U.S. patent number 3,865,740 [Application Number 05/332,864] was granted by the patent office on 1975-02-11 for multifunctional lubricating oil additive.
This patent grant is currently assigned to Chevron Research Company. Invention is credited to Alfred Goldschmidt.
United States Patent |
3,865,740 |
Goldschmidt |
February 11, 1975 |
MULTIFUNCTIONAL LUBRICATING OIL ADDITIVE
Abstract
The N-substituted, S-aminomethyl dithiophosphates, wherein said
substituent is selected from the group consisting of hydrocarbyl,
hydrocarbyl-substituted amines, and hydrocarbyl-substituted
succinimides, are found to function as extreme pressure agents,
oxidation inhibitors and ashless dispersants in lubricating
oils.
Inventors: |
Goldschmidt; Alfred (El
Cerrito, CA) |
Assignee: |
Chevron Research Company (San
Francisco, CA)
|
Family
ID: |
26944807 |
Appl.
No.: |
05/332,864 |
Filed: |
February 14, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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255605 |
May 22, 1972 |
|
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Current U.S.
Class: |
508/289; 548/413;
987/209 |
Current CPC
Class: |
C10M
137/105 (20130101); C07F 9/1651 (20130101); C10M
2209/105 (20130101); C10M 2207/282 (20130101); C10M
2209/104 (20130101); C10N 2050/10 (20130101); C10M
2205/024 (20130101); C10M 2223/047 (20130101); C10M
2229/02 (20130101); C10M 2223/08 (20130101); C10M
2207/34 (20130101); C10M 2207/04 (20130101); C10M
2205/028 (20130101); C10M 2205/026 (20130101); C10M
2223/00 (20130101); C10M 2209/103 (20130101); C10M
2223/063 (20130101); C10M 2205/00 (20130101); C10M
2229/05 (20130101); C10M 2207/283 (20130101); C10M
2209/108 (20130101); C10M 2205/02 (20130101) |
Current International
Class: |
C10M
137/00 (20060101); C10M 137/10 (20060101); C07F
9/00 (20060101); C07F 9/165 (20060101); C10m
001/48 () |
Field of
Search: |
;252/46.7
;260/326.5F |
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. La
Paglia; S. R.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
The present application is a continuation-in-part of U.S.
application Ser. No. 255,605, filed May 22, 1972 and now abandoned.
Claims
I claim:
1. A lubricating composition comprising an oil of lubricating
viscosity and from 0.1 to 10 percent by weight of an N-substituted,
S-aminomethyl dithiophosphate, wherein said substituent is a
hydrocarbyl-subtituted succinimide of a hydrocarbyl polyamine, and
wherein said hydrocarbyl substituent contains at least 40 carbon
atoms.
2. A lubricating oil composition according to claim 1, wherein said
hydrocarbyl-substituted succinimide is an imide of alkylene
polyamine.
3. A lubricating oil composition according to claim 2, wherein said
hydrocarbyl group is a polypropenyl or polybutenyl substituent
containing from 40 to about 300 carbon atoms, and said alkylene
polyamine is ethylene or propylene polyamine.
4. A lubricating oil composition according to claim 3 wherein said
hydrocarbyl substituent is a polyisobutenyl group containing from
40 to about 100 carbon atoms.
5. A lubricating oil composition containing an oil of lubricating
viscosity and from 0.1 to 10 percent by weight of a lubricating oil
additive of the general formula ##SPC2##
wherein R.sup.1 and R.sup.2 are alkyl, aryl, alkaryl or aralkyl
groups of from about one to 20 carbon atoms, and X and Y are
radicals, one of which may be hydrogen, but at least one of which
is a hydrocarbyl-substituted succinimide of a hydrocarbyl
polyamine, and wherein said hydrocarbyl substituent contains at
least 40 carbon atoms.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
Auto manufacturers report a number of cases of extreme oil
thickening have occurred in customer service with certain engine
models and crankcase oils. These oils, which are excellent for
light-duty, stop-and-go service, oxidized and thickened under
conditions of sustained high speed, heavy load operations. It is
not possible to properly lubricate an engine under conditions of
extreme lubricating oil viscosity and as a consequence extensive
damage to the engine can occur.
