U.S. patent number 3,899,432 [Application Number 05/475,687] was granted by the patent office on 1975-08-12 for all-purpose lubricating oil composition with anti-chatter characteristics for wet disc brakes.
This patent grant is currently assigned to Chevron Research Company. Invention is credited to Donald D. Dexter, Lester M. Hartmann, Kenneth Rothert.
United States Patent |
3,899,432 |
Rothert , et al. |
August 12, 1975 |
All-purpose lubricating oil composition with anti-chatter
characteristics for wet disc brakes
Abstract
Lubricating oil compositions are provided which comprise (A) a
major amount of oil of lubricating viscosity, and (B) an effective
amount of each of: (1) an oil-soluble substantially neutral Group
II metal salt of a hydrocarbyl sulfonic acid; (2) an oil-soluble
overbased Group II metal salt of a hydrocarbyl sulfonic acid; (3)
an oil-soluble Group II metal salt of a dihydrocarbyl
dithiophosphoric acid; (4) tricresyl phosphate; and (5) a
sulfurized mixture of C.sup.10.sup.-25 olefins and fatty acid
esters of C.sup.10.sup.-25 fatty acids and C.sup.1.sup.-25 alkyl or
alkenyl alcohols, in an olefin-to-ester mol ratio of about 1-2:1
wherein the fatty acid and/or alcohol is unsaturated. These
lubricating oil compositions are useful as functional fluids in a
variety of systems. They are particularly useful in the hydraulic
and gear box systems of large industrial and farm tractors
providing excellent lubrication, increased braking capacity and
reduced chatter of wet-type disc brakes.
Inventors: |
Rothert; Kenneth (San
Francisco, CA), Dexter; Donald D. (Concord, CA),
Hartmann; Lester M. (Tiburon, CA) |
Assignee: |
Chevron Research Company (San
Francisco, CA)
|
Family
ID: |
23888674 |
Appl.
No.: |
05/475,687 |
Filed: |
June 3, 1974 |
Current U.S.
Class: |
508/330; 252/75;
508/336; 508/337; 508/338 |
Current CPC
Class: |
C10M
159/24 (20130101); C10M 137/10 (20130101); C10M
135/02 (20130101); C10M 135/06 (20130101); C10M
163/00 (20130101); C10M 137/04 (20130101); C10M
135/04 (20130101); C10M 135/10 (20130101); C10M
163/00 (20130101); C10M 135/02 (20130101); C10M
135/04 (20130101); C10M 135/06 (20130101); C10M
135/10 (20130101); C10M 137/04 (20130101); C10M
137/10 (20130101); C10M 159/24 (20130101); C10M
2223/04 (20130101); C10M 2219/044 (20130101); C10N
2010/04 (20130101); C10M 2217/06 (20130101); C10N
2040/08 (20130101); C10M 2217/023 (20130101); C10M
2205/00 (20130101); C10M 2219/02 (20130101); C10M
2219/046 (20130101); C10M 2217/028 (20130101); C10M
2223/045 (20130101); C10M 2219/022 (20130101); C10M
2219/024 (20130101); C10M 2223/041 (20130101); C10N
2040/02 (20130101); C10M 2205/026 (20130101) |
Current International
Class: |
C10M
163/00 (20060101); C10m 001/48 (); C10m 001/46 ();
C10m 001/40 () |
Field of
Search: |
;252/32.7E,33,33.4,75 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Vaughn; I.
Attorney, Agent or Firm: Magdeburger; G. F. Tonkin; C. J.
Fehringer; B. G.
Claims
What is claimed is:
1. A lubricating oil composition comprising:
A. a major amount of an oil of lubricating viscosity, and
B. an effective amount of each of:
1. an oil-soluble substantially neutral Group II metal salt of a
hydrocarbyl sulfonic acid;
2. an oil-soluble overbased Group II metal salt of a hydrocarbyl
sulfonic acid;
3. an oil-soluble Group II metal salt of a dihydrocarbyl
dithiophosphoric acid;
4. tricresyl phosphate; and
5. a sulfurized mixture of C.sup.10-25 olefins and fatty acid
esters of C.sup.10-25 fatty acids and C.sup.1-25 alkyl or alkenyl
alcohols, in an olefin-to-ester mol ratio of about 1-2:1 wherein
the fatty acid and/or alcohol is unsaturated.
2. A lubricating oil composition of claim 1 wherein:
A. said Group II metal of said Group II metal salt of a hydrocarbyl
sulfonic acid is magnesium, calcium or barium,
B. said Group II metal of said Group II metal salt of a
dihydrocarbyl dithiophosphoric acid is zinc, and
C. said fatty acid esters are derosinified tall oil esters of a
C.sup.1-25 alkyl or alkenyl alcohol.
