CC BY
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AZERBAIJAN CHEMICAL JOURNAL № 2 2019
UDC 665.7.038
MULTIFUNCTIONAL ADDITIVE FOR MOTOR OILS ON THE BASIS OF
DODECYLPHENOL
E.A.Naghiyeva, A.K.Kazim-zadeh, Kh.N.Mammadyarova, A.A.Gadirov, M.N.Aliyeva,
Y.B.Ramazanova
A.Guliyev Institute of Chemistry of Additives, NAS of Azerbaijan
aki05@mail.ru
Received 29.01.2019
The results on synthesis and research of high alkaline alkylphenolate AKI-134 additive have been introduced. AKI-134 additive is a carbonated calcium salt of the condensation product of dodecylphenol, formaldehyde, ammonia and p-aminobenzoic acid. Due to the presence of 2 nitrogen atoms, carboxylate and phenolate groups, the additive shows high anticorrosion, antioxidative and detergent properties. Using AKI-134 additive and commodity additives the M-10r2 motor oil has been developed that by their physical-chemical and functional properties meet the standards.
Keywords: dodecylphenol, formaldehyde, ammonia, p-aminobenzoic acid, additive, motor oil. https://doi.org/10.32737/0005-2531-2019-2-48-51
Introduction
The improvement of the design of internal combustion engines leads to increased demands on the quality of motor oils.
Application of the effective additives is one of the more progressive methods for the quality increase of motor oils.
In composition of modern motor oils as one of the main components a significant part is given to detergent-dispersant additives.
This group of additives includes al-kylphenolates, sulphonates and alkylsalicylates. Alkylphenolate additives are found in most modern motor oils. This is due to the availability of raw materials, simple technology of production and multifunctionality of alkylpheno-late additives [1-4].
Up to the middle of 1990 in the republics of CIS, most of the alkylphenolate type deter-gent-dispersant additives produced in industry were barium containing products (BFK, IKhP-101, SIATIM-339 and others). Low alkalinity and high ash content of these additives were the main reason for the reduction or cessation of production of these obsolete additives [5], that didn't meet modern requirements and were inferior to foreign analogues (Amoko-9230, Par-anox-51 and others). However they had fulfilled their mission, at that time. By using them, various types of motor oils were developed. In this
regard, there is an urgent need to update the range of alkylphenolate additives and improve their quality.
Analysis of scientifico-, technical and patent literature of the last decade showed that of particular interest are high alkaline carbonated alkylphenolates containing metal (most often -calcium).
The most perspective are high alkaline multifunctional additives that in low in small concentrations at the same time improve some properties of lubricating oils [6].
High alkalinity indicates high neutralizing properties of additives [7].
The need in high alkaline multifunctional additives is due to their ability to show high neutralizing and detergent properties in composition of lubricating oils [8].
By introducing various heteroatoms and functional groups into the additive molecules, their antioxidant, anticorrosive and detergent properties are improved [9, 10].
It is known that among metal containing additives for oils alkylsalicylate additives that possess high detergent, thermo-oxidative and other properties have also found wide application. However, in industry they are produced by multi-stage technology, which ultimately complicates the creation of the production technology of this type of additives [11, 12].
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MULTIFUNCTIONAL ADDITIVE FOR MOTOR OILSON THE BASIS
Experimental part
In connection with the above, we have proposed a method of obtaining new multifunctional additive for motor oils - AKI-134, which combine simultaneously the properties of al-kylphenolate and alkylsalicylate additives.
The process of obtaining the additive includes the following main stages:
- sequential condensation of dodecylphe-
49
nol with formaldehyde, ammonia and p-aminobenzoic acid;
- neutralization of condensation product by calcium hydroxide;
- carbonation of neutralization products and desiccation;
- separation of mechanical impurities by centrifugation.
The estimated formula for AKI-134 additive is:
O-
Ca
CH2 -NH-CH
C12H25
O
ch2 -nh-c6h4coo
C12H25
■ Ca- CaCO ■ Ca(OH)2- n
The additive is a viscous lIRuid that is of 130-150 mg KOH/g alkaline number.
Following optimal conditions for obtaining additive: dodecylphenol:ammonia:forma-linp-aminobenzoic acid:Ca(OH)2 - 100:(30-35):(40-45):(10-12):(35-40) were established. During carbonation 5% (of alkylphenol) ethy-lene glycol was used as a promoter. The structure of derived additive has been confirmed by IR spectroscopy that was performed on "Nicolet is 10" spectrometer around 400-4000 cm-1.
