U.S. patent number 3,890,363 [Application Number 05/473,129] was granted by the patent office on 1975-06-17 for oil additive.
This patent grant is currently assigned to Ethyl Corporation. Invention is credited to Robert E. Malec.
United States Patent |
3,890,363 |
Malec |
June 17, 1975 |
Oil additive
Abstract
Compounds having the formula: ##SPC1## Wherein R'is selected
from the group consisting of aliphatic hydrocarbon radicals
containing about 8-100 carbon atoms, and
hydrocarbylaminohydrocarbyl radicals having the formula: R.sub.1
--NR""--R.sub.2 -- wherein R.sub.1 is an aliphatic hydrocarbon
radical containing about 8-100 carbon atoms, R"" is selected from
the group consisting of hydrogen and C.sub.1-4 alkyls and R.sub.2
is a divalent aliphatic hydrocarbon radical containing about 2-10
carbon atoms, R.sub.3 and R.sub.4 are selected from the group
consisting of hydrogen and alkyl radicals containing about 1-4
carbon atoms, R" is selected from the group consisting of hydrogen
and C.sub.1-4 alkyls and R"' is selected from the group consisting
of hydrogen and salt cations, are effective antiwear and antirust
additives in lubricating oils and greases.
Inventors: |
Malec; Robert E. (Birmingham,
MI) |
Assignee: |
Ethyl Corporation (Richmond,
VA)
|
Family
ID: |
26995811 |
Appl.
No.: |
05/473,129 |
Filed: |
May 24, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
348625 |
Apr 6, 1973 |
3833496 |
|
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Current U.S.
Class: |
558/238;
508/444 |
Current CPC
Class: |
C10M
1/08 (20130101); C10M 2215/26 (20130101); C10M
2223/045 (20130101); C10N 2010/02 (20130101); C10M
2207/125 (20130101); C10M 2219/066 (20130101); C10M
2215/04 (20130101); C10N 2050/10 (20130101); C10M
2205/028 (20130101); C10M 2219/068 (20130101); C10M
2223/065 (20130101); C10M 2205/026 (20130101); C10N
2010/14 (20130101); C10M 2205/02 (20130101); C10M
2207/027 (20130101); C10M 2209/084 (20130101); C10M
2207/281 (20130101); C10M 2205/00 (20130101); C10M
2207/129 (20130101); C10M 2207/286 (20130101); C10M
2217/06 (20130101); C10M 2219/046 (20130101); C10N
2010/04 (20130101); C10N 2010/06 (20130101); C10M
2219/085 (20130101); C10M 2209/103 (20130101); C10M
2207/283 (20130101); C10M 2215/062 (20130101); C10M
2219/044 (20130101); C10M 2207/34 (20130101); C10M
2217/046 (20130101); C10N 2010/16 (20130101); C10M
2207/282 (20130101) |
Current International
Class: |
C07C 155/04 ();
C07C 155/06 (); C07C 155/08 () |
Field of
Search: |
;260/455A |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lewis Gotts
Assistant Examiner: Phillips; D. R.
Attorney, Agent or Firm: Johnson; Donald L. Linn; Robert A.
Odenweller; Joseph D.
Parent Case Text
This application is a division of application Ser. No. 348,625,
filed April 6, 1973, now U.S. Pat. No. 3,833,496.
Claims
I claim:
1. An antiwear-antirust additive for lubricating oils and greases,
said additive having the formula: ##SPC4##
wherein R' is selected from the group consisting of aliphatic
hydrocarbon radicals containing about 8-100 carbon atoms, and
hydrocarbylaminohydrocarbyl radicals having the formula:
R.sub.1 --NR""--R.sub.2 --
wherein R.sub.1 is an aliphatic hydrocarbon radical containing
about 8-100 carbon atoms, R"" is selected from the group consisting
of hydrogen and C.sub.1-4 alkyls and R.sub.2 is a divalent
aliphatic hydrocarbon radical containing about 2-10 carbon atoms,
R.sub.3 and R.sub.4 are selected from the group consisting of
hydrogen and alkyl radicals containing about 1-4 carbon atoms, R"
is selected from the group consisting of hydrogen and C.sub.1-4
alkyls and R"' is selected from the group consisting of hydrogen
and salt cations.
