U.S. patent number 3,920,562 [Application Number 05/329,476] was granted by the patent office on 1975-11-18 for demulsified extended life functional fluid.
This patent grant is currently assigned to Chevron Research Company. Invention is credited to Edward G. Foehr.
United States Patent |
3,920,562 |
Foehr |
November 18, 1975 |
DEMULSIFIED EXTENDED LIFE FUNCTIONAL FLUID
Abstract
Functional fluid lubricating oil compositions are provided which
comprise (A) a major amount of an oil of lubricating viscosity, and
(B) an effective amount of each of the following: (1) an alkyl
succinimide, (2) a Group II metal salt of a dihydrocarbyl
dithiophosphoric acid, (3) a hydroxy fatty acid ester of a dihydric
or polyhydric alcohol or oil-soluble alkoxylated derivatives
thereof, and (4) a Group II metal salt of a hydrocarbyl sulfonic
acid. Such lubricating compositions are useful as functional fluids
in systems requiring fluid coupling, hydraulic fluid and/or
lubrication of relatively moving parts. The lubricating
compositions of the invention are particularly useful as the
functional fluid in automatic transmissions, particularly in
passenger automobiles. In addition, the fluids do not form stable
emulsions with water.
Inventors: |
Foehr; Edward G. (San Rafael,
CA) |
Assignee: |
Chevron Research Company (San
Francisco, CA)
|
Family
ID: |
23285587 |
Appl.
No.: |
05/329,476 |
Filed: |
February 5, 1973 |
Current U.S.
Class: |
508/294; 508/494;
508/501; 252/75 |
Current CPC
Class: |
C10M
1/08 (20130101) |
Current International
Class: |
C10M 001/48 () |
Field of
Search: |
;252/37.7E,33.4,52A,75 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Garvin; Patrick P.
Assistant Examiner: Metz; Andrew H.
Attorney, Agent or Firm: Magdeburger; G. F. Tonkin; C.
J.
Claims
We claim:
1. A lubricating oil composition which comprises:
A. a major amount of an oil of lubricating viscosity,
B. a dispersant amount of an alkenyl succinimide of a polyalkylene
polyamine,
C. an antioxidant amount of a Group II metal salt of a
dihydrocarbyl dithiophosphoric acid,
D. a friction modifying amount of a hydroxy fatty acid ester of a
dihydric or polyhydric alcohol or an oil-soluble oxalkylated
hydroxy fatty acid ester of a dihydric or polyhydric alcohol,
and
E. a detergent amount of a Group II metal salt of a
hydrocarbylsulfonic acid.
2. A lubricating oil composition of claim 1 wherein (1) said
alkenyl substituent of said succinimide is derived from
polyisobutene, (2) said hydrocarbyl groups of said dithiophosphoric
acid contain from 4 and 12 carbon atoms, (3) said fatty alkyl group
of said hydroxy fatty acid contains from 14 to 20 carbon atoms, and
(4) said Group II metal of said Group II metal salt of a
hydrocarbylsulfonic acid is magnesium, calcium or barium.
3. A lubricating oil composition of claim 1 wherein (1) said
alkenyl succinimide has the following formula: ##SPC5##
wherein:
a. R.sub.1 represents an alkenyl group,
b. the "Alkylene" radical contains from 1 to 8 carbon atoms,
c. A represents a hydrocarbyl group, an amine-substituted
hydrocarbyl group or hydrogen, and
d. n represents an integer of from 1 to 10;
2. said dithiophosphoric acid salt has the following formula: II
##SPC6##
wherein:
e. R.sub.2 and R.sub.3 each independently represent hydrocarbyl
radicals, and
f. M.sub.1 represents a Group II metal cation;
3. said hydroxy fatty acid ester has one of the following formulae:
##SPC7##
wherein:
g. R.sub.4 represents a hydrocarbyl radical containing 12 to 18
carbon atoms and zero to one site of olefinic unsaturation;
h. R.sub.5 represents the remainder of a dihydric or polyhydric or
polyhydric alcohol containing from 2 to 5 carbon atoms and from 2
to 4 hydroxyl groups,
i. R.sub.6 represents the remainder of a dihydric or trihydric
alcohol containing 2 to 3 carbon atoms;
j. R.sub.7 represents an alkylene containing 2 to 3 carbon
atoms;
k. x represents 1 or 2,
l. y represents 2 or 3, and
m. z represents an integer from 0 to 22 such that the total number
of --R.sub.7 O-- groups is from 1 to 22; and
4.
