U.S. patent number 3,773,664 [Application Number 05/179,159] was granted by the patent office on 1973-11-20 for basic barium-containing compositions.
This patent grant is currently assigned to The Lubrizol Corporation. Invention is credited to William Monroe Lesuer.
United States Patent |
3,773,664 |
Lesuer |
November 20, 1973 |
BASIC BARIUM-CONTAINING COMPOSITIONS
Abstract
Compositions useful to improve power transmission in automatic
transmission fluids, hydraulic fluids and the like as replacements
for basic barium salts of sperm oil are obtained by reacting an
excess of a barium base with the combination of a phenol
(preferably an alkylphenol), a fatty acid and an alcohol, wherein
the fatty acid and alcohol together contain at least 26 carbon
atoms in straight-chain configuration. The compositions are
preferably further reacted with carbon dioxide, and they may
additionally be reacted with about 1-5% of anthranilic acid.
Inventors: |
Lesuer; William Monroe
(Cleveland, OH) |
Assignee: |
The Lubrizol Corporation
(Wickliff, OH)
|
Family
ID: |
22655469 |
Appl.
No.: |
05/179,159 |
Filed: |
September 9, 1971 |
Current U.S.
Class: |
508/457; 508/454;
508/586; 508/460; 554/71; 554/156 |
Current CPC
Class: |
C10M
159/22 (20130101); C10M 2203/024 (20130101); C10M
2215/28 (20130101); C10M 2213/062 (20130101); C10M
2215/225 (20130101); C10M 2215/202 (20130101); C10M
2217/023 (20130101); C10M 2205/00 (20130101); C10M
2209/02 (20130101); C10M 2219/022 (20130101); C10M
2227/02 (20130101); C10M 2203/022 (20130101); C10M
2209/111 (20130101); C10M 2207/123 (20130101); C10M
2229/05 (20130101); C10M 2215/082 (20130101); C10M
2223/04 (20130101); C10M 2223/065 (20130101); C10M
2207/286 (20130101); C10M 2219/083 (20130101); C10N
2050/10 (20130101); C10M 2201/02 (20130101); C10M
2203/06 (20130101); C10M 2211/06 (20130101); C10M
2205/026 (20130101); C10M 2207/302 (20130101); C10M
2207/404 (20130101); C10M 2215/226 (20130101); C10M
2225/04 (20130101); C10M 2207/34 (20130101); C10M
2215/26 (20130101); C10N 2040/02 (20130101); C10M
2207/40 (20130101); C10M 2215/06 (20130101); C10M
2207/021 (20130101); C10N 2010/04 (20130101); C10M
2207/028 (20130101); C10M 2207/282 (20130101); C10M
2215/12 (20130101); C10M 2229/041 (20130101); C10M
2215/22 (20130101); C10M 2219/024 (20130101); C10M
2219/082 (20130101); C10M 2223/12 (20130101); C10M
2229/044 (20130101); C10M 2215/30 (20130101); C10M
2203/02 (20130101); C10M 2207/281 (20130101); C10M
2213/02 (20130101); C10M 2217/046 (20130101); C10M
2223/042 (20130101); C10M 2209/084 (20130101); C10M
2219/068 (20130101); C10M 2207/22 (20130101); C10M
2215/221 (20130101); C10M 2219/044 (20130101); C10M
2229/04 (20130101); C10M 2207/283 (20130101); C10M
2209/00 (20130101); C10M 2207/402 (20130101); C10M
2209/103 (20130101); C10M 2219/087 (20130101); C10M
2223/041 (20130101); C10M 2207/046 (20130101); C10M
2215/04 (20130101); C10M 2219/046 (20130101); C10M
2225/041 (20130101); C10M 2229/043 (20130101); C10M
2203/04 (20130101); C10M 2207/125 (20130101); C10M
2209/109 (20130101); C10M 2211/08 (20130101); C10M
2215/086 (20130101); C10M 2219/088 (20130101); C10M
2207/027 (20130101); C10M 2207/18 (20130101); C10M
2209/086 (20130101); C10M 2209/104 (20130101); C10M
2217/06 (20130101); C10M 2223/045 (20130101); C10N
2020/01 (20200501); C10M 2201/063 (20130101); C10M
2207/262 (20130101); C10M 2209/105 (20130101); C10M
2209/108 (20130101); C10M 2229/042 (20130101); C10N
2070/02 (20200501); C10M 2209/10 (20130101); C10M
2215/08 (20130101); C10M 2219/089 (20130101); C10M
2229/02 (20130101); C10M 2205/024 (20130101); C10M
2207/129 (20130101); C10N 2040/08 (20130101) |
Current International
Class: |
C10M
159/22 (20060101); C10M 159/00 (20060101); C10m
003/48 () |
Field of
Search: |
;252/18,40.5,33.6,40.7,42.7,51.5A ;260/414 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wyman; Daniel E.
