, while the figure for the Hightech 6060M additive is 85 g/m2.
Researched sulphonates decrease the oil's aptitude for varnishing at high temperature, while displaying good detergent and anti oxidative properties. The maximum drop of varnish equivalent takes place when adding the oil of medium alkaline strontium sulphonate.
62 A.N.AGAYEV et al.
Table 1. Characteristics of synthetic sulphonate additives
T A- Sulphonate additives
Indicators OCCsr CC-150sr Hightech 6060M
Alkaline number, mg KOH/g 48 153 142
Mass fraction, % :
sulphonate material 63.5 33.2 30
metal 4.70 11.85 -
sulphur 3.12 1.23 -
mechanical impurities 0.02 0.03 0.05
Sulphonate ash, mas. % 18.2 37.1 23.1
Purity level, mg/100 g 180 200 300
Detergent properties on installation PZV, points* 0.5 0 0.5
Dispersant ability at 2500C, %* 62 70 60
Lead corrosion, g/m2* 46 22 85
Stability against oxidation, %:
deposit 0.3 0.1 0,9
viscosity increase 51 43 78
Varnish equivalent at 3300C, points* 7 6.5 7
Thermal stability:
Temp.,0C, to correspond mass loss
10% 305 320 290
50% 410 430 400
Solubility in oil full
: the test was carried out in M-11 oil with 5% additive
Received data agree with the results of thermo analytical studies of additives. Synthesized sulphonates possess high thermal stability and with that parameter they exceed the foreign analogue. Thus, temperature in which the mass loss of hydroxyl alkyl benzyl sulphonates OCCsr and CC-150sr makes up 50% reach respectively 410 and 4300C against 4000C for Hightech 6060M additive.
Revealed multifunctionality and high efficiency of the obtained additives are, obviously explained by the presence in their
structure of phenol hydroxyl, long alkyl radical, sulphonate fragment and their intramolecular synergism.
Medium alkaline strontium containing CC-150sr additive was studied as detergent component in additive composition of motor oil M-10r2k designed for diesel engines without boost. Results of laboratory studies (Table 2) showed that the use of synthesized sulphonate provides the obtaining of test oil M-10F2 with high physico-chemical and functional properties meeting the requirements set for these oils.
Table 2. Characteristics of test oil M-10 r2k
Indicators Motor oil M-10 r2k
norm test
Kinematic viscosity at 1000C, mm2/s 11±0.5 11.2
Viscosity index, no less than 95 95
Alkaline number, mg KOH to 1 g oil no less than 6.0 7.6
Sulphonate ash,% no more than 1.15 1.11
Flash point in an open crucible, 0C no less 220 220
Congelation point, not higher -18 -18
Corrosiveness of lead plates, g/m2, no more than absent
Detergent properties PZV, points, no more than 0.5 0
Thermoxidative stability at 2500C, min, no less than 65 70
Sedimentation stability by the induction period, h, no less than 50 50
Color on colorimeter CNT with dilution in ratio 15:85, CNT unit no more than 5.0 3.5
Mass fraction of mechanical impurities, % 0.015 0.009
STRONTIUM CONTAINING SULPHONATES ON THE BASIS OF ALKYLPHENOL
б3
Conclusions
On the basis of sulphomethylated alkyl-phenol, derived from phenol alkylation with industrial chloroparafin C25-C30, effective base and medium alkaline strontium sulphonates were synthesized, which are effective multifunctional additives for lubricating oils and are characterized with high thermal stability. The process of obtaining sulphonates is low-waste, eliminates the formation of acid sludge, which is characteristic for the production of commodity additives. High efficiency of developed additives allows them to be used as a detergent-dispersant component in additive packages for modern motor oils.
References
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5. Кулиев А.М. Химия и технология присадок к маслам и топливам. Л.: Химия. 1985. 312 с.
6. Мишунина И.И., Мысак Н.П., Фиалковский Р.В. Синтез и функциональные свойства высокощелочных нефтяных сульфонатов с различными катионами // Нефтепереработка и нефтехимия. 1981. № 21. С. 45-47.
7. Главати Е.В., Рабинович И.Л., Главати О.Л. Оценка диспергирующих свойств моторных масел // Химия и технология топлив и масел. 1975. № 3. С. 60-63.
8. Папок К.К., Зарубин А.П., Петрова Н.И. Оценка лакообразующих свойств моторных масел // Химия и технология топлив и масел. 1973. № 4. С. 52-55.
ALKÍLFENOL OSASINDA STRONSÍUM SAXLAYAN SULPHONATLAR SÜRTKÜ YAGLARINA
COXFUNKSÍYALI A§QARLAR KÍMÍ
A.N.Agayev, S.M.Valiyeva, LC.Gübliyev, M.N.eiiyeva, S.O.Hasanova
Sulphometilbíjmiíj alkil (C25-C30) fenol asasinda sulphonat tipli a§qarlarin yeni modifika-siyasi-stronsium hidroksialkilbenzilsulphonatlar sintez edilib, tadqiq olunmu§dur. ͧlanib hazirlan-mi§ asasi va orta qalavili sulphonatlar yüksak fiziki-kimyavi va funksional xassalarina malik olub, xarici analoq olan Хайтек 6060M a§qarindan üstündürlar. Qoxfunksiyali a§qarlar olaraq, hidroksialkilbenzilsulphonatlar baza yaginin yuyucu-dispersiyaedici, korroziyaya va oksidla§maya qar§i xassalarini ahamiyyatli daraca yax§ila§dirmaqla yana§i ham da yüksak termiki stabilliya malkdirlar. Alinmiíj orta qalavili a§qarin i§tiraki ila keyfiyyat gostaricilarina gora bütün talablara cavab veran M-10r2k tacrübi motor yagi i§lanib hazirlanmi§dir.
Agar sozlar: alkilfenol, sulphometilh§m3, goxfunksiyah a§qarlar, motor yaglari, funksional xassabr.
СТРОНЦИЙСОДЕРЖАЩИЕ СУЛЬФОНАТЫ НА ОСНОВЕ АЛКИЛФЕНОЛА КАК МНОГОФУНКЦИОНАЛЬНЫЕ ПРИСАДКИ К СМАЗОЧНЫМ МАСЛАМ
А.Н.Агаев, С.М.Велиева, И.Д.Кулалиев, М.Н.Алиева, С.А.Гасанова
На основе сульфометилированного алкил(С25-С30)фенола синтезированы и исследованы новые модификации присадок сульфонатного типа - гидроксиалкилбензилсульфонаты стронция. Разработанные основной и среднещелочой сульфонаты характеризуются высокими физико-химическими и функциональными свойствами и превосходят зарубежный аналог - присадку Хайтек 6060М. Являясь присадками многофункционального действия, они значительно улучшают моюще-диспергирующие, противокоррозионные свойства, стабильность против окисления базового масла, а также обладают повышенной термической стабильностью. С использованием полученной среднещелочной присадки разработано опытное моторное масло М-10 Г2к, которое по показателям качества отвечает предъявляемым требованиям.
Ключевые слова: алкилфенол, сульфометилирование, многофункциональные присадки, моторные масла, функциональные свойства.
