DOI: https://doi.org/10.15587/1729-4061.2017.118784

Synergism of stable nitroxyl radicals and amines during the oxidation process of motor fuels and oils at increased temperatures

Oleksandr Vasylkevych, Oleksii Kofanov, Olena Kofanova, Kostiantyn Tkachuk

Abstract


The alkylphenol Mannich bases (N-(4-methylphenyl)-N,N-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)amine, N,N-dibenzyl-N-(3,5-di-tert-butyl-4-hydroxybenzyl)amine and tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine), which are promising antioxidants for fuels and lubricants, were synthesized by condensation of 2,6-di-tert-Butylphenol with formaldehyde and amines (n-toluidine, dibenzylamine and ammonia). Mannich bases also were synthesized by condensation of alkylphenols with diethylenetriamine.

The induction periods of the fuels and lubricants oxidation on the example of the vaseline oil at a temperature of 200 oC were determined by the method of oxygen absorption for the obtained Mannich bases and stable nitroxyl radicals (in particular 2,2,6,6-tetramethyl-4-oxopiperidin-1-oxyl and di-(2,2,6,6-tetramethyl-1-oxyl-4-piperidyl)isophthalate). It was found that in the case of the inhibited oxidation of hydrocarbons of fuels and lubricants, even at high temperatures (~200 oC), there is also a synergetic effect of stable nitroxyl radicals with the nitrogen-containing compounds, including the alkylphenol Mannich bases, which have −NH or β-CH< groups in relation to Nitrogen. So, the obtained results confirm the perspectiveness of the alkylphenol Mannich bases usage as the high-temperature oxidation inhibitors for fuels and lubricants (motor fuels and oils).


Keywords


Mannich base; additive; additives to fuels and lubricants; antioxidant; stable nitroxyl radicals.

References


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Fairfull-Smith, K. E., Blinco, J. P., Keddie, D. J., George, G. A., Bottle, S. E. (2008). A Novel Profluorescent Dinitroxide for Imaging Polypropylene Degradation. Macromolecules, 41 (5), 1577–1580. doi: 10.1021/ma701944p

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Kachovec, J., Pospišil, J. (1968). Prehled komercnich antioxidantu. Dodatek k monografii. J. Pospišil: Antioxidanty, 10.

Anisimov, I. G., Badyshtova, K. M., Bnatov, S. A. et. al.; Shkol'nikov, V. M. (Ed.) (1999). Fuels, lubricants, technical liquids. Assortment and application. Moscow: Izdatel'skiy tsentr "Tekhinform", 596.

Ferrar, M. W., Groves, W. (1965). Pat. No. 3173952 USA. Tris-(3,5-Dialkyl-4-hydroxy-benzyl)amines. published: 16.03.65.

Volod'kin, A. A., Ershov, V. V. (1962). Spatially hindered phenols. Message 1. Synthesis of some 3,5-di-tert-butylphenol-4-oxybenzamines. Izv. AN SSSR, 2, 343–345.

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GOST Style Citations


Pat. No. 494396 USSR. A stabilized composition based on the polyolefin [Text] / Aleksandrov, A. L., Kovtun, G. A., Golubev, V. A., Berezin, M. P., Makhonina, L. I. – No. 2037113; declareted: 17.06.1974; published: 03.08.1976, Bul. No. 45.

Sakai, K. Effective 2,6-substitution of piperidine nitroxyl radical by carbonyl compound [Text] / K. Sakai, K. Yamada, T. Yamasaki, Y. Kinoshita, F. Mito, H. Utsumi // Tetrahedron. – 2010. – Vol. 66, Issue 13. – P. 2311–2315. doi: 10.1016/j.tet.2010.02.004 

Rozantsev, E. G. Free iminoxyl radicals [Text] / E. G. Rozantsev. – Мoscow: Khimiya, 1970. – 216 p.

