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48 CHEMICAL PROBLEMS 2023 no. 1 (21) ISSN 2221-8688
UDS 547.436 + 621.892.86
SYNTHESIS OF AMINOMETHYL DERIVATIVES OF 3-MERCAPTO-2-HYDROXYPROPYL-1-ISOBUTYL ETHER AND THEIR STUDY AS PROTECTIVE
ADDITIVES TO LUBRICANT OILS
V.M. Farzaliyev1, Sh.R. Aliyev1, R.M. Babai1, R.F. Mammadova1, G.M. Guliyeva1,
A.M. Mammadov2, G.Sh. Eivazova1
1Acad. A.M. Guliyev Institute of Chemistry of Additives of the Ministry of Science and Education of
Azerbaijan
AZ1029, Baku, Boyukshor highway, quarter 2062 2Acad. H. Mammadaliyev Institute of Petrochemical Processes of the Ministry of Science and Education of
Azerbaijan
Az.1025, Baku, Khojalipr.30, e-mail: aki05@,mail.ru
Received 07.09.2022 Accepted 26.12.2022
Abstract: The electrochemical corrosion prevention of engines and mechanisms is a task of great national, economic and defense importance. Lubricating oils commonly used in engineering do not have sufficient protective properties and are unable to effectively protect it from corrosion, both during operation and during short-term and long-term inactivity. One of the simplest and most rational ways to solve this problem is the use of lubricants containing effective protective (conservation) additives, which, without worsening the normal working properties of oils provide them conservation properties. By the action of 3-mercapto-2-hydroxypropyl-1-isobutyl ether, taken as a synthon, with secondary aliphatic and heterocyclic amines under the conditions of the Mannich reaction, a number of aminomethyl derivatives were synthesized. Aminomethyl derivatives of 3-mercapto-2-hydroxypropyl-1-isobutyl ether are dissolved well in oils and are stable during storage. The protective properties of the synthesized compounds were studied in M-12 oil. The best test results were obtained with 3-piperidinomethilthio-2-hydroxypropyl-1-isobutyl ether - at a concentration of 1% to the lubricating oil M-12, the corrosion of a steel plate in a humid chamber is 3%, in sea water after 24 hours - 5%, the corrosion of a steel plate under the action of a 0.1% acid soluti on HBr - 3,5%. These results are higher than those of the standard - industrial additive urea succinimide. (SIM). Keywords: Potassium hydrosulfide, corrosion, protective additive, lubricant oils, piperidine, morpholine DOI: 10.32737/2221-8688-2023-1-48-56
Introduction
Various weather-climatic and atmospheric conditions during the operation of equipment require the adoption of appropriate measures to protect it both during operation and during storage, transportation and long-term storage.For these purposes, protective additives for lubricating oils are used, providing them with required working-conservation properties.
One of the most important problems in creating promising additives and their compositions is the study of the effect of their composition on various characteristics of the state of the surface layers of metals, including corrosion damage.
The contradictory requirements when using additives for operating-conservation oils under these conditions is that additives with high surface activity are desirable for realizing a high level of functional properties that provide a protective effect.. However, the high surface activity of the additives is associated with the possibility of their action in the direction of the adsorption decrease in the strength of the surface layers of the metal in contact with this additive.
Analysis of the literature [1-11] shows that compounds containing various functional groups and heteroatoms, such as N-, S- , are
CHEMICAL PROBLEMS 2023 no. 1 (21)
www.chemprob.org
used as protective organic compounds. These compounds are surfactants that protect metals
from electrochemical corrosion electrolyte-petroleum-metal system.
in
the
Results and their discussion
To obtain the above-mentioned compounds, 3 -mercapto-2-hydroxypropyl-1 -isobutyl ether was used as a synthon. Aminomethyl derivatives were synthesized by the interaction of formalin, secondary aliphatic
and heterocyclic amines with 3-mercapto-2-hydroxypropyl-1-isobutyl ether by the Mannich reaction.
The reactions were carried out in line with to the following scheme:
1.
CH3 I 3
CH3- CH-CH2OH +
2.