4. said Group II metal salt of a hydrocarbylsulfonic acid has the
following formula: ##SPC8##
wherein:
n. each R.sub.5 represents a hydrocarbyl group,
o. M.sub.2 represents a Group II metal cation. 4. A lubricating oil
composition of claim 3 wherein:
a. R.sub.1 represents an alkenyl group derived from
polyisobutene,
b. said alkylene radical contains from 2 to 4 carbon atoms,
c. A represents hydrogen,
d. n represent 3, 4 or 5,
e. R.sub.2 and R.sub.3 each represent a hydrocarbyl radical
containing from 4 to 12 carbon atoms,
f. M.sub.1 represents zinc,
g. R.sub.4 represents a hydrocarbyl radical containing 14 to 16
carbon atoms and one site of olefinic unsaturation,
h. x represents 1,
i. y represents 3,
j. z represents 1 to 17, and
k. M.sub.2 represents magnesium, calcium or barium.
5. A lubricating oil composition of claim 4 wherein:
a. said alkylene radical contains two carbon atoms,
b. n represents 4,
c. R.sub.2 and R.sub.3 each represent a hydrocarbyl radical
containing 8 carbon atoms,
d. the group CH.sub.3--R.sub.4 (OH).sub.x --COO is derived from
castor oil, and
e. M.sub.2 represents calcium.
6. A lubricating oil composition of claim 5 wherein said
composition contains
1. from 1.4 to 4 percent weight of said alkenyl succinimide,
2. from 0.5 to 1.5 percent weight of said dithiophosphoric acid
salt,
3. from 0.1 to 0.8 percent weight of said hydroxy fatty acid esters
or oil-soluble oxyalkylated hydroxy fatty acid esters, and
4. from 0.9 to 1.8 percent weight of said Group II metal salt of a
hydrocarbylsulfonic acid.
7. A lubricating oil composition of claim 6 wherein said
composition contains
1. from 1.75 to 2.25 percent weight of said alkenyl
succinimide,
2. 0.75 to 1.0 percent weight of said dithiophosphoric acid
salt,
3. from 0.2 to 0.6 percent of said hydroxy fatty acid esters or
oil-soluble oxyalkylated hydroxy fatty acid esters, and
4. from 1.0 to 1.4 percent weight of said Group II metal salt of
hydrocarbylsulfonic acid.
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 in systems requiring fluid coupling, hydraulic fluid, and/or
lubrication of relatively moving parts. In a preferred embodiment,
this invention relates to a lubricating oil composition useful as
the functional fluid in automatic transmissions, particularly
automatic transmissions used in passenger automobiles.
The trend today is towards longer and longer periods of time
between servicing of the modern passenger automobile. This trend
includes servicing of the automatic transmission. Automobile
manufacturers, for the convenience of their customers, are seeking
to extend the time between fluid changes in the automatic
transmission to greater and greater mileages.
Automatic transmission fluids are required to have a variety of
desirable characteristics besides acting as a satisfactory fluid
coupling or torque converter. Among these are allowing the
transmission to shift smoothly, allowing the transmission to lock
up during a shift from one speed to another within a certain
specified period of time, and lubricating relatively moving parts
such as bearing surfaces and clutch plates.
An automatic transmission is a complicated piece of machinery. It
includes a turbine drive unit with a torque converter and one or
more clutches which are engaged and disengaged automatically by an
intricate hydraulic control unit. In a typical automatic
transmission the clutches are made up of alternating steel plates
and steel plates faced on both sides with a friction material such
as compressed paper.
To achieve a smooth shift, the clutch plates are not abruptly
engaged, but are compressed together at a controlled rate, with
pressure varying with speed and torque. Therefore, for a finite
measurable period of time, the friction facings and steel surfaces
are in relative motion until complete engagement occurs. The time
elapsed between when shifting begins and relative motion between
the plates ceases is called the time to lock up.
This time to lock up is an important specification to be met in
qualifying an automatic transmission fluid for use in the
transmission of an automobile manufacturer. In order to not cause a
great strain on the drive train and obtain a smooth shift, maximum
and minimum times to lock up are specified.
The functional fluid used in automatic transmissions is subjected
to very severe conditions of use. The temperature of the automatic
transmission fluid under normal operating conditions will reach
275.degree.F. Under more severe conditions, such as during climbing
hills, trailer towing, stop-and-go traffic in the metroploitan
areas, etc., the fluid temperature can increase significantly above
this, up to, for example, 325.degree.F. and higher. In addition,
the fluid is constantly being pumped and agitated, thereby being
brought into initmate contact with the atmosphere within the
automatic transmission. Fresh air and atmospheric moisture are
constantly introduced through the transmission housing breather
tube. Under these conditions of high temperature and thorough
mixing, the fluid tends to be oxidized, forming undesirable
contaminants in the fluid, and modifying or impairing the desirable
characteristics of the fluid.
The degradation products which are produced during use cause the
characteristics of the functional fluid to change. The smoothness
of the shift can be lost and the time it takes to transmission to
lock up during a shift from one speed to another increases. As will
be appreciated, when the lock-up time increases, the clutch facings
are in relative motion to each other for a greater period of time,
thereby allowing for the possiblity of greater wear higher clutch
facing temperatures, and greater heat input to the fluid.