Assistant Examiner: Sneed; H. M. S.
Claims
What is claimed is:
1. An oil-soluble, basic composition containing barium as the only
metallic element, said composition being prepared by reacting (A) a
barium base with a mixture comprising (B) a phenol, (C) at least
one fatty acid and (D) at least one aliphatic monohydric alcohol,
each of reagents C and D containing a straight chain of carbon
atoms such that at least 26 carbon atoms in straight-chain
configuration are present in the combination of said reagents C and
D, the ratio of equivalents of reagent A to the combination of
reagents B, C and D being at least about 1.5:1.
2. A composition according to claim 1 which has been further
reacted with carbon dioxide until the base number thereof
(phenolphthalein indicator) is below about 10.
3. A composition according to claim 2 wherein reagent B is a phenol
containing an alkyl substituent having at least about 6 carbon
atoms.
4. A composition according to claim 3 wherein reagent C contains
about 16-20 carbon atoms.
5. A composition according to claim 4 wherein reagent D is a
mixture of normal C.sub.12.sub.-20 primary alcohols.
6. A composition according to claim 5 wherein reagent C is tall oil
acid.
7. A composition according to claim 6 wherein reagent B is
heptylphenol.
8. A composition according to claim 7 wherein reagent A is barium
oxide or barium hydroxide.
9. A composition according to claim 8 wherein the ratio of
equivalents of reagent A to the combination of reagents B, C and D
is at least 3:1; the weight ratio of each of reagents C and D to
reagent B is between about 1.1:1 and 4:1; and the ratio of
equivalents of reagent C to reagent D is between about 0.5:1 and
2:1.
10. A composition according to claim 2 which has been further
reacted with about 1-5% by weight of anthranilic acid, based on the
amount of said basic barium-containing composition, at about
100.degree.-140.degree. C.
11. A composition according to claim 4 which has been further
reacted with about 1-5% by weight of anthranilic acid, based on the
amount of said basic barium-containing composition, at about
100.degree.-140.degree. C.
12. A composition according to claim 6 which has been further
reacted with about 1-5% by weight of anthranilic acid, based on the
amount of said basic barium-containing composition, at about
100.degree.-140.degree. C.
13. A composition according to claim 8 which has been further
reacted with about 1-5% by weight of anthranilic acid, based on the
amount of said basic barium-containing composition, at about
100.degree.-140.degree. C.
14. A lubricating composition comprising a major amount of a
lubricating oil and a minor effective amount of a composition
according to claim 1.
15. A lubricating composition comprising a major amount of a
lubricating oil and a minor amount of a composition according to
claim 2.
16. A lubricating composition comprising a major amount of a
lubricating oil and a minor effective amount of a composition
according to claim 4.
17. A lubricating composition comprising a major amount of a
lubricating oil and a minor effective amount of a composition
according to claim 6.
18. A lubricating composition comprising a major amount of a
lubricating oil and a minor effective amount of a composition
according to claim 8.
19. A lubricating composition comprising a major amount of a
lubricating oil and a minor effective amount of a composition
according to claim 12.
20. A lubricating composition comprising a major amount of a
lubricating oil and a minor effective amount of a composition
according to claim 13.
Description
This invention relates to new compositions of matter suitable for
use as lubricant additives, and to methods for their preparation.
More particularly, it relates to oil-soluble, basic
barium-containing compositions prepared by reacting (A) a barium
base with a mixture comprising (B) a phenol, (C) at least one fatty
acid and (D) at least one aliphatic monohydric alcohol, each of
reagents C and D containing a straight chain of carbon atoms such
that at least 26 carbon atoms in straight-chain configuration are
present in the combination of said reagents C and D, the ratio of
equivalents of reagent A to the combination of reagents B, C and D
being at least about 1.5:1.