3. A lubricating oil composition comprising:
A. a major amount of an oil of lubricating viscosity, and
B. an effective amount of each of:
1. an oil-soluble neutral Group II metal salt of a hydrocarbyl
sulfonic acid of the following formula: ##EQU3## wherein a. each
R.sup.1 represents a hydrocarbyl group, and
b. M.sup.1 represents a Group II metal cation;
2. an oil-soluble overbased Group II metal salt of a hydrocarbyl
sulfonic acid of the following formula: ##EQU4##
wherein R.sup.1 and M.sup.1 are as defined above; 3. an oil-soluble
Group II metal salt of a dihydrocarbyl dithiophosphoric acid of the
following formula: ##EQU5## wherein: c. R.sup.2 and R.sup.3 each
independently represent hydrocarbyl groups, and
d. M.sup.2 represents a Group II metal cation;
4.
4. tricresyl phosphate; and
5. a sulfurized mixture of C.sup.10-25 olefins and fatty acid
esters of C.sup.10-25 fatty acids and C.sup.1-25 alkyl or alkenyl
alcohol, in an olefin-to-ester mol ratio of about 1-2:1 wherein the
fatty acid and/or
alcohol is unsaturated. 4. A lubricating oil composition of claim 3
wherein:
a. M.sup.1 represents calcium, magnesium or barium,
b. R.sup.2 and R.sup.3 each represent a hydrocarbyl group
containing from 8 to 12 carbon atoms,
c. M.sup.2 represents zinc,
d. said olefin is a C.sup.11 -C.sup.18 alpha-olefin and said fatty
acid ester is a derosinified tall oil ester of a C.sup.10-20
alcohol.
5. A lubricating oil composition of claim 4 wherein:
a. said neutral Group II metal salt of a hydrocarbyl sulfonic acid
is present in from 1 to 6 weight percent of said composition;
b. said overbased Group II metal salt of a hydrocarbyl sulfonic
acid is present in from 1 to 6 weight percent of said
composition;
c. said Group II metal salt of a dihydrocarbyl dithiophosphoric
acid is present in from 1 to 4.5 weight percent of said
composition;
d. said tricresyl phosphate is present in from 0.5 to 1.5 weight
percent of said composition; and
3. said sulfurized mixture of said olefins and said fatty acid
esters is present in from 0.5 to 1.5 weight percent of said
composition.
6. A lubricating oil composition of claim 4 wherein:
a. said neutral Group II metal salt of a hydrocarbyl sulfonic acid
is present in from 1.4 to 4 weight percent of said composition;
b. said overbased Group II metal salt of a hydrocarbyl sulfonic
acid is present in from 1.4 to 4 weight percent of said
composition;
c. said Group II metal salt of a dihydrocarbyl dithiophosphoric
acid is present in from 1.2 to 2.25 weight percent of said
composition;
d. said tricresyl phosphate is present in from 0.75 to 1.25 weight
percent of said composition; and
e. said sulfurized mixture of said olefins and said fatty acid
esters is present in from 0.75 to 1.25 weight percent of said
composition.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to lubricating oil compositions,
particularly to lubricating oil compositions useful as functional
fluids is systems requiring fluid coupling, hydraulic fluid, and/or
lubrication of relatively moving parts. More particularly this
invention relates to lubricating oil compositions useful both as
hydraulic fluids and as lubricants in the transmissions and
differentials of heavy machinery such as high-power output
tractors. This lubricating oil composition is particularly useful
in machinery using wet-type disc brakes physically located within
the housing containing the lubricating oil composition.
The trend today in the field of heavy machinery is toward
increasing power and introducing devices which not only make the
machinery more efficient but reduce operator fatigue. Some of these
labor-saving devices include double-acting hydraulic systems, power
steering, and power brakes. Power brakes can either be of the drum
type or disc type. The disc brake is favored since it offers more
braking capacity than the drum-type brake. The wet type of disc
brake is preferred because it can be installed inside the
differential housing where it is isolated from the dirt and grime
of day-to-day operations.
The wet-type brake is in contact with the lubricating oil. A
special oil is required which lubricates all the relatively moving
parts such as the differential gears, transmission gears, etc. At
the same time, the lubricating oil must not prevent proper braking
action. Furthermore, it must not promote brake chatter. Chatter is
caused by slip-stick operation of the brakes when they are in
contact with certain types of fluids.
Equipment manufacturers would like to use one lubricating
functional fluid in all systems of the machinery except for the
motor crankcase. Thus, an all-purpose lubricating functional fluid
must provide proper lubrication of the relatively moving parts in
the transmission and differential as well as allow proper braking
action. It must also not prevent proper clutch lock-up in
wet-clutch power take-off (pto) units and must provide proper
lubrication for the power steering pump and the hydraulic system
pump.
