U.S. patent number 3,876,550 [Application Number 05/461,206] was granted by the patent office on 1975-04-08 for lubricant compositions.
This patent grant is currently assigned to The Lubrizol Corporation. Invention is credited to Zenowie Michael Holubec.
United States Patent |
3,876,550 |
Holubec |
April 8, 1975 |
Lubricant compositions
Abstract
Lubricant compositions comprising a novel additive combination
to improve the anti-oxidant and rust-inhibiting properties of these
compositions are disclosed. The additive combination comprises an
alkylene dithiocarbamate and an aliphatic hydrocarbon-substituted
succinic acid or certain derivatives thereof. Lubricant
compositions containing the novel additive combination are useful
in a variety of applications.
Inventors: |
Holubec; Zenowie Michael (Parma
Heights, OH) |
Assignee: |
The Lubrizol Corporation
(Wickliffe, OH)
|
Family
ID: |
23831623 |
Appl.
No.: |
05/461,206 |
Filed: |
April 15, 1974 |
Current U.S.
Class: |
508/263; 558/237;
508/297; 508/306; 508/444 |
Current CPC
Class: |
C10M
129/42 (20130101); C10M 135/18 (20130101); C10M
129/76 (20130101); C10M 145/26 (20130101); C10M
141/08 (20130101); C10M 141/08 (20130101); C10M
129/42 (20130101); C10M 129/76 (20130101); C10M
135/18 (20130101); C10M 161/00 (20130101); C10M
135/18 (20130101); C10M 145/26 (20130101); C10M
2217/024 (20130101); C10M 2219/087 (20130101); C10M
2219/104 (20130101); C10M 2229/042 (20130101); C10N
2040/13 (20130101); C10M 2205/022 (20130101); C10M
2203/06 (20130101); C10M 2203/102 (20130101); C10M
2203/108 (20130101); C10M 2205/024 (20130101); C10M
2207/129 (20130101); C10M 2207/287 (20130101); C10M
2209/105 (20130101); C10M 2219/082 (20130101); C10M
2223/04 (20130101); C10N 2040/255 (20200501); C10M
2227/061 (20130101); C10M 2229/02 (20130101); C10M
2209/084 (20130101); C10M 2219/085 (20130101); C10M
2223/045 (20130101); C10M 2205/00 (20130101); C10M
2211/06 (20130101); C10N 2040/26 (20130101); C10M
2213/02 (20130101); C10M 2215/26 (20130101); C10M
2217/043 (20130101); C10N 2040/253 (20200501); C10M
2229/045 (20130101); C10M 2207/283 (20130101); C10M
2211/044 (20130101); C10M 2203/104 (20130101); C10M
2207/026 (20130101); C10M 2211/022 (20130101); C10M
2229/041 (20130101); C10M 2203/024 (20130101); C10M
2207/34 (20130101); C10M 2229/047 (20130101); C10M
2203/10 (20130101); C10M 2217/042 (20130101); C10M
2223/041 (20130101); C10M 2217/046 (20130101); C10M
2219/046 (20130101); C10M 2219/10 (20130101); C10N
2040/12 (20130101); C10M 2225/04 (20130101); C10M
2215/042 (20130101); C10M 2223/042 (20130101); C10M
2205/02 (20130101); C10M 2207/289 (20130101); C10M
2219/088 (20130101); C10M 2219/102 (20130101); C10N
2040/135 (20200501); C10M 2207/22 (20130101); C10M
2205/026 (20130101); C10M 2207/40 (20130101); C10M
2215/202 (20130101); C10N 2010/00 (20130101); C10M
2203/04 (20130101); C10M 2209/109 (20130101); C10M
2219/02 (20130101); C10M 2219/024 (20130101); C10M
2227/02 (20130101); C10N 2040/252 (20200501); C10M
2209/106 (20130101); C10M 2213/062 (20130101); C10M
2219/066 (20130101); C10M 2203/02 (20130101); C10M
2207/282 (20130101); C10M 2209/10 (20130101); C10M
2219/089 (20130101); C10M 2223/061 (20130101); C10M
2227/06 (20130101); C10N 2040/20 (20130101); C10M
2211/08 (20130101); C10M 2207/404 (20130101); C10M
2209/104 (20130101); C10M 2229/046 (20130101); C10M
2219/106 (20130101); C10M 2209/107 (20130101); C10M
2205/04 (20130101); C10M 2205/14 (20130101); C10M
2209/02 (20130101); C10M 2223/06 (20130101); C10M
2229/05 (20130101); C10M 2219/044 (20130101); C10M
2219/068 (20130101); C10M 2219/022 (20130101); C10M
2207/281 (20130101); C10M 2207/125 (20130101); C10M
2219/083 (20130101); C10M 2223/12 (20130101); C10M
2203/022 (20130101); C10M 2207/123 (20130101); C10M
2207/402 (20130101); C10M 2207/286 (20130101); C10M
2215/04 (20130101); C10N 2040/28 (20130101); C10M
2229/048 (20130101); C10N 2010/02 (20130101); C10M
2203/106 (20130101); C10M 2209/00 (20130101); C10M
2209/103 (20130101); C10N 2070/02 (20200501); C10M
2207/288 (20130101); C10M 2217/06 (20130101) |
Current International
Class: |
C10M
141/00 (20060101); C10M 141/08 (20060101); C10m
001/38 (); C10m 001/24 () |
Field of
Search: |
;252/33.6,47.5,47
;260/455A |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Cannon; W.
Attorney, Agent or Firm: Adams, Jr.; J. Walter Hoback; Karl
F.