Basic barium salts of sperm oil have long been used as lubricant
additives, particularly in automatic transmission fluids, hydraulic
fluids and the like. They aid these lubricants to provide a smooth
transmission of power between clutch plates and the like when the
same become engaged, thus avoiding "squawking" noises and other
problems. The preparation and use in this way of basic barium salts
of sperm oil is described, for example, in U.S. Pat. No.
2,989,463.
The Unites States Government has recently taken action to prevent
the killing of whales, from which sperm oil is obtained, to avoid
their becoming extinct. The only source of sperm oil has therefore
"dried up" and it has become necessary to find substitutes for the
basic barium salts thereof, which can be cheaply and efficiently
produced and which provide the same advantageous properties to
lubricants.
A principal object of the present invention, therefore, is to
produce useful lubricant additives.
A further object is to produce lubricant additives which improve
power transmission in automatic transmissions and the like.
A further object is to produce basic barium salts which, when
incorporated in power-transmitting lubricants, improve their
lubricating properties.
Still another object is to produce compositions which may be
substituted for basic barium salts of sperm oil as lubricant
additives, and which provide the same properties as the sperm oil
salts.
Other objects will in part be obvious and will in part appear
hereinafter.
Reagent A in the compositions of this invention is a barium base.
It may be barium oxide, hydroxide, sulfide, hydrosulfide or the
like; the oxide and the hydroxide are preferred.
Reagent B is a phenol. Unsubstituted phenol and lower
alkyl-substituted phenols such as the cresols, ethylphenols,
butylphenols and the like may be used, but it is preferable to use
a phenol containing an alkyl substituent having at least about 6
carbon atoms such as heptylphenol, diisobutylphenol, n-decylphenol,
tetrapropenylphenol, octadecylphenol, polyisobutene-substituted
phenol and the like. Cycloalkyl-substituted phenols may also be
used. The phenol may contain other substituent groups in addition
to the alkyl or cycloalkyl groups; examples are halogen, nitro,
ether, ester and similar radicals. Also useful are the aldehyde
condensation products of the above-described phenols.
Reagent C is a fatty acid. As used herein, the term "fatty acid"
means an acid which may be obtained by hydrolysis of a naturally
occurring vegetable or animal oil. It may be a pure acid or a
mixture of acids. Suitable acids include palmitic acid, stearic
acid, oleic acid, linoleic acid, tall oil acid, acids derived from
palm oil, soybean oil or animal fats and oils, and the like. Acids
containing about 16-20 carbon atoms are preferred.
Reagent D is an aliphatic monohydric alcohol and is exemplified by
n-decanol, isodecanol, dodecanol, tridecanol, tetradecanol, oleyl
alcohol, stearyl alcohol, palmityl alcohol and mixtures of normal
primary alcohols in the C.sub.12.sub.-20 range, such as may be
obtained by the Oxo process.
The selection of reagents C and D is made so that at least 26
carbon atoms are present in straight-chain configuration in the
combination of said components. Thus, if reagent C is palmitic
acid, reagent D should contain a straight chain of at least 10
carbon atoms, and if reagent C is stearic or oleic acid reagent D
should contain a straight chain of at least 8 carbon atoms.
As previously mentioned, the ratio of equivalents of reagent A (the
barium base) to the combination or reagents B, C, and D in the
reaction mixture leading to the products of this invention is at
least about 1.5:1. Usually, it is at least 3:1 and it may be as
high as 10:1. As used herein, the term "equivalent" is a weight of
the reagent involved equal to its equivalent weight. For barium
bases the equivalent weight is one-half the molecular weight, while
for monohydric phenols and alcohols and monocarboxylic acids the
equivalent weight is equal to the molecular weight.
The relative amounts of reagents B, C and D may vary within wide
limits. Generally, the weight ratio of each of reagents C and D to
reagent B will be greater than 1; usually, it will be between about
1.1:1 and 4.0:1. The equivalent weight ratio of reagent C to
reagent D is usually between about 0.5:1 and 2:1.
In addition to the reagents described hereinabove, the reaction
mixture ordinarily contains a diluent which may be mineral oil,
petroleum naphtha, kerosene, xylene or the like. Mineral oil is
particularly preferred since the compositions are to be
incorporated in mineral oil to prepare a lubricant.
