U.S. patent application number 08/451888 was filed with the patent office on 2002-08-29 for lubricants with molybdenum containing compositions and methods of using the same.
Invention is credited to BOURGOGNON, HENRI, CONSTANS, BERNARD, COOK, SUSAN P., SCHWIND, JAMES J..
Application Number | 20020119895 08/451888 |
Document ID | / |
Family ID | 23794109 |
Filed Date | 2002-08-29 |
United States Patent
Application |
20020119895 |
Kind Code |
A1 |
COOK, SUSAN P. ; et
al. |
August 29, 2002 |
LUBRICANTS WITH MOLYBDENUM CONTAINING COMPOSITIONS AND METHODS OF
USING THE SAME
Abstract
This invention relates to a lubricating composition comprising a
major amount of an oil of lubricating viscosity and (A) an antiwear
improving amount of at least one molybdenum containing composition,
and (B) at least one member selected from the group consisting of
(i) at least one borated overbased metal salt of an acidic organic
compound, provided that (A) and (Bi) are not the same, (ii) a
combination of (a) at least one organic polysulfide or at least one
ashless dithiocarbamate containing composition and (b) at least one
component selected from the group consisting of a metal
thiophosphate, a phosphoric acid ester or salt thereof, a
phosphorus-containing carboxylic acid, ester, ether, or amide, a
borated dispersant, an alkali metal borate, a borated fatty amine,
a borated phospholipid, a borate ester, and mixtures thereof, and
(iii) a combination of (i) and (ii).
Inventors: |
COOK, SUSAN P.; (LITTLEOVER
DERB, GB) ; SCHWIND, JAMES J.; (DERBYSHIRE, GB)
; CONSTANS, BERNARD; (SEREZIN, FR) ; BOURGOGNON,
HENRI; (TASSIN LA DEMI, FR) |
Correspondence
Address: |
WILLIAM C TRITT
RENNER OTTO BOISSELLE & SKLAR
1621 EUCLID AVENUE
19TH FLOOR
CLEVELAND
OH
44115
|
Family ID: |
23794109 |
Appl. No.: |
08/451888 |
Filed: |
May 26, 1995 |
Current U.S.
Class: |
508/186 ;
508/187; 508/189; 508/322; 508/362; 508/363; 508/368; 508/379;
508/381; 508/421; 508/443 |
Current CPC
Class: |
C10M 2223/049 20130101;
C10N 2010/04 20130101; C10M 2223/045 20130101; C10M 2219/106
20130101; C10N 2010/02 20130101; C10M 2205/223 20130101; C10M
2219/046 20130101; C10M 2215/04 20130101; C10M 167/00 20130101;
C10M 2221/041 20130101; C10M 2215/28 20130101; C10M 2203/065
20130101; C10M 2229/02 20130101; C10M 2203/10 20130101; C10M
2201/18 20130101; C10M 2223/043 20130101; C10M 2207/028 20130101;
C10M 2219/024 20130101; C10N 2040/04 20130101; C10M 2205/22
20130101; C10M 2223/047 20130101; C10M 2203/1006 20130101; C10M
2219/08 20130101; C10M 2227/061 20130101; C10M 163/00 20130101;
C10M 2207/126 20130101; C10M 2223/042 20130101; C10M 2223/12
20130101; C10M 2207/26 20130101; C10M 2215/08 20130101; C10M
2207/08 20130101; C10M 2219/068 20130101; C10M 2219/082 20130101;
C10M 2223/041 20130101; C10M 2207/28 20130101; C10N 2060/14
20130101; C10M 2201/087 20130101; C10M 2219/02 20130101; C10M
2223/04 20130101; C10N 2010/12 20130101; C10M 2215/04 20130101;
C10N 2060/14 20130101; C10M 2219/106 20130101; C10M 2215/04
20130101; C10M 2207/08 20130101; C10M 2223/047 20130101; C10M
2207/126 20130101; C10M 2223/047 20130101; C10M 2207/281 20130101;
C10M 2207/042 20130101; C10M 2215/04 20130101; C10N 2060/14
20130101 |
Class at
Publication: |
508/186 ;
508/187; 508/189; 508/322; 508/362; 508/363; 508/379; 508/381;
508/368; 508/421; 508/443 |
International
Class: |
C10M 141/00; C10M
141/12 |
Claims
1. A lubricating composition comprising a major amount of an oil of
lubricating viscosity and (A) an antiwear improving amount of at
least one molybdenum containing composition, and (B) at least one
member selected from the group consisting of (i) at least one
borated overbased metal salt of an acidic organic compound,
provided that (A) and (Bi) are not the same, (ii) a combination of
(a) at least one organic polysulfide or at least one ashless
dithiocarbamate containing composition and (b) at least one
component selected from the group consisting of a metal
thiophosphate, a phosphoric acid ester or salt thereof, a
phosphorus-containing carboxylic acid, ester, ether, or amide, a
borated dispersant, an alkali metal borate, a borated fatty amine,
a borated phospholipid, a borate ester, and mixtures thereof, and
(iii) a combination of (i) and (ii).
2. The composition of claim 1, wherein (A) is present in an amount
to provide from about 125 to about 900 ppm molybdenum to the
lubricating composition.
3. The composition of claim 1, wherein (A) is a molybdenum
containing alkali or alkaline earth metal overbased sulfonate,
carboxylate, or phenate.
4. The composition of claim 1, wherein (A) is molybdenum containing
alkali or alkaline earth metal sulfonate.
5. The composition of claim 4, wherein the alkaline or alkaline
earth metal is calcium or magnesium.
6. The composition of claim 1 wherein (A) is prepared by
carbonation of a mixture comprising at least one alkali or alkaline
earth metal compound, an acidic organic compound, and at least one
hydrocarbon insoluble organic molybdenum complex.
7. The composition of claim 6 wherein the organic molybdenum
complex is an amine molybdenum complex.
8. The composition of claim 1 wherein (A) is at least one
molybdenum thiophosphate or at least one molybdenum
thiocarbamate.
9. The composition of claim 1 wherein (A) is at least one
molybdenum oxysulfide dithiophosphate or at least one molybdenum
oxysulfide dithiocarbamate.
10. The composition of claim 1, wherein (B) is (i) and the borated
overbased salt of an acidic organic compound is a borated overbased
alkali or alkaline earth metal sulfonate, carboxylate or
phenate.
11. The composition of claim 1 wherein (B) is (i) and the borated
overbased salt of an acidic organic compound is a borated overbased
sodium, calcium or magnesium sulfonate or carboxylate.
12. The composition of claim 1, wherein (B) is (i) and the
lubricating composition further comprises (C) at least one
sulfurized organic compound or at least one ashless dithiocarbamate
containing compound, or (D) at least one phosphorus or boron
extreme pressure.
13. The composition of claim 1 wherein (B) is (ii) and the organic
polysulfide is a sulfurized oil, fatty acid or ester, olefin,
polyolefin or mixtures thereof.
14. The composition of claim 1 wherein (B) is (ii) and the ashless
dithiocarbamate containing composition (a) is prepared by reacting
a dithiocarbamic acid or salt with an unsaturated compound.
15. The composition of claim 14 wherein the unsaturated compound is
an acrylic ester of the formula
R.sup.1R.sup.2C.dbd.C(R.sup.3)COOR.sup.4, wherein R.sup.1, R.sup.2,
and R.sup.3 are each independently hydrogen or a hydrocarbyl group,
and R.sup.4 is a hydrocarbyl group containing from 1 to about 24
carbon atoms.
16. The composition of claim 14 wherein the unsaturated compound is
a methyl, ethyl, butyl, pentyl, or hexyl-acrylate or
methacrylate.
17. The composition of claim 1 wherein the phosphoric acid ester or
salt thereof (b) is a phosphoric acid ester prepared by reacting a
dithiophosphoric acid with an epoxide to form an intermediate, and
the intermediate is further reacted with a phosphorus acid or
anhydride, or a salt of the phosphoric acid ester.
18. The composition of claim 17 wherein the dithiophosphoric acid
is a dihydrocarbyl dithiophosphoric acid independently having from
1 to about 24 carbon atoms in each hydrocarbyl group.
19. The composition of claim 18 wherein the phosphoric acid ester
or salt thereof is prepared by reacting the phosphoric acid ester
with ammonia or an amine.
20. The composition of claim 19 wherein the amine is a tertiary
aliphatic primary amine.
21. The composition of claim 1 wherein the phosphoric acid ester or
salt thereof (b) is a phosphoric acid ester prepared by reacting a
phosphorus acid or anhydride with at least one alcohol wherein each
alcohol independently contains from about 1 to about 30 carbon
atoms, or a salt of the phosphoric acid ester.
22. The composition of claim 1 wherein the phosphoric acid ester or
salt thereof is a triarylphosphate.
23. The composition of claim 22 wherein the triarylphosphate is
tricresylphosphate.
24. The composition of claim 12, wherein (C) is a sulfurized
olefin.
25. A lubricating composition comprising a major amount of an oil
of lubricating viscosity and (A) an antiwear improving amount of at
least one molybdenum containing composition, and (B) at least one
borated overbased metal salt of an acidic organic compound,
provided that (A) and (B) are not the same.
26. The composition of claim 25, wherein (A) is present in an
amount to provide from about 125 to about 900 ppm molybdenum to the
lubricating composition.
27. The composition of claim 25, wherein (A) is a molybdenum
containing alkali or alkaline earth metal overbased sulfonate,
carboxylate, or phenate.
28. The composition of claim 25, wherein (A) is a molybdenum
containing alkali or alkaline earth metal overbased sulfonate.
29. The composition of claim 25 wherein (A) is prepared by
carbonation of a mixture comprising at least one alkali or alkaline
earth metal compound, an acidic organic compound, and at least one
hydrocarbon insoluble organic molybdenum complex.
30. The composition of claim 29 wherein the organic molybdenum
complex is an amine molybdenum complex.
31. The composition of claim 25 wherein (A) is a molybdenum
thiophosphate or a molybdenum thiocarbamate.
32. The composition of claim 25 wherein (A) is a molybdenum
oxysulfide dithiophosphate or a molybdenum oxysulfide
dithiocarbamate.
33. The composition of claim 25, wherein (B) the borated overbased
salt of an acidic organic compound is a borated overbased alkali or
alkaline earth metal sulfonate, carboxylate or phenate.
34. The composition of claim 25 A herein (B) is a borated overbased
sodium, calcium, or magnesium sulfonate or carboxylate.
35. The composition of claim 25, further comprises (C) at least one
organic polysulfide or at least one dithiocarbamate containing
compound, or (D) at least one phosphorus or boron antiwear or
extreme pressure, wherein (B) and (D) are not the same.
36. The composition of claim 35, wherein (C) is a sulfurized
olefin.
37. The composition of claim 35, wherein (C) is a dithiocarbamate
ester prepared by reacting a dithiocarbamic acid or salt with an
unsaturated compound.
38. A lubricating composition comprising a major amount of an oil
of lubricating viscosity, (A) at least one molybdenum containing
composition, and (B) at least one combination of (a) at least one
organic polysulfide or at least one ashless dithiocarbamate
containing composition and (b) a component selected from the group
consisting of a metal thiophosphate, a phosphoric acid ester or
salt thereof, a phosphorus-containing carboxylic acid, ester,
ether, or amide, a borated dispersant, an alkali metal borate, a
borated fatty amine, a borated phospholipid, a borate ester, and
mixtures thereof.
39. The composition of claim 38, wherein (A) is a molybdenum
containing alkali or alkaline earth metal sulfonate.
40. The composition of claim 38 wherein (A) is a molybdenum
thiophosphate or a molybdenum thiocarbamate.
41. The composition of claim 38 wherein (A) is a molybdenum
oxysulfide dithiophosphate or a molybdenum oxysulfide
dithiocarbamate.
42. A method of lubricating a transmission or a differential
comprising the steps of introducing to a transmission or
differential a lubricating composition comprising a major amount of
an oil of lubricating viscosity and (A) an antiwear improving
amount of at least molybdenum containing composition, and (B) at
least one member selected from the group consisting of (i) at least
one borated overbased metal salt of an acidic organic compound,
provided that (A) and (Bii) are not the same, (ii) a combination of
(a) at least one organic polysulfide or at least one ashless
dithiocarbamate containing composition and (b) at least one
component selected from the group consisting of a metal
thiophosphate, a phosphoric acid ester or salt thereof, a
phosphorus-containing carboxylic acid, ester, ether, or amide, a
borated dispersant, an alkali metal borate, a borated fatty amine,
a borated phospholipid, a borate ester, and mixtures thereof, and
(iii) a combination of (i) and (ii), and operating the differential
or transmission.
Description
FIELD OF THE INVENTION
[0001] This invention relates to a lubricating composition
comprising a molybdenum composition which improves the antiwear
properties of the lubricant. The invention also relates to methods
of lubricating a transmission or differential. These lubricating
compositions are particularly useful as manual transmission
fluids.
BACKGROUND OF THE INVENTION
[0002] Engine, transmission, and gear designs utilize a variety of
metallurgy in their designs. In transmissions, often a brass
synchronizer ring is used. This brass Add synchronizer engages with
a steel cone to affect changing of the transmission gears One
problem, associated with this design, is brass ring wear. It is
therefore desirable to have a lubricant which reduces brass on
steel wear.
[0003] Often lubricants contain mixtures of additives which are
intended to protect the engines, transmissions, and gears against
wear and oxidation. Many such mixtures are known to those in the
art. However, it would be desirable to have a specific mixture of
additives which also provide protection against brass on steel
wear.
[0004] U.S. Pat. Nos. 3,541,014 (LeSuer), and 5,143,633 (Gallo et
al) describe various molybdenum containing overbased metal
salts.
[0005] U.S. Pat. Nos. 3,446,735 (Wiese), 4,289,635 (Schroeck),
4,456,538 (Ripple), 4,692,256 (Umemura et al), 4,704,215 (Hata et
al), and 4,846,983 (Ward, Jr.) describe various molybdenum compound
and composition either used alone or used in combination with other
additives.
SUMMARY OF THE INVENTION
[0006] This invention relates to a lubricating composition
comprising a major e S amount of an oil of lubricating viscosity
and (A) an antiwear improving amount of at least one molybdenum
containing composition, and (B) at least one member selected from
the group consisting of (i) at least one borated overbased metal
salt of an acidic organic compound, provided that (A) and (Bi) are
not the same, (ii) a combination of (a) at least one organic
polysulfide or at least one ashless dithiocarbamate containing
composition and (b) at least one component selected from the group
consisting of a metal thiophosphate, a phosphoric acid ester or
salt thereof, a phosphorus-containing carboxylic acid, ester,
ether, or amide, a borated dispersant, an alkali metal borate, a
borated tatty amine, a borated phospholipid, a borate ester, and
mixtures thereof, and (iii) a combination of (i) and (ii). The
lubricating, compositions have improved antiwear properties. When
the lubricating composition is used in a manual transmission, the
amount of brass on steel wear is reduced.
DESCRIPTION OF THE INVENTION
[0007] The term "hydrocarbyl" includes hydrocarbon as well as
substantially hydrocarbon groups. Substantially hydrocarbon
describes groups which contain heteroatom substituents which do not
alter the predominantly hydrocarbon nature of the group. Examples
of hydrocarbyl groups include the following:
[0008] (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl
or alkenyl). alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, aromatic-, aliphatic- and alicyclic-substituted
aromatic substituents and the like as well as cyclic substituents
wherein the ring is completed through another portion of the
molecule (that is, for example, any two indicated substituents may
together form an alicyclic radical).
[0009] (2) substituted hydrocarbon substituents, i.e, those
substituents containing non-hydrocarbon groups which, in the
context of this invention, do not alter the predominantly
hydrocarbon nature of the substituent; those skilled in the art
will be aware of such groups (e.g., halo (especially chloro and
fluoro), hydroxy, mercapto, nitro, nitroso, sulfoxy, etc.);
[0010] (3) heteroatom substituents, i.e., substituents which will,
while having a predominantly hydrocarbon character within the
context of this invention, contain an atom other than carbon
present in a ring or chain otherwise composed of carbon atoms
(e.g., alkoxy or alkylthio). Suitable heteroatoms will be apparent
to those of ordinary skill in the art and include, for example,
sulfur, oxygen, nitrogen and such substituents as, e.g., pyridyl,
furyl, thienyl, imidazolyl, etc.
[0011] In general, no more than about 2, preferably no more than
one, hetero substituent will be present for every ten carbon atoms
in the hydrocarbyl group. Typically, there will be no such hetero
atom substituents in the hydrocarbyl group. Therefore, the
hydrocarbyl group is purely hydrocarbon.
[0012] In the specification and claims, the term "lubricating
composition" refers to the combination of an oil of lubricating
viscosity and additives. The percentages by weight are based on the
amount of total amount of the additive and the oil of lubricating
viscosity.
[0013] As described herein, the use of molybdenum containing
compositions in combination with specific additives improves the
antiwear properties of lubricants, especially brass on steel wear.