Eventually, the time to lock up will increase until it becomes too
long to be acceptable. Prior to this point, the automatic
transmission fluid must be changed to avoid permanent damage to
clutches and/or bands.
In addition to the possibility of permanent damage to friction
members, the degraded oil contains various contaminants which can
either coagulate and settle out or plate out as a film throughout
the transmission. This is particularly detrimental in the small
passages and close fitting spool valves of the hydraulic control
unit where a small amount of deposit can significantly change the
size of the openings, cause sluggish valve movement thereby
changing flow rates and pressures which, in turn, can markedly
affect the performance of the entire transmission. In addition,
should particules or lumps form in the fluid, they could completely
block small openings such as in screens or filters and totally
impair the function of the transmission.
In addition to possessing the necessary properties for use in an
automatic transmission, the fluid must sometimes exhibit special
properties because of conditions exisiting at the point of assembly
and initial filling of the transmission.
During assembly and testing of transmissions at some assembly
plants, large quanties of the fluid are spilled or otherwise escape
from the transmission. This fluid is recovered and reused.
Unfortunately, with age of the assembly facilities has come
problems. One of these problems includes water leaks into the fluid
recovery system. Before reuse of the recovered fluid, the water and
other foreign materials must be removed. This is accomplished by
passing the fluid through water separation and filtration
facilities.
However, the additives present in the fluid tend to promote forming
stable or semistable emulsions of the oil and water, a totally
unacceptable situation. Accordingly, fluids to be used for initial
fill of automatic transmissions in assembly facilities having a
water problem in the fluid recovery system, must exhibit all the
properties for long service life between changes. They must also
not form emulsions or must form unstable emulsions which break
relatively fast. The fluids of this invention are intended to meet
these requirements.
2. DESCRIPTION OF THE PRIOR ART
The use of amines and amine salts including hydroxyalkyl amines in
lubricting compositions is known. See Stuart and Lowe, U.S. Pat.
No. 2,758,086. Lubricating oil compositions containing heterocyclic
nitrogen-containing detergent polymers, oil-soluble salts of
amino-imides of long-chain mono-substituted polymeric hydrocarbyl
succinic anhydrides and thiophosphates are described in Henderson
et al., U.S. Pat. No. 3,265,618. The use of metal salts of
phosphorodithioic acid to improve the oxidative stability of
lubricating compositions has been often disclosed. See, for
example, Meinhardt, U.S. Pat. No. 3,347,790, and Rutherford et al.,
U.S. Pat. No. Re.22,829. The combination of N,N-dialkyl
aminoalkylene alkenyl succinimides and metal dithiophoshphates are
disclosed as being good detergent combinations in crankcase
lubricating oils which prevent the formation of sludges and
varnishes without contributing to the deposit of large amounts of
ash in the combustion chamber are described in Anderson et al.,
U.S. Pat. No. 3,018,247. "Lubricating Oil Compositions suitable for
use as automatic transmission fluids" are described in Butler et
al., U.S. Pat. No. 3,396,109. These compositions, which contain the
reaction product of a dihydrocarbyl phosphonidithioic acid with an
amine, are described as oxidation inhibitors and anitwear agents.
Lube oil compositions containing a basic alkaline earth metal
petroleum sulfonate, a copolymer of C-vinyl pyridine and an alkyl
methacrylate, and a succinimide of mono(polyolefin)succinic
anhydride and a polyalkylene polyamine have been described as
useful as turbine oils, gear oils, etc., in Henderson, U.S. Pat.
No. 3,438,897. These compositions can optionally contain zinc
dialkyl dithiophosphate.
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) an alkenyl
succinimide, (2) a Group II metal salt of a dihydrocarbyl
dithiophosphoric acid, (3) a hydroxy fatty acid ester of dihydric
or polyhydric alcohol or oil-soluble alkoxylated derivatives
thereof, and (4) a Group II metal salt of a hydrocarbyl sulfonic
acid. These lubricating oil compositions are useful as the
functional fluids in systems requiring fluid coupling, hydraulic
fluids and/or lubrication of relatively moving parts. These fluids
are particularly valuable since their useful life is significantly
greater than functional fluids currently available.
DESCRIPTION OF THE INVENTION
As described above, the extended life functional fluid compositions
of this invention comprise a major amount of an oil of lubricating
viscosity and an effective amount of each of an alkenyl
succinimide, a Group II metal salt of a dihydrocarbyl
dithiophosphoric acid, a hydroxy fatty acid ester, and a Group II
metal salt of a hydrocarbyl sulfonic acid.
The alkenyl succinimide is present to, among other things, act as a
dispersant and prevent formation of deposits formed during
operation of the system containing the functional fluid. Alkenyl
succinimides are well known. They are the reaction product of a
polyolefin polymer-substituted succinic anhydride with an amine,
preferably a polyalkenyl polyamine. The polyolefin
polymer-substituted succinid anhydries are obtained by the reaction
of a polyolefin polymer or a derivative thereof with maleic
anydride. The succinic anhydride thus obtained is reacted with the
amine. The preparation of the alkenyl succinimides has been
described many times in the art. See, for example, U.S. Pat. No.