Claims
What is claimed is:
1. A lubricant composition comprising a major proportion of a
lubricating oil and a minor proportion, sufficient to improve the
anti-oxidant and rust-inhibiting properties of the composition, of
an additive combination comprising (A) one or more alkylene
dithiocarbamates and (B) one or more rust inhibitors selected from
the group consisting of aliphatic hydrocarbon-substituted succinic
acid, aliphatic hydrocarbon-succinic acid anhydride, and the
reaction product obtained by the esterification of the acid or the
anhydride with from about 0.1 mole to about 1.0 mole per mole of
the acid or the anhydride, of at least one alkylene oxide or
alkylene glycol containing up to about 20 carbon atoms; wherein the
alkylene dithiocarbamate corresponds to the formula:
R.sub.1 R.sub.2 N--C(S)--S--X--S--(S)C--NR.sub.3 R.sub.4
in which R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently
radicals selected from the group consisting of hydrogen and alkyl,
or R.sub.1 and R.sub.2, taken together with the nitrogen to which
they are attached, are R.sub.5, or R.sub.3 and R.sub.4 taken
together with the nitrogen to which they are attached, are R.sub.6,
wherein R.sub.5 and R.sub.6 are independently 5- or 6- membered
heterocyclic groups, and the combined total number of carbon atoms
of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is at least about 8, and
X represents an alkylene radical having up to about 8 carbon
atoms.
2. The lubricant composition of claim 1, wherein the anti-oxidant
component of the additive combination is present in the range of
from about 0.1 to about 5%.
3. The lubricant composition of claim 1, wherein the anti-rust
component of the additive combination is present in the range of
from about 0.01 to about 1%.
4. The lubricant composition of claim 1, wherein R.sub.5 and
R.sub.6 are heterocyclic radicals selected from the group
consisting of pyrrolidinyl and piperidino.
5. The lubricant composition of claim 1, wherein the aliphatic
hydrocarbon substituent of the aliphatic hydrocarbon-succinic acid
or anhydride has from about 8 to about 30 aliphatic carbon
atoms.
6. The lubricant composition of claim 5, wherein the anti-rust
component of the additive combination is the reaction product of
the succinic acid or its anhydride with an alkylene oxide or
alkylene glycol having from 2 to 6 carbon atoms.
7. The lubricant composition of claim 6, wherein R.sub.5 and
R.sub.6 are heterocyclic radicals selected from the group
consisting of pyrrolidinyl and piperidino.
8. The lubricant composition of claim 6, wherein R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are, independently, alkyl radicals having from
1 to 8 carbon atoms.
9. The lubricant composition of claim 6, wherein the alkylene
radical, X, is a methylene radical.
10. The lubricant composition of claim 6, wherein the anti-rust
component is present in the range of from about 0.02 to about 0.1%
and the anti-oxidant component is present in the range of from
about 0.25 to about 1%.
11. The lubricant composition of claim 5, wherein the anti-rust
component of the additive combination is an aliphatic
hydrocarbon-succinic acid.
12. The lubricating composition of claim 11, wherein R.sub.5 and
R.sub.6 are heterocyclic radicals selected from the group
consisting of pyrrolidinyl land piperidino.
13. The lubricant composition of claim 11, wherein R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 are, independently, alkyl radicals
having from 1 to 8 carbon atoms.
14. The lubricating composition of claim 11, wherein the anti-rust
component is present in the range of from about 0.01 to about 0.1%
and the anti-oxidant component is present in the range of from
about 0.25 to about 1%.
15. The lubricating composition of claim 11, wherein the alkylene
radical, X, is a methylene radical.
16. An additive concentrate comprising a substantially inert
carrier and from about 20 to about 90 percent of the additive
combination of claim 1.
17. An additive concentrate comprising a substantially inert
carrier and from about 20 to about 90 percent of the additive
combination of claim 8.
18. An additive concentrate comprising a substantially inert
carrier and from about 20 to about 90 percent of the additive
combination of claim 15.
19. A steam turbine lubricant composition comprising a major
proportion of lubricating oil and a minor proportion, sufficient to
improve the anti-oxidant and rust-inhibiting properties of the
composition, of an additive combination comprising (A) one or more
alkylene dithiocarbamates and (B) one or more rust inhibitors
selected from the group consisting of aliphatic
hydrocarbon-substituted succinic acid, aliphatic
hydrocarbon-succinic acid anhydride, and the reaction product
obtained by the esterification of the acid or anhydride with from
about 0.1 mole to about 1.0 mole per mole of the acid or anhydride,
of at least one alkylene oxide or alkylene glycol containing up to
about 20 carbon atoms; wherein the alkylene dithiocarbamate
corresponds to the formula:
R.sub.1 R.sub.2 N--C(S)--S--X--S--(S)C--NR.sub.3 R.sub.4
in which R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently
radicals selected from the group consisting of hydrogen and alkyl,
or R.sub.1 and R.sub.2, taken together with the nitrogen to which
they are attached, are R.sub.5, or R.sub.3 and R.sub.4 taken
together with the nitrogen to which they are attached, are R.sub.6,
wherein R.sub.5 and R.sub.6 are independently 5- or 6-membered
heterocyclic groups, and the combined total number of carbon atoms
of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is at least about 8, and X
represents an alkylene radical having up to about 8 carbon atoms.
Description
The invention herein is concerned with lubricating compositions
comprising a novel combination of additives to improve both the
anit-oxidant and rust-inhibiting properties of these
compositions.
More specifically, the subject lubricating compositions comprise a
major proportion of a lubricating oil, and a minor proportion,
sufficient to improve the anti-oxidant and rust-inhibiting
properties of the composition, of an additive combination. This
additive combination comprises (A) one or more anti-oxidants based
upon alkylene dithiocarbamates and (B) one or more rust inhibitors
based upon hydrocarbon-substituted succinic acids or certain
derivatives thereof.
The additive combination of the present invention is effectively
employed in the lubricating compositions designed for a variety of
uses. Likewise, the combination is effective in compositions based
upon both natural and synthetic oils of lubricating viscosity.
Also, the subject additive combination is effective in lubricating
compositions containing additional additives.