Measurements show that temperatures in excess of 300.degree.F. are
not uncommon oil temperatures in engines operating at high speeds
under conditions of heavy loads, as in trailer towing.
5.degree.-10.degree.F. can be added to oil temperature by power
consuming options such as air conditioning. Further increases in
engine operating temperatures are caused by changes in engine
design to reduce exhaust emissions. For example, high temperature
thermostats, reduced compressin ratio, compression spark timing,
and lean air-fuel ratios tend to either increase the thermal loads
on the engine cooling system or increase the operating temperature.
Oil oxidation is promoted and oil thickening is thereby accelerated
by lean air-fuel ratios which produce blow-by gases containing high
concentrations of oxides of nitrogen. It is believed that the oil
thickening problem is related to unusually high engine temperatures
and resultant oxidation. The trend toward the operation of
passenger cars at higher sustained road speeds and heavier load
conditions makes this a potentially serious problem in the
formulation of ashless crankcase oils.
Very little is known about the role of oil composition in oxidative
oil thickening. It has been established, Lubrication, Vol. 57, No.
7, 1971, that certain viscosity increases in crankcase oils under
high load conditions are correlated with oil oxidation. The
mechanism of oil thickening is a very complex chemical process
involving primarily oxidation and nitration of the oil. The cited
reference also shows that additional zinc dithiophosphate, which is
a commonly used oxidation inhibitor, offers little benefit towards
improving the thickening resistance of motor oils, in some types of
formulations, within the lubricant performance range of commercial
interest. It is also believed that the presence of large amounts of
ash-containing basic detergent/dispersant, which is needed for low
temperature anti-sludge performance, fosters oxidative thickening
of the crankcase oils at high temperature.
Consequently, it is necessary to find other oxidation inhibitors
and dispersants for lubricating oils which improve the antioxidant
properties of the lubricating oils as well as low temperature
anti-sludge dispersancy. These additives are preferably ashless. It
is found that a formaldehyde of condensation products of
formadlehyde and certain dithiophosphoric acid esters with certain
high molecular weight amines and imides, which are hereafter
described as N-substituted, S-aminomethyl dithiophosphates, form an
improved class of antioxidants/dispersants for lubricating oil
compositions. The N-substituted, S-aminomethyl dithiophosphates
were also found to function as extreme pressure agents.
2. Description of the Prior Art
U.S. Pat. No. 2,586,656 describes certain low molecular weight
S-aminoalkylidene dithiophosphoric acid triesters which may serve
as antioxidant additives in lubricating oil compositions.
SUMMARY OF THE INVENTION
A class of dithiophosphoric acid ester derivatives has been found
to possess a surprising lubricating additive trifunctionality, in
that they function as effective extreme pressure agents,
antioxidants and ashless dispersants when present in 0.5 to 10
percent by weight in lubricating oil compositions. These additives
are N-substituted, S-aminomethyl dithiophosphates, wherein said
substituent is selected from the group consisting of hydrocarbyl,
hydrocarbyl-substituted amine, and hydrocarbyl-substituted
succinimide, and said hydrocarbyl-substituents contain at least 40
carbon atoms. They have the additional advantage of being
ashless.
DESCRIPTION OF PREFERRED EMBODIMENTS
The dithiophosphates of the present invention are O,O-diesters of
dithiophosphoric acid. These dithiophosphates are alkyl, aryl,
alkaryl or aralkyl diesters of dithiophosphoric acid. The
N-substituted, S-aminomethyl dithiophosphates of the present
invention are derived from the dithiophosphates by concensing the
O,O-diester of dithiophosphoric acid with formaldehyde, or another
aldehyde, and a hydrocarbyl-substituted amine, polyamine, or
hydrocarbyl-substituted succinimide of a polyamine. The
condensation is believed to proceed according to the following
reaction: ##SPC1##
R.sup.1 and R.sup.2 are alkyl, aryl, alkaryl or aralkyl radicals,
or heteroatom-substituted hydrocarbyl radicals, of from low to
moderate molecular weight and they may be the same or different.