Furthermore, the fluid should be able to take up a certain amount
of free water which may accidentally enter the system, for example,
during a rainstorm. This prevents damage to relatively moving parts
by preventing their coming into contact with a large mass of free
water, thereby temporarily losing lubrication. It is generally
assumed that small amounts of water, generally one-half to one
weight percent of the lubricating oil composition, will be
vaporized as the system warms up to operating temperatures.
Lubricating functional fluids generally become quite hot when the
systems containing them have been in operation for awhile. These
fluids must therefore exhibit long-term thermal stability and
anti-oxidation properties in order for the fluids to have a
reasonably long useful life. The fluids of this invention are
designed to meet the above criteria.
SUMMARY OF THE INVENTION
The lubricating oil compositions of this invention comprise (A) a
major amount of an oil of lubricating viscosity, and (B) an
effective amount of each of the following: (1) a neutral Group II
metal salt of a hydrocarbyl sulfonic acid; (2) an overbased Group
II metal salt of a hydrocarbyl sulfonic acid; (3) a Group II metal
salt of a dihydrocarbyl dithiophosphoric acid; (4) tricresyl
phosphate; and (5) a sulfurized mixture of olefins and fatty acid
esters. These fluids are particularly valuable since they provide
excellent lubrication between relatively moving parts, are fully
satisfactory as hydraulic fluids and greatly reduced chatter in
wet-type disc brakes.
DESCRIPTION OF THE INVENTION
As described above, the lubricating functional fluid compositions
of this invention comprise a major amount of oil of lubricating
viscosity and an effective amount of each of a substantially
neutral Group II metal salt of the hydrocarbyl sulfonic acids; an
overbased Group II metal salt of a hydrocarbyl sulfonic acid, a
Group II metal salt of a dihydrocarbyl dithiophosphoric acid,
tricresyl phosphate, and a sulfurized mixture of olefins and fatty
acid esters.
The Neutral Sulfonate
The substantially neutral Group II metal salt of a hydrocarbyl
sulfonic acid is present to improve, among other things, the water
tolerance of the lubricating oil composition. This means that the
lubricating oil composition will absorb a certain amount, generally
one-half to one weight percent, of free water rather than allow it
to accumulate in the bottom of the housing containing these
lubricating oil compositions. This prevents damage to the
lubricated parts by preventing these parts from coming into contact
with a large mass of free water, thereby temporarily losing
lubrication. Generally, the neutral Group II metal sulfonate
disperses the water in the lubricating oil composition. The water
is then generally vaporized and expelled the next time the system
is warmed up and operated.
The neutral Group II metal salts of hydrocarbyl sulfonic acids also
function as detergents and dispersants. They prevent the deposit of
contaminants formed during high temperature operation of the system
containing the functional fluid.
The Group II metal salts of hydrocarbyl sulfonic acids are well
known. Many of these salts have been used as additives for
lubricating oil compositions. These salts comprise the
neutralization product obtained by reacting a Group II metal base
with a hydrocarbyl sulfonic acid. The hydrocarbyl portion of the
sulfonate can be derived from a hydrocarbon oil stock or synthetic
organic moiety.
Several processes for preparing the sulfonates are briefly outlined
in U.S. Pat. No. 2,398,713. Other processes are also discussed in
U.S. Pat. No. 2,388,677.
The oil-derived hydrocarbyl moiety is a mixture of different
hydrocarbyl groups, the specific composition of which depends upon
the particular oil stock which was used as a starting material. The
fraction of the oil stock which is sulfonated is predominantly an
aliphatic-substituted carbocyclic ring. The sulfonic acid group
generally attaches to the carbocyclic ring. The carbocyclic ring is
predominantly aromatic in nature, although a certain amount of the
cycloaliphatic content of the oil stock will also be sulfonated.
The aliphatic substituent of the carbocyclic ring affects the oil
solubility and detergent properties of the sulfonate. Suitably, the
aliphatic substituent contains from about 12 to about 30 carbon
atoms and preferably from about 15 to 25 carbon atoms. The
aliphatic substituent can be straight or branched chain and can
contain a limited number of olefinic linkages; preferably less than
5% of the total carbon-to-carbon bonds are unsaturated.
Synthetic organic moieties suitable for conversion to hydrocarbyl
sulfonic acids include alkylated aromatics. A particularly suitable
alkylated aromatic is known as synthetic heavy alkylate. This
material is obtained as a by-product from the preparation of hard
detergent alkylate (C.sup.12 -C.sup.15 alkyl benzenes prepared by
alkylating benzene with propylene tetramer and pentamer in the
presence of hydrofluoric acid). During alkylation, some
fragmentation of the alkyl polymer occurs, yielding light, hard
benzenes (mostly C.sup.4 -C.sup.6 monosubstituted benzenes). These
light materials are alkylated a second time with C.sup.18-20
straight-chain cracked wax olefin to yield the synthetic heavy
alkylates. The sulfonic acid can be obtained by sulfonating the
alkylate with 26% sulfuric acid. The Group II metal salts can be
obtained by neutralizing the sulfonic acid with sodium hydroxide
and converting the salt thus obtained to the Group II metal salt by
metathesis.