The reaction mixture may also contain a small amount of water
(generally not more than about 5 percent, based on the weight of
reagent A, although more may be used in some instances) which aids
in fluidizing the barium base. It is necessary to remove this water
during the formation of the product. This is easily done since the
reaction is ordinarily carried out at about 120.degree.-200.degree.
C., at which temperature the water distills. In addition to any
water added to fluidize the barium compound, water present as water
of hydration in reagent A is removed at these temperatures.
The order of reagent addition is not critical and may be widely
varied. It is frequently convenient to add reagent A to a mixture
of reagents B, C and D. However, it may sometimes be advantageous
to add reagent C after reagent A, or to add reagents A and C
portionwise in alternation. Inverse addition, wherein B, C and D
are added to A either as a mixture or portionwise, may also be
employed.
Following the preparation of a basic barium composition by the
method described above, it is usually preferred to react said
composition with carbon dioxide in order to reduce its titratable
basicity. The carbon dioxide treatment is ordinarily effected at
about 120.degree.-200.degree. C. and is usually continued until the
base number of the composition (phenolphthalein indicator) is below
about 10. This treatment appears to have two beneficial effects:
first, it clarifies the process mixture and renders it more
oil-soluble, and second, it allows the incorporation of
significantly more barium into the product. It is apparent that
this latter effect can be realized only when there is present in
the reaction mixture an appreciable quantity of oil-insoluble
barium compounds. Thus, it is important that the carbonation step,
if used, precede any separation (as by filtration) of oil-insoluble
barium compounds from the reaction mixture.
It is also frequently advantageous to react the compositions of
this invention, subsequent to their formation, with anthranilic
acid at about 100.degree.-140.degree. C. The amount of anthranilic
acid used is usually about 1-5 percent by weight, based on the
amount of basic barium salt. Anthranilic acid treatment frequently
improves the oxidation and corrosion inhibiting properties of the
lubricants containing the compositions of this invention.
The preparation of the compositions of this invention is
illustrated by the following examples. All parts are by weight.
EXAMPLE 1
A mixture of 2926 parts of mineral oil, 300 parts (1.56
equivalents) of heptylphenol and 347 parts (1.64 equivalents) of a
mixture of normal C.sub.12.sub.-18 primary alcohols is heated to
132.degree. C. under nitrogen, with stirring. Barium hydroxide
monohydrate, 248 parts, is added with stirring over one-half hour
while water is collected by distillation. When water evolution has
ceased, the mixture is dried for 15 minutes at 137.degree. C. There
is then added 713 parts (2.6 equivalents) of a eutectic mixture of
palmitic and stearic acids, followed by 1702 parts (total 20.6
equivalents) of barium hydroxide monohydrate, the latter being
added portionwise over 31/2 hours while water is again removed by
distillation. The temperature is increased to 150.degree. C. during
the final portion of barium hydroxide addition. The mixture is then
blown with carbon dioxide at 150.degree. C. for 21/4 hours and
purged with nitrogen at 150.degree. C. Finally, a filter aid
material is added and the mixture is filtered, yielding a 53%
solution in mineral oil of the desired basic barium salt which
contains 37.06% barium sulfate ash.
EXAMPLE 2
A mixture of 1849 parts of the product of Example 1 and 111 parts
of mineral oil is heated to 45.degree. C., and 40 parts of
anthranilic acid is added. The mixture is heated at
110.degree.-120.degree. C. for 1 hour and filtered with the
addition of filter aid. The product contains 33.04% barium sulfate
ash.
EXAMPLE 3
To a mixture of 142 parts (0.5 equivalent) of stearic acid, 134
parts (0.5 equivalent) of oleyl alcohol, 115 parts (0.6 equivalent)
of heptylphenol and 1100 parts of mineral oil is added slowly, at
room temperature, 674 parts (8 equivalents) of barium oxide. An
exothermic reaction takes place which causes the temperature to
rise to 70.degree. C. Water, 101 parts, is added gradually,
whereupon the temperature rises to 120.degree. C. The mixture is
held for 4 hours at 130.degree.-140.degree. C. and then heated to
160.degree. C. for 1/2 hour to remove volatile materials. It is
then blown with carbon dioxide at 145.degree.-150.degree. C. until
it is neutral to phenolphthalein. Finally, it is filtered using a
filter aid material. The filtrate is a 50% solution in mineral oil
of the desired basic barium salt containing 34.99% barium sulfate
ash.