The O,O-diester of dithiophosphoric acid is produced by the
reaction of phosphorus pentasulfide with an alcohol, mixture of
alcohols, or alkylphenol from which R.sup.1 and R.sup.2 are
derived. R.sup.1 and R.sub.2 can be alkyl, aryl, alkaryl or aralkyl
groups of from about 1 to about 20 carbon atoms. R.sup.1 and
R.sup.2 can also be derived from ether-capped polyoxyalkylene
glycols. Preferably, R.sup.1 and R.sup.2 are hydrocarbyl or
substituted hydrocarbyl groups of relatively low molecular weight,
such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl,
tetradecyl, dodecyl, decyl, octadecyl, phenyl, naphthyl, methyl
phenyl, butyl phenyl, isooctyl, polypropenyl, polyisobutenyl,
etc.
The aldehyde which is the preferred condensing agent for the
preparation of the products of this invention is formaldehyde, in
which case R.sup.3 is hydrogen. However, formaldehyde may be
replaced by other aldehydes, for example, benzaldehyde,
isobutyraldehyde, butyraldehyde, propionaldehyde, acetaldehyde,
valeraldehyde, hexaldehyde, etc., in which case R.sup.3 is a
hydrocarbyl or substituted hydrocarbyl group.
HNXY represents a substituted primary or secondary amine of
relatively high molecular weight (500-10,000). X and Y are radicals
of which one may be hydrogen, but at least one is chosen from the
group consisting of hydrocarbyl, hydrocarbyl-substituted amine and
hydrocarbyl-substituted succinimide of a polyamine. Consequently,
the reactant HNXY is a hydrocarbyl-substituted amine or polyamine,
or a hydrocarbyl-substituted succinimide of a polyamine.
Hydrocarbyl, as used herein, denotes a monovalent organic radical
composed of carbon and hydrogen, except for minor, insubstantial,
sometimes adventitious, amounts of other elements such as oxygen,
nitrogen, halogen, etc., which may be aliphatic, alicyclic,
aromatic, or combinations thereof, e.g., aralkyl. Preferably the
hydrocarbyl group will be relatively free of aliphatic
unsaturation, i.e., ethylenic and acetylenic, particularly
acetylenic unsaturation.
The hydrocarbyl substituent in HNXY contains an average of at least
40 and preferably less than an average of 300 carbon atoms. It is
preferably aliphatic, having preferably from zero to two sites of
ethylenic unsaturation and most preferably from zero to one such
site. Hydrocarbyl groups derived from a polyolefin, itself derived
from olefins (normally 1-olefins) of from two to six carbon atoms
(ethylene being copolymerized with a higher olefin), or from a
higher molecular weight petroleum-derived hydrocarbon, are
preferred, and of these, polyisobutene containing from 40 to about
100 carbon atoms is most preferred. Illustrative sources for the
high molecular weight hydrocarbyl substituents are petroleum
mineral oils such as naphthenic bright stocks, polypropylene,
polyisobutylene, poly-1-butene, copolymers of ethylene and
propylene, poly-1-pentene, poly-4-methyl-1-pentene, poly-1-hexene,
poly-3-methylbutene-1, etc.