CH-CH2-CH2C1
\ / o
H2S04 fh3
-►CH3- CH-CH2-0-CH2-CH-CH2Cl
OH
CH3 I 3
CH3- CH-CH20-CH2-(pH-CH2Cl + KHS OH
3.
CH3 I 3
CH3- CH-CH20-CH2-<pH-CH2SH OH
ÇH3 CH3
I J I
ch3- ch-ch20-ch2-<pH-ch2sh + ch2o + hnr2-»-ch3- ch-ch2-0-ch2-ch-ch2sch2nr2
oh ¿h
nr2 = -n(c2h5)2(3-i),-n(c4h9)2(3-ii), (3"m) ' - (3_iv)
Obtaining 3-chloro-2-hydroxypropyl-1-isobutyl ether (1)
30 g of ephichlorohydrin and 36 g of isobutyl alcohol were added to a 100 ml three-necked reaction flask. Then, 3 ml of 98% sulfuric acid was added dropwise to the mixture. Then, the mixture was stirred at a temperature of 90-950 C for 6 hours. After completion of the reaction, the mixture was extracted with toluene, washed with water, dried over Na2SO4, and the toluene was distilled off. The residue was distilled under vacuum in an oil bath. Physical-chemical characteristics of 3-chloro-2-hydroxypropyl-1-isobutyl ether are given in Table 1. The structure and composition of 3-chloro-2-hydroxypropyl-1-isobutyl ether were confirmed by 1H, 13C NMR spectroscopy and elemental analysis. Signals of the 13C NMR spectrum of 3-chloro-2-hydroxypropyl-1-isobutyl ether are as follows: 1H NMR
spectrum (fig.1), (C6 D6, 5, ppm): 0.78 (d.,6H,CH3), 1.7 (m., 1H, CH-(CH3)2), 2.93 (d.,2H, CH2Cl), 3.24 (m.,4H,CH2O), 3.41 (m.,CHOH).
13C NMR spectrum (fig.2), (C6 D6 , 5, ppm): 18.94 (CH3 ), 28.18 ( CH(CH3 >2 ), 46.06 (CH2 Cl), 72.89 (CH2 O CH2 -), 78.03 (CHOH). Synthesis of 3-mercapto-2-hydroxypropyl-1-isobutyl ether (2)
12 g of 3-chloro-2-hydroxypropyl-1-isobutyl ether, 20 ml of ethyl alcohol and potassium hydrosulfide (KHS), which was obtained by the reaction KOH+ H2S= KHS+H2O (in a solution of 7 g of KOH within 0.5 hours served H2S) were placed in a three-necked reaction flask with a capacity of 100 ml, equipped with a mechanical stirrer, a condenser and a thermometer.
Fig.1. 1H NMR spectrum of 3-chloro-2-hydroxypropyl-1-isobutyl ether
Fig. 2. 13C NMR spectrum of 3-chloro-2-hydroxypropyl-1-isobutyl ether
The reaction mixture was stirred at a temperature of 75-800 C for 5-6 hours. Then it was extracted with benzene, washed, dried over Na2SO4, the residue was distilled under vacuum on an oil bath. Physical-chemical constants of the obtained compounds are given in table 1. The structure and composition of 3-mercapto-2-hydroxypropyl-1-isobutyl ether was confirmed by 'H, 13C NMR spectroscopy and elemental analysis. The signals of the 'H, 13C NMR
spectrum of 3-mercapto-2-hydroxypropyl-1-isobutyl ether are as follows: 1H NMR spectrum (fig. 3), (C6D6, 5, ppm): 0.81 (d., 6H, CH3), 1.75 (m., 1H, (CH3)2CH), 2.70 (m., 1H, CHOH), 3.02 (d., 4H, CH2O), 3.37 (d., 2H, CH2SH), 3.94 (s., 1H, SH), 4.34 (s., 1H, OH). 13 C NMR spectrum (fig. 4), (C6D6, 5, ppm): 19.13 and 28.27 (CH3), 36.83 ((CH-^CH), 70.01(CHOH), 73.69(CH2-O- CH2), 78.05(CH2-SH).