EXAMPLE 4
A mixture of 368 parts (1.3 equivalents) of oleic acid, 150 parts
(0.8 equivalent) of heptylphenol, 260 parts (1.3 equivalents) of
tridecyl alcohol, 1515 parts of mineral oil and 32 parts of water
is heated to 76.degree. C., and 184 parts of barium hydroxide
monohydrate is added over 7 minutes at 76.degree.-92.degree. C.
Additional barium hydroxide monohydrate, to a total of 982 parts
(10.4 equivalents), is added over about 2 hours. The mixture is
then heated at 145.degree.-157.degree. C. and blown with carbon
dioxide for 2 hours. After all water has been removed, the product
is filtered, yielding a 54% solution in mineral oil of the desired
basic barium salt which has a barium sulfate ash content of
36.2%.
EXAMPLE 5
Following the procedure of Example 4, a basic barium salt is
obtained from 150 parts (0.8 equivalent) of heptylphenol, 368 parts
(1.3 equivalents) of oleic acid, 982 parts (10.4 equivalents) of
barium hydroxide monohydrate, 370 parts (1.75 equivalents) of a
mixture of normal C.sub.12.sub.-14 primary alcohols, 1405 parts of
mineral oil and 32 parts of water. The product contains 36.07%
barium sulfate ash.
EXAMPLE 6
Following the procedure of Example 4, a basic barium salt is
prepared from 760 parts (2.6 equivalents) of oleic acid, 347 PARTS
(1.64 equivalents) of a mixture of normal C.sub.12.sub.-18 primary
alcohols, 1950 parts (20.6 equivalents) of barium hydroxide
monohydrate, 300 parts (1.56 equivalents) of heptylphenol, 2900
parts of mineral oil and 65 parts of water. The product is a 53%
solution in mineral oil and contains 37.19% barium sulfate ash.
EXAMPLE 7
A mixture of 1845 parts of the product of Example 6 and 115 parts
of mineral oil is heated to 45.degree. C., and 40 parts of
anthranilic acid is added. The mixture is then heated to
110.degree.-120.degree. C. for 1 hour and filtered. The product
contains 33.89% barium sulfate ash.
EXAMPLE 8
Following the procedure of Example 4, a basic barium salt is
prepared from 150 parts (0.8 equivalent) of heptylphenol, 368 parts
(1.3 equivalent) of oleic acid, 982 parts (10.4 equivalents) of
barium hydroxide monohydrate, 324 parts (1.3 equivalents) of oleyl
alcohol, 1451 parts of mineral oil and 32 parts of water. The
product, a 56% solution in mineral oil, contains 35.65% barium
sulfate ash.
EXAMPLE 9
Barium hydroxide monohydrate, 1950 parts (20.6 equivalents) is
added over 20 minutes to 3000 parts of mineral oil at 140.degree.
C., while water is removed by distillation. Tridecyl alcohol, 300
parts, is then added and the mixture is purged with nitrogen. A
mixture of 720 parts (2.6 equivalents) of tall oil acid and 300
parts (1.56 equivalents) of heptylphenol is added slowly; at one
point the addition thereof is interrupted and an additional 220
parts of tridecyl alcohol (total 2.6 equivalents) is added. The
mixture is heated at 150.degree. C. for 21/4 hours and is then
blown with carbon dioxide at 150.degree. C. After removal of all
volatile materials, the mixture is filtered, yielding the desired
52% solution in mineral oil of a basic barium salt containing
33.75% barium sulfate ash.
EXAMPLE 10
A mixture of 1960 parts of the product of Example 9 and 40 parts of
anthranilic acid is heated to 115.degree.-120.degree. C. for 1 hour
and filtered, yielding the desired product which contains 33.63%
barium sulfate ash.
EXAMPLE 11
Following the procedure of Example 4, a basic barium salt is
prepared from 720 parts (2.6 equivalents) of tall oil acid, 300
parts (1.56 equivalents) of heptylphenol, 1900 parts (20.1
equivalents) of barium hydroxide monohydrate, 374 parts (1.64
equivalents) of a mixture of normal C.sub.12.sub.-18 primary
alcohols and 65 parts of water. The product, a 53% solution in
mineral oil of the desired basic salt, contains 37.79% barium
sulfate ash.