3,390,082, in Cols. 2 through 6, wherein such a description is set
forth. Many of the alkenyl succinimides prepared by the techniques
set forth therein are suitable for use in the present
invention.
Particularly good results are obtained with the lubricating oil
compositions of this invention when the alkenyl succinimide is
derived from a polyisobutene substituted succinic anhydride an a
polyalylene polyamine.
The polyisobutene from which the polyisobutene substituted succinic
anhydride is derived is obtained from the polymerization of
isobutene and can vary widely in its compositions. The average
number of carbon atoms can range from 30 or less to 250 or more,
with a resulting average molecular weight of about 400 or less to
3,000 or more. Preferably, the average number of carbon atoms per
polyisobutene molecule will range from about 50 to about 100 with
the polyisobutenes having a number average molecular weight of
about 600 to about 1,500. More preferably, the average number of
carbon atoms per polyisobutene molecule ranges from about 60 to
about 90, and the number average molecular weight range from about
800 to about 1,300. The polyisobutene is reacted with maleic
anhydride according to well-known procedures to yield the
polyisobutene substituted succinic anhydride.
The substituted succinic anhydride is reacted with a polyalkylene
polyamine to yield the corresponding succinimide. Each alkylene
radical of the polyalkylene polyamine usually has up to about 8
carbon atoms. The number of alkylene radicals can range up to about
8. The alkylene radical is exemplified by ethylene, propylene,
butylene, trimethylene, tetramethylene, pentamethylene,
hexamethylene, octamethylene, etc. The number of amino groups
generally, but not necessarily, is one greater than the number of
alkylene radicals present in the amine, i.e., if a polyalkylene
polyamine contains 3 alkylene radicals, it will usually contain 4
amino radicals. The number of amino radicals can range up to about
9. Preferably, the alkylene radical contains from about 2 to about
4 carbon atoms and all amine groups are primary or secondary. In
this case the number of amine groups exceeds the number of alkylene
groups by 1. Preferably the polyalkylene polyamine contains from 3
to 5 amine groups. Specific examples of the polyalkylene polyamines
include ethylenediamine, diethylenetriamine, triethylenetetramine,
propylenediamine, tripropylenetetramine, tetraethylenepentamine,
trimethylenediamine, pentaethylenehexamine,
di-(trimethylene)-triamine, tri-(hexamethylene)-tetraamine,
etc.
Other amines suitable for preparing the alkenyl succinimide useful
in this invention include the cyclic amines such as piperizine,
morpholine and dipiperizines.
Preferably the alkenyl succinimides used in the compositions of
this invention have the following formula: ##SPC1##
wherein:
a. R.sub.1 represents an alkenyl group, preferably a substantially
saturated hydrocarbon derived from the polymerization of aliphatic
mono-olefins. Preferably R.sub.1 is derived from isobutene and has
an average number of carbon atoms and a number average molecular
weight as described above.
b. the "Alkylene" radical represents a substantially hydrocarbyl
group containing up to about 8 carbon atoms and preferably
containing from about 2-4 carbon atoms as described
hereinabove.
c. A represents a hydrocarbyl group, an amine-substituted
hydrocarbyl group, or hydrogen. The hydrocarbyl group and the
amine-substituted hydrocarbyl groups are generally the alkyl and
amino-substituted alkyl analogs of the alkylene radicals described
above. Preferably A represents hydrogen,
d. n represents an integer of from about 1 to 10, and preferably
from about 3-5.
The alkenyl succinimide is present in the lubricating oil
compositions of the invention is an amount effective to act as a
dispersant and prevent the deposit of contaminants formed in the
oil during operation of the system containing the functional fluid.
This effective amount can vary widely and is relatively high
compared to the levels of alkenyl succinimide normally used in
lubricating oils. For example, the amount of alkenyl succinimde can
range from about 1.4 percent to about 4 percent weight of the total
lubricating oil composition. Preferably the amount of alkenyl
succinimide present in the lubricating oil composition of the
invention ranges from about 1.75 to about 2.25 percent by weight of
the total composition.
As set forth above, the lubricating oil compositions of the
invention contain a Group II metal salt of a dihydrocarbyl
dithiophosphoric acid. One function of this salt is to act as an
oxidation inhibitor thereby preventing the formation of a variety
of oxygenated hydrocarbon products which impair the usefulness and
shorten the useful life of the lubricating oil.
As stated above, the temperatures to which the function fluids of
automatic transmissions are subjected are often severe. Under these
thermally severe conditions, not only is the lubricating oil quite
prone to oxidation, but antioxidant additives quite often undergo
thermal degradation. Accordingly, for a functional fluid to have an
extended useful life, the oxidation inhibitor added to the
lubricating oil must have good thermal stability at these
relatively high temperatures, or its thermal degradation products
must also exhibit antioxidation properties.