The hydrocarbyl-substituted amines are derived from lower molecular
weight amines (LMW amine), preferably alkylene polyamines and
polyalkylene polyamines, by, for example, the reaction of a
halogenated hydrocarbon with the LMW amine. Examples of such LMW
amines include ethylenediamine, methylamine, 2-aminoethyl
piperazine, decylamine, diethylenetriamine, octadecylamine,
di(trimethylene) triamine, ethylene dipiperazine,
dipropylenetriamine, piperazine, triethylenetetramine,
tripropylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, etc. The LMW amines encompass substituted
and alkyl-substituted amines, e.g., N-methylethylenediamine,
hydroxyethyl piperazine, N,N'-dimethylethylenediamine,
N,N-dimethylpropylenediamine, N,N-dimethyldiamino propane,
N-hydroxyethyl ethylenediamine, etc. Amines having up to about 12
amino nitrogens and up to about 36 carbon atoms are especially
preferred LMW amines. The hydrocarbyl-substituted amines are
prepared, in general, by the reaction of halogenated hydrocarbon
with the LMW amine. Details of such preparations and further
description of certain hydrocarbyl amines can be found in Hotten
and Anderson U.S. Pat. No. 3,565,804.
In preparing the compositions of this invention, rarely will a
single compound be employed. With both the polymers and the
petroleum-derived hydrocarbyl groups, the composition is a mixture
of materials having various structures and molecular weights.
Therefore, in referring to molecular weight, average molecular
weights are intended. Furthermore, when speaking of a particular
hydrocarbyl group, it is intended that the group include the
mixture that is normally contained with materials which are
commercially available; that is, polyolefins are known to have a
range of molecular weights. Furthermore, depending on the method of
preparation, the end group of the polymer may vary and may be
terminated, not only with an isobutene group, but also with a 1- or
2-butene group. In addition, alkylene polyamines which are
commercially available are frequently mixtures of various alkylene
polyamines and branched chain isomers having one or two species
dominating. Thus, in commerically available tetraethylene
pentamine, there will also be small amounts of pentaethylene
hexamine and triethylene tetramine. In referring to
hydrocarbyl-substituted tetraethylene pentamine, which is the
preferred amine, it is intended not only to include the pure
compound, but those mixtures which are obtained with commercially
available alkylene polyamines. Finally, as indicated, in preparing
the compounds of this invention, where the various nitrogen atoms
of the alkylene polyamine are not equivalent, the product will be a
mixture of the various possible isomers.
The hydrocarbyl-substituted succinimides which find use as nitrogen
substituents in the N-substituted, S-aminomethyl dithiophosphate
are prepared by first making a monohydrocarbyl succinic acid or
anhydride derivative and then reacting the resultant anhydride or
acid with a polyamine. These compounds are described in more detail
in numerous references in the art. See, for example, U.S. Pat. No.
3,219,666, as well as U.S. Pat. Nos. 3,018,250; 3,087,936;
3,172,892; 3,630,902; and 3,202,678.
The mono-hydrocarbyl succinic acids or anhydrides are prepared by
forming the adduct of maleic anhydride with a suitable olefin
polymer, chlorinated hydrocarbon, etc. This reaction proceeds upon
mixing and heating of the components at temperatures in the range
of from about 100.degree.-200.degree.C. The preparation of these
mono-hydrocarbyl succinimides is then effected by the reaction of,
for example, mono-hydrocarbyl succinic anhydride with such LMW
primary amines or polyamines containing a primary amino nitrogen
atom as ethylamine, propylamine, butylamine, tetraethylene
pentamine, triethylene tetramine.
The preparation of certain of the hydrocarbyl-substituted
succinimides of use in the present invention has been described in
U.S. Pat. No. 3,018,291 and the other cited U.S. Patents. In the
preparation of these succinimides, LMW polyalkylene polyamines
having up to about 12 amino nitrogens are especially preferred. It
is understood that the reaction products comprise amides, amine
salts, and amidines, as well as the principal imide.
The preferred succinimides are polyisobutenyl succinimides prepared
by reaction of a substituted succinic acid or anhydride derived
from a polybutene having at least 40 carbon atoms and tetraethylene
pentamine or triethylene tetramine. The succinic acid or anhydride
and the polyamine are preferably reacted in approximately equal
molar ratio to obtain the succinimide product.
