Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
2 ~ 2 9 ~
Case No. 2627R/B -~
.
Title: LUBRICATING COMPOSITIONS, GREASES, AND AQUEOUS
FLUIDS CONTAINING THE COMBINATION OF- A
S DITHIOCARBAMATE COMPOUNl:) AND AN ORGANIC
POLYSULFIDE
Technica Field of the Invention
This Invention relates to lubricating compositions, greas s, and aqueous fluids
containing a di~iocarbamate ~ompound and an organic polysulfide. I~hese
compositions possess improYed antiwear or extreme pressure properties.
Background of the Invention
Lubricating compositions, greases, and aqueous fluids are used to maintain a
film of lubricant between surfaces that are moving with respect to each other. The
compositions minimize contact of the moving surfaces thus preventing harmful wear ~;
to the surfaces. The compositions generally also lower the coefficient of friction.
To be effective, the compositions should have suf~lcient antiwear, antiweld, and i~
extreme pressure properties to minimize metal damage from metal-to-metal contactunder high load conditions.
Polysulfides have been used to provido extreme pressure protection to
lubricating compositions. High levels of polysulfides generally lead to higher extreme
~; pressure protection. However, high~ leve!s of polysulfides can lead to copper
corrosion, seal compatibility, oxidation stability, and thermal stability problems. It
~; ~ IS beneficial to find a material that when combined with a polysulfide has good
extlreme pressure properties without the adverse effects caused by high levels of
polysulfide.
Dithiocarbamate acid esters and their preparation have been described in U.S.
Patent 2,710,872 (Thompson et al.~, 2,897,l52 (Elliott et al.), 3,890,360 (Malec3,
3,833,496 (Malec)? 4,064,265 (Varsanyi et al.), 4,758,362 (Butke), 4,885,365 (Lam),
and 4,957,643 (Lam).
'"~-.
i ~,
2~2911 68
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The sulfunzed compositions prepared from unsaturated compounds and
olefinic compounds have been described in U.S. Patents 4,119,549 (Davis),
4,119,550 (Davis et al.), 4,191,659 (Davis), and 4,344,854 (Davis et al.).
Summarv of the Invention
S This invention relates to a lubricating composition comprising a major amount
of an oil of lubricating viscosity, (A) at least one dithiocarbamate compound, and (B)
at least one organic polysulfide. The invention also relates to greases and aqueous
compositions which contain this combination. The compositions have good antiwearor extreme pressure properties. The combination also provides improved oxidationresistance and thermal stability to fluids.
Description of the Preferred Embodiments
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. l~xamples of hydrocarbyl groups include the following:
(1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, aromatic-9 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);(2~ substituted hydrocarbon substituents, i.e., those substituents containing
non-hydrocarbon groups which, in the context of this invention, do not alter thepredominantly 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.);
(3) heteroatom substituents, i.e., substituents which will, while having a
predominantly hydsocarbon 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.
'- '.', '' ,~
` 2 1 2 ~1 1 6 8 : ~
-3-
In general, no more than about 2, preferably no more than one, hetero
substituent will be present for every ten earbon 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.
S As described above, the compositions include the combination of (A) a
dithiocarbamate compound and (B) an organic polysulfide. Generally, from about
0.25 up to about 2, or from about 0.5 up to about 1.8, or from about 0.75 up to
about 1.5 of the dithiocarbamate compound (A) are used with each pa~t of the organic
polysulfide (B~. Here as well elsewhere in the specification, the ratio and range
limits rnay be combined. -
The dithiocarbam2te compounds include reaction products of a dithiocarbamic
acid or salt and an unsaturated amide, carboxylic acid, anhydride, or ester, or ether,
alkylene-coupleddithiocarbamate, andbis(S-alkyldithiocarbamoyl)disulfides. Inoneembodiment, the dithiocarbamate compounds are ashless, i.e. metal free. The
dithiocarbamate compounds (A) are prepared by reacting a dithiocarbamic acid or salt
with an unsaturated compound. The dithiocarbamate compounds may also be
prepared by simultaneously reacting an amine, carbon disulfide and an unsaturated
compound. Generally, the reaction occurs at a temperature from about 25C, or
from about 50C to about 125C, or to about 100C. U. S. Patents 4,758,362 and
4,997,969 describe dithiocarbamate compounds and methods of making the same.