It has now been found that the above-mentioned Group II metal salts
of dihydrocarbyl dithiophosphoric acids exhibit the antioxidant and
thermal stability properties required for the severe service
proposed. Group II metal salts of phosphorodithioic acids have been
described previously. See, for example, U.S. Pat. No. 3,390,080,
cols. 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
composition of this invention contain from about 4 to about 12
carbon atoms, preferably from about 6 to about 12 carbon atoms, and
most preferably 8 carbon atoms, in each of the hydrocarbyl
radicals. The metals suitable for forming these salts include
barium, calcium, strontium, zinc and cadmium, of which zinc is
preferred.
Preferably, the Group II metal salt of dihydrocarbyl
dithiophosphoric acid have the following formula: ##SPC2##
wherein:
e. R.sub.2 and R.sub.3 each independently represent hydrocarbyl
radicals as described above, and
f. M.sub.1 represents a Group II metal cation as described
above.
The dithiophosphoric 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 0.5 to about 1.5
percent by weight of the total composition, preferably the salt is
present in an amount ranging from about 0.75 to about 1.0 percent
by weight of the total lubricating oil composition.
The hydroxy fatty acid ester contained in the lubricating oil
compositions of the invention principally acts as a friction
modifier to give the lubricating oil the proper frictional
charcteristics. These frictional characteristics are particularly
important where the functional fluid is to be used in automatic
transmissions. The frictional properties of the oil are an
important factor in how the oil lubricated clutch plates lock up
during shifting. Each manufacturer of automatic transmissions
specifies certain lock-up characteristics for the transmissions it
manufactures. Various friction modifiers are introduced into the
functional fluid to give the oil the proper characteristics to meet
the "shift feel" requirements of various manufacturers. The
friction modifiers contained in the lubricating oil compositions of
the present invention are particularly suited to maintain the
friction characteristics desired by General Motors Corporation over
an extended service interval.
The hydroxy fatty acid esters of the lubricating oil of the present
invention are selected from hydroxy fatty acid esters of dihydric
or polyhydric alcohols or oil-soluble oxyalkylenated derivatives
thereof.
The fatty acid moiety must be of sufficient length to make the
ester oil soluble. Suitably, the fatty acid moiety contains from 14
to 20 carbon atoms exclusive of alkoxylation, which can be in a
branched, but preferably are in a predominately straight chain
containing from zero to one, preferably one, site of olefinic
unsaturation. The fatty acid moiety is conveniently derived from
naturally occurring substances. For example, castor oil is
predominately a triglyceride in which the esterified acids are more
than 85 percent mono- and dihydroxy-substituted 18 carbon atom
acids with 0-1 sites of olefinic unsaturation.
In a preferred embodiment of this invention, the hydroxy fatty acid
ester has one of the following formulae: ##SPC3##
wherein:
g. R.sub.4 represents an alkylene, preferably substantially
straight chain, containing from 12 to 18 carbon atoms and zero to
one, preferably one site of olefinic unsaturation, such as the
alkylene necessary to complete oleic acid;
h. R.sub.5 represents the remainder of a dihydric or polyhydric
alcohol containing from 2 to 5 carbon atoms and 1 to 3 hydroxyl
groups;
i. R.sub.6 represents the remainder of a dihydric or trihydric
alcohol containing 2 to 3 carbon atoms;
j. R.sub.7 represents an alkylene preferably containing from 2 to 3
carbon atoms such as ethylene or propylene. If z represents an
integer greater than 1, R.sub.7 can represent mixtures of
alkylenes. Preferably, R.sub.7 does not represent mixed
alkylenes;
k. x represents 1 or 2, preferably 1;
l. y represents 2 to 3, preferably 3; and
m. z represents an integer from 0 to 22, preferably 1 to 17.
As the number of oxyalkylene groups contained in the compounds of
Formula IV increases, the oil solubility of the ester is reduced.
Accordingly, it is preferred that the total number of oxyalkylene
groups be no more than 22. This is conveniently determined by the
hydroxyl number of the compound. This number is determined by
reacting te compound with acetic anhydride and then titrating the
acetic acid produced with potassium hydroxide. The hydroxyl number
is expressed as the number of milligrams of potassium hydroxide
needed to neutralize the acetic acid produced by one gram of the
compound reacted with the acetic anhydride. Compounds of Formula IV
useful in the fluids of this invention preferably are those in
which y represents 3, R.sub.4 contains about 16 carbon atoms,
R.sub.7 represents ethylene, and the compound has a hydroxyl number
of from 100 to 160. In these compounds, z has an average value of
about 1 to about 7.
As discussed above, the fatty acid moiety can be derived from
natural sources which yield fatty acids of the requisite carbon
content. An excellent source of fatty acids for the preparation of
the compounds of Formula III is castor oil. The ricinoleic acid
derived therefrom can be esterified with various dihydric and
polyhydric alcohols such as ethylene glycol, propylene glycol,
glycerol and pentaerythritol.