Method of Preparation
Typically, one mol of substituted amine is diluted with benzene,
approximately 0.9-1.1 mols of CH.sub.2 O are added, and stirred for
about one hour at 120.degree.-150.degree.F. Approximately 1 mol of
dithiophosphoric acid is then added, and the mixture is heated for
3-5 hours at 170.degree.-190.degree.F. The product is then stripped
of solvent and analyzed.
Example 1
650 g. of polyisobutenyl ethylene diamine (80 percent concentrate
in a 100 SSU at 100.degree.F. neutral oil), wherein the number
average molecular weight of the polyisobutenyl was 1,400 (average
carbon number of 100), was diluted with 300 ml of benzene. 37 g. of
a 37 percent aqueous CH.sub.2 O solution was added, whereupon the
temperature rose from 75.degree. to 87.degree.F. The mixture was
stirred one-half hour and 120 g. of di(isooctyl)dithiophosphoric
acid was added in 100 ml. of benzene. The temperature rose to
107.degree.F, whereupon heat was applied and the mixture was
stirred for 5 hours at 170.degree.-180.degree.F. 150 g. of a 100
SSU at 100.degree.F. neutral petroleum oil was added, and the
product stripped of solvent at 220.degree.F for 3 minutes. Percent
phosphorus, 1.04.
Example 2
700 g. of polyisobutenyl succinimide of ethylene diamine (as 50
percent concentrate in 100 SSU at 100.degree.F. neutral petroleum
oil), wherein the number average molecular weight of the
polyisobutenyl was 950, was diluted with 200 ml of benzene. 10.5 g.
of paraformaldehyde was added and the mixture was stirred for 1
hour at 120.degree.-130.degree.F. 120 g. of
di(isooctyl)dithiophosphoric acid was added in 50 ml. of benzene.
The mixture was heated for four hours at 185.degree.F and stripped
at 210.degree.F for 4 minutes. Percent phosphorus, 1.1 percent.
Example 3
830 g. of a 50 percent concentrate of polyisobutenyl succinimide of
tetraethylene pentamine, wherein the number average molecular
weight of the polyisobutenyl was 950, was diluted with 250 ml. of
benzene. 8.5 grams of paraformaldehyde was added and the mixture
was stirred for one hour at 130.degree.F. 9.6 g. of a
di(isooctyl)dithiophosphoric acid in 50 ml. of benzene was then
added and the mixture was heated for five hours at 190.degree.F.
The product was stripped at 210.degree.F for 5 minutes. Percent
phosphorus, 0.88 percent.
Example 4
Analogous to Example 3, using a bis(polypropenyl phenol)
dithiophosphoric acid.
Lubricant Composition
The lubricating oils which comprise the basis for the composition
of this invention are those oily or greasy materials employed in
lubrication. Examples of these materials are natural and synthetic
oils and greases made from these oils, and synthetic oils.
Synthetic oils include alkylene polymers, such as polymers of
propylene, butylene, etc., and mixtures thereof; alkylene
oxide-type polymers, e.g., alkylene oxide polymers prepared by
polymerization of alkylene oxide in the presence of water or
alcohols, such as propylene oxide polymer, ethylene oxide polymer;
carboxylic acid esters, such as those which are prepared by
esterifying carboxylic acid, e.g., adipic acid, suberic acid,
fumaric acid, etc. with alcohols such as butyl alcohol, hexyl
alcohol, pentaerythritol, etc.; polymers of silicon; alkylbiphenyl
ethers and other ethers, etc. The base oils can be used
individually or in combinations wherever miscible or whenever made
so by use of mutual solvents. Oils of lubricating viscosity
generally have viscosities of 35-50,000 SUS at 100.degree.F.
The lubricating compositions of the present invention contain a
major amount of an oil of lubricating viscosity and will also
contain a functional amount, from 0.1 to 10 percent by weight, of
the N-substituted, S-aminomethyl dithiophosphate of the present
invention. In concentrates, the weight percent of this additive
will usually range from about 20 to 60 percent by weight.