Both the oil-derived and synthetic hydrocarbyl moieties are
predominately hydrocarbyl in nature. However, they may contain
small, sometimes adventitious, amounts of atoms other than carbon
and hydrogen. The functional groups containing these other atoms
(such as nitrogen, oxygen and sulfur) should not cause any
substantial degradation of the properties of the neutral sulfonate
as discussed above.
The neutral sulfonates are preferably substantially neutral, i.e.,
they have very little alkalinity value as discussed below. Any
alkalinity value which these neutral sulfonates may have is
generally caused by a slight excess of the Group II metal base used
to neutralize the sulfonic acid.
The Group II metal cation of the sulfonate suitably is magnesium,
calcium, strontium, barium, or zinc, and preferably is magnesium,
calcium or barium. Most preferably the Group II metal is
calcium.
Preferably, the Group II metal salt of the hydrocarbyl sulfonic
acid has the following formula: ##EQU1## wherein: (a) each R.sup.1
represents a hydrocarbyl group as described above, and (b) M.sup.1
represents a Group II metal cation as described above.
The oil-soluble substantially neutral Group II metal salts of
hydrocarbyl sulfonic acids are present in the lubricating oil
compositions of the invention in an amount effective to prevent
deposit of contaminants formed in the oil during severe high
temperature operation of the system and to impart water tolerance
to the composition. This effective amount can vary widely and
typically ranges from 1 to about 6 weight percent, preferably from
about 1.4 to about 4 weight percent of the total lubricating oil
composition.
The Overbased Sulfonate
The oil-soluble overbased Group II metal salt of a hydrocarbyl
sulfonic acid is present to impart, among other things, thermal
stability, oxidation inhibition, and rust inhibition.
These oil-soluble overbased Group II metal salts of hydrocarbyl
sulfonic acids are well known. Many of these salts have been used
as additives for lubricating oil compositions.
These overbased sulfonates are obtained by "overbasing" the neutral
Group II metal hydrocarbyl sulfonates discussed above and
illustrated in formula I.
These overbased materials are characterized by metal content in
excess of that which would be present according to the
stoichiometry of the metal cation and the sulfonic acid compound
which is overbased. Thus, a monosulfonic acid, when neutralized
with a Group II metal basic compound, e.g., a calcium compound will
produce a normal or neutral sulfonate containing one equivalent of
calcium for each equivalent of acid. In other words, the normal
metal sulfonate will contain 1 mol of calcium for each 2 mols of
the monosulfonic acid.
By using well-known procedures, "overbased" or "basic" complexes of
the sulfonic acid can be obtained. These overbased materials can
contain amounts of metals many times in excess of that required to
neutralize the acid. The stoichiometric excess can vary
considerably, e.g., from about 0.1 to about 30 or more equivalents
depending upon the reaction, the process, the conditions, etc.
The degree of overbasing can be expressed several ways. One method
is to describe the "metal ratio". This method describes the ratio
of the total chemical equivalents of metal in the product to the
chemical equivalents of compound that is overbased, based on the
known chemical reactivity and stoichiometry of the two reactants.
Thus, in a normal (neutral) calcium sulfonate, such as that
discussed above and exemplified in formula I, the metal ratio is
one (1) and in an overbased sulfonate, the metal ratio can range
from about 1.1 to 30 or more generally from about 5 to about
25.
Another method of expressing the degree of overbasing is to
describe the "base ratio". This method describes the ratio of
chemical equivalents of basic metal to the chemical equivalents of
neutral metal. The neutral metal is the metal which would be
expected to react with the compound to be overbased, i.e., the
metal required to neutralize the sulfonate. The basic metal is the
metal in excess of the neutral metal, i.e., it is the metal
available to neutralize acidic materials present in the lubricating
oil composition. Thus, a normal (neutral) calcium sulfonate has a
base ratio of zero (0) and an overbase sulfonate can have a base
ratio ranging from about 0.1 to about 30 or more generally from
about 4 to about 24.
Another method of specifying the degree of overbasing is by stating
the alkalinity value (AV) of the composition. The method for
determining the alkalinity value of an overbased composition is set
forth in ASTM method D-2896. Briefly, the alkalinity value is
stated as the number of milligrams of potassium hydroxide per gram
of composition to which the overbasing is equal. For example, if
the composition is overbased to the extent that it has the same
acid-neutralizing capacity per gram as 10 milligrams of potassium
hydroxide, the composition is given an alkalinity value of 10.