The subject additive combination can be effectively employed in a
variety of lubricating compositions formulated for a variety of
uses. Thus, lubricating compositions containing the subject
additive combination are effective as crankcase lubricating oils
for spark-ignited and compression-ignited internal combustion
engines, including automobile and truck engines, two-cycle engine
lubricants, aviation piston engines, marine and low-load diesel
engines, and the like. Also, automatic transmission fluids,
transaxle lubricants, gear lubricants, metal-working lubricants,
hydraulic fluids, and other lubricating oil and grease compositions
can benefit from the incorporation of the present additive
combination therein.
Lubricant compositions containing the subject additive combination
are particularly useful as lubricants for steam turbines. Lubricant
compositions designed for use in large steam turbines are unique in
that they require very careful formulation to protect the machinery
from rust and corrosion under very severe conditions of use.
Technically, these steam turbines are used for the generation of
electricity, and are of either stationary or marine installation.
The volume of lubricant required for a turbine can, typically, be
in the range of 10,000 or 20,000 gallons of lubricant. The change
interval of lubricant for present day turbines is in the range of 3
to 5 years, and it is desired to increase this interval to about 10
years, if suitable lubricating compositions can be developed.
Lubricating compositions used in these turbines are continuously
subjected to operating temperatures in the neighborhood of about
340.degree.F., and it is desired for increased efficiency of the
turbines to use operating temperatures in the range of
600.degree.-700.degree.F., if suitable lubricating compositions can
be developed. Another problem encountered in the operation of these
turbines is that moisture from the steam is continuously being
introduced into the lubricant. The anti-oxidant component in the
majority of lubricating compositions presently used for steam
turbines is based upon a hindered phenol type additive. While these
hindered phenols are excellent anti-oxidants, they suffer from the
fact that they sublime under the operating temperatures employed
and, accordingly, provision must be made to continuously introduce
a new supply of antioxidant into the lubricating composition to
replenish that lost through sublimation.
The anti-oxidant component of the subject additive combination
comprises one or more alkylene dithiocarbamates corresponding to
the general formula;
R.sub.1 R.sub.2 N--C(S)--S--X--S--(S)C--NR.sub.3 R.sub.4
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently
radicals selected from the group consisting of hydrogen and alkyl,
or R.sub.1 and R.sub.2 taken together with the nitrogen to which
they are attached are R.sub.5, or R.sub.3 and R.sub.4 taken
together with the nitrogen to which they are attached are R.sub.6,
wherein R.sub.5 and R.sub.6 are independently 5- or 6-membered
heterocyclic groups. The combined total number of carbon atoms of
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is at least about eight and X
represents an alkylene radical having up to about 8 carbon atoms.
This component is used in the range of from about 0.1 to about 5%
by weight of the lubricant composition, with a preferred range of
from about 0.25 to about 1.0%.
Each of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 will preferably be an
alkyl radical having from 1 to about 18 carbon atoms. The preferred
range of carbon atoms in each of these alkyl radicals is from 1 to
about 8. The total number of carbon atoms in R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 is at least about 8 with an upper limit of
about 70 carbon atoms. However, the upper limit of the total number
of carbon atoms is usually about 32.
When R.sub.1 and R.sub.2 are taken together with the nitrogen atom
to which they are attached, they form a 5- or 6-membered
heterocyclic group, R.sub.5, and when R.sub.3 and R.sub.4 are taken
together with the nitrogen atom to which they are attached, they
form a 5- or 6-membered heterocyclic group, R.sub.6. Thus, R.sub.5
and R.sub.6 are, independently, heterocylic radicals selected from
the group consisting of pyrrolidinyl, piperidino, morpholino, and
piperazinyl. The heterocyclic radicals, R.sub.5 and R.sub.6, may
contain one or more, preferably one to three alkyl substituents
(C.sub.1 -C.sub.6) on the heterocyclic ring. Thus, for example,
R.sub.5 or R.sub.6, may be 2-methylmorpholino,
3-methyl-5-ethylpiperidino, 3-hexylmorpholino,
tetramethylpyrrolidinyl, piperazinyl, 2,5-dipropylpiperazinyl,
piperidino, 2-butylpiperazinyl, 3,4,5-triethylpiperidino,
3-hexylpyrrolidinyl, or 3-ethyl-5-isopropylmorpholino. Preferably,
R.sub.5 and R.sub.6 are, independently, members selected from the
group consisting of pyrrolidinyl and piperidino.
The alkylene radical, X, in the subject dithiocarbamates may be
either a straight-chain alkylene, a branched-chain alkylene, or an
aromatically substituted alkylene. In general, the range of carbon
atoms in this alkylene group is from 1 to about 8. The preferred
alkylene radical is methylene (--CH.sub.2 --).
The alkylene dithiocarbamates are known in the art and several
methods for their preparation are also known. The anti-oxidant
activity in motor oil of various alkylene dithiocarbamates has been
reported by Denton and Thompson, Inst. Petrol. Rev. 20 (230) 46-54
(1966).
U.S. Pat. No. 2,384,577 issued to Thomas discloses a suitable
general method for the preparation of the subject alkylene
dithiocarbamates. This method involves the reaction of a salt of a
dithiocarbamic acid with a suitable dihaloacyclic hydrocarbon in
the presence of a suitable reaction medium. Suitable reaction media
include alcohols, such as ethanol and methanol; ketones, such as
acetone and methyl ethyl ketone; ethers, such as dibutyl ether and
dioxane; and hydrocarbons, such as petroleum ether, benzene and
toluene. This reaction is generally carried out at a temperature
within the range of from about 25.degree. to 150.degree.C.
depending upon the boiling point of the solvent used as the
reaction medium. Nakai, Shioya, and Okawara, Makromol. Chem. 108
95-103 (1967) have reported the preparation of various ethylene
dithiocarbamates by the reaction of an ethanolic solution of
ethylenedichloride with an ethanolic solution of the appropriate
sodium N,N-di-substituted dithiocarbamates.