In addition to the N-substituted, S-aminomethyl dithiophosphate,
these lubricating compositions can also contain other lubricating
oil and grease additives such as oiliness agents, extreme pressure
agents, rust inhibitors, other oxidation inhibitors, corrosion
inhibitors, viscosity index improving agents, dyes, detergents,
dispersants, etc. Usually, for oils to be used in an internal
combustion engine, the total amount of these additives will range
from about 0.1-20 percent by weight, and more usually from about
0.5-10 weight percent. The individual additives may vary in amounts
from about 0.01-10 weight percent of the total composition. In
concentrates, the weight percent of these additives will usually
range from about 20-60 weight percent.
Evaluation
The Falex test results are given in Table I. The Falex test is a
test for extreme pressure properties. In this test stationary
vee-blocks are pressed on either side of a rotating pin by a
nutcracker arrangement of lever arms. Test specimens are immersed
in a tank of test lubricant which is at a known temperature.
Loading is automatically increased until seizure occurs. This
failure point is indicated by shearing of the pin holding the
vertical shaft. The load at shear in pounds is taken as a
quantitative measure of the extreme pressure property of the oil
composition. Mineral oils may fail at 600-900 pounds. Oils with EP
additives will fail at 1,000-2,000 pounds. The wear is determined
by conducting the test at constant load and measuring the pin
weight loss in milligrams.
The N-substituted, S-aminomethyl dithiophosphates have also been
tested for antiwear properties by means of the well-known 4-Ball
Test. In this test, three 1/2-diameter steel balls are clamped
together and immersed in the test lubricant. A fourth ball is then
rotated at about 1,800 rpm in contact with the other three balls. A
20-50 kg. load is applied, forcing the rotating ball against the
three stationary balls. The test is run for 60-30 minutes and the
sizes of the wear scars on the three stationary balls are measured
and the average scar size in millimeters reported. The smaller the
scar, the greater the anti-wear properties of the test lubricant.
These EP properties are reported in Table I and II. Note that
reference oils containing well-known EP agents give Falex Shear
test results of 850-1,450 pounds. Similar properties are obtained
with the additives of the present invention, but the Falex wear is
much less with the additives of the present invention. This
excellent wear result is confirmed in the 4-Ball test results given
in Table II.
TABLE I ______________________________________ Falex Falex Shear,
Wear, Additive.sup.a lbs. ______________________________________ 1.
0.7% zinc di(isooctyl)dithio- phosphate + 5% polyisobutenyl
succinimide of tetraethylene- pentamine 1450 7.5 2. 1.7% zinc
bis(polypropenyl- phenyl) dithiophosphate + 5% polyisobutenyl
succinimide of tetraethylenepentamine 850 31.8 3. 4.5% of the
product of Example 1 1300 1.6 4. 4.5% of the product of Example 2
1400 4.6 5. 6.0% of the product of Example 3 1300 1.9 6. 6.3% of
the product of Example 4 1000 3.3
______________________________________ .sup.a Percent by weight.
All test lubricants contain 15 mM/g P in a 496 SSU at 100.degree.F.
neutral petroleum oil.
TABLE II ______________________________________ 4-Ball
Additive.sup.a Wear, mm ______________________________________ 1.
5% polyisobutenyl succinimide of tetraethylenepentamine + 1.7% zinc
bis(polypropenylphenyl)- dithiophosphate 1.80 2. 6.3% of the
product of Example 4 0.45 ______________________________________
.sup.a See footnote a of Table I.
The Oxidator B test is our laboratory designation for a test
measuring resistance to oxidation by means of a Dorntetype oxygen
absorption apparatus (R.W.Dornte, "Oxidation of While Oils,"
Industrial and Engineering Chemistry, Vol. 28, p. 26, 1936).
Normally, the conditions are 1 atmosphere of pure oxygen at
340.degree.F and one reports the hours to absorption of 1,000 ml.
of O.sub.2 by 100 grams of oil. In the Oxidator B test a catalyst
is used and a reference additive package is included in the oil.