Alkalinity values can range up to about 600. Of course, the lower
limit is zero for a neutral sulfonate, with values of 10 to 50
being common for slightly overbased sulfonates. Highly overbased
sulfonates have values ranging from about 275 to about 450.
A discussion of the general method of preparing overbased
sulfonates and other overbased products is disclosed in Le Suer,
U.S. Pat. No. 3,496,105 issued Feb. 17, 1970, particularly at
columns 3 and 4.
The oil-soluble overbased Group II metal salts of hydrocarbyl
sulfonic acids are present in the lubricating oil composition of
the invention in an amount effective to impart thermal stability,
oxidation inhibition, and/or rust inhibition. The effective amount
can vary widely and typically ranges from about 1 to about 6 weight
percent, preferably from about 1.4 to about 4 weight percent of the
total lubricating oil composition.
The Dithiophosphoric Acid Salt
As mentioned above, the lubricating functional fluid compositions
of the invention contain Group I metal salts of dihydrocarbyl
dithiophosphoric acids. The function of this salt is to act as an
oxidation inhibitor thereby preventing the formation of a variety
of oxygenated hydrocarbon products which impairs the usefulness and
shortens the useful life of the lubricating oil. It also functions
as an anti-wear agent.
As stated above, the temperatures to which the functional fluids of
the hydraulic and transmission systems are subjected are often
severe. Under these thermally severe conditions, not only is the
lubricating oil quite prone to oxidation, but the anti-oxidants
themselves quite often undergo thermal degradation. Accordingly,
the oxidation inhibitor used must have good thermal stability at
these relatively high temperatures, or its thermal degradation
products must also exhibit anti-oxidation properties.
It has now been found that the above-mentioned Group II metal salts
of dihydrocarbyl dithiophosphoric acids exhibit the anti-oxidant
and thermal-stability properties required for the severe service
proposed. Group II metal salts of phosphodithioic acids have been
described previously. (See, for example, U.S. Pat. No. 3,390,080,
columns 6 and 7, wherein these compounds and their preparation are
described generally.)
Suitably, the Group II metal salts of the dihydrocarbyl
dithiophosphoric acids useful in the lubricating oil compositions
of this invention contain from about 4 to about 12 carbon atoms,
preferably from about 6 to about 12 carbon atoms, more preferably
from about 8 to 12 carbon atoms, and most preferably 8 carbon atoms
in each of the hydrocarbyl radicals.
Examples of suitable hydrocarbyl groups include butyl, sec-butyl,
iso-butyl, tert-butyl, pentyl, n-hexyl, sechexyl, n-octyl, mixed
primary octyls, 2-ethylhexyl, decyl, dodecyl, and the like. A
hydrocarbyl group which gives excellent results is dithiophosphates
in the oils of this invention is n-octyl.
The metals suitable for forming these salts include barium,
calcium, strontium, zinc, and cadmium, of which zinc is
preferred.
Preferably the Group II metal salts of the dihydrocarbyl
dithiophosphoric acids have the following formula: ##EQU2##
wherein: (c) R.sup.2 and R.sup.3 each independently represent
hydrocarbyl groups as described above, and (d) M.sup.2 represents
Group II metal cation as described above.
The dithiophosphoric acid salt is present in the lubricating oil
compositions of this invention in an amount effective to inhibit
the oxidation of the lubricating oil. This effective amount can
vary widely and typically ranges from about 1 to about 4.5 weight
percent, preferably from about 1.2 to about 2.25 weight percent of
the total lubricating oil composition.
Tricresyl Phosphate
The lubricating oil compositions of this invention include
tricresyl phosphate. This material is present in the lubricating
oil compositions of this invention in order to provide the proper
environment for break-in of new or "green" gears. Tricresyl
phosphate provides this break-in protection by acting as an extreme
pressure (EP) agent. It provides the requisite load-carrying
ability of the fluid without adversely affecting the other
performance characteristics of the fluid.
Tricresyl phosphate is the phosphoric acid ester of cresol. Cresol
is hydroxy toluene and is available in ortho, meta and para
isomers. A common source of cresol is petroleum from which the
cresol (cresylic acid) is obtained by distillation and extraction.
Because of its ready availability and low cost, mixed cresols
obtained from petroleum are preferred for preparing the tricresyl
phosphate used in the lubricating oil composition for this
invention.
The tricresyl phosphate is present in the lubricating oil
compositions of this invention in an amount effective to impart
extreme-pressure protection properties to the oil. This effective
amount can vary widely and typically ranges from about 0.5 to about
1.5 weight percent, preferably from about 0.75 to about 1.5 weight
percent of the total lubricating oil composition.