UiJU
A_JLi
Fig. 3. NMR spectrum of 3-mercapto-2-hydroxypropyl-1-isobutyl ether
im iio 140 iaa im «w «•• m m n m a* 40 as m *» mm " •-«
13
Fig. 4. C NMR spectrum of 3-mercapto-2-hydroxypropyl-1-isobutyl ether
Syntesis of 3-piperidinomethylthio-2-hydroxypropyl-1-isobutyl ether (3-IV)
6 ml of a 37% aqueous solution of formalin and 20 ml of benzene were placed into a reaction flask with a capacity of 100 ml, and added dropwise 3.6 g of piperidine at a temperature of 200 to 250 C. The temperature of the mixture was raised to 30°-35° C, and then 5.5 g of 3-mercapto-2-hydroxypropyl-1-isobutyl ether dissolved in 15 ml of benzene was added to the mixture. The mixture was stirred at a temperature of 700-750 C for 5 hours. After completion of the reaction, the mixture was washed; then, gaseous HCl was added to the mixture to remove the unreacted 3-mercapto-2-
hydroxypropyl-1-isobutyl ether. The resulting triple amine was precipitated as a quaternary ammonium salt. The quaternary ammonium salt was washed twice with benzene, then treated with ammonium hydroxide and after treatment, it again turned into a converted to the triple amine. This resulted in pure 3-piperidinomethilthio-2-hydroxypropyl-1-isobutyl ether. Its physicochemical constants are given in table 1. The signals of the 1H, 13C NMR spectrum of 3-piperidinomethilthio-2-hydroxypropyl-1-isobutyl ether are as follows: 1H NMR spectrum (fig. 5), (C6D6, 5, ppm): 0.84 (d., 6H, CH3), 1.77 (m., 1H, (CHs^CH), 2.77 (m., 1H, CHOH), 3.06 (d., 4H, CH2O),
3.43 (m., 2H, CH2S), 1.72, 2.81, 3.43 (m., 6H, CH2), 4.02 (S., 1H, OH). 13 C NMR spectrum (fig. 6), (C6D6, 5, ppm):
19.14 (CH3), 28.36 (CH3-CH), 70.14 (CHOH), 78.04 (CH2O), 37.01, 73.06,(CH2)
Fig. 5. 1H NMR of 3-piperidinomethilthio-2-hydroxypropyl-1-isobutyl ether
11 I1
*LL
»«» no*'"
Fig. 6. 13C NMR spectrum of 3-piperidinomethilthio-2-hydroxypropyl-1-isobutyl ether
190 (40 1M 110 110 100 00 M 70 00 «0 40 30 30 10
The protective properties of these compounds were studied in M-12 oil in accord with methods 1, 4 and 5 according to GOST 9.054-75. Tests according to method - 1 were carried out in the humidity chamber T-4 in the mode of periodic moisture condensation on samples of steel - 10.
First, the samples were exposed to air at a temperature of 40 ± 20 C and a relative humidity of 95 ± 3 % for 7 hours. Then conditions were created for moisture
condensation on the samples by cooling them to a temperature lower than the temperature in the chamber by 5-100 C. During the tests, the samples were examined at regular intervals -from the beginning of the tests until the appearance of the first corrosion center.
According to method 4, a steel plate saturated with oil is kept in sea water for 24 hours and the corrosion process on the plate is observed.
Method 5 tests are carried out under the influence of 0,1% HBr acid solution and corrosion of the steel plate is observed within 4 hours. The test results are shown in table 2.
The best test results were obtained with compounds (III) and (IV). So, when adding 3-piperidinomethilthio-2-hydroxypropyl-1-isobutyl ether at a concentration of 1% to the
lubricating oil M-12, the corrosion of a steel plate in a humid chamber is 3%, in sea water after 24 hours - 5%, the corrosion of a steel plate under the action of a 0.1% acid solution HBr - 3,5%. These results are higher than those of the standard - industrial additive urea succinimide (SIM).
n ffi
H
n >
o
Cd
r
H
S
C/5 K»
o
N> Ui
s
©
K»
¡Table 2. Test results of 3-mercapto-2-hydroxypropyl-l -isobutyl ether and its annnomethyl derivatives as protective additives in M-12 oil
Ul J-
№ Samples Mite £S8£g8& a ÖQB, % (mass.) Corrosion steel.-10 (GOST 9.054-75)
in a humid chamber (method 1) In sea water (method 4) for 24 hours. When expo: (method 5) wi >edto HBr thin 4 hours.
