U.S. patent number 3,773,668 [Application Number 05/204,329] was granted by the patent office on 1973-11-20 for lubricating compositions.
This patent grant is currently assigned to Institut Francais du Petrole des Carburants et Lubrifiants. Invention is credited to Jacques Denis, Guy Parc.
United States Patent |
3,773,668 |
Denis , et al. |
November 20, 1973 |
LUBRICATING COMPOSITIONS
Abstract
Lubricating compositions, particularly useful for manufacturing
multigrade oils, hydraulic fluids, oils for industrial gears and
cutting oils, comprising 5 - 95 percent by weight of a hydrocarbon
oil produced according to a conventional process and 5-95 percent
by weight of a compound selected from the group consisting of the
esters of polyalkyleneglycol ethers complying with the general
formula: ##SPC1## Wherein R.sub.1 is a divalent hydrocarbon radical
having from one to 34 carbon atoms, R.sub.2 and R'.sub.2 are
divalent aliphatic radicals having from two to five carbon atoms,
R.sub.3 and R'.sub.3 are monovalent hydrocarbon radicals having
from one to twenty-five carbon atoms and n.sub.1 and n.sub.2 are
integers from two to 50, and those complying with the general
formula: ##SPC2## Wherein R.sub.4 is a hydrocarbon radical of
valency m, having from three to 15 carbon atoms, R.sub.5 is a
monovalent hydrocarbon radical having from one to 25 carbon atoms,
R.sub.2 is a divalent aliphatic radical having from two to five
carbon atoms, n is an integer from two to 50 and m is an integer
from two to four.
Inventors: |
Denis; Jacques (Ville d'Avray,
FR), Parc; Guy (Rueil Malmaison, FR) |
Assignee: |
Institut Francais du Petrole des
Carburants et Lubrifiants (Rueil-Malmaison, FR)
|
Family
ID: |
26216083 |
Appl.
No.: |
05/204,329 |
Filed: |
December 2, 1971 |
Foreign Application Priority Data
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|
|
|
|
Dec 3, 1970 [FR] |
|
|
7043605 |
Apr 15, 1971 [FR] |
|
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7113437 |
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Current U.S.
Class: |
508/494; 554/227;
560/199; 252/79; 560/198; 560/200 |
Current CPC
Class: |
C10M
1/08 (20130101); C10N 2020/01 (20200501); C10N
2040/22 (20130101); C10N 2040/241 (20200501); C10M
2209/104 (20130101); C10N 2040/042 (20200501); C10N
2040/044 (20200501); C10M 2207/282 (20130101); C10N
2040/242 (20200501); C10N 2040/04 (20130101); C10N
2040/246 (20200501); C10M 2205/02 (20130101); C10M
2209/106 (20130101); C10M 2207/281 (20130101); C10N
2040/247 (20200501); C10M 2207/34 (20130101); C10M
2209/109 (20130101); C10N 2040/24 (20130101); C10M
2209/11 (20130101); C10M 2215/068 (20130101); C10N
2040/244 (20200501); C10M 2203/10 (20130101); C10M
2207/289 (20130101); C10M 2209/103 (20130101); C10N
2040/245 (20200501); C10N 2040/08 (20130101); C10M
2203/102 (20130101); C10M 2209/084 (20130101); C10M
2205/00 (20130101); C10M 2215/086 (20130101); C10N
2040/02 (20130101); C10N 2040/243 (20200501); C10M
2207/283 (20130101); C10M 2215/28 (20130101); C10M
2209/105 (20130101); C10N 2040/046 (20200501); C10M
2207/286 (20130101); C10M 2209/107 (20130101); C10M
2203/108 (20130101) |
Current International
Class: |
C10m 001/26 () |
Field of
Search: |
;252/56R,56S,52A,79
;260/485P,485G |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wyman; Daniel E.
Assistant Examiner: Cannon; W.
Claims
What we claim is :
1. A lubricating composition containing from 5 to 95 percent by
weight of a compound (A) consisting of a hydrocarbon oil selected
among the solvent-refined mineral oils, from acid-refined mineral
oils, the hydrorefined oils and the synthetic oils obtained by
oligomerization of olefinic hydrocarbons having from two to 20
carbon atoms per molecule and from 5 to 95 percent by weight of a
compound (B) selected among the esters of polyalkyleneglycol ethers
resulting from the esterification of a polyalkyleneglycol and
polyol ether having the formula : ##SPC11##
wherein R.sub.4 is an aliphatic hydrocarbon radical of valency m,
having from three to 15 carbon atoms, R.sub.2 is a divalent
aliphatic radical having from two to five carbon atoms, n is an
integer from two to 50, and m is an integer from two to four, by a
mixture of monocarboxylic acids of the formula ##SPC12##
wherein
R.sub.5 is a monovalent aliphatic hydrocarbon radical having from
one to 25 carbon atoms and of dicarboxylic acids of the formula
##SPC13##
wherein R.sub.1 is a divalent aliphatic hydrocarbon radical having
from one to 34 carbon atoms.