The Sulfurized Mixture of Olefins and Fatty Acid Esters
The lubricating oil compositions of this invention include
sulfurized mixtures of olefins and fatty acid esters. These
sulfurized mixtures are hereinafter referred to as
"cross-sulfurized ester-olefins". These cross-sulfurized
ester-olefins are present to provide extreme-pressure properties
and impart additional oiliness to the lubricating oil. They usually
exhibit equivalent or better oiliness and extreme-pressure
properties than the sulfurized sperm whale oil materials presently
available in relatively small quantities because the United States
Federal Government has placed whales on the endangered species
list. In addition, these crosssulfurized ester-olefins have
extremely good thermal stability. (They also appear to counteract
any tendency for wet disc brakes to chatter.)
The esters are derived from fatty acids containing 10-25 carbon
atoms. Examples of the fatty acids include unsaturated monoethenoid
acids such as oleic acid (C.sup.17 H.sub.33 COOH), palmitoleic acid
(C.sup.14 H.sub.27 COOH), petroselenic acid (C.sup.17 H.sub.33
COOH), urucic acid (C.sup.21 H.sup.41 COOH), gadoleic acid
(C.sup.19 H.sup.37 COOH), vaccenic acid (C.sup.17 H.sub.33 COOH),
and other naturally occurring and synthetic acids of the formula
CnH.sup.2 n.sup.-1 COOH; and unsaturated polyethenoid acids such as
linoleic acid (C.sup.17 H.sup.31 COOH). Also included are saturated
acids such as n-undecanoic (C.sup.10 H.sup.21 COOH), lauric
(C.sup.11 H.sup.23 COOH), myristic (C.sup.13 H.sup.27 COOH),
palmitic (C.sup.15 H.sup.31 COOH), stearic (C.sup.17 H.sup.35
COOH), and other naturally occurring and synthetic acids of the
formula CnH.sup.2 n.sup..sup.+1 COOH. Branched-chain fatty acids
are also included, as well as substituted acids such as ricinoleic
(C.sup.17 H.sup.32 OHCOOH).
Another suitable acid is tall oil. Tall oil is a byproduct of the
sulfate process for the manufacture of wood pulp. It consists of
about 50 percent resin acids. The resin obtained from various
species of pine is called rosin, which is chiefly abietic acid,
C.sup.20 H.sup.30 O.sup.2. The remaining 50 percent of tall oil
consists of unsaturated fatty acids, chiefly oleic and linoleic
acids. Thus, "derosinified tall oil" is a convenient source of
these unsaturated acids. Rosin is a source of the undesirable
auxiliary properties of lube oil additives when it is present in
high percentage in tall oil prior to neutralization and/or
sulfurization. Derosinified tall oil is commercially available. For
use in embodiments of the present invention, the derosinified tall
oil contains less than five percent of rosin.
The esters are illustrated by isopropyl oleate, ethyl linoleate,
pentadecyl oleate, eicosyl linoleate, decenyl stearate, eicosenyl
laurate, propyl linoleate, pentadecenyl linoleate, undecyl
ricinoleate, pentadecyl tallate, etc.
It is essential that either the alcohol or the fatty acid of the
ester be unsaturated. This is necessary for effective
cross-sulfurization. Although the usefulness of these materials as
lubricating additives is independent of any particular supposition
about the structure of the sulfurized products, it is believed that
the sulfurization step introduces sulfur by forming linkages with
-(S)n- between ethylenic double-bond positions. Thus it is believed
that either the alcoholic or acidic portions of the ester molecule
must be unsaturated to form effective linkages with the
olefins.
Examples of the alcohols which find use in preparing the ester used
in the present invention are methyl alcohol, propyl alcohol, butyl
alcohol, hexanol, octanol, undecanol, tetradecanol, etc.
Monoethenoid and polyethenoid alcohols are also included, such as
1-hydroxy-3-hexene, 2-hydroxy-5,7-dodecadiene,
1-hydroxy-4,7-pentadecadiene, 2-hydroxy-10-docosene, etc. The
alcohols can be straight-chain or branchedchain or partially
branched and partially straight-chain alcohols. Substituted
alcohols are also included, such as the 1,2-glycols, 1,3-glycols,
etc.
The olefins are aliphatic alkenes. Particularly preferred are the
cracked wax olefins, which are predominantly straight-chain
C.sup.10- C.sup.25 alpha-olefins. Other olefins within the scope of
this invention include monoethenoid and polyethenoid olefins,
conjugated olefins, and partially substituted olefins. The olefins
may be straight chain or branched, or they may be partially
straight chain and partially branched.
An excellent cross-sulfurized ester-olefin is obtained from a
mixture of the ester of oleic or linoleic acid with a C.sup.10
-C.sup.20 alcohol, such as undecyl alcohol and a C.sup.11 -C.sup.18
fraction of cracked wax olefins which is sulfurized to a sulfur
content of about 10 percent; the ratio of olefin to ester in the
mixture being about 1-2:1.