2. An antiwear-antirust additive of claim 1, said additive having
the formula: ##SPC5##
wherein R.sub.1 is an aliphatic hydrocarbon radical containing from
about 8-100 carbon atoms, R.sub.2 is a divalent aliphatic
hydrocarbon radical containing from 2 to about 10 carbon atoms, and
R.sub.3 and R.sub.4 are selected from the group consisting of
hydrogen and alkyl radicals containing 1 to about 4 carbon
atoms.
3. An additive of claim 2 wherein R.sub.1 contains about 8-22
carbon atoms, R.sub.2 is the trimethylene radical, R.sub.3 is the
methyl radical, and R.sub.4 is hydrogen.
4. An additive of claim 3 wherein R.sub.1 is the oleyl radical.
5. An additive of claim 3 wherein R.sub.1 is the stearyl
radical.
6. An additive of claim 3 wherein R.sub.1 is the palmyl radical.
Description
BACKGROUND
Additives are conventionally added to lubricating oil and grease to
improve their properties. Antiwear additives used in the past
include compounds such as zinc dialkyldithiophosphates, sulfurized
sperm oil, and the like. Antirust protection can be provided by
compounds such as overbased calcium sulfonates. Long chain amines
such as polybutenyl ethylenediamine have been used to improve
dispersancy of lubricating oils.
SUMMARY OF THE INVENTION
According to the present invention, lubricating oils and greases
having improved antiwear and antirust properties are provided by
including in the lubricating oil composition certain
3-mercaptoalkanoic acid, [(alkylamino)alkyl] dithiocarbamates such
as 3-mercaptobutyric acid, [3(oleylamino)-propyl]
dithiocarbamate.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A preferred embodiment of the invention is an antiwear-antirust
additive for lubricating oils and greases having the formula:
##SPC2##
Wherein R' is selected from the group consisting of aliphatic
hydrocarbon radicals containing about 8-100 carbon atoms, and
hydrocarbylaminohydrocarbyl radicals having the formula:
R.sub.1 --NR""--R.sub.2 --
wherein R.sub.1 is an aliphatic hydrocarbon radical containing
about 8-100 carbon atoms, R"" is selected from the group consisting
of hydrogen and C.sub.1-4 alkyls and R.sub.2 is a divalent
aliphatic hydrocarbon radical containing about 2-10 carbon atoms,
R.sub.3 and R.sub.4 are selected from the group consisting of
hydrogen and alkyl radicals containing about 1-4 carbon atoms, R"
is selected from the group consisting of hydrogen and C.sub.1-4
alkyls and R"' is selected from the group consisting of hydrogen
and salt cations. Useful salt cations include the cations of the
alkaline earth metals such as calcium, magnesium, strontium, and
barium; ammonium ions formed from ammonia; alkyl and alkenyl amines
such as methylamine, dimethylamine, trimethylamine, triethylamine,
tributylamine, ethanolamine, diethanolamine, triethanolamine,
morpholine, stearylamine, oleylamine, palmylamine, laurylamine,
eicosylamine, eicosenylamine, and the like; and other metal cations
such as zinc, aluminum, nickel, manganese, iron, and the like.
Representative examples of the above additives include:
3-mercaptopropionic acid, n-octyldithiocarbamate
3-mercaptobutyric acid, stearyldithiocarbamate
calcium 3-mercaptobutyrate, oleyldithiocarbamate
zinc 3-mercaptopropionate, palmyldithiocarbamate
trimethylammonium 3-mercaptohexanoate, C.sub.100 -polybutenyl
dithiocarbamate
manganese 3-mercaptobutyrate, stearyldithiocarbamate
barium 3-mercaptoheptanoate, eicosyldithiocarbamate
magnesium 3-mercaptobutyrate, eicosenyldithiocarbamate
triethanolammonium 3-mercaptobutyrate, oleyldithiocarbamate
A most preferred embodiment of this invention is an
antiwear-antirust additive for lubricating oils and greases, said
additive having the formula: ##SPC3##
wherein R.sub.1 is an aliphatic hydrocarbon radical containing from
about 8-100 carbon atoms, R.sub.2 is a divalent aliphatic
hydrocarbon radical containing from 2 to about 10 carbon atoms, and
R.sub.3 and R.sub.4 are selected from the group consisting of
hydrogen and alkyl radicals containing 1 to about 4 carbon atoms.