The molybdenum composition is generally used at a level sufficient
to deliver from about 125 up to about 900 ppm, preferably from
about 200 up to about 800 ppm, more preferably from about 250 up to
about 700 ppm of molybdenum metal to the lubricating composition.
Here, as well as elsewhere in the specification, the ratios and
range limits may be combined. The molybdenum metal is in an oil
soluble or dispersible form. The molybdenum compositions include a
molybdenum containing overbased salt of an acidic organic
composition, a molybdenum thiocarbamate, and a molybdenum
thiophosphate. In one embodiment, the molybdenum composition is
other than a molybdenum containing dispersant such as a molybdenum
containing succinimide.
[0014] Molybdenum Overbased Compositions
[0015] In one embodiment, the molybdenum composition is in the form
of a molybdenum overbased salt of an acidic organic compound. The
molybdenum overbased metal salts are particularly useful in
lubricants which require thermal stability. The molybdenum
containing overbased salts are characterized by a metal content in
excess of that which would be present according to the
stoichiometry of the metal and the particular organic compound
reacted with the metal. The amount of excess metal is commonly
expressed in terms of metal ratio. The term "metal ratio" is the
ratio of the total equivalents of the metal to the equivalents of
the acidic organic compound. A salt having 4.5 times as much metal
as present in a normal salt will have metal excess of 3.5
equivalents per equivalents of organic acid or a ratio of 4.5. The
molybdenum containing overbased salts preferably have a metal ratio
from about 1.5, or from about 3. The molybdenum containing
overbased salts generally have a metal ratio up to about 40, or up
to about 30, or up to about 25. In one embodiment, the metal salts
have a metal ratio from about 10, preferably from about 12 up to
about 40, or up to about 30.
[0016] The molybdenum containing overbased salts additionally may
contain an alkali or alkaline earth metal. Examples of such metals
include sodium, potassium, lithium, magnesium, calcium, barium,
titanium, manganese, cobalt, nickel, copper, and zinc, preferably
sodium, potassium, calcium, and magnesium. The alkali or alkaline
earth metal may typically be present in an amount from about 2% up
to about 20%, or from about 4% up to about 18%, or from about 6 to
about 14% by weight of the molybdenum containing overbased
salts.
[0017] The acidic organic compounds used to prepare the molybdenum
containing overbased metal salts are generally selected from the
group consisting of sulfonic acids, carboxylic acids, phosphorus
acids, phenols, and derivatives thereof. Preferably, the overbased
materials are prepared from sulfonic acids, carboxylic acids, or
derivatives of these acids, such as esters, anhydrides, etc. The
sulfonic acids are preferably mono-, di-, and tri-aliphatic
hydrocarbon-substituted aromatic sulfonic acids. The
hydrocarbon-substituent may be derived from a polyalkene. The
polyalkenes include homopolymers and interpolymers of polymerizable
olefin monomers having from 2 up to about 16, preferably from 2 to
about 8, more preferably from 2 to about 4 carbon atoms. The
olefins may be monoolefins, such as ethylene, propylene, 1-butene,
isobutene, and 1-octene, or a polyolefinic monomer, such as
1,3-butadiene and isoprene. In one embodiment, the interpolymer is
a homopolymer. An example of a preferred homopolymer is a
polybutene, preferably a polybutene in which about 50% of the
polymer is derived from isobutylene. The polyalkenes are prepared
by conventional procedures.
[0018] The polyalkene is generally characterized as containing from
at least about 8, or at least about 15, or at least about 20 carbon
atoms. The polyalkene generally contains up to about 40 carbon
atoms, or up to about 30 carbon atoms. In one embodiment, the
polyalkenes have a {overscore (M)}n from about 250, or from about
300 up to about 600, or up to about 500, or up to about 400. The
abbreviation {overscore (M)}n is the conventional symbol
representing number average molecular weight. Gel permeation
chromatography (GPC) is a method which provides both weight average
and number average molecular weights as well as the entire
molecular weight distribution of the polymers. For purpose of this
invention a series of fractionated polymers of isobutene,
polyisobutene, is used as the calibration standard in the GPC.
[0019] Examples of sulfonic acids include mahogany sulfonic acids,
bright stock sultonic acids, petroleum sulfonic acids, mono- and
polywax-substituted naphthalene sulfonic acids, saturated,
hydroxy-substituted, and unsaturated paraffin wax sulfonic acids,
wax-substituted benzene or naphthalene sulfonic acids,
tetraisobutylene sulfonic acids, tetra-amylene sulfonic acids,
dodecylbenzene sulfonic acids, didodecylbenzene sulfonic acids,
dinonylbenzene sulfonic acids, sulfonic acids derived by the
treatment of at least one of the above-described polyalkenes
(preferably polybutene) with chlorosulfonic acid, and the like.
[0020] The sulfonic acids include dodecyl benzene "bottoms"
sulfonic acids. Dodecyl benzene bottoms, principally mixtures of
mono- and di-dodecyl benzenes, are available as by-products from
the manufacture of household detergents. Similar products obtained
from alkylation bottoms formed during manufacture of linear alkyl
sulfonates (LAS) are also useful in making the sulfonates used in
this invention. The production of sulfonic acids is well known to
those skilled in the art. See, for example, the article
"Sulfonates" in Kirk-Othmer "Encyclopedia of Chemical Technology",
Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley
& Sons, N.Y. (1969).
[0021] In one embodiment, the acidic organic compound may be a
carboxylic acid, or derivative thereof. Suitable carboxylic acids
include aliphatic, cycloaliphatic, and aromatic mono- and polybasic
carboxylic acids. In one embodiment, the carboxylic acid, or
derivative thereof, is an aliphatic acid, or derivative thereof,
containing from about 8, or from about 12. The carboxylic acid or
derivative thereof generally contains up to about 50, or up to
about 25 carbon atoms. Illustrative carboxylic acids and
derivatives thereof include 2-ethylhexanoic acid, palmitic acid,
stearic acid, oleic acid, linoleic acid, behenic acid,
octadecyl-substituted adipic acid, stearyl-benzoic acid,
polybutenyl substituted succinic acid or anhydride derived from
polybutene ({overscore (M)}n is from about 200-1500, preferably
from about 300-1500, more preferably from about 800-1200),
polypropylene substituted succinic acid or anhydride derived from
polypropene ({overscore (M)}n is from about 200-2000, preferably
from about 300-1500, more preferably from about 800-1200), acids
formed by oxidation of petrolatum or of hydrocarbon waxes,
commercially available mixtures of two or more carboxylic acids,
such as tall oil acids and rosin acids, and mixtures of the above
acids, and/or their derivatives.
[0022] In one embodiment, the carboxylic acid or derivative thereof
is a hydrocarbyl-substituted carboxylic acylating agent. The
acylating agent includes halides, esters, anhydrides, etc.,
preferably acid, esters, or anhydrides, more preferably anhydrides.
Preferably the carboxylic acylating agent is a succinic acylating
agent. The acylating agent may he derived from a monocarboxylic or
a polycarboxylic acylating agent and one or more of the above
described polyalkenes. In one embodiment, the polyalkene is
characterized by an {overscore (M)}n of at least about 400, or at
least about 500. Generally, the polyalkene is characterized by an
{overscore (M)}n from about 500 up to about 5000, or from about 700
up to about 2500, or from about 800 up to about 2000, or from about
900 up to about 1500. In one embodiment, the hydrocarbyl group of
the carboxylic acylating agent has a {overscore (M)}n from about
400 to about 1200, preferably from about 400 to about 800.
[0023] In another embodiment, the hydrocarbyl group is derived from
polyalkenes having an {overscore (M)}n from about 1300 up to about
5000, and the {overscore (M)}w/{overscore (M)}n value is from about
1.5 up to about 4, or from about 1.8 to about 3.6, or from about
2.5 to about 3.2. The hydrocarbyl-substituted carboxylic acylating
agents are prepared by known procedures. In another embodiment, the
acylating agents are prepared by reacting the above described
polyalkenes with an excess of maleic anhydride to provide
substituted succinic acylating agents wherein the number of
succinic groups for each equivalent weight of substituent group is
from about 1.3 to about 4.5 succinic groups per equivalent weight
of substituent groups. A suitable range is from about 1.4 up to
3.5, or from about 1.5 up to about 2.5 succinic groups per
equivalent weight of substituent groups. In this embodiment, the
polyalkene has an {overscore (M)}n from about 1300 to about 5000. A
more preferred range for {overscore (M)}n is from about 1500 to
about 2800, and a most preferred range of {overscore (M)}n is from
about 1500 to about 2400.
[0024] Carboxylic acids or derivatives thereof (e.g. acylating
agents) and their preparation are described in U.S. Pat. Nos.
3,215,707 (Rense); 3,219,666 (Norman et al); 3,231,587 (Rense);
3,912,764 (Palmer); 4,110,349 (Cohen); and 4,234,435 (Meinhardt et
al); and U.K. 1,440,219. The disclosures of these patents are
hereby incorporated by reference.
[0025] In another embodiment, the acidic organic compound is an
alkyloxyalkylene-acetic acid or alkylphenoxy-acetic acid, more
preferably alkylpoly-oxyalkylene-acetic acid or derivatives
thereof. Some specific examples of these compounds include:
iso-stearylpentaethyleneglycolacetic acid;
iso-stearyl-O--(CH.sub.2CH.sub.2O).sub.5CH.sub.2CO.sub.2Na;
lauryl-O--(CH.sub.2CH.sub.2O).sub.2 5CH.sub.2CO.sub.2H;
lauryl-O--(CH.sub.2CH.sub.2O).sub.3 3CH.sub.2CO.sub.2H;
oleyl-O--(CH.sub.2CH.sub.2O).sub.4CH.sub.2CO.sub.2H;
lauryl-O--(CH.sub.2CH.sub.2O).sub.4 5CH.sub.2CO.sub.2H;
lauryl-O--(CH.sub.2CH.sub.2O).sub.10CH.sub.2CO.sub.2H;
lauryl-O--(CH.sub.2-CH.sub.2O).sub.16CH.sub.2CO.sub.2H;
octyl-phenyl-O--(CH.sub.2CH.sub.2O).sub.8CH.sub.2CO.sub.2H;
octyl-phenyl-O--(CH.sub.2CH.sub.2O).sub.19CH.sub.2CO.sub.2H;
2-octyldecanyl-O--(CH.sub.2CH.sub.2O).sub.6CH.sub.2CO.sub.2H. These
acids are available commercially from Sandoz Chemical under the
tradename Sandopan acids.
[0026] In another embodiment, the acidic organic compound is an
aromatic carboxylic acid. A group of useful aromatic carboxylic
acids are those of the formula 1
[0027] wherein R.sub.1 is an aliphatic hydrocarbyl group derived
from the above-described olefins or polyalkenes, a is a number in
the range of 1 to about 4, usually 1 or 2, Ar is an aromatic group,
each X is independently sulfur or oxygen, preferably oxygen, b is a
number in the range from 1 to about 4, usually from 1 to 2, c is a
number in the range of zero to about 4, usually 1 to 2, with the
proviso that the sum of a, b, and c does not exceed the number of
valences of Ar. Examples of aromatic acids include substituted
benzoic, phthalic, and salicylic acids. The R.sub.1 group is a
hydrocarbyl group that is directly bonded to the aromatic group Ar.
Examples of R.sub.1 groups include substituents derived from the
above described polyalkenes.
[0028] Ar may be mono- or polynuclear. Mononuclear groups include a
phenyl, a pyridyl, or a thienyl. The polynuclear groups may be of
the fused type wherein an aromatic nucleus is fused at two points
to another nucleus such as found in naphthyl, anthranyl, etc. The
polynuclear group can also be of the linked type are linked through
bridging linkages such as alkylene, ether, keto, sulfide disulfide,
and polysulfide, containing 3 to about 6 sulfur atoms, linkages.
Examples of the aromatic groups include phenyl, phenylene, and
naphthalenyl groups.
[0029] In one embodiment, the carboxylic acid or derivative thereof
is a salicylic acid or derivative thereof. Preferably the salicylic
acid or derivative thereof is an aliphatic hydrocarbon-substituted
salicylic acid or derivative thereof. The hydrocarbon substituent
is generally derived from one or more of the above described
polyalkenes.
[0030] The above aromatic carboxylic acids are known or can be
prepared according to procedures known in the art. Carboxylic acids
of the type illustrated by these formulae and processes for
preparing their neutral and basic metal salts are well known and
disclosed, for example, in U.S. Pat. Nos. 2,197,832; 2,197,835;
2,252,662; 2,252,664; 2,714,092; 3,410,798; and 3,595,791. These
patents are incorporated by reference for their disclosure of
aromatic carboxylic acids, salts thereof and methods of making the
same.
[0031] In another embodiment, the acidic organic compound is a
phosphorus-containing acid, or derivative thereof. The
phosphorus-containing acids, or derivatives thereof, include
phosphorus acids, such as phosphoric acid or esters; and
thiophosphorus acids or esters, including mono and dithiophosphorus
acids or esters. In one embodiment, the phosphorus-containing acid
is the reaction product of one or more or the above polyalkenes and
a phosphorus sulfide. Useful phosphorus sulfides, include
phosphorus pentasulfide, phosphorus sesquisulfide, phosphorus
heptasulfide and the like. The reaction of the polyalkene and the
phosphorus sulfide generally may occur by simply mixing the two at
a temperature above 80.degree. C., usually between 100.degree. C.
and 300.degree. C. Generally, the products have a phosphorus
content from about 0.05% to about 10%, preferably from about 0.1%Y
to about 5%. The relative proportions of the phosphorizing agent t
the olefin polymer is generally from 0.1 part to 50 parts of the
phosphorus sulfide per 100 parts of the polyalkene. The
phosphorus-containing acids are described in U.S. Pat. No.
3,232,883 issued to LeSuer. This reference is herein incorporated
by reference for its disclosure to the phosphorus-containing acids
and methods for preparing the same.
[0032] In another embodiment, the acidic organic compound is a
phenol. The phenols may be represented by the formula
(R.sub.1).sub.a--Ar--(OH).sub.b- , wherein R.sub.1 is defined above
for the aromatic carboxylic acids; Ar is an aromatic group, as
defined above; a and b are independently numbers of at least one,
the sum of a and b being in the range of two up to the total number
of displacable hydrogens on the aromatic nucleus or nuclei of Ar.
Preferably, a and b are independently numbers in the range of 1 to
about 4, or to about 2. In one embodiment, R.sub.1 and a are such
that there is an average of at least about 8 aliphatic carbon atoms
provided by the R.sub.1 groups for each phenol compound.
[0033] In another embodiment, the molybdenum containing overbased
metal salts are borated molybdenum containing overbased metal
salts. The molybdenum containing borated overbased metal salts are
prepared by reacting one of the below described borated overbased
metal salts with a molybdenum containing anion. Alternatively, the
molybdenum containing borated overbased metal salts may be prepared
by incorporating the boron compound into the initial reaction
mixture used to make the molybdenum containing metal salts.
[0034] Preparation of the Molybdenum Containing Overbased
Composition
[0035] In one embodiment, the molybdenum containing overbased
compositions are prepared by reacting molybdenum containing anions
with an alkali or alkaline earth metal overbased salt of an acidic
organic compound. The alkali or alkaline earth metal salts are
prepared by reacting an acidic material, described below (typically
carbon dioxide), with a mixture comprising an acidic organic
compound. such as those described above, a reaction medium
comprising at least one inert, organic solvent for the organic
material, a stoichiometric excess of the alkali or alkaline earth
basic metal compound, typically a metal hydroxide or oxide, and a
promoter, including alcoholic and phenolic promoters, such as
alcohols having about one to about 12 carbon atoms (such as
methanol, ethanol, amyl alcohol, octanol, isopropanol, and mixtures
of these), and alkylated phenols (such as heptylphenols,
octylphenols, and nonylphenols).
[0036] Illustrative of alkali or alkaline earth basic metal
compounds include hydroxides, oxides, alkoxides (typically those in
which the alkoxy group contains up to 10 and preferably up to 7
carbon atoms), hydrides and amides of alkali or alkaline earth
metals. Useful basic metal compounds include lithium hydroxide,
sodium hydroxide, potassium hydroxide, magnesium oxide, calcium
hydroxide, calcium oxide, and barium hydroxide. The alkali and
alkaline earth metal salts and methods of making the same are
described in U.S Pat. No. 4,627,928. This patent is hereby
incorporated by reference for such disclosure. A comprehensive
discussion of suitable promoters is found in U.S. Pat. Nos.
2,777,874; 2,695,910; 2,616,904; 3,384,586; and 3,492,231. These
patents are incorporated by reference for their disclosure of
promoters.
[0037] The temperature at which the acidic material is contacted
with the remainder of the reaction mass depends to a large measure
upon the promoting agent used. With a phenolic promoter, the
temperature usually ranges from about 80.degree. C. to about
300.degree. C. and preferably from about 100.degree. C. to about
200.degree. C. When an alcohol or mercaptan is used as the
promoting agent, the temperature usually will not exceed the reflux
temperature of the reaction mixture.