Another excellent cross-sulfurized ester-olefin is obtained when
derosinified tall oil is reacted with an alkyl alcohol and mixed
with cracked-wax olefin. The mixture is sulfurized to the extent of
4-10 percent of sulfur by weight. More preferably, derosinified
tall oil is reacted with a C.sup.10- C.sup.20 alkyl alkanol and
mixed with C.sup.11- C.sup.18 cracked wax olefin in a mol ratio of
1:1-2 and the mixture sulfurized to the extent of 4-10 percent
sulfur by weight.
Method of Preparation
Cross-sulfurized ester-olefin for use in this invention can be
prepared by a variety of methods. The methods which have been
utilized are designated as the 1-Step, 11/2-Step, and 2-Step
process, respectively.
In the 1-Step Process, a mixture of alcohol, fatty acid, olefin and
sulfur is heated under an inert atmosphere for a period of from
about 5 to about 25 hours and preferably from about 10 to about 20
hours. The reaction temperature is maintained at about 160.degree.C
to about 180.degree.C, and preferably about 165.degree.C to about
175.degree.C. The reaction product is a crosssulfurized
ester-olefin.
The 2-Step Process proceeds by acid-catalyzed esterification of the
fatty acid as the first step. The ester is then mixed with the
olefin and sulfur and cross-sulfurized as in the 1-Step Process.
The 11/2-Step Process comprises a noncatalytic esterification of
the fatty acid, followed by the usual cross-sulfurization with
olefin.
In the 1-Step Process, the mol ratio of olefin to acid to alcohol
can vary from about 0.5:1:1 to about 4:1:1, but about 1-2:1:1 is
the preferred ratio. Similar mol ratios are preferred in the other
processes.
The cross-sulfurized ester-olefins are present in the lubricating
oil compositions of this invention in amounts effective to provide
extreme-pressure properties and to reduce chatter of the brakes.
The effective amount usually ranges from about 0.5 to 1.5 weight
percent, more usually from about 0.75 to about 1.25 weight percent
of total lubricating oil composition.
The Lubricating Oil
The lubricating oils used for the hydraulic and transmission fluids
generally have viscosities in the range from about 75 to 1,000 SUS
(Saybolt Universal Seconds) at 100.degree.F and from about 35 to 75
SUS at 210.degree.F. The base oils for these functional fluids are
generally light lubricating oils ordinarily having a viscosity in
the range of about 50 to 400 SUS at 100.degree.F and 30 to 50 SUS
at 210.degree.F. The viscosity of both the base oil and the
finished lubricating oil can be chosen and tailored to meet the
requirements of the individual manufacturer of the equipment in
which the oil is to be used. For example, Deere and Company specify
in their specification J14B that the finished oil should have a
maximum viscosity at 0.degree.F, extrapolated, of 12,000 SUS and a
viscosity at 210.degree.F of 54 to 58 SUS. Mixtures of base oils
and various viscosity index improvers can be combined to provide
oils having the proper viscosity.
The base stock generally is a lubricating oil fraction of
petroleum, either naphthenic or paraffinic base, unrefined,
acid-refined, hydrotreated, or solvent-refined, as required by the
particular lubricating need.
Also, synthetic oils meeting the viscosity requirements, either
with or without viscosity index improvers may be used as the base
stock.
Other Additives
The functional fluids of this invention will normally contain a
number of other additives. It is usually necessary to heavily
compound such oils in order to meet the exacting requirements
specified by the manufacturers of heavy-duty equipment.
Included among the other additives which can be used are anti-foam
agents such as various silicone and fluorosilicone compounds
commercially available.
Another useful functional fluid additive is a seal swell agent. A
variety of compositions are useful for this function and include
the bottom product from catalytic cracking units used in producing
gasoline. These materials, containing a high percentage of
condensed ring aromatics, are commercially available from a number
of sources. One excellent seal swell agent is available from
Lubrizol Corp. under the name "Lubrizol 725." Another is available
from Ashland Oil Co., "ASHLAND APON".
Also generally included in functional fluids are viscosity
improving agents. These are normally high-molecularweight polymers
such as the acrylate polymers. Useful examples include the
copolymer of alkyl methacrylate with vinyl pyrrolidine available
under the trade name "Acryloid" from Rohm and Haas. Other alkyl
methacrylate copolymers with nitrogencontaining substituted vinyl
are also available. Terpolymers derived from styrene, alkyl
acrylate and nitrogen-containing polymer precursors are available
from Lubrizol Corp. under the name "Lubrizol 3,700" Series.
Methacrylates are available from Texaco Inc. Other viscosity
improving agents include hydrocarbon polymers such as
polyisobutylene or ethylene/propylene copolymers.