U.S. Pat. Nos. 1,726,647 and 1,736,429 issued to Cadwell describe
the preparation of phenylmethylene bis(dialkyldithiocarbamates),
such as phenylmethylene bis(dimethyldithiocarbamate). The
preparative procedure of Cadwell's patents is similar to that
disclosed by Thomas and involves the reaction of a salt of a
dialkyldithiocarbamate with benzal chloride to prepare the subject
phenylmethylene bis(dialkyldithiocarbamates). Cadwell also
discloses the preparation of the intermediate salt of a
dialkyldithiocarbamate by the reaction of a dialkylamine, carbon
disulfide, and an inorganic base.
A rather elegant process for the preparation of ethylene
dithiocarbamates has been reported by Pilgram, Phillips and Korte,
J. Org. Chem. 29 1848-50 (1964). This process involves the reaction
of cyclic phosphoramidites derived from ethylene glycol with
tetraalkylthiuram disulfides to form the corresponding ethylene bis
(dialkyldithiocarbamates). The preparation of ethylene
bis(dipropyldithiocarbamates) from tetrapropylthiuram disulfide and
2-piperidino-1,3,2-dioxaphospholane is exemplary of the Pilgram et
al. process.
Unsymmetrical alkylene dithiocarbamates, such as ethylene
(tetramethylene dithiocarbamate) (dibutyl dithiocarbamate) are
conveniently prepared by suitable modification of the above
procedures. Thus, one such modification involves the reaction of a
mixture of amines with carbon disulfide and the inorganic base to
prepare the intermediate salts, i.e., the substituted
dithiocarbamates. The substituted dithiocarbamates derived from the
mixed amines is then reacted with the appropriate dihaloalkane.
Another modification involves the reaction of an excess of the
dihaloalkane with one substituted dithiocarbamate, isolating the
resulting monoester-halide, and reacting this monoesterhalide with
the other substituted dithiocarbamate.
The anti-rust component of the subject additive combination
comprises one or more rust inhibitors selected from the group
consisting of aliphatic hydrocarbon-substituted succinic acids,
aliphatic hydrocarbon-substituted succinic anhydrides and
esterified reaction products obtained by the partial esterification
of the aliphatic hydrocarbon-substituted acids or their anhydrides
with at least one alkylene oxide or alkylene glycol. This partially
esterified reaction product is prepared by the esterification of
from about 0.1 mole to about 1.0 mole of the alkylene oxide or the
alkylene glycol per mole of the aliphatic hydrocarbon-substituted
succinic acid or anhydride.
This anti-rust component of the additive combination is used in an
amount sufficient to improve the rust-inhibiting properties of the
subject lubricant composition. Generally, the amount of the
anti-rust component is in the range of from about 0.01 to about 1%
by weight of the lubricant composition. The preferred range of the
anti-rust component is from about 0.02 to about 0.1% by weight.
The compounds comprising the rust inhibitor used to prepare the
subject lubricating compositions are known in the art, as well as
methods for their preparation.
The aliphatic hydrocarbon-substituted succinic acids, which may be
used as an anti-rust component and which are the precursor acids of
the anhydride and ester anti-rust components, correspond to the
general formula: ##SPC1##
wherein R' respresents the aliphatic hydrocarbon substituent.
The aliphatic hydrocabon substituent, R', will have from about 6 to
about 80 aliphatic carbon atoms, with a preferred range of carbon
atoms in the range of from about 8 to about 30. Accordingly, the
molecular weight of the hydrocarbon substituent will, broadly, be
in the range of from about 80 to about 1,150, with a preferred
range of from about 110 to about 450.
This hydrocarbon substituent, R', is either a saturated or a
substantially saturated aliphatic hydrocarbon substituent,
depending upon the preparative method used. It may contain olefinic
unsaturation up to a maximum of about 5 percent olefinic linkage
based upon the total number of carbon-to-carbon covalent linkages
present in the substituent. Preferably, the number of olefinic
linkages will not exceed about 2 percent of the total covalent
linkages. The hydrocarbon substituent may contain inert polar
substituents provided they do not alter substantially the
hydrocarbon character of the hydrocarbon substituent. Preferably,
the upper limit on the percentage of polar substituent is about 10
percent by weight based upon the total weight of the hydrocarbon
substituent. Exemplary polar substituents include halo, carbonyl,
oxo (--O--), formyl, nitro, thio (--S--), etc.
The exact nature of the hydrocarbon substituent depends upon the
method used to prepare the acids or their anhydrides. In essence,
the preparation of these acids or anhydrides involves the reaction
of an olefinic aliphatic hydrocarbon compound or a halogenated
olefinic aliphatic hydrocarbon compound with maleic acid or
anhydride to form the corresponding substituted succinic acid or
anhydride. The product of this reaction is an alkenyl succinic acid
or anhydride, which may be hydrogenated to the completely
saturated, alkyl succinic acid or anhydride.
The source of the olefinic aliphatic hydrocarbon compound used for
the preparation of the aliphatic hydrocarbon-substituted succinic
acids or anhydrides depends upon the molecular weight range and
nature of the substituent desired. For the preparation of the
subject succinic acids or anhydrides with a hydrocarbon substituent
of lower molecular weight, a preferred source of this hydrocarbon
substituent is the low molecular weight polymers of the C.sub.2
-C.sub.4 olefins. Representative examples of these lower molecular
weight polymers are tetrapropylene, triisobutylene,
tetraisobutylene, etc. For the preparation of the succinic acids or
anhydrides with a higher molecular weight substituent, a convenient
source is the substantially saturated polymers or copolymers of
monoolefins having from 2 to about 30 carbon atoms. Exemplary of
these, are the higher molecular weight polymers of ethylene,
propene, 1-butene, isobutylene, 1-octene, and
3-cyclohexyl-1-butene. Exemplary of useful copolymers are those
derived from the copolymerization of isobutene with butadiene,
isobutene with chloroprene, 1-hexene with 1,3-hexadiene and
1-octene with 1-hexene. Polymers of medial olefins, i.e., olefins
in which the olefinic linkage is not at the terminal position, are
also useful. These are illustrated by 2-butene, 3-pentene and
4-octene. Other convenient sources of the higher molecular weight
aliphatic hydrocarbon substituent include substantially saturated
petroleum fractions, saturated aliphatic hydrocarbons derived from
highly refined high molecular weight white oils, and synthetic
alkanes such as those obtained by the hydrogenation of high
molecular weight olefin polymers.