[0038] Acidic materials, which are reacted with the mixture of the
acidic organic compound, the promoter, the metal compound and the
reactive medium, are also disclosed in the above cited patents, for
example, U.S. Pat. No. 2,616,904. Included within the known group
of useful acidic materials are formic acid, acetic acid, nitric
acid, boric acid, sulfuric acid, hydrochloric acid, hydrobromic
acid, carbamic acid, substituted carbamic acids, etc. Acetic acid
is a very useful acidic material. Inorganic acidic compounds such
as HCl, SO.sub.2, SO.sub.3, CO.sub.2, H.sub.2S, N.sub.2O.sub.3,
etc., may also he employed as the acidic materials. Preferred
acidic materials are SO.sub.2, SO.sub.3, carbon dioxide and acetic
acid, more preferably carbon dioxide.
[0039] The methods for preparing the overbased materials are well
known in the prior art and are disclosed, for example, in the
following U.S. Pat. Nos.: 2,616,904; 2,616,905; 2,616,906;
3,242,080; 3,250,710; 3,256,186; 3,274,135; 3,492,231; and
4,230,586. These patents disclose processes, materials which can be
overbased, suitable metal bases, promoters, and acidic materials.
These patents are incorporated herein by reference for these
disclosures. Other descriptions of basic m sulfonate salts and
techniques for making them can be found in the following U.S. Pat.
Nos.: 2,174,110; 2,202,781; 2,239,974; 2,319,121; 2,337,552;
3,488,284; 3,595,790; and 3,798,012. These are hereby incorporated
by reference for their disclosures in this regard.
[0040] As described above the alkali or alkaline earth overbased
compositions may be reacted with molybdenum containing anions to
form the molybdenum containing overbased metal salts of acidic
organic compounds. The molybdenum anions are delivered as molybdic
acid or ammonium or alkali metal salts of molybdic acid including
(NH.sub.4).sub.6 Mo.sub.7 O.sub.24, (NH.sub.4).sub.2 Mo.sub.2
O.sub.7 and various hydrates, such as (NH.sub.4).sub.6 Mo.sub.7
O.sub.24 4H.sub.2O. In one embodiment, the reaction is facilitated
by the use of a peptizing agent. Peptizing agents include one or
more of the dispersants described herein. This process and the
molybdenum containing overbased compositions are described in U.S.
Pat. No. 3,541,014 (LeSuer). This patent is incorporated by
reference for this disclosure.
[0041] In another embodiment, the molybdenum containing overbased
compositions are prepared by reacting the components used in the
overbasing process in the presence of at least one organic
molybdenum complex. The molybdenum containing organic complex is
preferably an amine-molybdenum complex, which are typically
prepared by a reaction of an acidic and organic molybdenum compound
with an amine. The molybdenum compounds include molybdic acid,
alkali metal molybdates, sodium hydrogen molybdate, ammonium
molybdate, MoOCl.sub.4, and molybdenum trioxide Sodium molybdate
and ammonium molybdate are preferred. The amine-molybdenum complex
is in general prepared in an aqueous medium. The amine is added to
an aqueous solution of an inorganic molybdenum compound. The
reaction mixture is kept at a temperature between about 20.degree.
and about 100.degree. C., preferably between about 50.degree. and
about 90.degree. C., for about 0.5 to about 3 hours after the
addition of the amine. The amount of acid necessary to neutralize
the reaction mixture is added before or after the introduction of
the amine. A strong mineral acid is used, preferably sulfuric acid.
The amine-molybdenum complex precipitates. It is recovered by
filtering off, washed with water and dried, if appropriate. The
complex has a solid or pasty appearance, depending on the type of
amine used. Its color varies from white to blue. It is virtually
insoluble or very sparingly soluble in hydrocarbons.
[0042] The atomic ratio of nitrogen to molybdenum in the complex is
in general from about 0.25 to about 4, preferably from about 0.5 to
about 2. The molybdenum content of the complex varies depending on
the nature of the amine used: it is between about 10% and about
45%. Among the organic molybdenum complexes, the complexes with
oxygen-containing compounds may also be used. The 1,2-, 1,3- and
1,4-glycols are very particularly suitable. Ethylene glycol and
propylene glycol are preferably used. Amongst the polyols, are
glycerol and trimethylolpropane.
[0043] Some amines, or polyamines which are alkoxylated, preferably
with ethylene oxide or propylene oxide, are also suitable. The
derivatives of diethanolamine or of triethanolamine may be
mentioned.
[0044] The preparation of the molybdenum containing overbased
compositions can be carried out by heating the oxygen-containing
compound at about 90.degree.-100.degree. C. in the presence of a
molybdenum compound, such as ammonium molybdate. The water produced
by the reaction is removed using a stream of nitrogen. The
molybdenum content of the complexes obtained varies between about
7% and about 50% by weight, depending on the degree to which
unreacted oxygen-containing compound has been removed.
[0045] The organic molybdenum complex can be sulfurized, for
example, by the action of hydrogen sulfide (H.sub.2S) on a
suspension of the complex in an aromatic solvent such as xylene or
toluene, at a temperature of between about 40.degree. C. and about
100.degree. C. From the introduction of hydrogen sulfide, the color
of the suspension changes from blue-green to orange, and then to
red. The amount of hydrogen sulfide introduced is such that the
atomic ratio of sulfur to molybdenum is between about 1 and about
3.
[0046] The overbased products containing molybdenum, obtained
according to the invention, are clear and stable and colored brown
in the case of the sulfonates, deep green in the case of the
phenolates and black in the case of the salicylates. The color is
generally red for the overbased detergents in the presence of a
sulfurized complex. The proportion of molybdenum incorporated in
the additive is close to 100%, higher than the proportions obtained
during incorporation of inorganic molybdenum derivatives. The
additive contains from about 0.1% to about 10% by weight,
preferably from about 1% to about 4% of molybdenum. The overbased
additives according to the invention are soluble or dispersible in
hydrocarbons. The molybdenum containing overbased salts prepared
with molybdenum amine complexes are described in U.S. Pat. No.
5,143,633. This patent is incorporated by reference for its
description of the molybdenum containing overbased salts and
methods of making the same.
[0047] The following Examples relate to molybdenum containing
overbased compositions and methods of making the same. In the
Examples, as well as elsewhere in the specification and claims,
unless the context indicates otherwise, the parts and percentages
are by weight, the temperature is degrees Celsius, and the pressure
is atmospheric. In the examples the basicity of these overbased
additives is characterized by their neutralization number or AV
(alkali value) is expressed in mg of KOH per gram of product. It is
determined by titration with aid of a strong acid in accordance
with the standard ASTM D-2896.
EXAMPLE M-1
[0048] (a) A solution of 41.17 g of sodium molybdate
Na.sub.2MoO.sub.42.H.sub.2O in 100 ml of water is prepared in a
reactor fitted with a temperature control and a stirrer device. The
mixture is acidified by adding 55.6 g of 30%f H.sub.2SO.sub.4 and
then heated to 60.degree. C. This is followed by the addition of 21
g of Dinoram C from CECA SA. Dinoram C corresponds to the formula
R--N--H--(CH.sub.2).sub.3-N- H.sub.2, where R is a mixture of
straight-chain saturated alkyl radicals containing 60% of C.sub.12,
20% of C.sub.14, 10% of C.sub.16 and 5% of C.sub.18. The blue
precipitate is recovered by filtering off and then washing with
water and with methanol before drying. Finally, 47.1 g of blue
solid containing 32.6% of molybdenum and 4.4% of nitrogen are
recovered.
[0049] (b) A reaction vessel is charged with 520 ml of xylene and
30 grams of the Dinoram C/molybdenum complex from above. The
mixture is stirred. Then, 131.8 g of alkyixylenesulfonic acid
having C.sub.16-18 straight-chain alkyl chain and a molecular
weight of 430 and containing 96% of active substance, 168 g of
diluent oil 100 Neutral solvent, 113.24 g of slaked lime of 96%
purity and 48 ml of methanol are added to the mixture. After
neutralization of the sulfonic acid with the lime, which, if
appropriate, can be carried out by heating the reaction mixture at
60.degree. C. for 30 minutes, 55.2 g of carbon dioxide gas are then
introduced into the mixture which is kept at a temperature of
42.degree. C.
[0050] After carbonation and removal of water and methanol under
partial vacuum, the solid residues are removed by centrifuging.
After evaporating off the solvent, 448 g of molybdenum-containing
superbasic sulfonate are recovered; neutralization number=300, its
calcium contents is 11.7% and its molybdenum content 2.17%. It is
stable on dilution in lubricant oils.
EXAMPLE M-2
[0051] (a) A dispersion of 20 g of the complex prepared in Example
M-1 in 200 ml of xylene is prepared in a 250 ml reactor fitted with
a temperature control, a stirrer and a gas bubbling system. 6.7 g
of H.sub.2S are injected into the dispersion kept at 80.degree. C.;
the deep red solid collected after removal of the solvent contains
28.4% of molybdenum, 3.8% of nitrogen and 23.7%o of sulfur.
[0052] (b) The procedure is as in Example M-1, but 28 g of
sulphurized Dinoram C/molybdenum complex (Example M-2(a) are
suspended in 520 ml of xylene, this being, carried out before the
introduction of the other reactants. The sequence of operations is
identical to that of Example M-1 except that the residues are
removed by centrifuging. A molybdenum-containing superbasic
sulphonate is d collected; AV=304. The molybdenum, sulphur and
calcium contents are, respectively, 1.63, 3.4 and 11.7%. The
product obtained has a brown-red color and it is stable on dilution
in lubricant oils.
EXAMPLE M-3
[0053] (a) A 2-ethylhexylamine/molybdenum complex is prepared as
follows: The procedure is as in Example M-1 but 9.9 g of 98%
2-ethylhexylamine are added at 60.degree. C. before heating and
acidification and are introduced in the course of 20 , minutes into
an aqueous solution containing 15.44 g of sodium molybdate and kept
B at 60.degree. C. After heating at 60.degree. C. for 45 minutes,
the mixture is acidified with 23.1 g of 30% sulfuric acid, before
washing and drying the product. The latter is in the a form of a
white solid containing 36.8% of molybdenum and 4.38% of
nitrogen.
[0054] (b) The procedure is as in Example M-1, but 28 g of the
2-ethylhexylamine complex prepared in Example M-3(a) are suspended
in 520 ml of xylene before the introduction of the other reactants.
The procedure is the same as in Example M-1 except that the
residues are removed by centrifuging. A brown product of AV=353 is
collected. The calcium and molybdenum contents are, respectively,
12.2 and 1.97%. The stability on dilution in lubricant oils is
perfect.
EXAMPLE M-4
[0055] The procedure is as in Example M-1(b), but 600 milliliters
of xylene, 132 grams of didodecylbenzenesulfonic acid having a
molecular weight of 520 and containing 70% of active substance 30
grams of tile complex prepared in Example M-1(a), 104 grams of
slaked lime, 52 milliliters of methanol. 4.4 milliliters of ammonia
and 90 rams of diluent oil are introduced successively into the
reactor. The product collected is brown, clear and stable in oils.
The calcium and molybdenum contents are, respectively, 10 and
2.35%.
[0056] The procedure is as in Example M-1, but 30 grams of the
complex prepared in Example M-1(a) are introduced into 520
milliliters of toluene before the addition of other reactants. The
sequence of operations is identical to that of Example 1 except
that 52.7 grams of CO.sub.2 are introduced during the carbonation.
After centrifuging, 448 grams of molybdenum-containing superbaseic
sulfonate are recovered, AV=298. The calcium and molybdenum
contents are, respectively.
EXAMPLE M-5
[0057] The procedure is as in Example M-4, but after filtration on
diatomaceous earth, 440 grams of molybdenum-containing overbased
sulfonate of AV=292 are recovered.
EXAMPLE M-4
[0058] (a) Preparation of barium overbased amine-formaldehyde
condensate: A reaction vessel is charged with 1000 parts of
N-octadecyl propylenediamine, 490 parts of mineral oil, 32 parts of
calcium oxide, and 143 parts of water at about 44.degree. C. and
slowly heated to 102.degree. C. under reflux conditions over a one
hour period. While maintaining the mixture at
100.degree.-105.degree. C., 303 parts of paraformaldehyde are added
to the reaction mixture over three hours. The temperature is
maintained for one hour, then the temperature is increased to
150.degree. C. over two and one half hours. Distillate (278 parts)
is removed and the residue is filtered.
[0059] A separate reaction vessel is charged with 197 parts of
mineral oil and 119 parts of heptylphenol. The mixture is heated to
93-99.degree. C. where barium hydroxide monohydrate (465 parts) is
added over four hours. The reaction temperature is then increased
to 150.degree. C. where 149 parts of the above amine-formaldehyde
product (Example M-3(a)) is added over one half hour. Carbon
dioxide is blown subsurface into the mixture at a rate of 15 parts
per hour for seven hours at 150.degree. C. Additional mineral oil
(100 parts) is added to the mixture and the mixture is blown with
nitrogen subsurface for two hours at 150.degree. C. The water
content of the mixture is reduced to 0.3%. The residue is filtered
through diatomaceous earth and the filtrate is the desired product.
The product has 36% mineral oil and 30.8%/m barium.
[0060] (b) An aqueous mixture of ammonium paramolybdate
tetrahydrate. (NH.sub.4).sub.6Mo.sub.7O.sub.244H.sub.2O, is
prepared by mixing 411 grams thereof with 300 grams of water and
maintaining the temperature of the mixture at about 60.degree. C.
Four 100-gram portions of this mixture are added to 457 grams of
the above barium overbased amine aldehyde condensate (Example
M-5(a)) over a 3.5 hour period while maintaining the temperature of
the reaction mass at about 95.degree. C. This results in a molar
ratio of barium to molybdenum of 3:1. During the addition of the
aqueous mixture, ammonia and carbon dioxide are evolved.
Thereafter, volatiles are removed from the reaction mass by heating
to 150.degree. C., while blowing with nitrogen. The residue is
filtered yielding 550 grams of an oil solution on the desired
molybdenum-containing complex. Analysis of the product establishes
that about 65% of the molybdenum employed in the reaction is
retained in the molybdenum-containing complex thus produced.
EXAMPLE M-5
[0061] (A) A mixture of 44 parts (all parts refer to parts by
weight) of the product of Example M-4(b), 10 parts mineral oil, and
24 parts of the reaction product of polyisobutene ({overscore
(M)}n=750)-substituted succinic anhydride with a commercial mixture
of polyethylene polyamines having an average composition
corresponding to that of tetraethylene pentamine (reacted in a
ratio of equivalents of 1:1 according to the procedure of U.S. Pat.
No. 3,172,892, e.g., Example 12 thereof) is prepared and heated to
about 75.degree. C. over a 1.5 hour period. The weight ratio of
peptizing agent to overbased material is 5:95. To this solution
there is added 520 parts of an aqueous ammonium molybdate solution
previously prepared by mixing 265 parts by weight of water and 265
parts by weight of a commercial ammonium molybdate (ammonium
dimolybdate sold by the Climax Molybdenum Company having a
composition corresponding to the formula
(NH.sub.4).sub.2MO.sub.2O.sub.7 containing about 56.5% by weight
molybdenum) over a 1.5 hour period while maintaining a temperature
at about 70-80.degree. C. resulting in a molar ratio of barium to
molybdenum of 1:1.53. The resulting reaction mass is heated under
reflux conditions at about 150.degree. C. for about 8.8 hours.
Subsequently, the mixture is blown with nitrogen at about 5 parts
per hour while maintaining the temperature at about 150.degree. C.
for an additional 1.3 hours. The nitrogen blowing is thereafter
ceased, the mixture is maintained at about 150.degree. C. for an
additional hour and the entire reaction mass is filtered. The
filtrate contains the desired molybdenum-containing complex and is
characterized by having 19.67% by weight molybdenum and 21.81% by
weight barium.
[0062] (B) To a mixture of 2.285 grams of the overbased product of
Example M-4(b) and 125 grams of the peptizing agent referred to
above (Example M-5(a)), there is added slowly over three hours 2600
grams of an aqueous solution of ammonium paramolybdate tetrahydrate
(prepared by mixing 1300 grams of the molybdate and 1300 grams of
water) while maintaining a temperature slightly above 70.degree. C.
The weight ratio of peptizing agent to overbased product is 5:95
and the barium to molybdenum molar ratio of 1:1.47. Ammonia, carbon
dioxide, and water are evolved during the ensuing reaction.
Thereafter, nitrogen is bubbled through the reaction mass to remove
water and gases during which time the product is heated to
170.degree. C. for four hours. Then a commercial filter aid is
added and the mass is filtered. The filtrate weighs 2.710 grams and
contains 20.2% by weight molybdenum, 21.6% by weight barium, and
25.3% by weight oil.
[0063] Molybdenum Containing Thiocarbamates and Thiophosphates
[0064] As described above, the molybdenum composition may be a
molybdenum containing thiocarbamate or thiophosphate. The
molybdenum compositions include molybdenum oxysulfide
thiocarbamates and molybdenum oxysulfide thiophosphates.