These additives will be present in the functional fluid in varying
amounts necessary to accomplish the purpose for which they were
included. For example, the antifoam agent will generally be present
in from about 2 to about 50 parts per million. The viscosity index
improver will normally be present in from about 0.5 to 15 weight
percent of the base oil, more usually from about 2 to about 10
weight percent of the base oil. The seal swell agent will be
present in an amount effective to control changes in the size of
the seals with which the functional fluid comes in contact. For
example, the bottoms from the catalytic cracking unit will be
present in an amount ranging from about 1 to about 10 percent, more
usually from about 2 to about 5 percent weight.
Quite often it is most convenient to prepare the lubricating oil
additives as a concentrate package which may be then shipped to the
user's location. The user then obtains the base oil from whatever
source he desires and blends the finished lubricating oil
compositions of this invention as needed.
Generally, to save shipping costs, the concentrate package contains
the smallest amount of diluent oil possible and the maximum amount
possible of each of the additives. The quantity of each additive
present in the concentrate will be correspondingly higher than that
found in the finished lubricating oil but the same relative
proportions of each of the additives will generally be maintained
in the concentrate. However, in some cases it may be found
desirable to prepare an additive package containing less than all
of the additives. In this case, generally two or more additive
packages are combined together with the base oil to provide the
finished lubricating oil. Such matters are well within those
skilled in the art and need not be further discussed.
EXAMPLES
The following examples are offered by way of illustration and not
by way of limitation.
EXAMPLE 1
An additive concentrate was prepared having the composition shown
in Table I. This concentrate was added to lubricating oil stocks
which contained a seal swell agent and low (Oil No. 1, Table II)
and high (Oil No. 2, Table II) levels of a viscosity index
improver. The concentrate was added to the lube oil stocks at the
rate of 8.10 weight percent. This provides a finished oil in which
components 1 through 6 are at the concentration shown in Table
I.
TABLE I ______________________________________ Additive Package
Concentration, Weight Percent Concen- Finished No. Component trate
Oil ______________________________________ 1 Neutral calcium salt
of a hydrocarbyl sulfonic acid prepared from a neutral lubricating
oil 25.27 2.05 2 Overbased version of compo- nent No. 1, 9.3 base
ratio, 11.4% calcium 26.04 2.11 3 Zinc di(n-octyl)dithio- phosphate
18.60 1.51 4 Tricresyl phosphate 12.35 1.0 5 Cross-sulfurized
mixture of the ester of a C.sub.12 --C.sub.13 alcohol &
derosinified tall oil & a cracked wax olefin (C.sub.15
--C.sub.18), 10.2 wt.% sulfur fluoro- silicone 12.35 1.0 6 Foam
inhibitor 0.2469 20 ppm 7 Diluent oil 5.1431
______________________________________
These two finished oils were tested for various physical properties
including rust prevention and copper corrosion. The results of
these tests are shown in Table II below.
TABLE II ______________________________________ Performance Tests
Fluid No. Viscosity 1 2 ______________________________________
-20.degree.F, (16 hr.) CP 26,800 17,200 -20.degree.F, (64 hr.) CP
30,500 20,100 0.degree.F, CP 4,010 3,900 0.degree.F, CSS*, CP 2,450
2,430 100.degree.F, SUS 269 273 210.degree.F, SUS 52.7 54.2 Index
115 128 Compatibility with Rubber Materials (JD Method) Volume
change, % 1.10 1.08 Durometer change none none Additive separation
none none Oxidation Test Evaporation loss 0.5 0.43 Viscosity
increase at 210.degree.F, % 1.0 0.25 Sludge formation none none
Additive separation none none Humidity Cabinet Test (ASTM-D-1748)
Hours to rust 100+ 100+ Copper Strip Corrosion Test 3 Hrs. at
212.degree.F (ASTM-D-130) 1A 1A Timken Test (ASTM 2782) OK load,
lbs -- 25 Foam Test (ASTM-D-892) T S T S Seq. I 0 0 5 0 Seq. II 20
0 25 0 Seq. III 0 0 0 0 ______________________________________ *CCS
= Cold Cranking Simulator
The above results demonstrate that an excellent hydraulic fluid is
provided by this invention.
In addition to the above tests, Oil No. 2 was tested for gear wear
protection according to the FZG Gear Test (DIN-51,354). In this
test, Dip-lubricated gears are weighed and operated at a fixed
speed and fixed initial oil temperature (90.degree.C) in the gear
oil under test. The load on the teeth is increased in increments.
After each load stage, the weight changes are determined and
recorded. For comparison, a gear oil containing a commercially
available additive prepared from sulfurized sperm whale oil was
tested. This additive has been the standard of the industry for the
past eight years. The results of the tests are shown in Table
III.
TABLE III ______________________________________ FZG Gear Test Load
Stage Oil No. 2 Reference oil
______________________________________ 1-11 pass pass 12 fail fail
______________________________________
These results demonstrate that results are obtained comparable to
the best obtained from the reference oil.
* * * * *