These patents are hereby incorporated by reference for their disclosure of
~ithiocarbamate compounds and method of making the sarne.
The dithiocarbamic acid or salt used to prepare the dithiocarbamate compounds
ars 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
hydroc~rbyl 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.
In one embodiment, the amines are primary amines. Examples of primary
amines use~ul in the present invention include ethylamine, propylamine, butylamine,
2-ethylhexylamine, octylamine, and dodecylamine.
,~ .
2129~6~
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In one embodiment, the primary amine is a fatty (C8 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" arnines ~roducts available from Akzo
S Chemicals, Chicago, Illinois), such as Akzo's Armeen C, Armeen O, Armeen OL,
Arrneen 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.
Other useful primary amines include primary f ther amines, such as those
represented by the formula, R"(OR')XNH2, wherein R' is a divalent alkylene grouphaving about 2 to about 6 carbon atoms; x is a number from one to about 150, or
from about one to about five, or one; and R" is a hydrocarbyl group of about 5 to
about 15Q carbon atoms. An example of an ether amine is available under the nameSURFAM~ amines produced and marketed by Mars Chemical Company, Atlanta,
Georgia. Preferred etheramines are exemplified by those identified as SURFAM
P14B (decyloxypropylamine), SURFAM P16A (linear Cl6), SURFAM P17B
(tridecyloxypropylamine). The carbon chain lengths (i.e., C14, etc.) of the
SUR~AMS described above and used hereinafter are approximate and include the
oxygen ether linkage.
In one embodiment, the amine is a tertiary-aliphatic primary amine.
Generally, the aliphatic group, preferably an alkyl group, contains from about 4 to
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~-C(RI'~2-NH2, wherein R~ i5 a hydrocarbyl group containing from one to about 27
carbon atoms and Rl' is a hydrocarbyl group containing from 1 to about 12 carbonatoms. Such amines are illustrated by tert-butylamine, tert-hexylamine,
l-methyl-l-amino-cyclohexane, teirt-octylamine, tert-decylamine, tert-dodecylamine,
tert-tetradecylamine,tert-hexadecylamine,tert-octadecylamine,tert-tetracosanylamine,
and tert-octacosanylamine.
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
Cll-C14 tertiary alkyl primary amines and "Primene JMT" which is a similar mixture
of C,8-C22 tertiary alkyl primary amines ~both are available from Rohm and Haas
'':;','~ '''':'"'
21~9~68
` .
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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. Patent 2,945,749 which is hereby incorporated by reference ~or its teaching in
S this regard.
In another embodiment~ the amine is a secondary amine. Specific of
secondaryaminesincludedirnethylamine,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.
In one embodiment, the dithiocarbamate compound (A~ is prepared by reacting
one or more dit}liocarbamic 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
acid or salt and an unsaturated arnide 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. Patents
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.
In one embodiment, the d;thiocarbamate compound (A) is a reaction product
of a dithiocarbamic acid or salt with an unsaturated acid~ anhydride or ester.
~ixamples 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.
2~29:l6~
.
In one embodiment, the unsaturated carboxylic acid, or anhydride or ester
includes maleic, fumaric9 acrylic, methacrylic, itaconic, citraconic acids and esters.
The ester may be represented by one of the formulae: (R2)2C=C(R2)C(O)OR3, or
R3O-(O)C-HC=CH-C(O)OR3, wherein each R2 and R3 are independently hydrogen
or a hydrocarbyl group having 1 to about 18, or to about 12, or to about 8 carbon
atoms, R2 is hydrogen or an alkyl group ha~ing from 1 to about 6 carbon atoms. In
one embodiment, R2 is preferably hydrogen or a methyl group.