EXAMPLE 12
Following the procedure of Example 2, an anthranilic acid adduct of
the product of Example 11 is prepared. It is obtained as a 50%
solution in mineral oil and contains 33.58% barium sulfate ash.
EXAMPLE 13
A basic barium salt is obtained using the reagents and following
the procedure of Example 11, except that 300 parts (3.2
equivalents) of phenol is substituted for the heptylphenol. A
similar product is obtained.
EXAMPLE 14
A mixture of 300 parts (1.56 equivalents) of heptylphenol, 347
parts (1.64 equivalents) of a mixture of normal C.sub.12.sub.-18
primary alcohols and 2000 parts of mineral oil is heated to
100.degree.-105.degree. C., and 1960 parts (20.7 equivalents) of
barium hydroxide monohydrate is added over 18 minutes. The mixture
is heated to 150.degree. C. and water is collected by distillation.
After 98 parts of water have been collected, 360 parts of tall oil
acid is added over 20 minutes. Water distillation is continued for
21/2 hours, and then an additional 360 parts (total 2.6
equivalents) of tall oil acid is added. After an additional 1/2
hour of heating, the mixture is blown with carbon dioxide at
145.degree.-150.degree. C. for 3 hours. The mixture is purged with
nitrogen until substantially all volatile matter has been removed
and then 1098 parts of mineral oil is added and the mixture is
filtered, using a filter aid material. The filtrate is the desired
51% solution of a basic barium salt containing 36.6% barium sulfate
ash.
EXAMPLE 15
To a mixture of 1789 parts of mineral oil, 182 parts (0.9
equivalent) of heptylphenol and 300 parts (1.5 equivalents) of a
mixture of normal C.sub.12.sub.-14 primary alcohols, at 135.degree.
C., is added 1135 parts (12 equivalents) of barium hydroxide
monohydrate over 1 hour. Palmitic acid, 384 parts (1.5
equivalents), is then added over 1 hour at 140.degree.-150.degree.
C. The mixture is heated at 150.degree. C. for 1/2 hour and is then
blown with carbon dioxide for 3 hours. Finally, it is purged with
nitrogen at 150.degree. C. to remove volatile materials and is
filtered using a filter aid material. The product is the desired
50% solution in mineral oil of a basic barium salt having a barium
sulfate ash content of 36.4%.
As previously mentioned, the composition of this invention are
useful as additives to improve power transmission and prevent
"squawk." As such, they can be employed in a variety of lubricating
compositions based on diverse oils of lubricating viscosity,
including natural and synthetic lubricating oils and mixtures
thereof. The compositions contemplated include principally
automatic transmission fluids, transaxle lubricants and hydraulic
fluids, but other lubricating oil and grease compositions can also
benefit from the incorporation of the present compositions.
Natural oils include animal oils and vegetable oils (e.g., castor
oil, lard oil) as well as solvent-refined or acid-refined mineral
lubricating oils of the paraffinic, naphthenic, or mixed
paraffinic-naphthenic types. Oils of lubricating viscosity derived
from coal or shale are also useful base oils. Synthetic lubricating
oils include hydrocarbon oils and halo-substituted hydrocarbon oils
such as polymerized and interpolymerized olefins (e.g.,
polybutylenes, polypropylenes, propylene-isobutylene copolymers,
chlorinated polybutylenes, etc.); alkylbenzenes (e.g.,
dodecylbenzenes, tetradecylbenzene, dinonylbenzenes,
di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,
terphenyls, etc.); and the like. Alkylene oxide polymers and
interpolymers and derivatives thereof where the terminal hydroxyl
groups have been modified by esterification, etherification, etc.,
constitute another class of known synthetic lubricating oils. These
are exemplified by the oils prepared through polymerization of
ethylene oxide or propylene oxide, the alkyl and aryl ethers of
these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol
ether having an average molecular weight of 1000, diphenyl ether of
polyethylene glycol having a molecular weight of 500-1000, diethyl
ether of polypropylene glycol having a molecular weight of
1000-1500, etc.) or mono- and polycarboxylic esters thereof, for
example, the acetic acid esters mixed C.sub.3 -C.sub.8 fatty acid
esters, or the C.sub.13 Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the
esters of dicarboxylic acids (e.g., phthalic acid, succinic acid,
maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric
acid, adipic acid, linoleic acid dimer, etc.) with a variety of
alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol,
2-ethylhexyl alcohol, pentaerythritol, etc.). Specific examples of
these esters include dibutyl adipate, di(2-ethylhexyl) sebacate,
di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate,
diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl
sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the
complex ester formed by reacting one mole of sebacic acid with two
moles of tetraethylene glycol and two moles of 2-ethylhexanoic
acid, and the like. Silicon-based oils such as the polyalkyl-,
polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate
oils comprise another useful class of synthetic lubricants (e.g.,
tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)
silicate, tetra-(4-methyl-2-tetraethyl) silicate,
tetra-(p-tert-butylphenyl) silicate,
hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)-siloxanes,
poly(methylphenyl)-siloxanes, etc.). Other synthetic lubricating
oils include liquid ester of phosphorus-containing acids (e.g.,
tricresyl phosphate, trioctyl phosphate, diethyl ester of decane
phosphonic acid, etc.), polymeric tetrahydrofurans, and the
like.