These aliphatic hydrocarbon-substituted succinic acids and
anhydrides are known in the art, and methods for their preparation,
as well as representative examples of the types useful in the
present invention are described in detail in the following U.S.
Pat. Nos.: 3,172,892; 3,216,936; 3,219,666; 3,271,310; 3,272,746;
3,278,550; 3,281,428; 3,306,908; 3,316,771; 3,373,111; 3,381,022;
3,341,542; 3,344,170; 3,448,048; 3,454,607; 3,515,669; 3,522,179;
3,542,678; 3,542,680; 3,579,450; 3,632,510; 3,632,511; and
3,639,242. These patents are expressly incorporated herein by
reference for their disclosure of the preparation of the subject
acids or anhydrides and specific representative examples of such
acids or anhydrides.
The alkylene oxides or alkylene glycols used to prepare the
esterified reaction product with the above aliphatic
hydrocarbon-substituted succinic acids or anhydrides will have from
2 to about 20 carbon atoms. Preferably, they will have from 2 to
about 6 carbon atoms.
Representative examples of alkylene oxides useful in the
preparation of the esterified reaction products of this invention
are ethylene oxide, propylene oxide, 1,2-butylene oxide,
2,3-butylene oxide, cyclohexene oxide, and 1,2-octylene oxide.
The glycols used to prepare the subject partially esterified
reaction product may be either an alkylene glycol or a polyalkylene
glycol. These glycols contain at least one alkylene oxide unit
having from 2 to 7 carbon atoms. The most satisfactory glycols are
those derived from ethylene oxide or propylene oxide or mixtures of
these.
The polyethylene glycols correspond to the formula;
HO(CH.sub.2 CH.sub.2 O).sub.n CH.sub.2 CH.sub.2 OH
wherein n is an integer having a value of from 1 to about 9,
preferably 1 or 2.
The polypropylene glycols correspond to the formula;
HO[CH(R")--CH(R'")--O].sub.m CH(R")--CH(R'")OH
wherein either R" or R'" is a methyl group and the other R is a
hydrogen, and m is an integer having a value of from 1 to about 6,
preferably 1 or 2.
Representative examples of alkylene glycols useful in the
preparation of the esterified reaction products of this invention
are ethylene glycol, propylene glycol, trimethylene glycol,
butylene glycol, diethylene glycol, triethylene glycol,
tetraethylene glycol, dipropylene glycol, tripropylene glycol,
diisobutylene glycol, and tributylene glycol.
Additional useful alkylene glycols include the following:
HO(CH.sub.2 CH.sub.2 O).sub.7 CH.sub.2 CH.sub.2 OH;
HO[CH(CH.sub.3)CH.sub.2 O].sub.5 CH(CH.sub.3)CH.sub.2 OH;
HO[CH.sub.2 CH.sub.2 O].sub.3 --[CH(CH.sub.3)CH.sub.2 O].sub.3
--CH(CH.sub.3)CH.sub.2 OH.
The esterified reaction product of the hydrocarbon-substituted
succinic acids or anhydrides is a partially esterified product.
Thus, from about 0.1 mole to about 1.0 of the alkylene oxide of
alkylene glycol is reacted per mole of the acid or anhydride. This
partially esterified product may be prepared by any of several
methods known in the art. One such method consists of mixing the
anhydride and the glycol in the absence of a solvent and heating
this mixture at a temperature above about 100.degree.C., preferably
between about 150.degree. and 300.degree.C. for a period of time
sufficient to effect the reaction. When the partial esterification
is effected using an alkylene oxide a convenient preparative method
involves adding the alkylene oxide portion-wise to the anhydride at
a temperature within the range of from about 50.degree. to about
100.degree.C.
Of course, the substituted succinic acid can be used in any of the
preparative methods in the place of the anhydride. However, since
the succinic acid readily undergoes dehydration at temperatures
above about 100.degree.C. to form the anhydride, in most cases it
is preferred to use the anhydride.
In some instances it may be advantageous to conduct the
esterification using a solvent as this improves mixing and control
of the reaction temperature. Useful solvents include xylene,
toluene, diphenylether, chlorobenzene, and mineral oil. Any water
formed during this esterification is conveniently removed by
distillation as the reaction proceeds.
The esterification may be conducted in the presence of a catalyst.
Useful esterification catalysts include sulfuric acid, pyridine
hydrochloride, hydrochloric acid, benzenesulfonic acid, and
p-toluenesulfonic acid. The amount of catalyst used is generally in
the range of from about 0.1 to about 5% by weight.
Further details concerning the esterification of the subject type
of hydrocarbon-substituted succinic acids and anhydrides with
alkylene oxides and alkylene glycols is found in the prior art,
such as U.S. Pat. Nos. 2,962,443; 3,405,042; 3,117,091; 3,255,108;
and 3,381,022.
The additive combination of the present invention is effectively
employed using base oils of lubricating viscosity derived from a
variety of sources. Thus, base oils derived from both natural and
synthetic sources are contemplated for the preparation of
lubricating oil and grease compositions of the present invention.
The natural oils include animal oils, such as lard oil; vegetable
oils, such as castor oil; and mineral oils, such as solvent-refined
or acid-refined mineral oils of the paraffinic and/or naphthenic
type. Also base oils derived from coal or shale are useful.
Useful synthetic lubricating base oils include hydrocarbon oils
derived from the polymerization or copolymerization of olefins,
such as polypropylene, polyisobutylene and propylene-isobutylene
copolymers; and the halo-hydrocarbon oils, such as chlorinated
polybutylene. Other useful synthetic base oils include those based
upon alkyl benzenes, such as dodecylbenzene, tetradecylbenzene, and
those based upon polyphenols, such as biphenyls, and
terphenyls.