Thiocarbamates and their preparation are described below.
Molybdenum containing thiocarbamates, including dithiocarbamates
are known to those in the art. These materials are described in
U.S. Pat. Nos. 4,098,705, 4,259,194, 4,259,195, 4,265,773,
4,272,387, 4,282,822, 4,283,295, 4,369,119, 4,395,423, and
4,402,840. These patents are incorporated by reference for their
disclosure of molybdenum containing carbamates and methods of
making the same. Examples of commercially available molybdenum
containing thiocarbamates include Sakura Lube 500 (20% molybdenum
dithiocarbamate from Sakura Chemical), and Molyvan 807 (5%
molybdenum dithiocarbamate from Vanderbilt Chemical). The inventors
have discovered that the molybdenum containing dithiocarbamates are
useful in lubricating compositions which require thermal stability.
The level of molybdenum preferred for molybdenum containing
dithiocarbamates is from about 200 to about 800, preferably from
about 250 to about 600, more preferably from about 300 to about 500
ppm.
[0065] In another embodiment, the molybdenum containing composition
is a molybdenum thiophosphate. The molybdenum salts of
thiophosphorus acids are know those in the art. The thiophosphorus
acids, including dithiophosphoric acids, are described below.
Molybdenum salts and the methods of their preparation are described
in U.S. Pat. Nos. 3,223,625, 3,256,184, 3,400,140, 3,494,866,
3,840,463, and 4,156,099. These patents are hereby incorporated by
reference for such disclosure.
[0066] Borated Overbased Salts
[0067] In one embodiment, the molybdenum containing compositions
are used in combination with borated overbased metal salts. The
borated overbased metal salts are prepared by reacting a boron
compound with one or more of the above overbased metal salts, or by
using boric acid to overbase an acidic organic compound. The
borated overbased metal salts are generally used in an amount from
about 0.1% up to about 5%, or from about 0.5% up to about 3%, or
from about 0.5% up to about 2% by weight of the lubricating
compositions.
[0068] Boron compounds include boron oxide, boron oxide hydrate,
boron trioxide, boron trifluoride, boron tribromide, boron
trichloride, boron acid such as boric acid, tetraboric acid and
metaboric acid, boron hydrides, boron amides and various esters of
boron acids. The boron esters are preferably lower alkyl (1-7
carbon atoms) esters of boric acid. A preferred boron compound is
boric acid. Generally, the overbased salts are reacted with a boron
compound at about 50.degree. C. to about 250.degree. C., preferably
from about 100.degree. C. to about 200.degree. C. The overbased
salts are generally reacted with a boron compound in amounts to
provide at least about 0.5%, or at least about 1% by weight boron
to the composition. The overbased metal salt is generally reacted
with a boron compound in an amount to provide up to about 5%, 4, or
up to about 4%, or up to about 3% by weight boron to the
composition.
[0069] Borated overbased compositions, lubricating compositions
containing the same and methods of preparing borated overbased
compositions are found in U.S. Pat. No. 4,744,920, issued to
Fischer et al; U.S. Pat. No. 4,792,410 issued to Schwind et al and
PCT Publication WO 88/03144. The disclosures relating to the above
are hereby incorporated by reference.
[0070] In another embodiment, the borated overbased metal salts are
prepared by reacting the acidic organic compound with a basic metal
salts in the presence of a boron compound. The metals include
transition metals, such as zinc, copper, and cadmium. These borated
overbased compositions and methods of their preparation are
described in U.S. Pat. No. 5,064,545 (Steckel). This patent is
incorporated by reference for such disclosure.
[0071] The following examples relate to borated overbased metal
salts.
EXAMPLE B-1
[0072] (a) A mixture of 853 grams of methyl alcohol, 410 grams of
blend oil, 54 grams of sodium hydroxide, and a neutralizing amount
of additional sodium hydroxide is prepared. The amount of the
latter addition of sodium hydroxide is dependent upon the acid
number of the subsequently added sulfonic acid. The temperature of
the mixture is adjusted to 49.degree. C. A mixture (1070 grams) of
straight chain dialkyl benzene sulfonic acid ({overscore (M)}w=430)
and blend oil (42% by weight active content) is added while
maintaining the temperature at 49-57.degree. C. Polyisobutenyl
({overscore (M)}n=950)-substituted succinic anhydride (145 grams)
is added to the reaction vessel. Then, 838 grams of sodium
hydroxide (838 grams) are added and the temperature is adjusted to
71.degree. C. The reaction mixture is blown with 460 grams of
carbon dioxide. The mixture is flash stripped to 149.degree. C.,
and filtered to clarity to provide the desired God product. The
product is an overbased sodium sulfonate having a base number
(bromophenol blue) of 440, a metal content of 19.4% by weight, a
metal ratio of 20, a sulfate ash content of 58% by weight, and a
sulfur content of 1.3% by weight.
[0073] (b) A reaction vessel is charged with 1000 grams of the
above overbased sodium salt (Example B-1(a)), 0.13 gram of an
antifoaming agent (kerosene solution of Dow Coring 200 Fluid having
a viscosity of 1000 cSt at 25.degree. C.), and 133 grams of blend
oil is heated to 74-79.degree. C. with stirring. Then, 486 grams of
boric acid are added to the reaction mixture. The reaction mixture
is heated to 121.degree. C. to liberate water of reaction and
40-50% by weight of the CO.sub.2 contained in the above overbased
sodium salt. The reaction mixture is heated to 154-160.degree. C.
and maintained at that temperature until the free and total water
content is reduced to 0.3% by weight or less and approximately 1-2%
by weight, respectively. The reaction product is cooled to room
temperature and filtered.
EXAMPLE B-2
[0074] (a) A mixture of 1000 grams of a primarily branched chain
monoalkyl benzene sulfonic acid ({overscore (M)}w=500), 771 grams
of o-xylene, and 75.2 grams of polyisobutenyl ({overscore
(M)}n=950) succinic anhydride is prepared and the temperature is
adjusted to 46.degree. C. Magnesium oxide (87.3 grams), acetic acid
(35.8 grams), methyl alcohol (31.4 grams), and water (59 grams) are
added sequentially to the reaction mixture. The reaction mixture is
blown with 77.3 grains of carbon dioxide at a temperature of
49-54.degree. C. Then, 87.3 grams of magnesium oxide, 31.4 grams of
methyl alcohol and 59 grams of water are added, and the reaction
mixture is blown with 77.3 grams of carbon dioxide at 49-54.degree.
C. The foregoing steps of magnesium oxide, methyl alcohol and water
addition, followed by carbon dioxide blowing are repeated once.
O-xylene, methyl alcohol and water are removed from the reaction
mixture using atmospheric and vacuum flash stripping The reaction
mixture is cooled and filtered to clarity. The product is an
overbased magnesium sulfonate having a base number (bromophenol
blue) of 400, a metal content of 9.3% by weight. a metal ratio
14.7, a sulfate ash content of 46.0%, and a sulfur content of 1.6%
by weight.
[0075] (b) A reaction vessel is charged with 1000 grams of the
above overbased magnesium salt (Example B-2(a)) and 181 grams of
diluent oil is heated to 79.degree. C. Then, 300 grams of boric
acid are added to the reaction mixture and the mixture is heated to
124.degree. C. over a period of 8 hours. The reaction mixture is
maintained at 121-127.degree. C. for 2-3 hours until the magnesium
content remains constant at 6.8% by weight. A nitrogen sparge is
started and the reaction mixture is heated to 149.degree. C. to
remove water until the water content is 3% by weight or less. The
reaction mixture is filtered to provide the desired product.
[0076] The molybdenum containing composition may be used in
combination with (i) an organic polysulfide or an ashless
dithiocarbamate composition and (ii) a phosphorus or boron extreme
pressure agent. The organic polysulfide or the ashless
dithiocarbamate composition are generally used in an amount from
about 0.5% up to about 5%, or from about 1% up to about 4%, or from
about 2% up to about 3.57 by weight of the lubricating
composition.
[0077] Organic Polysulfide or Ashless Dithiocarbamate Containing
Composition
[0078] The organic polysulfide is characterized as having sulfide
linkages having from at least 2 to about 10 sulfur atoms,
preferably 2 to about 6 sulfur atoms, more preferably 2 to about 4
sulfur atoms. The organic polysulfides are generally di-, tri- or
tetrasulfide compositions with trisulfide compositions
preferred.
[0079] The organic polysulfides of the present invention provide
from about 1% to about 3% sulfur to the lubricating compositions
Generally, the organic polysulfides contain from about 10% to about
60% sulfur, preferably from about 20% to about 50%, and more
preferably from about 35% to about 45% sulfur. Materials which may
be sulfurized to form the organic polysulfides include oils, fatty
acids or esters, or olefins, or polyolefins. These materials are
sulfurized by their reaction with sulfurizing agents, such as
elemental sulfur, sulfur halides, combinations of sulfur with
hydrogen sulfide, etc.
[0080] Oils which may be sulfurized are natural or synthetic oils
including mineral oils, lard oil, carboxylate esters derived from
aliphatic alcohols and fatty acids or aliphatic carboxylic acids
(e.g., myristyl oleate and oleyl oleate), sperm whale oil and
synthetic sperm whale oil substitutes and synthetic unsaturated
esters or glycerides.
[0081] Fatty acids generally contain from about 4 up to about 30,
or from about 8 up to about 24 carbon atoms such as palmitoleic,
oleic, ricinoleic, linoleic, oleostearic, etc. Sulfurized fatty
acid esters are prepared from mixed unsaturated fatty acid esters
such as those obtained from animal fats and vegetable oils and
including tall oil, linseed oil, rape oil, fish oil, sperm oil,
etc.
[0082] The olefinic compounds which may be sulfurized contain at
least one olefinic double bond. The double bond is defined as a
non-aromatic double bond; that is, one connecting two aliphatic
carbon atoms. In its broadest sense, the olefin may he defined by
the formula
R*.sup.1R*.sup.2C.dbd.CR*.sup.3R*.sup.4
[0083] wherein each of R*.sup.1, R*.sup.2, R*.sup.3 and R*.sup.4 is
hydrogen or an organic group. In general, the R groups in the above
formula which are not hydrogen may be satisfied by such groups as
--C(R*.sup.5).sub.3, --COOR*.sup.5, --CON(R*.sup.5).sub.2,
--COON(R*.sup.5).sub.4, --COOM, --CN, --X, --YR*.sup.5 or --Ar,
wherein: each R*.sup.5 is independently hydrogen, alkyl, alkenyl,
aryl, substituted alkyl, substituted alkenyl or substituted aryl,
with the proviso that any two R*.sup.5 groups can be alkylene or
substituted alkylene whereby a ring of up to about 12 carbon atoms
is formed; M is one equivalent of a metal cation (preferably Group
I or II, e.g., sodium, potassium, barium, calcium); X is halogen
(e.g., chloro, bromo, or iodo); Y is oxygen or divalent sulfur; Ar
is an aryl or substituted aryl group of up to about 12 carbon
atoms. Any two of R*.sup.1, R*.sup.2, R*.sup.3 and R*.sup.4 may
also together form an alkylene or substituted alkylene group; i.e.,
the olefinic compound may be alicyclic.
[0084] The olefinic compound is usually one in which each R* group
which is not hydrogen is independently alkyl, alkenyl or aryl
group. Monoolefinic and diolefinic compounds, particularly the
former, are preferred, and especially terminal monoolefinic
hydrocarbons; that is, those compounds in which R*.sup.3 and
R*.sup.4 are hydrogen and R*.sup.1 and R*.sup.2 are alkyl or aryl,
especially alkyl (that is, the olefin is aliphatic) having 1 to
about 30, preferably 1 to about 16, more preferably 1 to about 8,
and more preferably 1 to about 4 carbon atoms. Olefinic compounds
having about 3 to about 30 and especially about 3 to about 16 (most
often less than about 9) carbon atoms are particularly
desirable.
[0085] Isobutene, propylene and their dimers, trimers and
tetramers, and mixtures thereof are especially preferred olefinic
compounds. Of these compounds, isobutylene and diisobutylene are
particularly desirable because of their availability and the
particularly high sulfur containing compositions which can be
prepared therefrom.
[0086] In one preferred embodiment, the organic polysulfide
comprise sulfurized olefins, where the olefins are described above.
For example, organic polysulfides may be prepared by the
sulfochlorination of olefins containing four or more carbon atoms
and further treatment with inorganic higher polysulfides according
to U.S. Pat. No. 2.708,199.
[0087] In one embodiment, sulfurized olefins are produced by (1)
reacting sulfur monochloride with a stoichiometric excess of a low
carbon atom number olefin. (2) treating the resulting product with
an alkali metal sulfide in the presence of free sulfur in a mole
ratio of no less than 2:1 in an alcohol-water solvent, and (3)
reacting that product with an inorganic base. This procedure is
described in U.S. Pat. No. 3,471,404, and the disclosure of U.S.
Pat. No. 3,471,404 is hereby incorporated by reference for its
discussion of this procedure for preparing sulfurized olefins and
the sulfurized olefins thus produced. Generally, the olefin
reactant contains from about 2 to about 5 carbon atoms and examples
include ethylene, propylene, butylene, isobutylene, amylene,
etc.
[0088] The sulfurized olefins which are useful in the compositions
of the present invention also may be prepared by the reaction,
under superatmospheric pressure, of olefinic compounds with a
mixture of sulfur and hydrogen sulfide in the presence of a
catalyst, followed by removal of low boiling materials. This
procedure for preparing sulfurized compositions which are useful in
the present invention is described in U.S. Pat. No. 4,191,659, the
disclosure of which is hereby incorporated by reference for its
description of the preparation of useful sulfurized
compositions.
[0089] In one embodiment, the organic polysulfide may be prepared
by reaction of a mercaptan and sulfur in the presence of a
catalyst, such as magnesium oxide, alumina catalyst. The mercaptans
used to make the polysulfide may be hydrocarbyl mercaptans, such as
those represented by the formula R--S--H, wherein R is a
hydrocarbyl group as defined above. In one embodiment, R is an
alkyl, an alkenyl, cycloalkyl, or cyclo-alkenyl group. R may also
be a haloalkyl, hydroxyalkyl, or hydroxyalkyl substituted (e.g.
hydroxymethyl, hydroxyethyl, etc.) aliphatic groups. R generally
contains from about 2 to about 30 carbon atoms, or from about 2 to
about 24, or from about 3 to about 18 carbon atoms. Examples
include butyl mercaptan, amyl mercaptan, hexyl mercaptan, octyl
mercaptan, 6-hydroxymethyloctanethiol, nonyl mercaptan, decyl
mercaptan, 10-amino-dodecanethiol, dodecyl mercaptan,
10-hydroxymethyl-tetradecanethiol, and tetradecyl mercaptan. These
organic polysulfides and processes for making them are disclosed in
U.S. Pat. No. 4,564,709, issued to Koyama et al and U.S. Pat. No.
5,146,000, issued to Ozbalik. These patents are incorporated by
reference for such disclose.
[0090] The following example relates to organic polysulfides.
EXAMPLE S-1
[0091] Sulfur (526 parts, 16.4 moles) is charged to a jacketed,
high-pressure reactor which is fitted with an agitator and internal
cooling coils. Refrigerated brine is circulated through the coils
to cool the reactor prior to the introduction of the gaseous
reactants. After sealing the reactor, evacuating to about 2 torr
and cooling, 920 parts (16.4 moles) of isobutene and 279 parts (8.2
moles) of hydrogen sulfide are charged to the reactor. The reactor
is heated using steam in the external jacket, to a temperature of
about 182.degree. C. over about 1.5 hours. A maximum pressure of
1350 psig is reached at about 168.degree. C. during this heat-up.
Prior to reaching the peak e reaction temperature, the pressure
starts to decrease and continues to decrease steadily as the
gaseous reactants are consumed. After about 10 hours at a reaction
temperature of about 182.degree. C., the pressure is 310-340 psig
and the rate of pressure change is about 5-10 psig per hour. The
unreacted hydrogen sulfide and isobutene are vented to a recovery
system. After the pressure in the reactor has decreased to
atmospheric, the sulfurized mixture is recovered as a liquid.
EXAMPLE S-2
[0092] Sulfur monochloride (2025 grains, 15.0 moles) is heated to
45.degree. C. Through a sub-surface gas sparge, 1468 grams (26.2
moles) of isobutylene gas are fed into the reactor over a 5-hour
period. The temperature is maintained between 45-50.degree. C. At
the end of the sparging, the reaction mixture increases in weight
of 1352 grams. In a separate reaction vessel are added 2150 grams
(16.5 moles) of 60% flake sodium sulfide, 240 grams (7.5 moles)
sulfur, and a solution of 420 ml. of isopropanol in 4000 ml. of
water. The contents are heated to 40.degree. C. The adduct of the
sulfur monochloride and isobutylene previously prepared is added
over a three-quarter hour period while permitting the temperature
to rise to 75.degree. C. The reaction mixture is heated to reflux
for 6 hours, and afterward the mixture is permitted to form into
separate layers. The lower aqueous layer is discarded. The upper
organic layer is mixed with two liters of 10% aqueous sodium
hydroxide, and the mixture is heated to reflux for 6 hours. The
organic layer is again removed and washed with one liter of water.