Since the compounds contain both a basic amine functional group and
a carboxylic acid they can exist in the form of a zwitterion and
are shown in that form in Formula II.
Representative examples of such additives include:
3-mercaptopropionic acid,
[2(9-eicosenylamino)ethyl]dithiocarbamate
3-mercapto-2-methylbutyric acid,
[6(octylamino)hexyl]dithiocarbamate
3-mercaptoheptanoic acid, [10(laurylamino)decyl]dithiocarbamate
3-mercapto-2-methylhexanoic acid, [4(1-hexylbutylamino) butyl]
dithiocarbamate
3-mercapto-2-butylheptanoic acid, [3(pentacontenylamino) propyl]
dithiocarbamate
3-mercaptobutyric acid,
[2(hexacontylamino)ethyl]dithiocarbamate
3-mercaptopropionic acid,
[3(octacontylamino)propyl]dithiocarbamate
3-mercaptohexanoic acid, [3(C.sub.100 -polybutenylamino) propyl]
dithiocarbamate
3-mercaptobutyric acid, [3(C.sub.90 -polypropenylamino) propyl]
dithiocarbamate
3-mercaptooctanoic acid,
[3(dodecenylamino)butyl]dithiocarbamate
3-mercaptopropionic acid,
[3(tetracosylamino)propyl]dithiocarbamate
3-mercaptobutyric acid, [6(stearylamino)hexyl]dithiocarbamate
3-mercaptopentanoic acid, [4(palmylamino)butyl]dithiocarbamate
3-mercaptobutyric acid,
[3(2-nonacontenylamino)propyl]dithiocarbamate
A preferred class of additives are those of Formula II wherein
R.sub.1 contains about 8-22 carbon atoms, R.sub.2 is the
trimethylene radical --(CH.sub.2).sub.3 --, R.sub.3 is the methyl
radical, and R.sub.4 is hydrogen. Examples of these compounds
are:
3-mercaptobutyric acid, [3(oleylamino)propyl]dithiocarbamate
3-mercaptobutyric acid, [3(stearylamino)propyl]dithiocarbamate
3-mercaptobutyric acid, [3(palmylamino)propyl]dithiocarbamate
The additives are readily prepared by reacting an aliphatic
hydrocarbylaminohydrocarbylamine with carbon disulfide to form the
corresponding hydrocarbylaminohydrocarbyl dithiocarbamic acid and
reacting this with an appropriate alpha-unsaturated aliphatic
carboxylic acid such as acrylic acid, crotonic acid, .alpha.-methyl
crotonic acid, .alpha.,.beta.-diethyl acrylic acid, .beta.-butyl
acrylic acid, .alpha.-butyl acrylic acid, and the like (N.
Kreutzkamp et al, Arch. Pharm. 304, p. 477-481, July 1971).
The aliphatic hydrocarbylaminohydrocarbylamines can be prepared by
reacting an aliphatic hydrocarbyl chloride with an aliphatic
diamine. For example, reaction of oleyl chloride with
1,3-propanediamine yields oleylaminopropylamine. Likewise, reaction
of lauryl chloride with 1,6-hexanediamine forms
laurylaminohyexylamine. Similarly, reaction of C.sub.100
-polybutenyl chloride with ethylenediamine forms C.sub.100
-polybutenylaminoethylamine. The polyolefin chlorides are readily
formed by reacting a polyolefin (e.g., polypropylene, polybutene,
and the like) with chlorine.
The following example illustrates the manner in which the additives
can be prepared.