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.
In another embodiment, the unsaturated carboxylic ester is a vinyl ester. The
vinyl ester may be represented by the formula R4CH=CH-O(O)CR5, wherein R4 is
a hydrocarbyl group having from 1 to about 30, or to about 12 carbon atoms,
preferably hydrogen, and R5 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, vinylbutanoate, etc.
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 R6-CH - CH-OR7 wherein R6 is independently hydrogen or a hydrocarbylgroup having from 1 up to about 30, or up to about 24, or up to about 12 carbon
- atoms. R7 is a hydrocarbyl group defined the same as R6. Examples of vinyl ethers
include methyl vinyl ether, propyl vinyl ether, 2-e~hylhexyl vinyl ether and the like.
In one embodiment, the dithiocarbamate compound (A) is an alkylene-coupled
dithiocarbamate. The allylene-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 25C up to about
2129168
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~50C, or up to about 100C. U.S. Patent 3,876,550 issued to Holubec describes
alkylene dithiocarbamate compounds, and U.S. Patents 1,726,~7 and 1,736,429,
issued to Cadwell describe, phenylmethylene bis(dithiocarbamates) and methods ofmaking the same. These patents are incorporated by reference for their teachingsS 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.
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 dithiocarbamategroups 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., S2C12),
sulfur dichloride, sulfur monobromide, sulfur dibromide, or mixtures of any of the
above sulfur halides with elemental sulfur in varying amounts.
The sulfur halide utilized in the first stejp (A) may be sulfur monochloride
~i.e., S2C12), 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
olefims are disclosed below for the organic polysulfilde. 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.
The reaction between the sulfur intermediate and the dithiocarbamate salts
generally is conducted from ambient temperature to the reflux temperature of themixture. The reaction is conducted until the reaction is completed which is ~enerally
2~29~8
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from about 5 to about 24 hours. A~ the end of the reaction, the aques)us phase is
separatea, and the product is reco,rered from the organic phase.
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
S 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
par~ally wit}l sulfide groups. The bis(S-allyldithiocarbamoyl) disulfides are described
in U.S. Patent 2,599,350, issued to Rudel et al. This patent is incorporated by
reference for its disclosure of bis(S-alkyldithiocarbamoyl) disulfide.
In the compositions of the present invention, the dithiocarbamate compounds
(A) esters are used in combination with (B) an organic polysulfide. The organic
polysulfides are generally characterized as having sulfide linkages having from at least
2 to about 10 sulfur atoms, or from 2 to about 6 sulfur atoms, or from 2 to about 4
sulfur atoms. The organic polysulfides are generally di-, tri- or tetrasulfide
compositions with trisulfide compositions prefened. The organic polysulfides maybe a mi~cture of di-, tri- or tetrasulfide materials with materials having a majority of
trisulfide being preferred. Materials having at least 70% trisulfide are preferred, with
materials containing greater than 80% trisulfide more preferred.
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, or from 20% to about 50%, and or
from about 35 % to about 45 % sulfur. Materials which may be sul~urized to form the
organic polysulfides include oils, fatty acids or esters, or olefins, or polyolefins.
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), and synthetic
unsaturated esters or glycerides.
Fatty acids generally contain from about 8 up to about 30, or from about 12
up to about 24 carbon atoms. Examples of fatty acids include such as palmitoleic,
oleic, ricinoleic, linoleic, oleostearic~ etc. Sulfurized fatty acid esters prepared from
212~16~ ;
,
9 : .
mixed unsaturated fatty acid esters such as are vbtained from animal fats and
vegetable oils including tall oil, linseed oil, rape oil, fish oil, etc., also are usefi l.