The washed product is dried by heating at 90.degree. C. and 30 mm.
Hg, pressure for 30 minutes. The residue is filtered through
diatomaceous earth filter aid to give 2070 grams of a clear
yellow-orange liquid
[0093] The ashless dithiocarbamate compositions include reaction
products of a dithiocarbamic acid or salt and an unsaturated amide,
carboxylic acid, anhydride, or ester, or ether, alkylene-coupled
dithiocarbamate, and bis(S-alkyldithiocarbamoyl) disulfides. The
dithiocarbamate compounds (A) may be prepared by reacting a
dithiocarbamic acid or salt with an unsaturated compound. The
dithiocarbamate compositions may also be prepared by simultaneously
reacting an amine, carbon disulfide and an unsaturated compound.
Generally, the reaction occurs at a temperature from about
25.degree. C. to about 125.degree. C., or from about 50.degree. C.
to about 100.degree. C. U.S. Pat. Nos. 4,758,362 and 4,997,969
describe dithiocarbamate compositions and methods of making the
same. These patents are hereby incorporated by reference for their
disclosure of dithiocarbamate compositions and method of making the
same.
[0094] The dithiocarbamic acid or salt used to prepare the
dithiocarbamate compositions are prepared by reacting an amine with
carbon disulfide. The amine may be a primary or a secondary amine.
The amines may be primary or secondary amines, with secondary
amines most preferred. The amines generally may contain hydrocarbyl
groups. Each hydrocarbyl group may independently contain from one
up to about 40, or from about two up to about 30, or from three up
to about 24, or even up to about 12 carbon atoms. Examples of
groups which may be on the amines include ethyl, propyl, butyl,
hexyl, octyl and dodecyl groups.
[0095] In one embodiment, the amines are primary amines. Examples
of primary amines useful in the present invention include
ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine,
and dodecylamine.
[0096] In one embodiment, the primary amine is a fatty (C.sub.8-30)
amine which include n-octylamine, n-decylamine, n-dodecylamine,
n-tetradecylamine, n-hexadecylamine, n-octadecylamine, oleyamine,
etc. Also useful fatty amines include commercially available fatty
amines such as "Armeen" amines (products available from Akzo
Chemicals, Chicago, Ill.), such as Akzo's Ameen C, Armeen O. Armeen
OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter
designation relates to the fatty group, such as cocoa, oleyl,
tallow, or stearyl groups.
[0097] Other useful primary amines include primary ether amines,
such as those represented by the formula, R"(OR').sub.xNH.sub.2,
wherein R' is a divalent alkylene group having from about 2 to
about 6 carbon atoms; x is a number from one to about 150, or from
one to about five, or one; and R" is a hydrocarbyl group of about 5
to about 150 carbon atoms. An example of an ether amine is
available under the name SURFAM.RTM. amines produced and marketed
by Mars Chemical Company, Atlanta, Ga. Preferred etheramines are
exemplified by those identified as SURFAM P14B
(decyloxypropylamine), SURFAM P16A (linear C.sub.16), SURFAM P17B
(tridecyloxypropylamine). The carbon chain lengths (i.e., C.sub.14,
etc.) of the SURFAMS described above and used hereinafter are
approximate and include the oxygen ether linkage.
[0098] In one embodiment, the amine is a tertiary-aliphatic primary
amine. Generally, the aliphatic group, preferably an alkyl group,
contains from about 4 to 44, about 30, or from about 6 to about 24,
or from about 8 to about 22 carbon atoms. Usually the tertiary
alkyl primary amines are monoamines represented by the formula
R.sub.1-C(R.sub.1').sub.2-NH.sub.2, wherein R.sub.1 is a
hydrocarbyl group containing from one to about 27 carbon atoms and
R.sub.1' is a hydrocarbyl group containing from 1 to about 12
carbon m atoms. Such amines are illustrated by tert-butylamine,
tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine,
tert-decylamine, tert-dodecylamine, tert-tetradecylamine,
tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine,
and tert-octacosanylamine.
[0099] Mixtures of amines are also useful for the purposes of this
invention. Illustrative of amine mixtures of this type are "Primene
81R" which is a mixture of C.sub.11-C.sub.14 tertiary alkyl primary
amines and "Primene JMT" which is a similar mixture of
C.sub.18-C.sub.22, tertiary alkyl primary amines (both are
available from Rohm and Haas Company). The tertiary alkyl primary
amines and methods for their preparation are known to those of
ordinary skill in the art. The tertiary alkyl primary amine useful
for the purposes of this invention and methods for their
preparation are described in U.S. Pat. No. 2,945,749 which is
hereby incorporated by reference for its teaching in this
regard.
[0100] In another embodiment, the amine is a secondary amine.
Specific of secondary amines include dimethylamine, diethylamine,
dipropylamine, dibutylamine, diamylamine, dihexylamine,
diheptylamine, methylethylamine, ethylbutylamine, ethylamylamine
and the like. In one embodiment, the secondary amines may be cyclic
amines such as piperidine, piperazine, morpholine, etc.
[0101] In one embodiment, the dithiocarbamate compound (A) is
prepared by reacting one or more dithiocarbamic acids or salts with
an unsaturated amide. Examples of unsaturated amides include
acrylamide, N,N'-methylene bis(acrylamide), methacrylamide,
crotonamide, and the like. In one embodiment, the dithiocarbamate
containing composition is derived from the reaction product of a
diamylamine or dibutylamine with carbon disulfide which forms a
dithiocarbamic acid or a salt which is ultimately reacted with a
acrylamide. If the reaction products of the dithiocarbamic is, acid
or salt and an unsaturated amide has additional NH group which are
capable of reacting, then the reaction product may be further
reacted with a linking or a coupling compound, such as formaldehyde
or paraformaldehyde. The reaction products of dithiocarbamic acids
and salts with unsaturated amides are disclosed in U.S. Pat. Nos.
4,758,362 (Butke) and 4,997,969 (Luciani) which are incorporated by
reference for their disclosures of dithiocarbamic acids and salts,
unsaturated amides and their reaction products including coupled
products.
[0102] In one embodiment, ashless the dithiocarbamate composition
(A) is a reaction product of a dithiocarbamic acid or salt with an
unsaturated acid, anhydride or ester. Examples of unsaturated
carboxylic acids and anhydrides include acrylic acid, methacrylic
acid, itaconic acid, maleic acid, fumaric acid, and maleic
anhydride. If an unsaturated carboxylic acid or anhydride is used,
an ester may then be formed by subsequent reaction of the
dithiocarbamate-unsaturated carboxylic acid or anhydride adduct
with an alcohol such as those alcohols discussed herein. In one
embodiment, the alcohol has from 1 to about 12 carbon atoms.
[0103] In one embodiment, the unsaturated carboxylic acid, or
anhydride or ester X includes maleic, fumaric, acrylic,
methacrylic, itaconic, citraconic acids and esters. The ester may
be represented by one of the formulae:
(R.sub.1).sub.2C.dbd.C(R.sub.1)C(O)OR.sub.2, or
R.sub.2O--(O)C--HC.dbd.CH--C(O)OR.sub.2, wherein each R.sub.1 and
R.sub.2 are independently hydrogen or a hydrocarbyl group having 1
to about 18, or to about 12, or to about 8 carbon atoms, R.sub.1 is
hydrogen or an alkyl group having from 1 to about 6 carbon atoms.
In one embodiment, R.sub.1 is preferably hydrogen or a methyl
group.
[0104] Examples of unsaturated carboxylic esters include methyl
acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl
acrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, ethyl
maleate, butyl maleate and 2-ethylhexyl maleate. The above list
includes mono- as well as diesters of maleic, fumaric, and itaconic
acids and anhydrides. In one embodiment, the dithiocarbamate acid
or salt is formed from diethylamine or dibutylamine and carbon
disulfide. The resulting dithiocarbamic acid is then reacted with
methyl acrylate.
[0105] In another embodiment, the unsaturated carboxylic ester is a
vinyl ester. The vinyl ester may he represented by the formula
R.sub.1CH.dbd.CH--O(O)CR.sub.2, wherein R.sub.1 is a hydrocarbyl
group having from 1 to about 30, or to about 12 carbon atoms,
preferably hydrogen, and R.sub.2 is a hydrocarbyl group having 1 to
about 30, or to about 12, or to about 8 carbon atoms. Examples of
vinyl esters include vinyl acetate, vinyl 2-ethylhexanoate, vinyl
butanoate, etc.
[0106] In one embodiment, the dithiocarbamate compound (A) is a
reaction product of a dithiocarbamic acid or salt and a vinyl
ether. The vinyl ether is represented by the formula
R.sub.1--CH.dbd.CH--OR.sub.2 wherein R.sub.1 is independently
hydrogen or a hydrocarbyl group having from 1 up to about 30, or up
to about 24, or up to about 12 carbon atoms. R.sub.1 is a
hydrocarbyl group defined the same as R.sub.1. Examples of vinyl
ethers include methyl vinyl ether, propyl vinyl ether, 2-ethylhexyl
vinyl ether and the like.
[0107] In one embodiment, the dithiocarbamate compound (A) is an
alkylene-coupled dithiocarbamate. The alkylene-coupled
dithiocarbamates useful in the present invention may be prepared by
the reaction of a salt of a dithiocarbamic acid, described above,
with a suitable dihalogen containing hydrocarbon. The reaction is
generally carried out at a temperature within the range from about
25.degree. C. up to about 150.degree. C., or up to about
100.degree. C. U.S. Pat. No. 3,876,550 issued to Holubec describes
alkylene dithiocarbamate compounds, and U.S. Pat. Nos. 1,726,647
and 1,736,429, issued to Cadwell describe, phenylmethylene
bis(dithiocarbamates) and methods of making the same. These patents
are incorporated by reference for their teachings related to
dithiocarbamate compounds and methods for preparing the same. In
one embodiment, the alkylene-coupled dithiocarbamate is derived
from di-n-butyl amine, carbon disulfide and methylene
dichloride.
[0108] In another embodiment, the dithiocarbamate compound is a
bis(S-alkyldithiocarbamoyl) disulfide. These materials have
previously been referred to as sulfur-coupled dithiocarbamates. The
disulfides are prepared by (A) reacting a sulfur halide with about
a stoichiometric equivalent of (i) at least one olefinic
hydrocarbon, or (ii) an aldehyde or ketone, at a temperature and
for a period of time sufficient to produce a
di(halohydrocarbyl)sulfur intermediate or a dialdehyde or diketo
sulfur intermediate, and (B) reacting the intermediate with a salt
of a dithiocarbamate in an amount sufficient generally to replace
both halo groups with the dithiocarbamate groups or to react with
both carbonyl groups of the dialdehyde or diketone. The sulfur
halide utilized in the first step (A) may be sulfur monochloride
(i.e., S.sub.2Cl.sub.2), sulfur dichloride, sulfur monobromide,
sulfur dibromide, or mixtures of any of the above sulfur halides
with elemental sulfur in varying amounts.
[0109] The sulfur halide utilized in the first step (A) may be
sulfur monochloride (i.e., S.sub.2Cl.sub.2), sulfur dichloride,
sulfur monobromide, sulfur dibromide, or mixtures of any of the
above sulfur halides with elemental sulfur in varying amounts.
Various olefins and olefin mixtures may be used as the starting
material in step (A). The olefins are disclosed below for the
organic polysulfide. Specific examples of aldehydes that may be
reacted with sulfur halides include, for example, acetaldehyde,
propionaldehyde, butyraldehyde, isobutyraldehyde, 2-ethyl-hexanal,
and cyclohexanecarboxaldehyde. Examples of ketones include dimethyl
ketone, methyl ethyl ketone, diethyl ketone, methyl isopropyl
ketone, methyl isobutyl ketone, etc.
[0110] The reaction between the sulfur intermediate and the
dithiocarbamate salts generally is conducted from ambient
temperature to the reflux temperature of the mixture. The reaction
is conducted until the reaction is completed which is generally
from about 5 to about 24 hours. At the end of the reaction, the
aqueous phase is separated, and the product is recovered from the
organic phase.
[0111] The bis(S-alkyldithiocarbamoyl) disulfides also may be
prepared by a process which comprises the steps of (A) reacting an
olefinic hydrocarbon with a halogen to produce a halogen-containing
intermediate, and (B) reacting said intermediate with an alkali
metal sulfide and a salt of a dithiocarbamate in an amount
sufficient to replace the halogen groups present partially with
dithiocarbamate groups and/or partially with sulfide groups. The
bis(S-alkyldithiocarbamoyl) disulfides are described in U.S. Pat.
No. 2,599,350, issued to Rudel et al. This patent is incorporated
by reference for its disclosure of bis(S-alkyldithiocarbamoyl)
disulfide.
[0112] Phosphorus or Boron Agents:
[0113] As described above, the molybdenum containing composition
salts are used in combination with (i) an organic polysulfide or an
ashless dithiocarbamate containing composition, and (ii) at least
one phosphorus or boron containing antiwear/extreme pressure agent
selected from the group consisting of a metal thiophosphate, a
phosphoric acid ester or salt thereof, a phosphorus-containing
carboxylic acid, ester, ether, or amide, a borated dispersant, an
alkali metal borate, a borated fatty amine, a borated phospholipid,
and a borate ester. The phosphorus or boron containing agents are
typically present in the lubricants and functional fluids at a
level of up to about 20% by weight, preferably up to about 10% by
weight, based on the total weight of the lubricant, functional
fluid, or grease. Typically, the phosphorus or boron containing
antiwear/extreme pressure agent is present at a level from about
0.1%, or from about 0.5%, or from about 0.8% by weight. The
phosphorus or boron containing antiwear/extreme pressure agent is
present in an amount up to about 10%, or up to about 3%, or up to
about 2% by weight. In one embodiment, the lubricating
compositions, functional fluids, and greases contain more than
0.01% phosphorus, preferably greater than 0.05% phosphorus.
[0114] Examples of phosphorus or boron containing antiwear/extreme
pressure agents include a metal thiophosphate; a phosphoric acid
ester or salt thereof; a phosphorus-containing carboxylic acid,
ester, ether, or amide; a borated dispersant; an alkali metal
borate; a borated fatty amine; a borated phospholipid, and a borate
ester. The phosphorus acids include the phosphoric, phosphonic,
phosphinic and thiophosphoric acids including dithiophosphoric acid
as well as the monothiophosphoric acid, thiophosphinic and
thiophosphonic acids.
[0115] In one embodiment, phosphorus or boron containing
antiwear/extreme pressure agent is a phosphorus acid ester prepared
by reacting one or more phosphorus acid or anhydride with an
alcohol containing from one, or about 3 carbon atoms. The alcohol
generally contains up to about 30, or up to about 24, or up to
about 12 carbon atoms. The phosphorus acid or anhydride is
generally an inorganic phosphorus reagent, such as phosphorus
pentoxide, phosphorus trioxide, phosphorus tetroxide, phosphorus
acid, phosphorus halide, lower phosphorus esters, or a phosphorus
sulfide, including phosphorus pentasulfide, and the like. Preferred
phosphorus acids or anhydrides are phosphorus pentoxide, phosphorus
pentasulfide and phosphorus trichloride. Lower phosphorus acid
esters generally contain from 1 to about 7 carbon atoms in each
ester group. The phosphorus acid ester may be a mono-, di- or
triphosphoric acid ester. Alcohols used to prepare the phosphorus
acid esters include butyl, amyl, 2-ethylhexyl, hexyl, octyl, oleyl,
and cresol alcohols. Examples of commercially available alcohols
include Alfol 810 (a mixture of primarily straight chain, primary
alcohols having from 8 to 10 carbon atoms); Alfol 1218 (a mixture
of synthetic, primary, straight-chain alcohols containing 12 to 18
carbon atoms); Alfol 20+alcohols (mixtures of C.sub.18-C.sub.28,
primary alcohols having mostly C.sub.2, alcohols as determined by
CLC (gas-liquid-chromatography)); and Alfol 22+alcohols
(C.sub.18-C.sub.28 primary alcohols containing primarily C.sub.2,
alcohols). Alfol alcohols are available from Continental Oil
Company.
[0116] Another example of a commercially available alcohol mixtures
are Adol 60 (about 75% by weight of a straight chain C.sub.22
primary alcohol, about 15% of a C.sub.20 primary alcohol and about
8% of C.sub.18 and C.sub.24 alcohols) and Adol 320 (oleyl alcohol).
The Adol alcohols are marketed by Ashland Chemical.
[0117] A variety of mixtures of monohydric fatty alcohols derived
from naturally occurring triglycerides and ranging in chain length
of from about C.sub.8 to C.sub.18 are available from Procter &
Gamble Company. These mixtures contain various amounts of fatty
alcohols containing mainly 12, 14, 16, or 18 carbon atoms. For
example, CO-1214 is a fatty alcohol mixture containing 0.5% of
C.sub.10 alcohol, 66.0% of C.sub.12 alcohol, 26.0% of C.sub.14
alcohol and 6.5% of C.sub.16 alcohol.