EXAMPLE 1
To a solution of 175 grams of N-oleyl-1,3-propanediamine and 175
grams of isopropyl alcohol was added a solution of 40 grams of
carbon disulfide and 40 grams of isopropyl alcohol over a one hour
period at 0.degree.-10.degree.C. The unreacted carbon disulfide was
distilled off and 50 grams each of crotonic acid, isopropyl alcohol
and methanol was added. The mixture was stirred at
0.degree.-10.degree.C for 2 hours and then allowed to warm to room
temperature. The product was diluted with hexane and washed with
water, following which volatile material was distilled out under
vacuum to yield 184 grams of a low melting solid.
EXAMPLE 2
A portion of the product from Example 1 was diluted with hexane,
filtered, water washed, and then the hexane distilled out. The
resultant product was diluted with neutral mineral oil to obtain a
67 weight percent active concentrate. This was diluted with hexane
and washed with aqueous ammonia. Powdered solid carbon dioxide was
added and stirred into the mixture. The mixture was then water
washed, following which hexane was distilled out, leaving a viscous
yellow liquid concentrate.
Modification of the above procedure by substitution of different
starting hydrocarbylaminohydrocarbylamines and different
alpha-unsaturated aliphatic carboxylic acids will lead to the other
additives within the scope of this invention.
The additives are useful in lubricating oils and greases including
both mineral and synthetic. Synthetic oils include polyolefin oils
(e.g., polybutene oil, decene oligomer, and the like), synthetic
esters (e.g., dinonyl sebacate, trioctanoic acid ester of
trimethylolpropane, and the like), polyglycol oils, and the like.
Greases are made from these oils by adding a thickening agent such
as sodium, calcium, lithium, or aluminum salts of fatty acids such
as stearic acid. The oils and greases are prepared by blending an
antiwear and antirust amount of the additive into the oil or
grease. A useful concentration is from about 0.1 to 5 weight
percent. The additives may be added in the form of a concentrate
such as the mineral oil diluted concentrate described in Example
2.
Other additives may be included in the oil or grease compositions.
These include such additives as zinc dialkyldithiophosphates,
barium phenates, calcium phenates, calcium aryl sulfonates,
magnesium aryl sulfonates, overbased calcium aryl sulfonates,
barium polybutenyl phosphonates; antioxidants such as
4,4'-methylenebis(2,6-di-tert-butylphenol),
.alpha.-dimethylamino-2,6-di-tert-butyl-p-cresol; dispersants such
as polybutenyl succinimides of ethylenepolyamines, polybutenyl
ethylenediamines, viscosity index improvers such as polybutenes,
ethylene-propylene copolymers, polylauryl methacrylates, and the
like.
Tests have been carried out to demonstrate the antiwear and
antirust properties of the additives. The first is known as the
"four-ball cam and tappet test". In this test, three steel balls
are placed in a triangular manner in a circular retainer containing
the test oil. A fourth ball is placed on top of these three to form
a triangular pyramid. A 50 Kg load is placed on the top ball and it
is rotated at 1800 r.p.m. for one hour with the oil heated to
110.degree.C. This test has previously been shown to correlate well
with the cam and tappet wear of an internal combustion engine.
Criteria is the average scar diameter formed on the three bottom
balls. A scar diameter of 1 mm or less is considered
satisfactory.
The test was carried out on a non-additive neutral oil and on
triplicate samples containing 1 weight percent of the additive of
Example 1 -- 3-mercaptobutyric acid, [3(oleylamino)propyl]
dithiocarbamate. The results obtained were as follows.
TABLE 1 ______________________________________ Additive Average
scar diameter (mm) ______________________________________ None 2.3
Example 1 (1%) 0.92, 0.99, 0.89
______________________________________
The antirust property of the additives was determined using the
ASTM D-665 spindle rust test. In this test, spindles are rotated in
a mixture of oil and synthetic seawater at 140.degree.F for 24
hours. The spindles are rated "pass" or "fail". A "pass" rating
requires that the spindle be rust-free. This test was carried out
using two non-additive mineral oil samples and four samples of the
same mineral oil containing 1 weight percent of the concentrate of
Example 2. The results were as follows.
TABLE 2 ______________________________________ Additive Results
______________________________________ None both fail Example 2
(1%) all pass ______________________________________
These results demonstrate the excellent antiwear and antirust
properties of the present additives.
* * * * *