Fairfull-Smith, K. E. A Novel Profluorescent Dinitroxide for Imaging Polypropylene Degradation [Text] / K. E. Fairfull-Smith, J. P. Blinco, D. J. Keddie, G. A. George, S. E. Bottle // Macromolecules. – 2008. – Vol. 41, Issue 5. – P. 1577–1580. doi: 10.1021/ma701944p 

Coseri, S. One-shot carboxylation of microcrystalline cellulose in the presence of nitroxyl radicals and sodium periodate [Text] / S. Coseri, G. Biliuta, L. F. Zemljič, J. S. Srndovic, P. T. Larsson, S. Strnad et. al. // RSC Advances. – 2015. – Vol. 5, Issue 104. – P. 85889–85897. doi: 10.1039/c5ra16183e 

Hodgson, J. L. One-Electron Oxidation and Reduction Potentials of Nitroxide Antioxidants: A Theoretical Study [Text] / J. L. Hodgson, M. Namazian, S. E. Bottle, M. L. Coote // The Journal of Physical Chemistry A. – 2007. – Vol. 111, Issue 51. – P. 13595–13605. doi: 10.1021/jp074250e 

Kovtun, G. A. Oxidation of aliphatic amines by molecular oxygen. Message 4. Regeneration of inhibitors in the oxidizing tertiary amines [Text] / G. A. Kovtun, A. L. Aleksandrov // Izv. AN SSSR. Ser.: Himiya. – 1974. – Issue 6. – P. 1274–1279.

Denisov, E. T. Autocatalysis by the Nitroxyl Radical in the Cyclic Mechanism of Chain Termination in Polymer Oxidation [Text] / E. T. Denisov // Kinetics and Catalysis. – 2016. – Vol. 57, Issue 6. − P. 750–757. doi: 10.1134/s0023158416060057 

Tikhonov, I. V. Stable nitroxyl radicals and hydroxylamines as inhibitors of methyl linoleate oxidation in micelles [Text] / I. V. Tikhonov, E. M. Pliss, L. I. Borodin, V. D. Sen’, T. S. Kuznetsova // Russian Chemical Bulletin. – 2015. – Vol. 64, Issue 10. – P. 2438–2443. doi: 10.1007/s11172-015-1175-0 

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Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds [Text] / R. G. Hicks (Ed.). – Chichester: John Wiley and Sons, 2010. – 588 p. doi: 10.1002/9780470666975 

Bakhturidze, G. Sh. Oxidation of amines by molecular oxygen. Message 9. Liquid-phase oxidation of dimethylamine [Text] / G. Sh. Bakhturidze, A. L. Aleksandrov, I. L. Edilashvili // Izv. AN SSSR. Ser.: Himiya. – 1979. – Issue 3. – P. 515–519.

Pat. No. 7683144 B2 USA. Process for Chain Stopping of PVC Polymerization [Text] / Pfaendner R., Wegmann A., Wannemacher T., Braun D. – No. US 10/513,179; declareted: 23.03.2003; published: 23.05.2010.

Pat. No. 8008423 B2 USA. Stabilized Polyolefin Compositions [Text] / Kumar V., Kumar R., Dhawan A., Yang S., Cholli A. L. – No. US 12/789,832; declareted: 28.05.2010; published: 30.08.2011.

Pat. No. 8710266 B2 USA. Nitrogen and Hindered Phenol Containing Dual Functional Macromolecular Antioxidants: Synthesis, Performances and Applications [Text] / Kumar R., Yang S., Kumar V., Cholli A. L. – No. US 13/298,948; declareted: 17.11.2011; published: 29.04.2014.

Kachovec, J. Prehled komercnich antioxidantu. Dodatek k monografii [Text] / J. Kachovec, J. Pospišil // J. Pospišil: Antioxidanty. − 1968. – P. 10.

Anisimov, I. G. Fuels, lubricants, technical liquids. Assortment and application [Text]: handbook / I. G. Anisimov, K. M. Badyshtova, S. A. Bnatov et. al.; V. M. Shkol'nikov (Ed.). – izd. 2-e pererab. i dop. – Moscow: Izdatel'skiy tsentr "Tekhinform", 1999. – 596 p.

Pat. No. 3173952 USA. Tris-(3,5-Dialkyl-4-hydroxy-benzyl)amines [Text] / Ferrar M. W., Groves W. – published: 16.03.65.

Volod'kin, A. A. Spatially hindered phenols. Message 1. Synthesis of some 3,5-di-tert-butylphenol-4-oxybenzamines [Text] / A. A. Volod'kin, V. V. Ershov // Izv. AN SSSR. – 1962. – Issue 2. – P. 343–345.

Sanin, P. I. Installation for the oxidation of organic substances with the automatic compensation and registration of consumable oxygen [Text] / P. I. Sanin, L. F. Chernyavskaya, V. V. Sher et. al. // Neftehimiya. – 1966. – Vol. 6, Issue 1. – P. 112–114.







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ISSN (print) 1729-3774, ISSN (on-line) 1729-4061