[0118] Another group of commercially available mixtures include the
"Neodol" products available from Shell Chemical Co. For example,
Neodol 23 is a mixture of C.sub.12 and C.sub.13 alcohols; Neodol 25
is a mixture of C.sub.12 and C.sub.15 alcohols; and Neodol 45 is a
mixture of C.sub.14 to C.sub.15 linear alcohols. Neodol 91 is a
mixture of C.sub.9, C.sub.10 and C.sub.11 alcohols.
[0119] Fatty vicinal diols also are useful and these include those
available from Ashland Oil under the general trade designation Ado
114 and Adol 158. The former is derived from a straight chain alpha
olefin fraction of C.sub.11-C.sub.14, and the latter is derived
from a C.sub.15-C.sub.18 fraction.
[0120] Examples of useful phosphorus acid esters include the
phosphoric acid esters prepared by reacting a phosphoric acid or
anhydride with cresol alcohols. An example of these phosphorus acid
esters is tricresylphosphate.
[0121] In another embodiment, the phosphorus or boron
antiwear/extreme pressure agent is a thiophosphorus acid ester or
salt thereof. The thiophosphorus acid ester may be prepared by
reacting a phosphorus sulfide, such as those described above. with
an alcohol, such as those described above. The thiophosphorus acid
esters may be mono- or dithiophosphorus acid esters. Thiophosphorus
acid esters are also referred to generally as thiophosphoric
acids.
[0122] In one embodiment, the phosphorus acid ester is a
monothiophosphoric acid ester or a monothiophosphate.
Monothiophosphates may be prepared by the reaction of a sulfur
source with a dihydrocarbyl phosphite. The sulfur source may for
instance be elemental sulfur. The sulfur source may also be a
monosulfide, such as a sulfur coupled oletfin or a sulfur coupled
dithiophosphate. Elemental sulfur is a preferred sulfur source. The
preparation of monothiophosphates is disclosed in U.S. Pat. No.
4,755,311 and PCT Publication WO 87/07638, which are incorporated
herein by reference for their disclosure of monothiophosphates,
sulfur sources, and the process for making monothiophosphates.
Monothiophosphates may also be formed in the lubricant blend by
adding a dihydrocarbyl phosphite to a lubricating composition
containing a sulfur source, such as a sulfurized olefin. The
phosphite may react with the sulfur source under blending
conditions (i.e., temperatures from about 30.degree. C. to about
100.degree. C. or higher) to form the monothiophosphate.
[0123] In another embodiment, the phosphorus or boron
antiwear/extreme pressure agent is a dithiophosphoric acid or
phosphorodithioic acid. The dithiophosphoric acid may be
represented by the formula (RO).sub.2PSSH wherein each R is
independently a hydrocarbyl group containing from about 3 to about
30 carbon atoms. R generally contains up to about 18, or to about
12, or to about 8 carbon atoms. Examples R include isopropyl,
isobutyl, n-butyl, sec-butyl, the various amyl, n-hexyl,
methylisobutyl carbinyl, heptyl, 2-ethylhexyl, isooctyl, nonyl,
behenyl, decyl, dodecyl, and tridecyl groups. Illustrative lower
alkylphenyl R groups include butylphenyl, amylphenyl, heptylphenyl,
etc. Examples of mixtures of R groups include: 1-butyl and 1-octyl:
1-pentyl and 2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl and
isoamyl; 2-propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl;
and isopropyl and isooctyl.
[0124] In one embodiment, the dithiophosphoric acid may be reacted
with an epoxide or a glycol. This reaction product may be used
alone, or further reacted with a phosphorus acid, anhydride, or
lower ester. The epoxide is generally an aliphatic epoxide or a
styrene oxide. Examples of useful epoxides include ethylene oxide,
propylene oxide, butene oxide, octene oxide, dodecene oxide,
styrene oxide, etc Propylene oxide is preferred. The glycols may be
aliphatic glycols having from 1 to about 12, preferably about 2 to
about 6, more preferably 2 or 3 carbon atoms, or aromatic glycols.
Glycols include ethylene glycol, propylene glycol, catechol,
resorcinol, and the like. The dithiophosphoric acids, glycols,
epoxides, inorganic phosphorus reagents and methods of reacting the
same are described in U.S. Pat. No. 3,197,405 and U.S. patent
3,544,465 which are incorporated herein by reference for their
disclosure to these.
[0125] The following Examples P-1 and P-2 exemplify the preparation
of useful phosphorus acid esters.
EXAMPLE P-1
[0126] Phosphorus pentoxide (64 grams) is added at 58.degree. C.
over a period of 45 minutes to 514 grams of hydroxypropyl
O,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reacting
di(4-methyl-2-pentyl)-phosphorodithioic acid with 1.3 moles of
propylene oxide at 25.degree. C.). The mixture is heated at
75.degree. C. for 2.5 hours, mixed with a diatomaceous earth and
filtered at 70.degree. C. The filtrate contains 11.8% by weight
phosphorus, 15.2% by weight sulfur, and an acid number of 87
(bromophenol blue).
EXAMPLE P-2
[0127] A mixture of 667 grams of phosphorus pentoxide and the
reaction product of 3514 grams of diisopropyl phosphorodithioic
acid with 986 grams of propylene oxide at 50.degree. C. is heated
at 85.degree. C. for 3 hours and filtered. The filtrate contains
15.3% by weight phosphorus, 19.6% by weight sulfur, and an acid
number of 126 (bromophenol blue).
[0128] Acidic phosphoric acid esters may be reacted with an amine
compound or a metallic base to form an amine or metal salt. The
salts may be formed separately and then the salt of the phosphorus
acid ester may be added to the lubricating composition.
Alternately, the salts may also be formed in situ when the acidic
phosphorus acid ester is blended with other components to form a
fully formulated lubricating composition.
[0129] The amine salts of the phosphorus acid esters may be formed
from ammonia, or an amine, including monoamines and polyamines. The
amines may be primary amines, secondary amines or tertiary amines.
In one embodiment, the amines are one or more of the amines
described above for preparing the dithiocarbamates. Useful amines
include those amines disclosed in U.S. Pat. No. 4,234,435 at Col.
21, line 4 to Col. 27, line 50, these passages being incorporated
herein by reference
[0130] The monoamines generally contain from 1 up to about 24
carbon atoms, or up to about 12, or up to about 6 carbon atoms.
Examples of monoamines include methylamine, ethylamine,
propylamine, butylamine, octylamine, and dodecylamine,
dimethylamine, diethylamine, dipropylamine, dibutylamine, methyl
butylamine, ethyl hexylamine, trimethylamine, tributylamine, methyl
diethylamine, ethyl dibutylamine, etc.
[0131] In one embodiment, the amine may be a fatty (C.sub.4 30)
amine which include n-hexylamine, n-octylamine, n-decylaminie,
n-dodecylamine, n-tetradecylamine, n-hexadecylamine,
n-octadecylamine, oleylamine, etc. Also useful fatty amines include
commercially available fatty amines such as "Armeen" amines
(products available from Armak Chemicals, Chicago, Ill.), such as
Armak's Armeen-C, Armeen-O, Armeen-OL, Armeen-T, Armeen-HT, Armeen
S and Armeen SD, wherein the letter designation relates to the
fatty group, such as cocoa, oleyl, tallow, or soya groups.
[0132] Other useful amines include primary ether amines, such as
those represented by the formula, R"(OR').sub.xNH.sub.2, wherein R'
is a divalent alkylene group having about 2 to about 6 carbon
atoms, x is a number from one to about 150 (preferably one), and R"
is a hydrocarbyl group of about 5 to about 150 carbon atoms. An
example of an ether amine is available under the name SURFAM.RTM.
amines produced and marketed by Mars Chemical Company, Atlanta, Ga.
Preferred etheramines are exemplified by those identified as SURFAM
P14B (decyloxypropylamine), SURFAM P16A (linear C.sub.16), SURFAM
P17B (tridecyloxypropylamine). The carbon chain lengths (i.e.,
C.sub.14, etc.) of the SURFAMS described above and used hereinafter
are approximate and include the oxygen ether linkage.
[0133] In one embodiment, the amine may be a hydroxyamine.
Typically, the hydroxyamines are primary, secondary or tertiary
alkanol amines or mixtures thereof. Such amines can be represented
by the formulae: H.sub.2--N--R'--OH, H(R'.sub.1)N--R'--OH, and
(R'.sub.1).sub.2--N--R'--OH- , wherein each R'.sub.1 is
independently a hydrocarbyl group having from one to about eight
carbon atoms or hydroxyhydrocarbyl group having from one to about
eight carbon atoms, or from one to about four, and R' is a divalent
hydrocarbyl group of about two to about 18 carbon atoms, or from
two to about four. The group --R'--OH in such formulae represents
the hydroxyhydrocarbyl group. R' can be an acyclic, alicyclic or
aromatic group. Typically, R' is an acyclic straight or branched
alkylene group such as an ethylene, propylene, 1,2-butylene,
1,2-octadecylene, etc. group. Where two R'1 groups are present in
the same molecule they can be joined by a direct carbon-to-carbon
bond or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to
form a 5-, 6-, 7- or 8-membered ring structure. Examples of such
heterocyclic amines include N-(hydroxyl lower alkyl)-morpholines,
-thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and
the like. Typically, however, each R'1 is independently a methyl,
ethyl, propyl, butyl, pentyl or hexyl group Examples of these
alkanolaminies include mono-, di-, and triethanolamine,
diethylethanolamine, ethylethanolamiine, butyldiethanolamine,
etc.
[0134] The hydroxyamines may also be an ether
N-(hydroxyhydrocarbyl)amine These are hydroxypoly(hydrocarbyloxy)
analogs of the above-described hydroxyamines (these analogs also
include hydroxyl-substituted oxyalkylene analogs). Such
N-(hydroxyhydrocarbyl) amines can he conveniently prepared by
reaction of one or more of the above epoxides with aforedescribed
amines and may he represented by the formulae:
H.sub.2N--(R'O).sub.xH, H(R'.sub.1)--N--(R'O).sub.x--H, and
(R'.sub.1).sub.2--N--(R'O).sub.x--H, wherein x is a number from
about 2 to about 15 and R, and R' are as described above. R'.sub.1
may also be a hydroxypoly(hydrocarbyloxy) group.
[0135] The amines may be hydroxyamines, such as those represented
by the formula 2
[0136] wherein R.sub.1 is a hydrocarbyl group generally containing
from about 6 to about 30 carbon atoms; R.sub.2 and each R.sub.3 is
independently an alkylene group containing up to about 5 carbon
atoms, preferably an ethylene or propylene group; a is zero or one;
and each z is independently a number from zero to about 10, with
the proviso that at least one z is at least one. These
hydroxyamines can be prepared by techniques well known in the art
and many such hydroxyamines are commercially available. The hydroxy
amines include mixtures of amines such as obtained by the
hydrolysis of fatty oils (e.g., tallow oils, sperm oils, coconut
oils, etc.). Specific examples of fatty amines, containing from
about 6 to about 30 carbon atoms, include saturated as well as
unsaturated aliphatic amines, such as octyl amine, decyl amine,
lauryl amine, stearyl amine, oleyl amine, dodecyl amine, and
octadecyl amine.
[0137] Useful hydroxyamines wherein a in the above formula is zero
include 2-hydroxyethyl, hexylamine; 2-hydroxyethyloctylamine;
2-hydroxyethyl, pentadecyl-amine; 2-hydroxyethyl, oleylamine;
2-hydroxyethyl,soyamine; bis(2-hydroxyethyl) hexylamine;
bis(2-hydroxyethyl)oleylamine; and mixtures thereof. Also included
are the comparable members wherein in the above formula at least
one of z is at least 2, as for example, 2-hydroxyethoxyethyl,
hexylamine.
[0138] A number of hydroxyamines wherein a in the above formula is
zero are available from the Armak Chemical Division of Akzona,
Inc., Chicago, Ill. under the general trade designations "Ethomeen"
and "Propomeen". Specific examples of such products include:
Ethomeen C/15 which is an ethylene oxide condensate of a coco alkyl
amine containing about 5 moles of ethylene oxide; Ethomeen C/20 and
C/25 which are ethylene oxide condensation products from coco alkyl
amine containing about 10 and 15 moles of ethylene oxide,
respectively; Ethomeen O/12 which is an ethylene oxide condensation
product of oleylamine containing about 2 moles of ethylene oxide
per mole of amine; Ethomeen S/15 and S/20 which are ethylene oxide
condensation products with stearyl amine containing about 5 and 10
moles of ethylene oxide per mole of amine, respectively; Ethomeen
T/12, T/15 and T/25 which are ethylene oxide condensation products
of tallow amine containing about 2, 5 and 15 moles of ethylene
oxide per mole of amine, respectively; and Propomeen O/12 which is
the condensation product of one mole of oleylamine with 2 moles
propylene oxide.
[0139] Commercially available examples of alkoxylated amines where
a in the above formula is one include Ethoduomeen T/13 and T/20
which are ethylene oxide condensation products of N-tallow
trimethylenediamine containing 3 and 10 moles of ethylene oxide per
mole of diamine, respectively.
[0140] The amine may also be a polyamine. The polyamines include
alkoxylated diamines, fatty diamines, alkylenepolyamines, hydroxy
containing polyamines, condensed polyamines and heterocyclic
polyamines. Commercially available examples of alkoxylated diamines
include those amines where a in the above formula is one. Examples
of these amines include Ethoduomeen T/13 and T/20 which are
ethylene oxide condensation products of
N-tallowtrimethylenediaminie containing 3 and 10 moles of ethylene
oxide per mole of diamine, respectively.
[0141] In another embodiment, the polyamine is a fatty diamine. The
fatty diamines include mono- or dialkyl, symmetrical or
asymmetrical ethylenediamines. propanediamines (1,2, or 1,3), and
polyamine analogs of the above Suitable commercial fatty polyamines
are Duomeen C (N-coco-1,3-diaminopropane), Duomeen S
(N-soya-1,3-diaminopropane), Duomeen T
(N-tallow-1,3-diaminopropane), and Duomeen O
(N-oleyl-1,3-diaminopropane) "Duonieens" are commercially available
from Armak Chemical Co., Chicago, Ill.
[0142] In another embodiment, the amine is an alkylenepolyamine.
Alkylenepolyamines are represented by the formula
HR.sub.1N-(Alkylene-N).- sub.n-(R.sub.1).sub.2, herein each R.sub.1
is independently hydrogen, or an aliphatic or hydroxy-substituted
aliphatic group of up to about 30 carbon atoms; {overscore (M)}n is
a number from 1 to about 10, or from about 2 to about 7, or from
about 2 to about 5; and the "Alkylene" group has from 1 to about 10
carbon atoms, or from about 2 to about 6, or from about 2 to about
4. In another embodiment, R.sub.1 is defined the same as R'.sub.1
above. Such alkylenepolyamines include methylenepolyamines,
ethylenepolyamines. butylenepolyamines, propylenepolyamines,
pentylenepolyamines, etc. The higher homologs and related
heterocyclic amines, such as piperazines and N-amino
alkyl-substituted piperazines, are also included. Specific examples
of such polyamines are ethylenediamine, triethylenetetramine,
tris-(2-aminoethyl)amine. propylenediamine, trimethylenediamine,
tripropylenetetramine, triethylenetetraamine,
tetraethylenepentamine, hexaethyleneheptamine,
pentaethylenehexamine, etc. Higher homologs obtained by condensing
two or more of the above-noted alkyleneamines are similarly useful
as are mixtures of two or more of the aforedescribed
polyamines.
[0143] In one embodiment, the polyamine is an ethylenepolyamine.
Such polyamines are described in detail under the heading Ethylene
Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2d
Edition, Vol. 7, pages 22-37, Interscience Publishers, New York
(1965). Ethylenepolyamines are often a complex mixture of
polyalkylenepolyamines including cyclic condensation products.
Other useful types of polyamine mixtures are those resulting from
stripping of the above-described polyamine mixtures to leave, as
residue, what is often termed "polyamine bottoms". In general,
alkylenepolyamine bottoms can be characterized as having less than
2%, usually less than 1% (by weight) material boiling below about
200.degree. C. A typical sample of such ethylenepolyamine bottoms
obtained from the Dow Chemical Company of Freeport, Tex. designated
"E-100" has a specific gravity at 15.6.degree. C. of 1.0168, a
percent nitrogen by weight of 33.15 and a viscosity at 40.degree.
C. of 121 cetitistokes. Gas chromatography analysis of such a
sample contains about 0.93% "Light Ends" (most probably
diethylenetriamine), 0.72% tirethylenetetraamine, 21.74%
tetraethylenepentaamine and 76.61% pentaethylenehexamine and higher
analogs These alkylenepolyamine bottoms include cyclic condensation
products, such as piperazine, and higher analogs of
diethylenetriamine, triethylenetetramine and the like. These
alkylenepolyamine bottoms may be reacted solely with the acylating
agent or they may be used with other amines, polyamines, or
mixtures thereof.