2. A composition according to claim 1, in which compound (B) is an
ester of polypropyleneglycol ether.
3. A composition according to claim 1, further containing from 2 to
20 percent by weight of a third solvent selected from the group
consisting of: (a) esters of dicarboxylic acids and aliphatic
monoalcohols, and (b) esters of monocarboxylic acids and aliphatic
polyols.
4. A composition as defined by claim 1, wherein compound (B) is
selected from the group consisting of the esters resulting from the
simultaneous esterification of an ether obtained by condensation of
propylene oxide with trimethylol propane with a mixture, in a molar
ratio of 4/1, of dodecanoic acid and azelaic acid, and the esters
resulting from the simultaneous esterification of an ether obtained
by condensation of propylene oxide with trimethylolpropane with a
mixture, in a molar ratio of 8/1, of dodecanoic acid and
isononadecanedioic acid.
5. A composition according to claim 1, wherein R.sub.4, R.sub.2,
R.sub.5, and R.sub.1 are saturated aliphatic hydrocarbyl
groups.
6. A lubricating composition as defined by claim 1, wherein
compound (B) is an ester of poly(ethylene-propylene) glycol ether,
said glycol having a ratio of ethylene oxide:propylene oxide of not
more than 1:1 respectively.
Description
This invention relates to new lubricating compositions consisting
of mixtures of conventional hydrocarbon oils and derivatives of
polyalkyleneglycols.
The conventional base oils are prepared according to different
methods. The main processes for manufacturing these oils are the
acid or solvent refining of vacuum distillates or deasphalted
vacuum residues from crude oils, the hydrotreatment of the same
petroleum cuts and the oligomerization of olefinic
hydrocarbons.
In the first of these processes, a vacuum distillate or deasphalted
vacuum residue can be subjected to a solvent extraction for example
by means of furfurol or phenol, so as to eliminate from the
petroleum cut the aromatic compounds contained therein, then to a
series of treatments such as dewaxing, clay bleaching and moderate
hydrogenation, at a temperature of from 250.degree. to
350.degree.C, under a hydrogen pressure of 20 to 80 kg/cm.sup.2 in
the presence of a catalyst.
In the case of certain crude oils containing a small proportion of
aromatic compounds, it is possible to replace the solvent
extraction by an acid treatment, generally with sulfuric acid.
The second process, the hydrotreatment of the abovementioned
petroleum cuts, may be achieved, for example, according to the
teaching of U.S. Pat. No. 3,560,370, in the name of the
applicant.
In this Patent, the hydrotreatment is conducted at a temperature of
from 350.degree. to 450.degree.C, under a hydrogen pressure of from
80 to 240 kg/cm.sup.2 and in the presence of a catalyst.
In the third process, the oil is manufactured by oligomerizing
olefinic hydrocarbons having from two to 20 and preferably from
nine to 16 carbon atoms per molecule.
This oligomerization may be achieved by the action of catalysts
consisting of aluminium halides, or by the action of heat, in the
presence of organic peroxides acting as initiators.
The oils prepared according to the above-described processes
generally exhibit viscosity indexes of from 50 to 160 and, more
particularly, from 50 to 110 for solvent refined oils, from 50 to
150 for the hydrorefined oils and from 110 to 160 for the
oligomerization oils.
It can be observed that the oils obtained in the two last
above-described processes already exhibit much better
characteristics than those obtained by the first process. For their
various uses, all these oils require the addition, besides the
conventional additives such as detergents or antioxidants, of more
or less substantial amounts of viscosity additives, which however,
exhibit inherent disadvantages such as poor thermal and/or
mechanical stability.
Moreover, these conventional oils necessitate a compromise between
a low cold viscosity, a sufficient viscosity at high temperature
(100.degree.- 150.degree.C) and a low volatility.
It is known that the above mentioned drawbacks have been partly
avoided by adding to the conventional base oils a certain amount of
synthetic oils consisting of esters of polycarboxylic acids or of
polyols. The improvement achieved by the use of these products is
however very limited, with respect to the viscosity index.