The catalyst is a mixture of soluble metal-naphthenates simulating
the average metal analysis of used crankcase oils. Thus, the
Oxidator B method measures the response to conventional inhibitors
in a simulated application. The results are given in Table III
where the composition of the present invention is compared to
compositions containing other dithiophosphates. Direct comparisons
are made in Table III between Additives 1 and 3, 4 and 5, and 6 and
7, which correspond to the zinc containing additive and the
corresponding ashless antioxidant of the present invention. These
results are uniformly outstanding in favor of the N-substituted,
S-aminomethyl dithiophosphates.
TABLE III ______________________________________ Oxidator B
Additive.sup.a hrs. ______________________________________ 1. 5%
polyisobutenyl succinimide of tetraethylenepentamine 0.6 2. .sup.b
2.5 3. 6% of the product of Example 3 5.1 4. 3.5% of polyisobutenyl
amine + 0.7% of zinc di(isooctyl) dithio- phosphate 3.1 5. 4.5% of
the product of Example 1 5.3 6. 3.8% polyisobutenyl succinimide of
ethylenediamine + 0.7% of zinc di(isooctyl)dithiophosphate 2.3 7.
4.5% of the product of Example 2 5.4
______________________________________ .sup.a See footnote .sup.a
of Table I. .sup.b Additive 2 of Table I.
In a further heat stability test, 6 percent of Example 3 in a 496
SSU at 100.degree.F neutral petroleum oil was heated for 48 hours
at 300.degree.F. The product was found to have an undiminished
oxidator B rating. When 4.5 percent of the additive of Example 2 in
the same base oil was heated for 48 hours at 300.degree.F, it was
found that the infrared spectrum remained practically
unchanged.
Table IV illustrates the detergency of the N-substituted,
S-aminomethyl dithiophosphates. The data refers to a severe
Caterpillar diesel engine test, run for 12 hours at 1,200 rpm, 280
brake means effective pressure in psi, water temperature of the
cooling jacket is 190.degree.F, the sulfur content of the fuel is
0.4 percent and is input at a rate which provides 6,900 BTU per
minute. The base oil was a 496 SSU at 100.degree.F. neutral
petroleum oil. In Table IV the rating of groove deposits is based
on a range of 0-100, 100 being completely filled grooves. The
rating for land deposits is based on a range of 1-800, 800 being
completely black. The rating for underhead deposits is based on a
range of 0-10, 10 being completely clean.
TABLE IV ______________________________________ Under- Additive
Grooves Lands head ______________________________________ 1. 6% of
the product 3.8, 0.6, 60-10-10 5.8 of Example 2 0.5, 0.5 2. 8% of
the product 7.1, 4.0, 200-10-10 7.2 of Example 3 0.6, 0.5
______________________________________
The N-substituted, S-aminomethyl dithiophosphates were also found
to be noncorrosive towards copper and lead bearings, as well as
being antioxidants, dispersants and extreme pressure agents. The
unique polyfunctionality of high molecular weight condensation
products of the present invention is in sharp contrast with the low
molecular weight analogs, which, for example, cannot function as
lubricating oil detergents/dispersants. It is unusual to find
polyfunctionality where each function depends on a different
physical or chemical property of the molecule. Multifunctionality
is especially unexpected where the functions are unrelated by a
common property such as metallic surface activity.
It is evident from the above results that the compositions of this
invention are excellent detergents/dispersants under the severe
conditions of the Caterpillar internal combustion engine, they are
also antioxidants and extreme pressure agents. Furthermore, the
compositions are compatible with other additives normally found in
compounded lubricating oils.
While the character of this invention has been described in detail
with several examples, this has been done by way of illustration
only and without limitation of the invention. It will be apparent
to those skilled in the art that numerous modifications and
variations of the illustrative examples can be made in the practice
of the invention within the scope of the following claims.
* * * * *