[0144] Another useful polyamine is a condensation reaction between
at least one hydroxy compound with at least one polyamine reactant
containing at least one primary or secondary amino group. The
hydroxy compounds are preferably polyhydric alcohols or polyhydric
amines. The polyhydric alcohols are described below. In one
embodiment, the hydroxy compounds are polyhydric amines. Polyhydric
amines include any of the above-described monoamines reacted with
an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene
oxide, etc.) having from two to about 20, or from two to about four
carbon atoms. Examples of polyhydric amines include
tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane,
2-amino-2-methyl-1,3-propanediol, N,N,N',N'-tetrakis
(2-hydroxypropyl) ethylenediamine, and N,N,N',N'-tetrakis
(2-hydroxyethyl) ethylenediamine, preferably tris(hydroxymethyl)
aminomethane (THAM).
[0145] Polyamines which may react with the polyhydric alcohol or
amine to form the condensation products or condensed amines, are
described above. Preferred polyamines include triethylenetetramine
(TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine
(PEHA), and mixtures of polyamines such as the above-described
"amine bottoms". The condensation reaction of the polyamine
reactant with the hydroxy compound is conducted at an elevated
temperature, usually from about 60.degree. C. to about 265.degree.
C., or from about 220.degree. C. to about 250.degree. C. in the
presence of an acid catalyst.
[0146] The amine condensates and methods of making the same are
described in PCT publication WO 86/05501 and U.S. Pat. No.
5,230,714 (Steckel) which are incorporated by reference for its
disclosure to the condensates and methods of making. A particularly
useful amine condensate is prepared from HPA Taft Amines (amine
bottoms available commercially from Union Carbide Co. with
typically 34.1% by weight nitrogen and a nitrogen distribution of
12.3% by weight primary amine, 14.4% by weight secondary amine and
7.4% by weight tertiary amine), and tris(hydroxymethyl)aminomet-
hane (THAM).
[0147] In another embodiment, the polyamines are polyoxyalkylene
polyamines, e.g. polyoxyalkylene diamines and polyoxyalkylenie
triamines, having average molecular weights ranging from about 200
to about 4000, or from about 400 to about 2000. The preferred
polyoxyalkylene polyamines include the polyoxyethylene and
polyoxypropylene diamines and the polyoxypropylene triamines. The
polyoxyalkylene polyamines are commercially available and may be
obtained, for example, from the Jefferson Chemical Company, Inc.
under the trade name "Jeffamines D-230, D-400, D-1000, D-2000,
T-403, etc.". U.S. Pat. Nos. 3,804,763 and 3,948,800 are expressly
incorporated herein by reference for their disclosure of such
polyoxyalkylene polyamines and acylated products made
therefrom.
[0148] In another embodiment, the polyamines are hydroxy-containing
polyamines. Hydroxy-containing polyamine analogs of hydroxy
monoamines, particularly alkoxylated alkylenepolyamines, e.g.,
N,N(diethanol)ethylene diamines can also be used. Such polyamines
can be made by reacting the above-described alkylene amines with
one or more of the above-described alkylene oxides. Similar
alkylene oxide-alkanol amine reaction products may also be used
such as the products made by reacting the above described primary,
secondary or tertiary alkanol amines with ethylene, propylene or
higher epoxides in a 1.1 to 1.2 molar ratio. Reactant ratios and
temperatures for carrying out such reactions are known to those
skilled in the art. Specific examples of hydroxy-containing
polyamines include N-(2-hydroxyethyl) ethylenedianminie,
N,N'-bis(2-hydroxyethyl)-et- hylenediamine,
1-(2-hydroxyethyl)-piperazine, mono(hydroxypropyl)-substitu- ted
tetraethylenepentamine. N-(3-hydroxybutyl)-tetramethylene diamine,
etc. Higher homologs obtained by condensation of the above
illustrated hydroxy-containing polyamines through amino groups or
through hydroxy groups are likewise useful. Condensation through
amino groups results in a higher amine accompanied by removal of
ammonia while condensation through the hydroxy groups results in
products containing ether linkages accompanied by removal of water.
Mixtures of two or more of any of the above described polyamines
are also useful.
[0149] In another embodiment, the amine is a heterocyclic amine The
heterocyclic polyamincs include aziridines, azetidines, azolidines,
tetra- and dihydropyridines, pyrroles, indoles, piperidines,
imidazoles, di- and tetrahydroimidazoles, piperazines, isoindoles,
purines, morpholines, thiomorpholines, N-aminoalkylmorpholines.
N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,
N,N'-di-aminoalkylpiperazines, azepines, azocines, azonines,
azecines and tetra-, di- and per-hydro derivatives of each of the
above and mixtures of two or more of these heterocyclic amines.
Preferred heterocyclic amines are the saturated 5- and 6-membered
heterocyclic amines containing only nitrogen, oxygen and/or sulfur
in the hetero ring, especially the piperidines, piperazines,
thiomorpholines, morpholines, pyrrolidines, and the like.
Piperidine, aminoalkyl substituted piperidines, piperazine,
aminoalkyl substituted piperazines, morpholine, aminoalkyl
substituted morpholines, pyrrolidine, and aminoalkyl-substituted
pyrrolidines, are especially preferred. Usually the aminoalkyl
substituents are substituted on a nitrogen atom forming part of the
hetero ring. Specific examples of such heterocyclic amines include
N-aminopropylmorpholine, N-aminoethylpiperazine, and
N,N'-diaminoethylpiperazine. Hydroxy heterocyclic amines are also
useful. Examples include N-(2-hydroxyethyl)cyclohexylamine,
3-hydroxycyclopentylamine, parahydroxyaniline,
N-hydroxyethylpiperazine, and the like.
[0150] The metal salts of the phosphorus acid esters are prepared
by the reaction of a metal base with the phosphorus acid ester. The
metal base may be any metal compound capable of forming a metal
salt. Examples of metal bases include metal oxides, hydroxides,
carbonates, sulfates, borates, or the like. The metals of the metal
base include Group IA, IIA, IB through VIIB, and VIII metals (CAS
version of the Periodic Table of the Elements). These metals
include the alkali metals, alkaline earth metals and transition
metals. In one embodiment, the metal is a Group IIA metal, such as
calcium or magnesium, Group IIB metal, such as zinc, or a Group
VIIB metal, such as manganese. Preferably the metal is magnesium,
calcium. mnanganese or zinc Examples of metal compounds which may
be reacted with the phosphorus acid include zinc hydroxide, zinc
oxide, copper hydroxide, copper oxide, etc.
[0151] In one embodiment, phosphorus or boron containing
antiwear/extreme pressure agent is a metal thiophosphate,
preferably a metal dithiophosphate. The metal thiophosphate is
prepared by means known to those in the art. Examples of metal
dithiophosphates include zinc isopropyl, methylamyl
dithiophosphate, zinc isopropyl isooctyl dithiophosphate, barium
di(nonyl) dithiophosphate, zinc di(cyclohexyl) dithiophosphate,
zinc di(isobutyl) dithiophosphate, calcium di(hexyl)
dithiophosphate, zinc isobutyl isoamyl dithiophosphate, and zinc
isopropyl secondary-butyl dithiophosphate.
[0152] The following Examples P-3 to P-6 exemplify the preparation
of useful phosphorus acid ester salts.
EXAMPLE P-3
[0153] A reaction vessel is charged with 217 grams of the filtrate
from Example P-1. A commercial aliphatic primary amine (66 grams),
having an average molecular weight of 191 in which the aliphatic
radical is a mixture of tertiary alkyl radicals containing from 11
to 14 carbon atom, is added over a period of 20 minutes at
25-60.degree. C. The resulting product has a phosphorus content of
10.2% by weight, a nitrogen content of 1.5% by weight, and an acid
number of 26.3.
EXAMPLE P-4
[0154] Following the procedures of Examples P-1 and P-3, 1320 parts
of the product described in P-1 was reacted with 584 parts of the
amine of P-3. The final product has 8.4% phosphorus and 10%
sulfur.
EXAMPLE P-5
[0155] The filtrate of Example P-2 (1752 grams) is mixed at
25-82.degree. C. with 764 grams of the aliphatic primary amine used
in of Example P-3 The resulting product has 9.9% phosphorus, 2.7%
nitrogen, and 12.6% sulfur.
EXAMPLE P-6
[0156] Phosphorus pentoxide (852 grams) is added to 2340 grams of
iso-octyl alcohol over a period of 3 hours. The temperature
increases from room temperature but is maintained below 65.degree.
C. After the addition is complete the reaction mixture is heated to
90.degree. C. and the temperature is maintained for 3 hours.
Diatomaceous earth is added to the mixture, and the mixture is
filtered. The filtrate has 12.4% phosphorus, a 192 acid
neutralization number (bromophenol blue) and a 290 acid
neutralization number (phenolphthalein).
[0157] The above filtrate is mixed with 200 grams of toluene, 130
grams of mineral oil, 1 gram of acetic acid, 10 grams of water and
45 grams of zinc oxide. The mixture is heated to 60-70.degree. C.
under a pressure of 30 mm Hg. The resulting product mixture is
filtered using a diatomaceous earth. The filtrate has 8.6% zinc and
7.0% phosphorus.
EXAMPLE P-7
[0158] Alfol 8-10 (2628 parts, 18 moles) is heated to a temperature
of about 45.degree. C. whereupon 852 parts (6 moles) of phosphorus
pentoxide are added over a period of 45 minutes while maintaining
the reaction temperature between about 45-65.degree. C. The mixture
is stirred an additional 0.5 hour at this temperature, and is
there- after heated at 70.degree. C. for about 2-3 hours. Primene
81-R (2362 parts, 12.6 moles) is added dropwise to the reaction
mixture while maintaining the temperature between about
30-50.degree. C. When all of the amine has been added, the reaction
mixture is filtered through a filter aid, and the filtrate is the
desired amine salt containing 7.4% phosphorus (theory, 7.1%).
EXAMPLE P-8
[0159] Phosphorus pentoxide (208 grams) is added to the product
prepared by reacting 280 grams of propylene oxide with 1184 grams
of O,O'-di-isobutylphosphorodithioic acid at 30-60.degree. C. The
addition is made at a temperature of 50-60.degree. C. and the
resulting mixture is then heated to 80.degree. C. and held at that
temperature for 2 hours The commercial aliphatic primary amine
identified in Example P-3 (384 grams) is added to the mixture,
while the temperature is maintained in the range of 30-60.degree.
C. The reaction mixture is filtered through diatomaceous earth. The
filtrate has 9.3% phosphorus, 11.4% sulfur, 2.5% nitrogen, and a
base number of 6.9 (bromophenol blue indicator).
[0160] In another embodiment, the phosphorus or boron
antiwear/extreme pressure agent is a metal salt of (a) at least one
dithiophosphoric acid and (b) at least one aliphatic or alicyclic
carboxylic acid. The dithiophosphoric acids are described above.
The carboxylic acid may be a monocarboxylic or polycarboxylic acid,
usually containing from 1 to about 3, or just one carboxylic acid
group. The preferred carboxylic acids are those having the formula
RCOOH, wherein R is an aliphatic or alicyclic hydrocarbyl group
preferably free from acetylenic unsaturation. R generally contains
from about 2, or from about 4 carbon atoms. R generally contains up
to about 40, or up to about 24, or to up about 12 carbon atoms. In
one embodiment, contains from 4, or from about 6 up to about 12, or
up to about 8 carbon atoms. In one embodiment, R is an alkyl group.
Suitable acids include the butanoic, pentanoic, hexanoic, octanoic,
nonanoic, decanoic, dodecanoic, octodecanoic and eicosanoic acids,
as well as olefinic acids such as oleic, linoleic, and linolenic
acids and linoleic acid dimer. A preferred carboxytic acid is
2-ethylhexanoic acid.
[0161] The metal salts may be prepared by merely blending a metal
salt of a dithiophoshoric acid with a metal salt of a carboxylic
acid in the desired ratio. The ratio of equivalents of
dithiophosphoric acid to carboxylic acid is from about 0.5 up to
about 400 to 1. The ratio may be from 0.5 up to about 200, or up to
about 100, or up to about 50, or up to about 20 to 1. In one
embodiment, the ratio is from 0.5 up to about 4.5 to one,
preferably from about 2.5 up to about 4.25 to one. For this
purpose, the equivalent weight of a dithiophosphoric acid is its
molecular weight divided by the number of -PSSH groups therein, and
the equivalent weight of a carboxylic acid is its molecular weight
divided by tire number of carboxy groups therein.
[0162] A second and preferred method for preparing the metal salts
useful in this invention is to prepare a mixture of the acids in
the desired ratio, such as those described above for the metal
salts of the individual metal salts, and to react the acid mixture
with one of the above described metal compounds. When this method
of preparation is used, it is frequently possible to prepare a salt
containing an excess of metal with respect to the number of
equivalents of acid present; thus the metal salts may contain as
many as 2 equivalents and especially up to about 1.5 equivalents of
metal per equivalent of acid may be prepared, the equivalent of a
metal for this purpose is its atomic weight divided by its valence.
The temperature at which the metal salts are prepared is generally
between about 30.degree. C. and about 150.degree. C., preferably up
to about 125.degree. C. U.S. Pat. Nos. 4,308,154 and 4,417,990
describe procedures for preparing these metal salts and disclose a
number of examples of such metal salts. These patents are hereby
incorporated by reference for those disclosures.
[0163] In one embodiment, the phosphorus or boron containing
antiwear/extreme pressure agent is a phosphorus containing amide.
The phosphorus containing amides are prepared by the reaction of
one of the above describe phosphorus acids, preferably a
dithiophosphoric acid, with an one of the above described
unsaturated amides. The reaction product of the phosphorus acid and
the unsaturated amide may be further reacted with a linking or a
coupling compound, such as formaldehyde or paraformaldehyde. The
phosphorus containing amides are known in the art and are disclosed
in U.S. Pat. Nos. 4,670,169, 4,770,807, and 4,876,374 which are
incorporated by reference for their disclosures of phosphorus
amides and their preparation.
[0164] In one embodiment, the phosphorus or boron antiwear/extreme
pressure agent is a phosphorus containing carboxylic ester. The
phosphorus containing carboxylic esters are prepared by reaction of
one of the above-described phosphorus acids, preferably a
dithiophosphoric acid, and one of the above described unsaturated
carboxylic acids or esters. If the carboxylic acid is used, the
ester may then be formed by subsequent reaction of the phosphoric
acid-unsaturated carboxylic acid adduct with an alcohol, such as
those described herein.
[0165] In one embodiment, the phosphorus or boron containing
antiwear/extreme pressure agent is a reaction product of a
phosphorus acid, preferably a dithiophosphoric acid, and one of the
above described vinyl ethers.
[0166] In another embodiment, the phosphorus or boron containing
antiwear/extreme pressure agent is an alkali metal borate. Alkali
metal berates are generally a hydrated particulate alkali metal
borate which are known in the art. Alkali metal borates include
mixed alkali and alkaline earth metal borates. These alkali metal
borates are available commercially. Representative patents
disclosing suitable alkali metal borates and their methods of
manufacture include U.S. Pat. Nos. 3,997,454; 3,819,521; 3,853,772;
3,907,601; 3,997,454; and 4,089,790. These patents are incorporated
by reference for their disclosures of alkali metal borates and
methods of their manufacture.
[0167] In another embodiment, the phosphorus or boron containing
antiwear/extreme pressure agent is a borated overbased compound,
provided that the borated overbased compound is different than B(i)
above. The borated overbased compounds are described above.
[0168] In another embodiment, the phosphorus or boron
antiwear/extreme pressure agent is a borated fatty amine. The
borated amines are prepared by reacting one or more of the above
boron compounds, such as boric acid, with one or more of the above
fatty amines, e.g. an amine having from about four to about
eighteen carbon atoms. The borated fatty amines are prepared by
reacting the amine with the boron compound at about 50.degree. C.
to about 300.degree. C., preferably about 100.degree. C. to about
250.degree. C., and at a ratio of 3:1 to 1:3 equivalents of amine
to equivalents of boron compound.
[0169] In another embodiment, the phosphorus or boron containing
antiwear/extreme pressure agent is a borated epoxide. The borated
fatty epoxides are generally the reaction product of one or more of
the above boron compounds, with at least one epoxide. The epoxide
is generally an aliphatic epoxide having at least 8, preferably
about 10, more preferably about 12, up to about 24, preferably 20
carbon atoms. Examples of useful aliphatic epoxides include heptyl
oxide, octyl oxide, stearyl oxide, oleyl oxide and the like.
Mixtures of epoxides may also be used, for instance commercial
mixtures of epoxides having from 14 to about 16 carbon atoms and
from 14 to about 18 carbon atoms. The borated fatty epoxides are
generally known and are disclosed in U.S. Pat. No. 4,584,115. This
patent is incorporated by reference for its disclosure of borated
fatty epoxides and methods for preparing the same.