In the IR spectrum of the product do-decylphenol condensation with formaldehyde, ammonia and p-aminobenzoic acid, bands of absorption of the OH group of the phenolic compound, OH group of p-aminobenzoic acid and NH group around 3200-3500 cm-1 were detected.
Valence vibrations of CO groups are registered around Vc=0-1716 cm"1 (1690-1760 cm"1), and CN bond around - 1181 cm"1 [13].
After the neutralization of condensation product by calcium hydroxide the 3408 cm-1, stripe appears that is characteristic to valence vibrations of NH group, which was previously covered by OH condensation groups. In the IR spectrum of the neutralization product, the band
of stretching vibrations of the CO of the acid group of 1716 cm-1 disappeared and the corresponding carboxylate of the COO- ions appeared symmetric and asymmetric v^. = 1349
cm-1 and v!!„„. =1580 cm-1 instead of it. Re-
COO"
garding calcium hydroxide, in the neutralization product there are absorption bands corresponding to the OH group voh= 3670 cm-1 and CO3 group of the average intensity band vco 2 = 1430 and 860 cm-1.
Results and discussion
Physico-chemical and functional properties of AKI-134 additive have been studied in the composition of the M-8 oil using the following standard methods.
Anticorrosive properties were determined according to rOCT 20502-75, anti-oxidative properties according to rOCT 11063-77, detergent properties according to rOCT 5726-2013.
Physico-chemical and functional properties of test additive in composition of M-8 oil are shown in Table 1, where for comparison the data of foreign commodity additives VNIINP-714, OLOA-218A and MASK are also presented.
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*precipitation up to 0.5% is considered absent
Table 2. Physico-chemical and functional properties of M-10r2 motor oil
50 E.A.NAGHIYEVA et al.
Table 1. Physico-chemical and functional properties of alkylphenolate additives
Additive Physico-chemical and functional properties of additives M-S oil + 5% additive
alkali number, mg KON/g sulfate ash content, % kinematic viscosity, at 1000C, mm2/s corrosiveness (in lead plates), g/m2 stability by induction period of precipitation (IPP 30 h of prec., % detergent properties (on PzV), point
AKI-134 145.2 1б. i 72.2 1.0 absent 0.5
AKI-134 150.1 1б.б 74.S 0.9 absent 0.5
VNIINP-714 143.0 17.2 - б.4 absent 0.5
OLOA-218A 147.0 17.б - 9.S absent 0.5
MASK 140.0 1б.8 - 4.5 absent 0.5
Indicators ГОСТ 8581-92 (norm) Test oil M-10^ Shell oil Rimula C30
Kinematic viscosity at 1000C, mm2/s 11±0.5 i i .45 10.8
Viscosity index, no more than 90 90 102
Alkali number, mg KON/g, no more than б.0 7.4 9.4
Sulfate ash content, %, no more than 1.б5 1.2б 1.3
Flash point in open crucible, 0C, no lower than 205 205 202
Freezing point, 0C, no lower than minus 15 minus 15 minus 15
Stability by induction period of precipitation (IPP) resistance, h 40 40 40
Corrosion (in lead plates), g/m2, no more than 20 absent absent
Detergent properties (on ELV), point 1.0 0.5 0.5
As can be seen on data from Table 1, under the conditions of the tests of test additive AKI-134 on anticorrosion properties surpass comparable industrial analogues, and on antioxidative and detergent properties are on the same level with them.
The improvement of exploitative properties of the additive is apparently related to the mutual influence of 2 nitrogen atoms, carbox-ylate and phenolate groups on the formation of a stable colloidal dispersion.
Synthesized AKI-134 additive in combination with commodity additives has been studied in the composition of the M-10r2 motor oil.
Results of M-10r2 oil analysis are shown on Table 2, there are also physico-chemical and functional properties of the foreign analogue -Shell oil.
From data on Table 2, we can see that M-10 r2 oil with AKI-134 additive meet the requirements of rOCT-8581-92 on exploitation properties and is not inferior to the foreign counterpart.
Conclusion
Thus, the possibility of using AKI-134 additive in the composition of М-10Г2 motor oil as the main component instead of ИХП-101 additive (barium alkylphenolate) is shown.
This work has been carried out with the financial support of the Foundation for the Development of Science under the President of the Republic of Azerbaijan - Grant №EIF / GAM-4-BGM-GIN 2017-3(29)-19/05/4.