An excellent source of the compounds of Formula IV is castor oil.
The hydroxyl groups of the ricinoleic acid can be oxyalkylenated
with various alkylene oxides such as ethylene oxide or propylene
oxide. The molecular weight, hydroxyl number and oil solubility can
be controlled by the number of moles of alkylene oxide added to a
mole of castor oil. Generally, the compounds useful in the
invention are adducts containing not more than 22 moles of alkylene
oxide per mole of castor oil.
Hydroxy fatty acid esters which have been found to be highly useful
in the compositions of this invention include compositions
available under the tradename "FLEXRICIN", particularly numbers
9-17 and compositions available under the tradename "SURFACTOL",
particularly numbers 318 and 340, all of which are available for
Baker Castor Oil Company.
Generally, the proper shift feel is obtained when the composition
contains from 0.1 to about 0.8 percent weight and preferably from
about 0.2 to about 0.6 percent weight hydroxy fatty acid ester
based on the total composition.
As stated above, the lubricating oil compositions of the invention
contain a Group II metal salt of a hydrocarbyl sylfonic acid. One
of the functions of this salt is to act as a detergent and
dispersant. Among other things it prevents 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 to
lubricating oil compositions. These salts comprise the
neutralization product obtained by reacting a Group II metal base
with the product obtained by treating a hydrocarbon oil with
sulfuric acid. The resulting oil-derived sulfonic acid, when
neutralized with the Group II metal compound, yields the sulfonate
which forms part of the composition of this invention.
Several processes for preparing these sulfonates are briefly
outlined in U.S. Pat No. 2,395,713. Other processes are also
discussed in U.S. Pat. No. 2,388,677.
The hydrocarbon portion of the sulfonate used in the lubricating
oil compositions of the invention is derived from a hydrocarbon oil
stock or synthetic organic moieties such as alkylated aromatics.
Being derived from such a material the hydrocarbon moiety is a
mixture of different hydrocarbyl groups, the specific composition
of which depends upon the particular oil stock which was used as
the starting material. The fraction of the oil stock which becomes
sulfonated is predominantly an aliphatic-substituted carbocyclic
ring. The sulfonic acid group 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 aliphateic substituent of the carbocyclic
ring affects the oil solubility and detergency properties of the
sulfonate. Suitably, the aliphatic substituent contains from about
12 to about 30 carbon atoms, and preferably from about 20 to 25
carbon atoms. The aliphatic substituent can be a straight or
branched chain and can contain a limited number of olefinic
linkages, preferably less than 5 percent of the total
carbon-to-carbon bonds are unsaturated.
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 I metal salt of a hydrocarbylsulfonic acid has
the following formula: ##SPC4##
wherein:
n. each R.sub.5 represents a hydrocarbyl group as described above,
and
o. M.sub.2 represents a Group II metal cation as described
above.
The group II metal salts of hydrocarbyl sulfonic acids are present
in the lubricating oil compositions of the invention in an amount
effective to prevent the deposit of contaminants formed in the oil
during severe high temperature operation of the system containing
the composition. This effective amount can vary widely and
typically ranges from about 0.9 percent to about 1.8 percent
weight, preferably from about 1.0 to about 1.4 percent weight of
the total lubricating oil composition.
AUTOMATIC TRANSMISSION FLUIDS
In a preferred embodiment the compositions of this invention are
particularly suited for use in automatic transmissions,
particularly in passenger automobiles. Automatic transmission
fluids generally have a viscosity 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 the automatic
transmission fluids are light lubricating oils and ordinarily have
a viscosity in the range of about 50 to 400 SUS at 100.degree.F.
and 33 to 50 SUS at 210.degree.F. The base stock is a lubricating
oil fraction of petroleum, either naphthenic or paraffinic base,
unrefined, acid refined, hydrotreated or solvent refined as
required in the particular lubricating need. Also, synthetic oils
meeting the necessary viscosity requirements, either with or
without viscosity index improvers, may be used as the base
stock.
To summarize, the various constituents will be present in the
automatic transmission fluid as follows. The alkenyl succinimide
used in this invention generally will be present on the functional
fluid in from about 1.4 to about 4 percent weight, more usually
from about 1.75 to about 2.25 percent weight. In concentrates
prepared for addition to the base oil prior to use, the alkenyl
succinimide can be present in from about 10 to about 35 weight
percent. The Group II metal salt of a dihydrocarbyl
dithiophosphoric acid will generally be present in the functional
fluid in from about 0.5 to about 1.5 percent weight, more usually
from abut 0.75 to about 1.0 percent weight. The dithiophosphoric
acid salts may be present in concentrates from about 5 to about 20
percent weight. The hydroxy fatty acid esters will generally be
present in the functional fluid in from about 0.1 to about 0.8
percent weight, more usually from about 0.2 to about 0.6 percent
weight. The amine may be present in concentrates in from about 2 to
about 6 percent weight. The group II metal salt of hydrocarbyl
sulfonic acid will generally be present in the functional fluid in
from about 0.9 to about 1.8 percent weight, more usually from about
1.0 to about 1.4 percent weight. The sulfonic acid salt may be
present in concentrates from about 5 to about 15 percent
weight.