[0170] In another embodiment, the phosphorus or boron containing
antiwear/extreme pressure agent is a borated phospholipid. The
berated phospholipids are prepared by reacting a combination of a
phospholipid and a boron compound. Optionally, the combination may
include an amine, an acylated nitrogen compound, such as reaction
products of carboxylic acylating agents and polyamines, a
carboxylic ester, such as reaction products of carboxylic
acrylating agents and alcohols and optionally amines, a Mannich
reaction product, or a basic or neutral metal salt of an organic
acid compound. Phospholipids, sometimes referred to as phosphatides
and phospholipins, may be natural or synthetic. Naturally derived
phospholipids include those derived from fish, fish oil, shellfish,
bovine brain, chicken eggs, sunflowers, soybean, corn, and
cottonseed. Phospholipids may be derived from microorganisms,
including blue-green algae, green algae, and bacteria.
[0171] The reaction of the phospholipid, the boron compound, and
the optional components usually occurs at a temperature from about
60.degree. C. to about 200.degree. C., or from about 90.degree. C.
up to about 150.degree. C. The reaction is typically accomplished
in about 0.5, or about 2 up to about 10 hours. The boron compound
and phospholipid are reacted at an atomic proportion ratio of boron
to phosphorus from about one up to about six to one, preferably
from about two up to about four to one, more preferably about three
to one. When the combination includes additional components, the
boron compound is reacted with the mixture of the phospholipid and
one or more optional ingredients in an amount of one atomic
proportion of boron to an equivalent of the mixture of a
phospholipid and an optional ingredient in a ratio from about
(1:1), up to about (6:1), or from about (2:1) up to about (4:1).
The equivalents of the mixture are based on the combined
equivalents of phospholipid based on phosphorus and equivalents of
the optional ingredients. The borated phospholipids are described
in European publication EP 540,700. This publication is
incorporated by reference.
[0172] In another embodiment, the molybdenum containing
compositions may be used in combination with a mixture of (i) a
borated overbased composition and (ii) an organic polysulfide or an
ashless dithiocarbamate containing composition and a phosphorus or
boron antiwear/extreme pressure agent. These components are
described above.
[0173] Lubricants
[0174] As previously indicated, the above combinations are useful
in lubricants where they can function primarily as antiwear,
antiweld, extreme pressure, anticorrosion antioxidation and/or
friction modifying agents. They can be employed in a variety of
lubricants based on diverse oils of lubricating viscosity,
including natural and synthetic lubricating oils and mixtures
thereof. These lubricants include crankcase lubricating oils for
spark-ignited and compression-ignited internal combustion engines,
including automobile and truck engines, two-cycle engines, aviation
piston engines, marine and railroad diesel engines, and the like.
They can also be used in gas engines, stationary power engines and
turbines and the like. Automatic or manual transmission fluids,
transaxle lubricants, gear lubricants, including open and enclosed
gear lubricants, tractor lubricants, metal-working lubricants,
hydraulic fluids and other lubricating oil and grease compositions
can also benefit from the incorporation therein of the compositions
of the present invention. They may also be used as wirerope,
walking cam, way, rock drill, chain and conveyor belt, worm gear,
bearing, and rail and flange lubricants.
[0175] The combinations may be used in lubricants or in
concentrates. The concentrate may contain the above combinations
and/or other components used in preparing fully formulated
lubricants. The concentrate also contains a substantially inert
organic diluent, which includes kerosene, mineral distillates, or
one or more of the oils of lubricating viscosity discussed below.
The combinations are present in a final product, blend, or
concentrate in any amount effective to act as an antiwear,
antiweld, and/or extreme pressure agents in lubricating
compositions.
[0176] In one embodiment, the lubricating composition contains up
to 1.5%, or up to about 1.0%, or up to about 0.5% by weight of
reaction product of a polyisobutenyl substituted succinic anhydride
and a polyalkylene polyamine. In another embodiment, the
lubricating compositions, such as gear lubricants, contain up to
2%, or up to 1.5%, or up to 1% by weight of a dispersant, such as
those described herein. In another embodiment, the lubricating
composition is free of added lead compounds, such as lead
napthanates, dithiophosphates and dithiocarbamates.
[0177] The lubricating compositions and methods of this invention
employ an oil of lubricating viscosity, including natural or
synthetic lubricating oils and mixtures thereof. Natural oils
include animal oils, vegetable oils, mineral lubricating oils, and
solvent or acid treated mineral oils. Synthetic lubricating oils
include hydrocarbon oils (polyalpha-olefins), halo-substituted
hydrocarbon oils, alkylene oxide polymers. esters of dicarboxylic
acids and polyols, esters of phosphorus-containing acids, polymeric
tetrahydrofurans and silicon-based oils. Unrefined, refined, and
rerefined oils, either natural or synthetic, may be used in the
compositions of the present invention. A description of oils of
lubricating viscosity occurs in U.S. Pat. No. 4,582,618 (column 2,
line 37 through column 3, line 63, inclusive), herein incorporated
by reference for its disclosure to oils of lubricating
viscosity.
[0178] In one embodiment, the oil of lubricating viscosity is a
polyalpha-olefin (PAO). Typically, the polyalpha-olefins are
derived from monomers having from about 3 to about 30, or from
about 4 to about 20, or from about 6 to about 16 carbon atoms.
Examples of useful PAOs include those derived from decene. These
PAOs may have a viscosity from about 3 to about 150, or from about
4 to about 100, or from about 4 to about 8 cSt at 100.degree. C.
Examples of PAOs include 4 cSt polyolefins, 6 cSt polyolefins, 40
cSt polyolefins and 100 cSt polyalphaolefins.
[0179] In one embodiment, the oil of lubricating viscosity are
selected to provide lubricating compositions with a kinematic
viscosity of at least about 3.5 cSt, or at least about 4.0 cSt at
100.degree. C. In one embodiment, the lubricating compositions have
an SAE gear viscosity grade of at least about SAE 75W. The
lubricating composition may also have a so-called multigrade rating
such as SAE 75W-80, 75W-90, 75W-90, 75W-140, 80W-90, 80W-140,
85W-90, or 85W-140. Multigrade lubricants may include a viscosity
improver which formulated with the oil of lubricating viscosity to
provide the above lubricant grades. Useful viscosity improvers
include but are not limited to polyolefins, such as
ethylene-propylene copolymers, or polybutylene rubbers, including
hydrogenated rubbers, such as styrene-butadiene or styrene-isoprene
rubbers; or polyacrylates, including polymethacrylates. In one
embodiment, the viscosity improver is a polyolefin or
polymethacrylate. Viscosity improvers available commercially
include Acryloid.TM. viscosity improvers available from Rohm &
Haas; Shellvis.TM. rubbers available from Shell Chemical;
Trilene.TM. polymers, such as Trilene.TM. CP-40, available
commercially from Uniroyal Chemical Co., and Lubrizol 3100 series
and 8400 series polymers, such as Lubrizol 3174 available from The
Lubrizol Corporation.
[0180] In one embodiment, the oil of lubricating viscosity includes
at least one ester of a dicarboxylic acid. Typically the esters
containing from about 4 to about 30, preferably from about 6 to
about 24, or from about 7 to about 18 carbon atoms in e each ester
group. Examples of dicarboxylic acids include glutaric, adipic,
pimelic, suberic, azelaic and sebacic. Examples of ester groups
include hexyl, octyl, decyl, and dodecyl ester groups. The ester
groups include linear as well as branched ester groups such as iso
arrangements of the ester group. A particularly useful ester of a
dicarboxylic acid is diisodecyl azelate.
[0181] In another embodiment, the oil of lubricating viscosity is
selected to provide lubricating compositions for crankcase
applications, such as for gasoline and diesel engines Typically,
the lubricating compositions are selected to provide an SAE
crankcase viscosity number of 10W, 20W, or 30W lubricants. The
lubricating composition may also have a so called multi-grade
rating such as SAE 5W-30, 10W-30, 10W-40, 20W-50, etc. As described
above, multi-grade lubricants include a viscosity improver which is
formulated with the oil of lubricating viscosity to provide the
above lubricant grades.
[0182] Other Additives
[0183] The invention also contemplates the use of other additives
together with the above combinations Such additives include, for
example, detergents and dispersants. corrosion- and
oxidation-inhibiting agents, pour point depressing agents, extreme
pressure agents, antiwear agents, color stabilizers and anti-foam
agents.
[0184] The detergents are exemplified by oil-soluble neutral and
basic salts (i.e. overbased salts) of alkali or alkaline earth
metals with sulfonic acids, carboxylic acids, phenols or organic
phosphorus acids, such as those described above. The oil-soluble
neutral or basic salts of alkali or alkaline earth metal salts may
also be reacted with a boron compound. Boron compounds are
described above. The overbased and borated overbased metal salts
are described above. Examples of useful overbased and borated
overbased metal salts include sodium, calcium and magnesium
overbased and borated overbased sulfonates and carboxylates,
including the above hydrocarbyl substituted carboxylic acylating
agents.
[0185] Detergents and dispersants are known in the art. The
following are illustrative.
[0186] (1) "Carboxylic dispersants," are the reaction products of
carboxylic acids (or derivatives thereof) containing at least about
34 and preferably at least about 54 carbon atoms and nitrogen
containing compounds (such as amines), organic hydroxy compounds
(such as phenols and alcohols), and/or basic inorganic materials.
These reaction products include imide, amide, and ester reaction
products of carboxylic acylating agents. The carboxylic dispersants
are generally prepared by reacting one or more of the above
described hydrocarbyl substituted carboxylic acylating agent
(described above) with an amine (described above), preferably the
polyalkylenepolyamine or the condensed polyamine, or hydroxy
containing compound, such as an alcohol and optionally an amine.
Examples of these materials include succinimide dispersants and
carboxylic ester dispersants. Examples of these "carboxylic
dispersants" are described in British Patent 1,306,529 and in many
U.S. patents including the following: U.S. Pat. Nos. 3,219,666,
3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170,
3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435,
5,230,714 and Re 26,433.
[0187] (2) "Amine dispersants" are the reaction products of
relatively high molecular weight aliphatic or alicyclic halides and
amines, preferably polyalkylene polyamines. These dispersants are
described above as polyalkene-substituted amines. Examples thereof
are described for example, in the following U.S. Pat. Nos.
3,275,554, 3,438,757, 3,454,555, and 3,565,804.
[0188] (3) "Mannich dispersants" are the reaction products of
alkylphenols anti aldehydes (especially formaldehyde) and amines
(especially amine condensates and polyalkylenepolyamines). The
materials described in the following U.S. patents are illustrative:
U.S. Pat. Nos. 3,036,003, 3,236,770, 3,414,347, 3,448,047,
3,461,172, 3,539,633. 3,586,629, 3,591,598, 3,634,515, 3,725,480,
3,726,882, and 3,980,569.
[0189] (4) "Post-treated dispersants" are the products obtained by
post-treating the carboxylic, amine or Mannich dispersants with
reagents such as urea, thiourea, carbon disulfide, aldehydes,
ketones, carboxylic acids, hydrocarbon-substituted succinic
anhydrides, nitrites, epoxides, boron compounds, phosphorus
compounds or the like. Exemplary materials of this kind are
described in the following U.S. Pat. Nos. 3,200,107, 3,282,955,
3,367,943, 3,513,093, 3,639,242, 3,649,659, 3,442,808, 3,455,832,
3,579,450, 3,600,372, 3,702,757,and 3,708,422.
[0190] (5) "Polymeric dispersants" are interpolymers of
oil-solubilizing monomers such as decyl methacrylate, vinyl decyl
ether and high molecular weight olefins with monomers containing
polar substituents, e.g., aminoalkyl acrylates or acrylamides and
poly-(oxyethylene)-substituted acrylates. Polymeric dispersants
include esters of styrene-maleic anhydride copolymers. Examples
thereof are disclosed in the following U.S. Pat. Nos. 3,329,658,
3,449,250, 3,519,656, 3,666,730, 3,687,849, and 3,702,300.
[0191] The above-noted patents are incorporated by reference herein
for their disclosures of ashless dispersants.
[0192] Auxiliary extreme pressure agents and corrosion- and
oxidation-inhibiting agents which may be included in the lubricants
of the invention are exemplified by chlorinated aliphatic
hydrocarbons such as chlorinated waxes; sulfurized alkylphenols;
phosphites including di- or trihydrocarbyl phosphites, such as
dibutyl phosphite, trioleyl phosphite and triphenyl phosphite;
phosphosulfurized hydrocarbons, such as the reaction product of a
phosphorus sulfide with turpentine or methyl oleate; metal
thiocarbamates, such as zinc dioctyldithiocarbamate, and barium
diheptylphenyl dithiocarbamate. Many of the above-mentioned extreme
pressure agents and corrosion- and oxidation-inhibitors also serve
as antiwear agents.
[0193] Pour point depressants are an additive often included in the
lubricating oils described herein. Examples of useful pour point
depressants are polymethacrylates; polyacrylates; polyacrylamides:
condensation products of haloparaffin waxes and aromatic compounds;
vinyl carboxylate polymers; and polymers of dialkylfumarates, vinyl
esters of fatty acids and alkyl vinyl ethers. Pour point
depressants useful for the purposes of this invention, techniques
for their preparation and their uses are described in U.S. Pat.
Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498;
2,666,746; 2,721,877; 2,721,878; and 3,250,715 which are hereby
incorporated by reference for their relevant disclosures.
[0194] Antifoam agents are used to reduce or prevent the formation
of stable foam. Typical antifoam agents include silicones or
organic polymers. Additional antifoam compositions are described in
"Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation,
1976), pages 125-162.
[0195] The following examples relate to lubricating compositions
containing the combination of a dithiocarbamate compound and an
organic polysulfide.
[0196] EXAMPLE 1
[0197] A lubricant is prepared by incorporating 1.5% by weight of
the product of Example M-1 and 1% of the product of Example B-2
into a 80W-90 gear oil base oil.
EXAMPLE 2
[0198] A lubricating composition is prepared as described in
Example 1, except a 10W-30 oil is used instead of the 80W-90
oil.
EXAMPLE 3
[0199] A lubricating oil is prepared by incorporating 1.5% of the
product of Example M-1, 2.5% of the product of Example S-1, and
1.2% by weight of the product of Example P-3 into an 80W-90 gear
oil.
EXAMPLE 4
[0200] A lubricating composition is prepared as described in
Example 3 except a 10W-30 oil is used instead of the 80W-90
oil.
EXAMPLE 5
[0201] A lubricating oil is prepared by incorporating 1.5% of the
product of Example M-1, 1% of the product of Example B-2, 2.5% of
the product of Example S-1, 1.2% of a mixed salt of isooctyl
dithiophosphoric acid and 2-ethylhexanoic acid, 0.7% of dibutyl
hydrogen phosphite, 1.8% of calcium overbased salt of an
alkylbenzene sulfonic acid (having a metal ratio of 12, 53%
diluent, comprising 100 neutral mineral oil and unreacted
alkylbenzene alkylate, a total base number of 30, and a 385
molecular weight for the sulfonic acid), 0.25% of oleylamide, and
0.07% of silicon antifoam agent into a 80W-90 oil.
EXAMPLE 6
[0202] A lubricating compositions is prepared by incorporating 0.2%
by weight of Sakura Lube 500, 3.8% by weight to the product of
Example S-1, 1.3% by weight of the product of Example P-3.
EXAMPLE 7
[0203] The lubricating composition is prepared by incorporating
0.2% of Sakura Lube 500, 3.8% by weight of the product of Example
S-1, 1.3% by weight of the product of Example P-4, 0.35% by weight
of oleo amine, 0.1% by weight oleo amide, and 0.1% by weight of the
reaction product of dimercaptothiadiazole, heptylamine and
paraformaldehyde into an 80W gear oil.
EXAMPLE 8-12
[0204] The following table contains examples of lubricating
compositions which are prepared by incorporating the ingredients
into an 80W-90 gear oil.
1 6 7 8 9 10 11 Example M-1 1.5 -- -- 2.5 1.0 -- Sakura Lube 500 --
0.2 -- -- -- 0.3 Molyvan 807 -- -- 0.5 -- -- -- Example B-1 1 -- --
1.5 -- 0.5 Example B-2 -- 0.8 -- -- 1 0.8 Example S-1 3.0 -- 2.5 --
-- 3.0 Example P-4 -- -- 1.2 -- -- -- Example P-4 1.2 -- -- 1.2 1.2
-- Phosphorus -- 1.5 -- -- -- 1.5 Containing ester.sup.1
Dithiocarbamate -- 2.5 1 -- 2.5 -- ester.sup.2 Dibutyl hydrogen 0.7
-- -- -- -- 1.0 phosphite .sup.1A reaction product of isobutyl,
amyl dithiophosphoric acid, methyl acrylate and propylene oxide.
.sup.2A reaction product diethyl amine, carbon disulfide, and
methyl acrylate.
[0205] While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover
such modifications as fall within the scope of the appended
claims.
* * * * *