U.S. patent number 3,764,534 [Application Number 05/115,811] was granted by the patent office on 1973-10-09 for new lubricating compositions.
This patent grant is currently assigned to Institut Francais du Petrole, des Carburants et Lubrifiants. Invention is credited to Claude Blejean, Bernard Bourdoncle.
United States Patent |
3,764,534 |
Blejean , et al. |
October 9, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
NEW LUBRICATING COMPOSITIONS
Abstract
A lubricating composition comprising a lubricating oil and at
least one thioorganometallic complex of the general formula :
##SPC1## In which M is selected from the transition metals and
zinc, cadmium, tin, lead, antimony and bismuth; n is the oxidation
degree of M, R.sub.1 and R.sub.2 are each a monovalent hydrocarbon
radical having one to 20 carbon atoms and 0 to 3 heteroatoms
selected from the group consisting of halogen, oxygen, sulfur and
nitrogen; Y is selected from the hydrogen atom and the radicals R',
R'O, R'S and R'CO in which R' is a hydrocarbon radical of one to 20
carbon atoms; Y and R.sub.1 or R.sub.2 may form a divalent
hydrocarbon radical containing one to 20 carbon atoms and 0-3
heteroatoms selected from oxygen, sulfur and nitrogen; and each
atom Z is oxygen or sulfur, at least one of the 2n atoms Z being
sulfur.
Inventors: |
Blejean; Claude (Paris,
FR), Bourdoncle; Bernard (Rueil Malmaison,
FR) |
Assignee: |
Institut Francais du Petrole, des
Carburants et Lubrifiants (Rueil Malmaison, FR)
|
Family
ID: |
9051138 |
Appl.
No.: |
05/115,811 |
Filed: |
February 16, 1971 |
Foreign Application Priority Data
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Feb 23, 1970 [FR] |
|
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7006455 |
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Current U.S.
Class: |
508/568;
252/400.51; 508/567; 252/74 |
Current CPC
Class: |
C10M
1/08 (20130101); C10M 2223/045 (20130101); C10M
2290/02 (20130101); C10N 2010/12 (20130101); C10N
2010/10 (20130101); C10N 2040/08 (20130101); C10N
2010/08 (20130101); C10N 2040/16 (20130101); C10N
2010/16 (20130101); C10N 2010/06 (20130101); C10M
2219/106 (20130101); C10M 2219/082 (20130101); C10N
2050/10 (20130101); C10M 2219/104 (20130101); C10N
2010/02 (20130101); C10M 2207/34 (20130101); C10M
2207/282 (20130101); C10N 2010/14 (20130101); C10M
2219/10 (20130101); C10M 2219/102 (20130101); C10N
2040/17 (20200501); C10N 2010/04 (20130101); C10M
2219/084 (20130101) |
Current International
Class: |
C10m 001/38 () |
Field of
Search: |
;252/42.7,46.4,74,400,DIG.11 ;260/429J |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Martell et al. "Chemistry of the Metal Chelate Compounds"
Prentice-Hall 1956 pages 168-169..
|
Primary Examiner: Wyman; Daniel E.
Assistant Examiner: Cannon; W.
Claims
What we claim as this invention is:
1. A lubricating composition comprising a lubricating oil and from
0.05 to 5 percent by weight with respect to the oil of at least one
thioorganometallic complex of the general formula: ##SPC11##
in which M is a metal in the divalent state selected from the group
consisting of the transition metals, zinc, cadmium, tin and lead; n
is 2; R.sub.1 and R.sub.2 when taken individually are each selected
from the group consisting of a monovalent hydrocarbon radical of
one to 20 carbon atoms, a halohydrocarbon radical of one to 20
carbon atoms and a methoxy phenyl radical; Y when taken
individually is selected from the group consisting of the hydrogen
atom and the radicals R', R'O, R'S and R'CO in which R' is a
hydrocarbon radical of one to 20 carbon atoms; Y and R.sub.1, when
taken together, form a divalent hydrocarbon radical of one to 20
carbon atoms; and each atom Z is oxygen or sulfur, providing that
at least one of the Z atoms of the complex is sulfur.