References
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2. Moiseeva L.S. Prisadki mnogofunktcionalnogo naznacheniia - alkilfenoliaty: sovershenstvovanie sposobov polucheniia. Tekhnologiia mashinostro-eniia. 2012. № 10. S. 37-47.
3. Kiazim-zade A.K., Nagieva E.A., Mamedova A.Kh., Mamedova R.A., Nasirova S.I. Polifun-
AЗЕРБAЙДЖAHCKИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 2 2019
MULTIFUNCTIONAL ADDITIVE FOR MOTOR OILSON THE BASIS
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ktcionalnaia prisadka k smazochnym maslam. Azerb. neftianoe hoz-vo. 2013. № 9. S. 59-61.
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5. Selezneva I.E., Levin A.Ia., Trofimova G.L., Ivanova O.V., Budanovskaia G.A. Novaia sverkhshchelochnaia alkilfenolnaia prisadka k motornym maslam. Himiia i tekhnologiia topliv i masel. 2009. № 4. S. 10-12.
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7. Lashhi V.L., Leimeter T., Shor G.I., Falkovich M.I. Shelochnoe chislo kak pokazatel sovme-stimosti prisadok k motornym maslam. Himiia i tekhnologiia topliv i masel. 2000. № 4. S. 10-12.
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nym maslam. Neftepererabotka i neftehimiia. 2010. № 9. S. 28-29.
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10. Kazimzada O.K., Nagiyeva E.G., Qadirov O.O., Mammadova R.O., Nasirova S.i. Yeni goxfunk-siyali alkilfenolyat a§qari modifikasiyasi. Azarb. Neft Tasarrufati. 2015. № 5. S. 41-43.
11. Zhurba A.S., Burlakova G.G., Burgov V.A. Effektivnost proizvodstva prisadok k maslam. Kiev: Naukova Dumka, 1990. 182 s.
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13. Nakanisi K. Infrakrasnye spektry i stroenie orga-nicheskikh soedinenii. M.: Mir. 1965. 216 s.
MOTOR YAGLARINA DODESiLFENOL OSASINDA COXFUNKSiYALI A§QAR
E.O.Nagiyeva, 0.K.Kazimzada, X.N.Mamm3dyarova, O.O.Qadirov, M.N.Oliyeva, Y.B.Ramazanova
Maqalada yuksak qalavili AKi-134 alkilfenolyat a§qannin sintezi va tadqiqi verilmi§dir. AKi-134 a§qan dodesilfenolun formaldehid, ammonyak va p-aminobenzoy tur§usunun kondensla§ma mahsulunun karbonatla§mi§ kalsium duzudur. A§qar molekulunda iki azot atomu karboksilat va fenolyat qruplarinin birga tasiri sayasinda yuksak korroziyaya, oksidla§maya qar§i davamli va yuyuculuq xassalarina malikdir. AKi-134 va amtaa a§qarlarini istifada etmakla, fiziki-kimyavi va funksional xassalarina gora standart normalarina cavab veran М-10Г2 motor yagi i§lanib hazirlanmi§dir.
Agar sozlar: dodesilfenol, formaldehid, ammonyak, p-aminobenzoy tur§usu, a§qar, motor yagi.
МНОГОФУНКЦИОНАЛЬНАЯ ПРИСАДКА К МОТОРНЫМ МАСЛАМ НА ОСНОВЕ
ДОДЕЦИЛФЕНОЛА
Э.А.Нагиева, А.К.Кязим-заде, Х.Н.Мамедьярова, А.А.Гадиров, М.Н.Алиева, Ю.Б.Рамазанова
Приведены результаты по синтезу и исследованию высокощелочной алкилфенолятной присадки AKi-134. Присадка AKi-134 представляет собой карбонизированную кальциевую соль продукта конденсации додецил-фенола, формальдегида, аммиака и п-аминобензойной кислоты. Присадка обладает высокими антикоррозионными, антиокислительными и моющими свойствами благодаря взаимному влиянию 2-х атомов азота, кар-боксилатной и фенолятной групп на свойства присадки. С применением присадки AKi-134 и товарных присадок разработано моторное масло М-10Г2, которое по своим физико-химическим и функциональным свойствам соответствует стандартам.
Ключевые слова: додецилфенол, формальдегид, аммиак, п-аминобензойная кислота, присадка, моторное масло.
AZORBAYCAN KIMYA JURNALI № 2 2019