Time to corrosion centerto appear.« days. Number of corrosion center Corrosio n. % Number of corrosion center Conosion, % Numb er of corrosion center Corrosion: %
1 M-12 w o additive - 2 94 47 90 45 88 44
2 M-12 + t:oC4H^O-CHrCH-CH:SH OH 1.0 10 50 25 62 31 48 24
3-0) M-12+ iro- CjH.O-CH -C-K-CH:SCH:N(C;H,): OH 1.0 15 25 12.5 32 16 22 11
(ID M-12 is* C.R.O-CH^H-CH^CH^C^Rj; OH 1.0 15 34 17 38 19 28 14
3- (III) M-12+ izo- C,H,0-CH.-<jH-CH SCH. N^3 OH 1.0 15 8 4 11 5.5 9 4.5
3-(IV) M-12+ IZO- C ,H O-CH -CH-C:H,3CH, OH 1.0 15 6 3 10 5 / 3.5
4 M-12+ SIM (standard) 1.0 15 12 6 20 10 16 8
References
1. Guliyev A.M. Chemistry and technology for oils and fuels. L.: Chemistry Publ., 1985. 312 p.
2. Foreign oils, lubricants, additives, technical fluids: International catalogue, issue 3, team of authors - Publishing house LLC Publishing center "Techinform MAI 2005, 380s.
3. Latyuk V.I., Kelarev V.I., Koshelev V.N., Korenev K.D. Sulfides of the simtriazine series as poorly soluble corrosion inhibitors. Chemistry and technology of fuels and oils, 2002, no. 5, pp. 23 -26.
4. Vipper A.B. On the study of the mechanism of action of additives to motor oils. Refining and petrochemistry. 2007, no. 1, pp. 35.
5. Allahverdiev M.A. On the reaction product of epichlorohydrin with furfural. Russian Journal of Organic Chemistry. 1995, vol. 31, no. 8, p.1252.
6. Abbasov V.M., Karimova N.G., Hasanov E.K. and others. Conservation oils based on salts of aromatic sulfonic acids and olefin nitration products. Processes of petrochemistry and oil refining. Baku, 2013, no.2 (13), pp. 14-16.
7. Balci M. Nuclear Magnetic Resonance
Spektroscopy. METU PRESS. ANKARA. 2000. 458p.
8. Abbasov V.M., Mahmudova L.A., Habibullaeva R.F., Alieva L.I., Talybov A.G. Influence of anti-corrosion additives on the properties of conservation liquids based on oil I-40. Neftepererabotka i neftechimiya -Oil refining and petrochemistry. 2008, no. 9, pp. 34-37. (In Russian).
9. Aliev Sh.R. Investigation of nitrogen-, sulfur- and phosphorus-containing derivatives of o-hydroxy alkyl thiophenols as additives to lubricating oils. Chemistry and Technology of Fuels and Oils. 2012, no.3, pp. 36-39. (In Russian).
10. Sharifova S.K. Synthesis and study of epoxy esters of aromatic acids and their derivatives Chemistry and Chemical Technology. 2014, no. 3, pp. 27-29. (In Russian).
11. Farzaliyev V.M., Aliyev S.R., Babayi R.M., Mammadova R.F. Synthesis of aminomethyl derivatives of Mercaptomethylmorpholine and their study as a preservative additive to oils. Azerbaijan Chemical Journal, 2012, no. 3, pp. 13-17.