Another known class of synthetic oils useful as base oils for the
subject lubricant compositions are those based upon alkylene oxide
polymers and interpolymers, and those oils obtained by the
modification of the terminal hydroxy groups of these polymers,
(i.e., by the esterification or etherification of the hydroxy
groups). Thus, useful base oils are obtained from polymerized
ethylene oxide or proplyene oxide or from the copolymers of
ethylene oxide and propylene oxide. Useful oils include the alkyl
and aryl ethers of the polymerized alkylene oxides, such as
methylpolyisopropylene glycol ether, diphenyl ether of polyethylene
glycol, and diethyl ether of propylene glycol. Another useful
series of synthetic base oils is derived from the esterification of
the terminal hydroxy group of the polymerized alkylene oxides with
mono- or polycarboxylic acids. Exemplary of this series is the
acetic acid esters or mixed C.sub.3 -C.sub.8 fatty acid esters or
the C.sub.13 Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oil comprise the
esters of dicarboxylic acids, such as phthalic acid, succinic acid,
oleic acid, azelaic acid, suberic acid, sebacic acid, with a
variety of alcohols. Specific examples of these esters include
dibutyl adipate, di(2-ethylhexyl)sebacate, and the like. Silicone
based oils such as polyalkyl-, polyaryl-, polyalkoxy-, or
polyaryloxy-siloxane oils and the silicate oils, i.e., tetraethyl
silicate, comprise another useful class of synthetic lubricants.
Other synthetic lubricating oils include liquid esters of
phosphorus-containing acid, such as tricresyl phosphate,
polymerized tetrahydrofurans, and the like.
The subject additive combination can be used alone or in
combination with other lubricant additives known in the prior art.
A brief survey of conventional additives for lubricating
compositions is contained in the publications, LUBRICANT ADDITIVES,
by C.V. Smalheer and R. Kennedy Smith, published by the
Lezius-Hiles Co., Cleveland, Ohio (1967) and LUBRICANT ADDITIVES,
by M.W. Ranney, published by Noyes Data Corp., Park Ridge, N.J.
(1973). These publications are incorporated herein by reference to
establish the state of the art in regard to identifying both
general and specific types of other additives which can be used in
conjunction with the additive combination of the present
invention.
In general, these additional additives include detergents of the
ash-containing type, ashless dispersants, viscosity index
improvers, pour point depressants, antifoam agents, extreme
pressure agents, anti-wear agents, other rust-inhibiting agents,
other oxidation inhibitors, and corrosion inhibitors.
The ash-containing detergents are the well known neutral basic
alkali or alkaline earth metal salts of sulfonic acids, carboxylic
acids or organo-phosphorus-containing acids. The most commonly used
salts of these acids are the sodium, potassium, lithium, calcium,
magnesium, strontium, and barium salts. The calcium and barium
salts are used more extensively than the others. The "basic salts"
are those metal salts known to the art wherein the metal is present
in a stoichiometrically larger amount than that necessary to
neutralize the acid. The calcium- and barium-overbased
petrosulfonic acids are typical examples of such basic salts.
The extreme pressure agents, corrosion-inhibiting agents, and
oxidation-inhibiting agents, are exemplified by chlorinated
aliphatic hydrocarbons, such as chlorinated wax; organic sulfides
and polysulfides, such as benzyldisulfide,
bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized sperm
oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol,
sulfurized dipentene, sulfurized terpene, and sulfurized
Diels-Alder adducts; phosphosulfurized hydrocarbons, such as the
reaction product of phosphorus sulfide with turpentine or
methyloleate; phosphorus esters such as the dihydrocarbon and
trihydrocarbon phosphites, i.e., dibutyl phosphite, diheptyl
phosphite, dicylohexyl phosphite, pentaphenyl phosphite,
dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite,
and polypropylene substituted phenol phosphite; metal
thiocarbamates, such as zinc dioctyldithiocarbamate and barium
heptylphenol dithiocarbamate; and Group II metal salts of
phosphorodithioic acid, such as zinc dicyclohexyl
phosphorodithioate, and the zinc salts of a phosphorodithioic
acid.
The ashless detergents or dispersants are a well known class of
lubricant additives and are extensively discussed and exemplified
in the above-cited publications by Smalheer et al. and Ranney and
the references cited therein. Particularly useful types of ashless
dispersants are based upon the reaction products of
hydrocarbon-substituted succinic acid compounds and polyamines or
polyhydric alcohols. These reaction products may be post-treated
with materials, such as alkylene oxides, carboxylic acids, boron
compounds, carbon disulfide and alkenyl cyanides to produce further
useful ashless dispersants.
Pour point depressing agents are illustrated by the polymers of
ethylene, propylene, isobutylene, and poly-(alkyl methacrylate).
Anti-foam agents include polymeric alkyl siloxanes, poly(alkyl
methacrylates), terpolymers of diacetone acrylamide and alkyl
acrylates or methacrylates, and the condensation products of alkyl
phenols with formaldehyde and an amide. Viscosity index improvers
include polymerized and copolymerized alkyl methacrylates and
polyisobutylenes.
When additional additives are used in lubricant compositions
comprising the subject additive combination, they are used in
concentrations in which they are normally employed in the art.
Thus, they will generally be used in a concentration of from about
0.001 up to about 25% by weight of total composition, depending, of
course, upon the nature of the additive and the nature of the
lubricant composition. For example, ashless dispersants can be
employed in amounts from about 0.1 to about 10% and
metal-containing detergents can be employed in amounts from about
0.1 to about 20% by weight. Other additives, such as pour point
depressants, extreme pressure additives, viscosity index improving
agents, anti-foaming agents, and the like, are normally employed in
amounts of from about 0.001 to about 10% by weight of the total
composition, depending upon the nature and purpose of the
particular additive.