2. A lubricating composition according to claim 1, wherein the
lubricating oil is selected from base oils of petroleum origin and
synthetic lubricants.
3. A lubricating composition according to claim 1, wherein the
content of the thioorganometallic complex is 0.2 - 2 percent by
weight.
4. A lubricating composition according to claim 1 wherein all Z are
sulfur and M is selected from the group consisting of nickel,
cobalt and zinc.
5. A lubricating composition according to claim 4 wherein M is
nickel.
6. A lubricating composition according to claim 4 wherein M is
zinc.
Description
This invention relates to the use of thioorganometallic complexes
as additives, for example in lubricating compositions, transmission
fluids, transformer oils, greases and elastomers.
It relates particularly to lubricating compositions comprising at
least one lubricating oil and at least one of said
thioorganometallic complexes, said compositions having an
unexpectedly increased stability to oxidation.
A known technique for improving the stability of lubricants and
particularly motor oils to oxidation consists of adding
antioxidants thereto, said antioxidants being usually zinc
dithiophosphates, dithiocarbamates, phenols or amines.
These products have one or more of the following disadvantages:
-- their antioxidant activity is rather low, particularly in the
presence of such metals as iron and copper,
-- they are affected by temperature increases,
-- they produce sludge,
-- they are corrosive with respect to certain engine parts, for
example the silver bearings.
It has now unexpectedly been found that the thioorganometallic
complexes hereafter defined have a high antioxidant activity, even
at high temperature and in the presence of metals at high
concentrations. These compounds may be used as well with base oils
of petroleum origin as with synthetic base oils. They give good
anti-wear and extreme pressure properties to the lubricating oils
to which they are added. The lubricating compositions of this
invention contain at least one thioorganic complex of the formula:
##SPC2##
These thioorganometallic complexes are based on the element M which
may be tin, antimony, lead, bismuth, zinc, cadmium or a transition
metal element, for example chromium, manganese, iron, cobalt,
nickel or copper, said element M, at the oxidation degree n, being
linked with n coordinates, either identical or different, as
hereinafter defined:
R.sub.1 and R.sub.2 are each a monovalent radical which may be a
hydrocarbon radical, for example an aliphatic, alicyclic or
aromatic radical, or a halo- or nitro-derivative thereof. They may
contain 1 to 3 heteroatoms such as oxygen, sulfur or nitrogen. They
usually contain one to 20 carbon atoms.
Y is a hydrogen atom or a radical R', R'-O-, R'-S- or R'-CO- in
which R' is a monovalent hydrocarbon radical of, for example, 1 to
20 carbon atoms.
Y and R.sub.1 or R.sub.2 may form a divalent hydrocarbon radical of
one to 20 carbon atoms with 0 to 3 oxygen, sulfur or nitrogen
atoms.
Each atom Z may be oxygen or sulfur, provided that at least one Z
is sulfur in at least one of the coordinates.
Each coordinate may have two mesomeric forms each having a negative
charge: ##SPC3##
It may be represented by only one formula: ##SPC4##
The following monovalent radicals are illustrative of R.sub.1 and
R.sub.2 : methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.
butyl, tert. butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl,
decyl, undecyl, dodecyl, heptadecyl, methoxy, ethoxy, propoxy,
butoxy, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl,
phenethyl, cumyl, para-iodophenyl, para-nitrobenzyl, methoxyphenyl,
vinylpropenyl, 2-butenyl-3-pentenyl, ethynyl, propynyl,
2-furyl,2-thienyl and trifluoromethyl.
The following monovalent radicals are illustrative of Y:
Methyl, ethyl, isopropyl, sec. butyl, octyl, decyl, dodecyl,
phenyl, benzyl, methoxy, ethoxy, propoxy, methylthio, ethylthio,
acetyl, propionyl, phenethyl, cyclopentyl, cyclohexyl and
cycloheptyl.