The functional fluid will normally contain a large number of other
additives. It is usually necessary to heavily compound such oils in
order to meet the exacting requirements specified.
Included among the other additives which can be used are additional
oxidation inhibitors, such as, for example, the adduct obtained by
combining terpene and phosphorous pentasulfide. Suitable materials
are commerically available under the trade names Santolube and
Hitec available from Monsanto Company and Edwin L. Cooper, Ltd.
respectively.
Also commonly used in functional fluids are antifoam agents such as
various fluorosilicone compounds commercially available. A
particularly good antifoam agent is available from Dow Corning
under the name FS 1265 Fluid.
Another useful functional fluid additive is a seal swell agent. A
variety of compounds are useful for this function and include the
bottoms product from catalytic cracking units used in the
production of gasolines. These materials, containing a high
percentage of condensed ring aromatics, are commerically available
from Lubrizol Corporation under the name Lubrizol 725.
Also included in functional fluids are viscosity improving agents
which are normally high molecular weight polymers such as the
acrylate polymers. Useful examples include the copolymers of alkyl
methacrylate with vinyl pyrrolidine available under the tradename
"Acryloid" from Rohm & Haas and terpolymers derived from
stryene, alkylacrylates and nitrogen-containing polymer precursors
available from Lubrizol Corporation under the name Lubrizol 3,700
Series and methacrylates 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, additional oxidation inhibitors such as the
terpene-phosophorous pentasulfide adduct may be present in amounts
ranging from about 0.1 percent to about 1 percent weight or more.
The fluorosilicone antifoam agent, for example, will generally be
present in from about 2 to about 50 ppm. The viscosity index
improver will normally be present in from about 0.5 to about 15
percent by weight of the base oil, more usually from about 2 to
about 10 percent by weight of the base oil. The seal swell agent
will be present in an amount effective to control 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.
Other additives include pour point depressants, antisquawk agents,
etc. Numerous automatic transmission fluid additives are listed in
U.S. Pat. Nos. 3,156,652, and 3,175,976, which disclosure is
incorporated herein by reference.
These various additives are also often incorporated into the
concentrates and will be present therein corespondingly higher
concentrations.
EXAMPLES
The following examples are offered by way of illustration and not
by way of limitation.
EXAMPLE 1
Demulsibility Testing Procedure
The following is a test procedure for determining the
demulsifibility of the fluids of this invention. Automatic
transmission fluids approved for use in General Motors automatic
transmissions must pass this test.
200 milliliters of the test oil at 80.degree.F. is placed in a
Waring.sup.R blender CC 8 W Model 1174. The blender is operated at
the lowest speed for 30 seconds at which time 20 milliliters of
distilled water is added. The blender is operated at the same speed
for an additional 60 seconds. The oil-water mixture is then placed
in a 400-ml. breaker which is covered with a watch glass and placed
in a constant temperature oven set at 160.degree.F. The rate of
water separation, oil clarity, water clarity, and interface layer
condition are observed at 2, 4 and 24 hours.
FLUID COMPOSITION
Table I shows the composition of a base fluid from which fluids in
accordance with this invention can be prepared.
Table I ______________________________________ Base Fluid
______________________________________ Quantity in Component Base
Fluid ______________________________________ Commercially available
styrene/ 4.0 % W alkylacrylate/nitrogen-containing polymer
precursor terpolymer Alkenyl succinimide derived by 4.0 % W
reacting a polyisobutene (number average molecular weight about
950) substituted succinic anhydride with tetraethylenepentamine;
mole ratio of amine to anhydride = 0.87 Zinc dioctyl
dithiophosphate derived 10 mM/kg from mixed primary octanols
Neutral calcium salt of a hydrocarbyl 8 mM/kg sulfonic acid
prepared from a neutral lubricating oil Antifoam agent -
commercially avail- 15 ppm able fluorosilicon Seal Swell Agent -
commercially 3.5 % W available hydrocarbon obtained as a bottoms
cut from the stream from a catalytic cracking unit used to produce
gasoline; predominately con- densed ring aromatic compounds Eastern
base oil having a viscosity to make 100 % W of 109 SUS at
100.degree.F and 40 SUS at 210.degree.F
______________________________________
Table II shows the results of demulsibility testing of several
fluids of the invention (Fluids 1-6). These fluids were prepared by
adding the materials indicated in the Table to the base fluid shown
in Table I. Fluid No. 7 is a currently approved fluid which lasts
475 hours in the AT-12 test described in Example II. However, as
shown, it will not pass the demulsibility test and is not
acceptable for use in plants having a water problem in the
transmission assembly facilities.
