Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 1, pp. 94−97.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
G.N. Kirichenko, V.I. Glazunova, A.A. Desyatkin, A.G. Ibragimov, U.M. Dzhemilev, 2009, published in Zhurnal Prikladnoi Khimii,
2009, Vol. 82, No. 1, pp. 94−98.
ORGANIC SYNTHESIS AND INDUSTRIAL
Synthesis of New Polyfunctional Additives to Lubricating Oils
G. N. Kirichenko, V. I. Glazunova, A. A. Desyatkin, A. G. Ibragimov, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Received April 9, 2008
Abstract—Possibility of synthesizing new polyfunctional sulfur-, phosphorus-, and zinc-containing compounds
with anti-wear and anti-scuff properties, promising as high-efficiency additives to lubricating oils, was studied.
Alkyl, cycloalkyl, and aryl dithiophospates of metals
(Zn, Mo, Ba, Cu, Ca) are widely used as additives
improving the lubricating, antioxidant, and anticorrosive
properties of mineral oils [1–4]. Heteroatomic compounds
containing nitrogen, boron, phosphorus, and sulfur atoms
are introduced into these additives to improve their
efﬁ ciency . The effect of heteroatomic additives is
based on that a metal-organic ﬁ lm is formed and prevents
direct contact between friction surfaces. In addition,
owing to the low, compared with steel, melting point of
iron sulﬁ de in the case of sulfur-containing additives, the
sulﬁ de ﬁ lm precludes scufﬁ ng and seizure of contacting
In order to extend the range of highly efﬁ cient and
competitive polyfunctional additives to transmission
oils, which would be promising for practical use
and simultaneously exhibit anti-wear and anti-scuff
properties, new types of additives were synthesized from
zinc dithiophosphates containing trithiolane substituents
produced from readily accessible methylol norbornene
and aliphatic and cyclic alcohols as raw materials.
The compounds synthesized were analyzed by the
GLC method on Khrom-5 and Khrom-41 instruments,
with a ﬂ ame-ionization detector, 1.2 m × 3 mm and 2.4 m ×
3 mm columns packed with 5% SE on N-AW Chromaton,
and helium as carrier-gas (50 ml min
). 1H NMR spectra
were recorded on an Tesla BS-467 instrument (60 MHz)
relative to TMS in CDCl3, and 13C NMR spectra, on
a Jeol-FX-90Q spectrometer with broadband proton
suppression in the homoresonance mode with partial
retention of the nuclear Overhauser effect, in CDCl
relative to TMS. Mass spectra were obtained on an MX-
1306 instrument with an ionizing electron energy of
70 eV and ionization chamber temperature of 200°C.
The anti-wear and anti-scuff properties of the zinc
dithiophosphates synthesized were tested on a four-ball
friction machine with ShKh-15 steel balls 12.7 mm in
diameter at a relative sliding velocity of friction surfaces
of 0.54 m s
and rotation rate of 1420 rpm. The zinc
dithiophosphates were introduced into TS-14.5 oil in an
amount providing that the sulfur content was about
0.8 wt %, The mean Hertz load (MHL), critical load P
and welding load P
were determined with a step-by-step
increase in the load.
A thermostated glass reactor equipped with an efﬁ cient
stirrer, thermometer, and reﬂ ux condenser was charged
with 50 mmol of 2-methylolbicyclo[2.2.1]hept-5-ene
(1) (4 : 1 mixture of stereoisomers of endo and exo
conﬁ gurations) and 1 mol % catalyst. The temperature was
raised to 125°C and 150 mmol of elementary sulfur was
added under vigorous agitation in the course of 30 min.
The reaction mass was agitated for 6 h and then cooled.
The reaction products were extracted with petroleum ether
(bp 42–64°C), which was then removed in a vacuum at
room temperature. Column chromatography was used to
(2) from the residue as a mixture of endo-and exo-isomers
in total yield of 75%; bp 54.5–55°C. 1H NMR spectrum,
δ, ppm: 1.29–2.00 (m, 5H, CH
), 2.17–2.48 (m, 2H, CH),
3.32–3.75 (m, 2H, CHS), 3.93–4.00, 4.24 + –4.31 (m,