A clear understanding of the new additive combination of this
invention and lubricant compositions containing this combination
may be obtained from the examples given below, which illustrate the
presently preferred best modes of carrying out this invention.
EXAMPLE 1
A lubricating composition suitable for use as a steam turbine
lubricating oil is prepared using a 200 N base mineral oil, 0.05%
of an oil solution (37% oil) of a partially esterified dodecenyl
succinic acid, 1% of methylene bis(dibutyldithiocarbamate), and 200
ppm of a conventional anti-foaming agent based upon a polymer of
2-ethylhexyl acrylate and ethyl acrylate.
The partially esterified dodecenyl succinic acid used above is
prepared by treating 95 parts by weight of a 61% oil solution of
dodecenyl succinic acid with 5 parts by weight of propylene
oxide.
The methylene bis(dibutyldithiocarbamate) used above is prepared by
the reaction of dibutylamine, carbon disulfide, sodium hydroxide
and methylene dichloride.
Thus, 627 grams (4.86 moles) of di-n-butylamine, 240 grams (3
moles) of a 50% aqueous solution of sodium hydroxide, 200 grams of
toluene, and 200 grams of isopropanol are added to a reactor.
Carbon disulfide (228 grams, 3 moles) is slowly added to the above
mixture over a period of about 5 hours, while the temperature of
the reaction mixture is maintained under about 42.degree.C. After
completion of the addition of the carbon disulfide, the mixture is
slowly heated to about 65.degree.C. to expell any unwanted carbon
dilsulfide. Methylene dichloride (255 grams, 3 moles) is added
slowly to the reaction mixture over a period of about 2.5 hours and
during this addition period the temperature will increase to about
75.degree.C. After the addition of the methylene dichloride, the
mixture is heated for an additional 2 hours at a temperature in the
range of 60.degree.-65.degree.C. The mixture is then washed with
four 150 ml portions of water and the last traces of volatile
material are stripped from the reaction mixture using a vacuum of
about 120 mm Hg at a temperature of about 122.degree.C. After
vacuum stripping, the mixture is filtered to yield the desired
clear liquid product, methylene bis(dibutyldithiocarbamate).
EXAMPLE 2
A lubricating composition suitable for use as a steam turbine
lubricating oil is prepared using a 200 N base mineral oil, 0.05%
of the oil solution of the partially esterified dodecenyl succinic
acid used in Example 1, and 0.5% of methylene
bis(dibutyldithiocarbamate).
When the methylene bis(dibutyldithiocarbamate) used as the
anti-oxidant of Example 2 is replaced with methylene
bis(tetramethylenedithiocarbamate), or benzylidene
bis(pentamethylenedithiocarbamate), or 1,4-butylene
bis(butyldithiocarbamate), or 1,8-octylene
bis(diethyldithiocarbamate), or 1,3-propylene
bis(decyldithiocarbamate), or 1,4-hexylene
bis(dipropyldithiocarbamate), or ethylene
bis(4-morpholinecarbodithioate), or ethylene
bis(1-piperazinecarbodithioate), suitable lubricating compositions
are obtained.
EXAMPLE 2-A
When the partially esterified dodecenyl succinic acid used above is
replaced with the reaction product (0.25:1 mole) of 1,2-butylene
oxide and dodecenyl succinic anhydride; or the reaction product
(0.1:1 mole) of dipropylene glycol and hexadecyl succinic
anhydride; or the reaction product (0.2:1 mole) of ethylene oxide
and a polyisobutenyl succinic anhydride, wherein the polyisobutenyl
substituent has about 24 aliphatic carbon atoms; or a polypropylene
succinic acid, wherein the polypropylene substituent has about 60
aliphatic carbon atoms; suitable lubricating compositions are
obtained.
EXAMPLE 3
A lubricating composition suitable for use as a steam turbine
lubricating oil is prepared using a 200 N base mineral oil, 0.05%
of the oil solution of the partially esterified dodecenyl succinic
acid used in Example 1, and 1% by weight of ethylidene
bis(dibutyldithiocarbamate).
The ethylidene bis(dibutyldithiocarbamate) used above is prepared
by a process analogous to that used to prepare the anti-oxidant
component in Example 1 using di-n-butylamine, carbon disulfide,
sodium hydroxide, and ethylidene dichloride.
EXAMPLE 4
A lubricating composition suitable for use as a gear oil is
prepared using a SAE 90 base mineral oil, 0.5% of zinc
2-ethylhexylisobutyl phosphorodithioate as a combination extreme
pressure agent and oxidation inhibitor, 0.1% of the partially
esterified dodecenyl succinic acid of Example 1, 1.6% (0.5% sulfur)
of methylene bis(dibutyldithiocarbamate), and 200 ppm of the
anti-foam agent of Example 1.
When the methylene bis(dibutyldithiocarbamate) is replaced with
benzylidene bis(diethyldithiocarbamate), or methylene
bis(3-ethylpiperidinecarbodithioate), or 1,4-butylene
bis(decyldithiocarbamate), or 1,8-octylene
bis(diisopropyldithiocarbamate), or ethylene
bis(3,4-dimethylpyrrolidinecarbodithioate), suitable lubricating
compositions are obtained.
EXAMPLE 4-A
When the partially esterified dodecenyl succinic acid used above is
replaced with the reaction product (0.3:1 mole) of trimethylene
glycol and a polyisobutenyl succinic anhydride, wherein the
polyisobutenyl substituent has about 80 aliphatic carbon atoms; or
the reaction product (0.9:1 mole) of propylene glycol and a
diisobutylene succinic anhydride; or a
poly(ethylene-propylene)substituted succinic acid, wherein the
poly(ethylene-propylene)substituent has about 30 aliphatic carbon
atoms; or the reaction product (1:1 mole) of an alkylene glycol
corresponding to the formula HO[CH.sub.2 CH.sub.2 O].sub.3
--[CH(CH.sub.3)CH.sub.2 O].sub.3 --CH(CH.sub.3)CH.sub.2 OH and
dodecenyl succinic anhydride; suitable lubricating compositions are
obtained.