In general, about 0.05-20.0 parts (by weight) of the composition of
this invention is dissolved in 100 parts of oil to produce a
satisfactory lubricant. The invention also contemplates the use of
other additives in combination with the products of this invention.
Such additives include, for example, detergents and dispersants of
the ash-containing or ashless type, oxidation and corrosion
inhibiting agents, pour point depressing agents, viscosity index
improvers, extreme pressure agents, "slip" agents, color
stabilizers and anti-foam agents.
The ash-containing detergents are exemplified by oil-soluble
neutral and basic salts of alkali or alkaline earth metals with
sulfonic acids, carboxylic acids, or organic phosphorus acids
characterized by at least one direct carbon-to-phosphorus linkage
such as those prepared by the treatment of an olefin polymer (e.g.,
polyisobutene having a molecular weight of 1000) with a
phosphorizing agent such as phosphorus trichloride, phosphorus
heptasulfide, phosphorus pentasulfide, phosphorus trichloride and
sulfur, white phosphorus and a sulfur halide, or phosphorothioic
chloride. The most commonly used salts of such acids are those of
sodium, potassium, lithium, calcium, magnesium, strontium and
barium.
The term "basic salt" is used to designate metal salts wherein the
metal is present in stoichiometrically larger amounts than the
organic acid radical. The commonly employed methods for preparing
the basic salts involve heating a mineral oil solution of an acid
with a stoichiometric excess of a metal neutralizing agent such as
the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a
temperature above 50.degree. C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid the
incorporation of a large excess of metal likewise is known.
Examples of compounds useful as the promoter include phenolic
substances such as phenol, naphthol, alkylphenol, thiophenol,
sulfurized alkylphenol, and condensation products of formaldehyde
with a phenolic substance; alcohols such as methanol, 2-propanol,
octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl
alcohol, and cyclohexyl alcohol; and amines such as aniline,
phenylenediamine, phenothiazine, phenyl-.beta.-naphthylamine, and
dodecylamine. A particularly effective method for preparing the
basic salts comprises mixing an acid with an excess of a basic
alkaline earth metal neturalizing agent, a phenolic promoter
compound, and a small amount of water and carbonating the mixture
at an elevated temperature such as 60.degree.-200.degree. C.
Ashless detergents and dispersants are illustrated by the
interpolymers of an oil-solubilizing monomer, e.g., decyl
methacrylate, vinyl decyl ether, or high molecular weight olefin,
with a monomer containing polar substituents, e.g., aminoalkyl
acrylate or poly-(oxyethylene)-substituted acrylate; the amine
salts, amides, and imides of oil-soluble monocarboxylic or
dicarboxylic acids such as stearic acid, oleic acid, tall oil acid,
and high molecular weight alkyl or alkenyl-substituted succinic
acid. Especially useful as ashless detergents are the acylated
polyamines and similar nitrogen compounds containing at least about
54 carbon atoms as described in U.S. Pat. No. 3,272,746; reaction
products of such compounds with other reagents including boron
compounds, phosphorus compounds, epoxides, aldehydes, organic acids
and the like; and esters of hydrocarbon-substituted succinic acids
as described in U.S. Pat. No. 3,381,022.