3-MERKAPTO-2-HiDROKSiPROPiL-1-iZOBUTiL EFiRiNiN AMiNOMETiL TOR8M8L8RiNiN SiNTEZi VO ONLARIN SURTKU YAGLARINA MUHAFiZOEDiCi
A§QAR KiMi TODQiQi
V.M. Farzaliyev1, §.R. aliyev1, R.M. Babayi1, R.F. Mammadova1, Q.M. Quliyeva1,
A.M. Mammadov1, Q.§. Eyvazova1
1Azsrbaycan Respublikasi Elm vs Tshsil Nazirliyi akad. d.M. Quliyev adina A§qarlar Kimyasi institutu
AZ1029, Baki §., Boyuk^or §ossesi,2062-ci mshslls 2Azsrbaycan Respublikasi Elm vs Tshsil Nazirliyi akad. Y.H.Msmmsdsliyev adina Neft- Kimya Proseslsri
institutu, AZ 1025, Baki §., Xocali pr. 30
Xulasa: Muharrik va mexanizmlarda gedan elektrokimyavi korroziyaya qar§i mubariza xalq tasarrufati ahamiyyatli masalalardan biridir. Texnikada istifada olunan surtku yaglarinin muhafizaedici effektivliyi az oldugu u9un, onlar istifada zamani qisa va uzun muddatli dayanmalarda muharriklarin hissalarini korroziyadan qoruya bilmir. Bu problemin hallinin sada va rasional yolu tarkibinda effektli muhafizaedici (konservasiya) xassalara malik olan a§qarlarin istifadasidir. Bu a§qarlar surtku yaglannin xassalarini pisla§dirmir va onlara konservasiya xassasi verir. Sinton madda kimi goturulmu§ 3-merkapto-2-hidroksipropil-1-izobutil efirina Mannix reaksiyasi §araitinda ikili alifatik va heterotsiklik aminlarla tasir etmakla bir sira aminometil
tóramalari sintez edilmi§dir. 3-Merkapto-2-hidroksipropil-1-izobutil efirinin aminometil tóramalari yaglarda yax§i hall olur va saxlanma zamani stabildilar.
A?ar sozlar: kalium hidrosulfid, korroziya, mühafizaedici a§qar, sürtkü yaglari, piperidin, morfolin.
СИНТЕЗ АМИНОМЕТИЛЬНЫХ ПРОИЗВОДНЫХ 3-МЕРКАПТО-2-ГИДРОКСИПРОПИЛ-1-ИЗОБУТИЛОВОГО ЭФИРА И ИССЛЕДОВАНИЕ ИХ В
КАЧЕСТВЕ ЗАЩИТНЫХ ПРИСАДОК К СМАЗОЧНЫМ МАСЛАМ
В.М. Фарзалиев1, Ш.Р. Алиев1, Р.М. Бабаи1, Р.Ф. Мамедова1, Г.М. Кулиева1,
А.М. Мамедов2, Г.Ш. Ейвазова1
1 Институт Химии Присадок им.акад. А.М.Кулиева, AZ1029, г.Баку, Боюкшорское шоссе, квартал 2062 2Институт Нефтехимических Процессов им. акад. Ю.Г. Мамедалиева AZ1025, Баку, прос. Ходжалы, 30
Аннотация: Борьба с электрохимической коррозией в двигателях и механизмах - задача большого народнохозяйственного и оборонного значения. Смазочные масла, обычно используемые в технике, не обладают достаточными защитными свойствами и не способны эффективно предохранять ее от коррозии, как в процессе эксплуатации, так и при кратковременном и длительном бездействии. Одним из наиболее простых и рациональных путей решения этой проблемы является использование смазочных материалов, содержащих эффективные защитные (консервационные) присадки, которые, не ухудшая обычные рабочие свойства масел, придают им консервационные свойства. Действием на 3-меркапто-2-гидроксипропил-1-изобутиловый эфир, взятого в качестве синтона, вторичными алифатическими и гетероциклическими аминами в условиях реакции Манниха был синтезирован ряд аминометильных производных. Аминометильные производные 3-меркапто-2-гидроксипропил-1-изобутилового эфира хорошо растворяются в маслах и стабильны при хранении. Наилучшие результаты в испытаниях получены с 3-пиперидинометилтио-2-гидроксипропил-1-изобутиловым эфиром - в концентрации 1% в смазочном масле М-12 коррозия стальной пластины во влажной камере составляет 3%, в морской воде через 24 часа - 5%, коррозия стальной пластины под действием 0.1% раствора кислоты HBr - 3.5%. Эти результаты выше, чем у эталона промышленной добавки сукцинимидмочевины (СИМ).
Ключевые слова: гидросульфид калия, коррозия, защитная присадка, смазочные масла, пиперидин, морфолин.