It is an object of this invention to provide new lubricating
compositions exhibiting viscosity-temperature characteristics so
improved that the amount of viscosity additives that must be
incorporated thereto is very substantially decreased (or even
nullified). Consequently, their thermal stability and mechanical
resistance to shearing are also improved and their volatility is
reduced. Moreover, they exhibit such an exceptional lubricating
power that their use makes it possible to avoid mechanical
difficulties such as seizing and pitting, as well as to reduce the
wear of the machines lubricated therewith. These qualities are
particularly useful for lubricating engines operating under severe
conditions, hydraulic circuits, gears of various types as well as
in machining metals.
The present invention relates to new lubricating compositions which
contain generally a compound (A) consisting of a hydrocarbon oil
and a compound (B) selected amongst the esters of
polyalkyleneglycol ethers.
The hydrocarbon oil (A) is selected among the mineral oils obtained
either by solvent refining or by acid treatment, or by severe
hydrotreatment of vacuum distillates or deasphalted vacuum residues
from crude oils and the synthetic oils obtained by oligomerizing
olefinic hydrocarbons having from two to 20 carbon atoms per
molecule.
Generally, compound (B) results from the esterification of a
dicarboxylic acid by at least one ether of polyalkyleneglycol and
of monoalcohol or by the esterification of an ether of
polyalkyleneglycol and of polyol by at least one monocarboxylic
acid. More particularly, compound (B) complies with the general
formula : ##SPC3## (1)
wherein R.sub.1 is a divalent hydrocarbon radical having from one
to 34 carbon atoms, R.sub.2 and R'.sub.2 are divalent aliphatic
radicals having from two to five carbon atoms, R.sub.3 and R'.sub.3
are monovalent hydrocarbon radicals having from one to 25 carbon
atoms, and n.sub.1 and n.sub.2 are integers from two to 50, or with
the general formula : ##SPC4## (2)
wherein R.sub.4 is a hydrocarbon radical of valency m, having from
three to 15 carbon atoms, R.sub.5 is a monovalent hydrocarbon
radical having from one to 25 carbon atoms, R.sub.2 is a divalent
aliphatic radical having from two to five carbon atoms, n is an
integer from two to 50 and m is an integer from two to four, with
the provision that radicals R.sub.2 and R.sub.5 and integer n may
be different from one chain to another.
Compound (B) may also result from the esterification of an ether of
polyalkyleneglycol and of polyol having the formula : ##SPC5##
wherein R.sub.2, R.sub.4, n and m are defined as above, by means of
a mixture of monocarboxylic acids ##SPC6##
and dicarboxylic acids ##SPC7##
wherein R.sub.1 and R.sub.5 are defined as above.
Most of the esters of polyalkeneglycol ethers contemplated
according to this invention are miscible with mineral or synthetic
oils in rather large proportions, their miscibility with fluid oils
being better than with more viscous oils, and better with
naphthenic oils than with paraffinic oils.
Moreover, since the polyethyleneglycol derivatives, for a given
oil, are less easily miscible than those of polypropyleneglycol,
there are used preferably polypropyleneglycol derivatives or still
mixed derivatives of poly (ethylene-propylene)glycol in which the
ratio ethylene oxide/propylene oxide is kept lower than or equal to
1/1.
In this latter case, it is preferred to make use of mixed
derivatives complying with formulae (1) and (2) wherein the
radicals R.sub.3 and R'.sub.3 on the one hand and the radicals
R.sub.5 on the other hand are relatively heavy and contain for
example from 10 to 25 carbon atoms.
As examples of compounds (B) that can be used in the compositions
according to the invention, there can be mentioned :
the dodecanedioate of the ether obtained by condensation of
propylene oxide with isobutanol;
the decanedioate of the ether obtained by condensation of a mixture
of ethylene and propylene oxides (25/75 by weight) with 2-ethyl
hexanol;
the didodecanoate of the ether obtained by condensation of
propylene oxide with neopentylglycol;
the diisotridecanoate of the ether obtained by condensation of
propylene oxide with 1,6-hexanediol;
the trinonanoate of the ether obtained by condensation of propylene
oxide with trimethylolpropane;
the triethylhexanoate of the ether obtained by condensation of
propylene oxide with glycerol;
the trioleate of the ether obtained by condensation of a mixture of
ethylene and propylene oxides (50/50 by weight) with
trimethylolhexane;
the tetraheptanoate of the ether obtained by condensation of
propylene oxide with pentaerythritol;
the ester resulting from the simultaneous treatment of the ether
obtained by condensation of propylene oxide with trimethylolpropane
by a mixture, in a molar ratio of 2/1, of heptanoic acid and
dodecanoic acid;
the ester resulting from the simultaneous treatment of the ether
obtained by condensation of propylene oxide with trimethylolpropane
by a mixture, in a molar ratio of 4/1, of dodecanoic acid and
azelaic acid; and
the ester resulting from the simultaneous treatment of the ether
obtained by condensation of propylene oxide with trimethylolpropane
by a mixture, in a molar ratio of 8/1, of dodecanoic acid and
isononadecanedioic acid.