The following compounds are illustrative of the compounds which may
be used in this invention: ##SPC5## ##SPC6## ##SPC7##
The thioorganic complexes may be manufactured according to known
methods, e.g., U. S. patent 3,184,410, especially at Column 2,
lines 6-7 and 51-53 pertaining to molybdenum complexes, as well as
the Bulletin of the Chemical Society of Japan, Volume 40, 2819-2822
(1967).
For example they can be manufactured from the corresponding .beta.
- diketones. In some cases, when the desired .beta. - diketones is
not available, they may be manufactured by any convenient method,
for example by reacting an ester with a monoketone. When the Y
group is not hydrogen, it may be directly linked to the .beta. -
diketone or after that a thiorganic complex has been formed with it
or one of its sulfur derivatives. For example a sodium salt of a
.beta. - diketone may be reacted with an alkyl halide to obtain an
alkyl group representative of Y.
The synthesis of the thioorganic complexes which are used in this
invention comprises the step of sulfurizing the available or
manufactured .beta. - diketone. This sulfurization is carried out
according to any known method. Hydrogen sulfide may be used, for
example, as the sulfurizing agent, either in acidic medium or not,
optionally in a solvent. This sulfurization may be carried out in
the presence of a salt of the desired metal. In that case there is
obtained the desired thioorganic complex or a mixture of complexes
of the given formula. When the sulfurization is carried out without
a metal salt, there is obtained, in some cases, a mono-thioketone
or a dithioketone, or a mixture of both, or a mixture of one or two
of them with the starting .beta. - diketone. It is sufficient as a
rule, to contact the desired salt of metal with the ketones or
their mixtures to obtain a thioorganic complex or a mixture of
thioorganic complexes of the given formula.
The present invention applies to all types of base oils, for
example those obtained by extracting petroleum fractions with
solvents or by any other refining or synthesis process.
The thioorganic complexes are added to the base oils in low
proportions, for example from 0.05 to 5 percent by weight and
preferably from 0.2 to 2 percent by weight.
The outstanding antioxidant properties that the thioorganic
complexes confer to the lubricating oils appear to result from the
hydroperoxides destruction power and the reactivity with free
radicals of these complexes.
The anti-wear and extreme-pressure properties are related to the
power of these complexes to adhere on the metal surfaces, which
results in a protection of the latter.
The following examples are given for illustration purposes.
EXAMPLES 1 TO 5
The thioorganometallic complexes of table I have been admixed with
the base oils in the given amounts. The resulting mixtures have
been subjected to a particularly severe oxidation test: the sample
is vigorously stirred with iron naphthenate (6 ppm) and lead oxide
(6 grams per liter) at 160.degree.C in oxygen: the amount of oxygen
absorbed in 7 hours is noted. The lower this amount, the better the
resistance to oxidation of the mixture.
By way of comparison a pure base oil of the solvent type, a base
oil of the solvent type containing a conventional antioxidant and a
pure synthetic oil of the ester type have been subjected to the
same test. The results are given in table I ##SPC8##
EXAMPLES 6 TO 8
The thioorganic complexes of table II have been admixed with base
oils in the amounts given in table II.
The resulting mixtures have been subjected to tests according to
the "Federal Test Method Standard" 791 a No 6 503 of Dec. 30, 1961.
There was used a "Precision Shell Four Ball E.P. Tester" machine
working at 1,500 rpm.
By way of comparison, the same tests have been carried out with a
pure base oil and a base oil containing a conventional
extreme-pressure additive. The results, expressed as the charge
before soldering, are given in table II. ##SPC9##
EXAMPLES 9 TO 12
The thioorganometallic complexes of table I have been admixed with
a base oil in the specified amounts. The resulting mixtures have
been subjected to a severe oxidation test: a sample is vigorously
stirred with iron naphthenate (6ppm) and lead oxide (6 grams per
liter) at 160.degree.C in oxygen: the oxygen amount absorbed in 7
hours is noted. The lower this amount the higher the resistance to
oxidation of the mixture.
The results are given in table III ##SPC10##
* * * * *