Table II
__________________________________________________________________________
Demulsibility Test Results Additives to Fluid of Table I 2 Hours 4
Hours 24 Hours
__________________________________________________________________________
glyceryl monoricinoleate 0.4 % W W.sup.(1) 20.sup.(2) 20 20 O 200
200 200 E 0 0 0 glyceryl monoricinoleate 0.4 % W W 20 20 20 O 200
200 200 E 0 0 0 ethylene oxide adduct of castor oil; W 20 20 20 OH
value = 112, 0.2 % W plus coco- O 200 200 200 nut oil fatty alkyl
diethanol amine, E 0 0 0 0.2 % W adduct of No. 3, 0.3 % W plus
amine of W 20 20 20 No. 3, 0.2 % W O 200 200 200 E 0 0 0 ethylene
oxide adduct of castor oil; W 10 15 20 OH value = 149, 0.2 % W plus
amine of O 10 10 200 No. 3, 0.2 % W E 200 195 0 penterythritol
monoricinoleate 0.2 % W W 10 20 20 O 10 200 200 E 200 0 0 coconut
oil fatty alkyl diethanol W 0 0 5 amine 0.2 % W O 0 0 25 E 220 220
190
__________________________________________________________________________
.sup.(1) W = Water, O = Oil, E = Emulsion .sup.(2) Volume in
milliliters of various phases
COMPATIBILITY TESTING
Fluids which pass the demulsibility test above must be compatible
in this test with other approved fluids in order to receive Genral
Motor's approval. This is determined by mixing 100 ml of the test
fluid with 100 ml of an approved fluid and testing the mixture in
the demulsification test. Table III shows the results of
compatibility testing several fluids. Fluid A is a currently
approved DEXRON.sup.R fluid available from Humble. This fluid
approved for 225 hours use in the AT-12 test (see Example II). The
fluid numbers refer to the oils in Table II.
Table III ______________________________________ Compatibility
testing Fluid 2 Hours 4 Hours 24 Hours
______________________________________ 8. A W 12 20 20 O 198 200
200 E 0 0 0 9. A + 1 W 0 7 20 O 20 20 200 E 200 193 0 10. A + 2 W
10 20 20 O 20 200 200 E 190 0 0 11. A + 3 W 0 0 20 O 20 20 200 E
200 200 0 12. A + 4 W 0 10 20 O 20 20 200 E 200 190 0
______________________________________
Oils 1-4 in Table II are compatible with the currently approved
automatic transmission. These results demonstrate that not only do
the fluids of this invention possess the required degree of
demulsibility but also exhibit th requisite compatibility.
EXAMPLE 2
General Motors AT-12 Test
Fluids proposed for use in General Motors automatic transmissions
must pass a simulated use conditions test designated AT- 12 or Low
Energy Cycling Test (LECT) 1970 Re-Revision.
The AT-12 test involves cycling a 350 cubic inch displacement
General Motors engine driving a dynamometer-loaded Chevrolet
Powerglide two-speed automatic transmission. Briefly, the cycle is
as follows. The engine, operating at idle, is given a preset amount
of throttle. Acceleration continues in "Lo" until the engine
reaches about 3,200 rpm (elapsed time 7.8.+-.0.1 seconds). The
transmission shifts to "Drive" during which engine speed drops to
about 2,300 rpm. This preset throttle condition is maintained for a
total of 30 seconds at which time output torque must be 230-235
foot pounds with input speed about 2,300 rpm and output speed about
1,920 rpm. The throttle is then returned to the idle position for
10 seconds. Deceleration takes place and includes a down-shift into
"Lo". At the end of 10 seconds when engine speed has reached about
1,100 rpm, the throttle is opened and the cycle is repeated.
This cycled test is continued 24 hours per day, generally
interrupted only mechanical difficulties, a shutdown for 24 hours
at about 150 test hours, and weekend layovers. The time to lockup
during the shift from Lo to Drive is measured regularly. Initial
lockup mut be in the range of 0.375 to 0.6 seconds. The useful life
of the fluid is considered spent when lock-up time exceeds 0.80
seconds. Current standards set by General Motors require the
0.80-second lock-up time not be reached for at least 225 hours.
Oil No. 1 of Table II was subjected to this test. A lock-up time of
0.6 seconds was reached after 436 hours of operation.
The above data demonstrate the long useful life of the functional
fluids of this invention when placed in service in passenger
autombile automatic transmissions. The useful life of the
functional fluid tested above in the very severe AT-12 test
exceeded the useful life specified by Genral Motors for such fluids
to used in transmissions manufactured by that company by 194
percent. This greatly extended useful life will allow greater oil
drain intervals and thereby reduced operating costs for the owner
of the vehicle.
While the invention has been described in detail and with reference
to specific embodiments, it will be obvious other variations and
embodiments can be effected within the spirit and scope of the
appended claims.
* * * * *