EXAMPLE 5
A lubricating composition suitable for use as a crankcase lubricant
is prepared using a 10W-40 mineral lubricating oil base and, as
additives, 8.8% of a polyisodecylacrylate viscosity index improver;
2.92% of an ashless dispersant, which is the reaction product (1:2
eq.) of a polyisobutenyl succinic anhydride and tetraethylene
pentamine prepared according to the procedure of U.S. Pat. No.
3,127,892; 3.05% of a dispersant which is the reaction product (1:1
eq) of a polyisobutenyl succinic anhydride and tetraethylene
pentamine and boric acid as described in U.S. Pat. No. 3,254,025;
1.61% of a dispersant which is the reaction product (1:1 eq) of a
polyisobutenyl succinic anhydride and pentaerythritol; 0.56% of a
61% solution of dodecenyl succinic acid in oil; 1.50% of methylene
bis(dibutyldithiocarbamate); 0.78% of a commercial hindered phenol
based anti-oxidant; and 40 ppm of an anti-foaming agent.
EXAMPLE 5-A
When the methylene bis(dibutyldithiocarbamate) used in the above
formulation is replaced with methylene
bis(tetramethylenedithiocarbamate), or ethylene
(tertramethylenedithiocarbamate)(pentamethylenedithiocarbamate), or
1,4-butylene(pentamethylenedithiocarbamate)(di-n-butyldithiocarbamate),
or benzylidene bis(pentamethylenedithiocarbamate), or methylene
(4-morpholinecarbodithioate)(1-piperazinecarbodithioate), suitable
lubricating compositions are obtained.
EXAMPLE 6
A lubricating composition suitable for use as a crankcase lubricant
is prepared using a 10W-40 mineral lubricating oil base, and, as
additives, 8.8% of a polyisodecylacrylate viscosity improving
agent; 2.92% of the ashless dispersant of Example 5; 3.05% of the
boron-containing dispersant of Example 5; 1.57% of a dispersant
based upon the reaction product of a chlorinated polyisobutene,
acrylic acid, tetraethylene pentamine and phthalic acid; 0.56% of a
61% solution of dodecenyl succinic acid in oil; 0.78% of a
commercial hindered phenol anti-oxidant; 0.75% of methylene
bis(dibutyldithiocarbamate); and 40 ppm of a conventional
anti-foaming agent.
EXAMPLE 7
A suitable crankcase lubricating composition is obtained when the
0.75% of methylene bis(dibutyldithiocarbamate) in the composition
of Example 6 is replaced with 1.5% of methylene
bis(dibutyldithiocarbamate).
EXAMPLE 8
A lubricating composition suitable for use as a crankcase lubricant
is prepared using a 10W-50 mineral lubricating oil base and, as
additives, 3.4% of a hydrogenated butadiene-styrene copolymer as a
viscosity index improver; 0.2% of a conventional pour point
depressant (PAM-140); 60ppm of a conventional anti-foaming agent;
1.0% of a dispersant based upon a reaction product of a polybutenyl
succinic anhydride, tetramethylene pentamine and phthalic acid;
0.1% of a commercial thiadiazole based copper deactivator (Amoco
150); 1.0% of a 61% oil solution of dodecenyl succinic anhydride;
and 1.0% of methylene bis(dibutyldithiocarbamate).
EXAMPLE 9
A lubricating composition suitable for use as a hydraulic fluid is
prepared using a 200 N mineral lubricating base oil, 1.0% of a
corrosion inhibitor based upon an adduct (1:1 eq) of
diisooctylphosphinodithioic acid and methyl acrylate, 0.05% of an
oil solution (37% oil) of the partially esterified dodecenyl
succinic acid described in Example 1, and 0.25% of methylene
bis(dibutyldithiocarbamate).
EXAMPLE 10
A lubricating composition suitable for use as a hydraulic fluid is
prepared using a 350 N mineral lubricating base oil, 0.50% of
tri(4-methyl-2-pentyl)phosphite as an extreme pressure agent, 0.05%
of an oil solution (37% oil) of the reaction product obtained by
the treatment of 1,000 parts of an oil solution (39% oil) of
dodecenyl succinic acid with 60.5 parts of propylene oxide, and
0.25% of methylene bis(dibutyldithiocarbamate).
EXAMPLE 11
A lubricating composition is prepared using a synthetic lubricating
base oil consisting essentially of the diethyl ether of propylene
glycol having an average molecular weight of about 15,000, 0.05% of
the oil solution of the partially esterified dodecenyl succinic
acid described in Example 1, and 1% of methylene
bis(dibutyldithiocarbamate).
In the above examples, as well as in the specification and claims,
all percentages are expressed as percentage by weight, and all
parts are expressed as parts by weight, unless otherwise indicated.
Likewise, all temperatures are expressed in .degree.C., unless
otherwise indicated.
The lubricating composition of the present invention may, of
course, be prepared by a variety of methods known in the art. One
convenient method is to add the additive combination in the form of
a concentrated solution or suspension to a sufficient amount of the
base lubricant to form the subject lubricating composition. This
additive concentrate contains the separate ingredients of the
combination in the proper ratio to each other to provide the proper
ratio of anti-oxidant and rust-inhibitor in the final lubricating
composition. The concrete may also contain appropriate amounts of
any additional additive which it is desired to incorporate in the
final composition. Generally, the concentrate will comprise from
about 20 to about 90 percent of the additive combination with the
balance being a substantially inert normally liquid solvent or
diluent, plus any additional additive used. Suitable solvents and
diluents include any of the above-discussed natural or synthetic
oils, kerosene, xylene, benzene, mixtures of two or more of these
and other solvents and diluents known in the art. Hereafter these
substantially inert, normally liquid solvents and diluents used in
the preparation of additive concentrates are referred to
collectively as carriers. Normally the carriers are oil-soluble, at
least to the extent of their concentration in the final lubricating
compositions prepared from them.
* * * * *