The compositions according to the invention may contain the
hydrocarbon oil (A) in a major proportion (50 to 95 percent by
weight) as compared with the ester of polyalkyleneglycol ether (B)
(5 to 50 percent by weight), or, on the contrary, the compound (B)
may be present in a major proportion (50 to 95 percent by weight)
as compared with the compound (A) (5 to 50 percent by weight). More
generally, the compositions containing from 5 to 95 percent by
weight of each of the compounds (A) and (B) are to be
considered.
In order to increase the miscibility of compounds (A) and (B), it
may be contemplated to add to their mixture an amount of about 2 to
20 percent by weight of a third solvent such as an ester of
dicarboxylic acid or of polyol, e.g., isodecyl adipate,
trimethylhexyl azelate, neopentylglycol pelargonate, ethylhexyl
sebacate, trimethylolpropane tripelargonate.
The compositions of the invention may be used for manufacturing
motor oils and particularly multigrade oils; they are also
advantageously used for manufacturing hydraulic fluids, oils for
gear-boxes, oils for industrial gears or oils for the cut or the
forming of metals. In all these applications, the lubricating and
anti-wear properties of the compositions according to the invention
appear of particular interest since they permit a good working
security and an extended life for the mechanisms lubricated
therewith.
The esters of polyalkyleneglycol ethers used in the lubricating
compositions of the invention may be prepared by direct
esterification of the ether obtained by condensing at least one
alkylene oxide with the suitable monoalcohol or polyol, by means of
one or more convenient mono or dicarboxylic acids, in the presence
of a convenient catalyst, the water produced being removable by
azeotropic entrainement by means of a solvent.
After the end of the reaction, the remaining acidic products may be
removed either by washing with a hydroalcoholic potash solution and
then with water or by clay treatment. The solvent is then expelled
under vacuum and the residue, consisting of the ester of
polyalkyleneglycol ether, may be recovered without having to be
distilled.
The following examples illustrate the invention but are not to be
considered in any way as limiting the scope thereof.
EXAMPLES 1 to 13
In these examples, various compositions according to the invention
have been prepared by determining the proportions of hydrocarbon
oil and of polyalkyleneglycol compound so as to obtain multigrade
oils having given viscosity characteristics.
By way of comparison, an attempt has been made to prepare
multigrade oils exhibiting the same viscosity characteristics from
pure hydrocarbon oils (examples 3, 5, 7, 9, 11 and 13).
The desired characteristics are indicated in Table I, below :
##SPC8##
To each of the base mixtures indicated in Table II, 6 percent by
weight of an anti-oxidant and detergent additive has been added.
The amount of viscosity additive (polymethacrylate) required for
obtaining the desired characteristics have been reported. TABLE II
##SPC9##
Test of Lubricating Power
A lubricating composition consisting of 50 percent by weight of 150
neutral mineral oil and 50 percent by weight of trioleate of the
ether obtained by condensation of a 50--50 mixture of ethylene
oxide and propylene oxide with trimethylolpropane, has been tested
for its anti-wear properties and its load capacity.
By way of comparison, a pure 150 neutral mineral oil and the same
oil containing 1 percent by weight of zinc dialkyldithiophosphate
of a commercial quality, have been also tested.
The tests have been carried out with a four balls E.P. machine.
The conditions of the anti-wear test are :
running speed : 1,500 runs per minute,
constant load : 30 kgf,
duration : 1 hour.
The average diameter of the three lower balls is an indication of
the anti-wear power under limit lubrication conditions.
The properties of load capacity have been tested according to the
standardized method ASTMD 2596 or federal test method standard 791
D No. 6503 - I
The results of the tests are given in Table III below :
##SPC10##
These results show that, in addition to the improved viscosity
performances, the lubricating compositions of the invention exhibit
anti-wear properties and a charge capacity particularly
satisfactory, which permit, if desired, to avoid the use of
specific additives, which otherwise may result in some drawbacks
such as :
an insufficient resistance to hydrolysis ;
a relatively low thermal stability.
* * * * *