Extreme pressure agents and corrosion-inhibiting and
oxidation-inhibiting agents are exemplified by chlorinated
aliphatic hydrocarbons such as chlorinated wax; organic sulfides
and polysulfides such as benzyl disulfide, bis(chlorobenzyl)
disulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized
methyl ester of oleic acid, sulfurized alkylphenol, sulfurized
dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons
such as the reaction product of a phosphorus sulfide with
turpentine or methyl oleate; phosphorus esters including
principally dihydrocarbon and trihydrocarbon phosphites such as
dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite,
pentyl phenyl phosphite, dipentyl phenyl phosphite, tridecyl
phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl
4-pentylphenyl phosphite, polypropylene (molecular weight
500)-substituted phenyl phosphite, diisobutyl-substituted phenyl
phosphite; metal thiocarbamates, such as zinc
dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate;
Group II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate,
barium di(heptylphenyl)phosphorodithioate, cadmium
dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic
acid produced by the reaction of phosphorus pentasulfide with an
equimolar mixture of isopropyl alcohol and n-hexyl alcohol.
It is possible to form the lubricating compositions of this
invention by dissolving the various additives, or oil solutions
thereof, directly in a mineral oil. However, it is generally more
convenient and is preferred to prepare additive concentrates
containing two or more of the desired additives, and to dissolve
these concentrates in the mineral oil to form the final lubricating
composition.
In addition to lubricating compositions comprising a major amount
of a lubricating oil and minor amounts of various additives
including the basic barium-containing compositions described
herein, water-oil emulsion type hydraulic fluids are contemplated
as being part of the present invention.
Typical lubricating compositions according to this invention are
listed in Tables I and II. Compositions A-D, listed in Table I, are
primarily useful as automatic transmission fluids. Compositions
E-G, in Table II, are primarily useful as tractor hydraulic fluids.
Composition H, in Table II, is an emulsion-type hydraulic fluid
chiefly useful in vane-type pumps and the like. Amounts given are
for actual chemicals and do not include mineral oil diluent. In all
of these, the basic barium compositions of this invention provide
properties similar to those previously provided by basic barium
salts of sperm oil.
T A B L E I
Parts by weight A BC D Mineral oil (automatic transmission fluid
base) 88.42 88.66 99.0 99.0 Product of Example 5 1.0 Product of
Example 8 1.0 Product of Example 10 0.54 0.54 Zinc salt of mixture
of polyisobutenyl succinic acid and
bis(chlorophenyl)phosphinodithioic acid 2.08 Zinc salt of
bis(C.sub.10.sub.-12 alkylphenyl)phosphinodithioic acid 1.23
Oleamide-linoleamide mixture 0.26 Basic calcium bright stock
sulfonate 1.09 1.09 Hydrocarbon resin seal swelling agent 3.52
Poly-(aminoalkyl methacrylate)viscosity index improver 4.09 8.48
Silicone anti-foam agent 0.02 0.02
T A B L E II
Parts by weight E FG H Mineral oil (hydraulic fluid base) 90.05
90.16 93.64 Mineral oil (naphthenic) 57.86 Water 40.00 Product of
Example 6 2.27 Product of Example 11 2.38 Product of Example 14
2.17 Zinc diisooctylphosphorodithioate 2.16 2.16 2.16 0.27 Zinc
bis(heptylphenyl)phosphorodithioate 0.39 Hydrocarbon resin seal
swelling agent 2.34 2.34 Basic barium petroleum sulfonate 1.06 1.06
1.06 Mixture of polyisobutenyl succinic anhydride and
polyoxy-ethylated sorbitan monooleate 1.03 C.sub.11.sub.-14
tertiary alkyl primary amine mixture 0.11 Lecithin 0.34
Polyisobutene 1.48 1.48 Terpolymer of vinyl acetate, ethyl vinyl
ether and C.sub.12.sub.-14 dialkyl fumarate 0.09 0.09 Poly-(alkyl
methacrylate)viscosity index improver 0.53 Oleamide-linoleamide
mixture 0.44 0.44 0.44 Silicone anti-foam agent 0.026 0.026 0.026
0.001
The compositions of this invention may also be used as stabilizers
for vinyl chloride polymers.
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