The olefinic compounds which may be sulfurized are diverse in nature. They
contain at least one olefinic double bond, which is defined as a non-aromatic double
bond; that is, one connecting two aliphatic carbon atoms. In its broadest sense, the
olefin may be defined by the forrnula
,
R-'R~2c=cR-3l~-
wherein each of R-l, R~2, R-3 and R4 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 5)3, -COOR 5, -( ON(R 5)2~ -COON(R 5)4, -COVM, -CN, -X, -YR 5
or -Ar, wherein: each R-5 is independently hydrogen, alkyl, alkenyl, aryl, substituted
alkyl, substituted alkenyl or substituted aryl, with the pro~iso that any two R-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-~, R-2, R-3 and R-4 may also together form an
alkylene or substituted alkylene group; i.e., the ole~lnic compound may be alicyclic.
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, partieularly the former, are preferred, and especially terminal
monoolefimic hydrocarbons; that is, those compounds in which R~3 and R'4 are hydro-
gen and R~l and R92 are alkyl or aryl groups, especially alkyl groups (that is, the
olefin is aliphatic) having 1 up to about 30, or up to about 16, or up to about 8, and
or up to about 4 carbon atoms. Olefinic compounds having about 3 to about 30 andespecially about 3 to about 16 (most often less than about 9) carbon atoms are
particularly desirable.
Isobutene, propylene and their dimers, trimers and tetramers, and mixtures
thereof are especially preferred ole~lnic compounds. Of these compounds, isobutyl-
212916~
, .
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ene and diisobutylene are particularly desirable because of their availability and the
particularly high sulfur containing compositions which can be prepared therefrom.
In one embodiment, the organic polysulfide comprises a sulfurized olefin,
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. Patent
2,70X,199
In one embodiment, sulfurized olefins are produced by (1) reacting sulfur
mono hloride with a stoichiometric excess of a lower olefin, e.g. contaming less than
eight carbon atoms, (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 isdescribed in U.S. Patent 3,471,404, and ~he disclosure of U.S. Patent 3,471,404 is
hereby incorporated by reference for its dis~ussion of this procedure for preparing
sulfurized olefins and the sulfurized ole~ms thus produced. Generally, the olefin
reac~ant generally contains from about 2 to 5 carbon atoms and examples include
ethylene, propylene, butylene, isobutylene, amylene, etc.
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. Patents 4,119,549, 4,119,550, 4,191,659, and 4,344,854, the
disclosures of which are hereby incoIporated by reference for their description of the
2S preparation of useful sulfurized compositions.
The following e~cample relates to organic polysulfides.
Example 1
Sulfur (526 parts, 16.4 moles) is charged to a jacketed, high-pressure reaGtor
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 sul~lde are charged
,:
2129168
to the reactor. The reactor is heated using steam in the external jacket, to a
temperature of about 182C over about l.S hours. A maximum pressure of 1350
psig is reached at about 168 C during this heat-up. Prior to reaching the peak
reaction temperature, the pressure starts to decrease and continues to decrease steadily
S as the gaseous reactants are consumed. After about 10 hours at a reaction
temperature of about 182CC, ~he pressure is 310-340 psig and the rate of pressure
change is about 5-10 psig per hour. The unreacted hydrogen sulfide and isobuteneare vented to a recovery system. Af~er the pressure in the reactor has decreased to
atmospheric, the sulfurized mixture is recovered as a liquid.
The mixture is blown with nitrogen at about 100C to remove low boiling
materials including unreacted isobutene, mercaptans and monosulfides. The residue
after nitrogen blowing is agitated with 5% Super Filkol and filtered, using a
diatomaceous earth filter aid. The filtrate is the desired sulfurized composition which
contains 42.5 % sulfur.
Phosphorus or Boron Agents (C~:
In one embodiment, the combination of a dithiocarbamate compound (A) and
organic polysulfide (B) is used with (C) at least one phosphorlls or boron containing
antiwear or exkeme pressure agent. In this embodiment, the phosphorus or boron
containing antiwear or extreme pressure agent (C) is present in an amount sufficient
to impart antiwear, antiweld, and/or extreme pressure properties to the lubricants and
functional fluids. The phosphorus or boron antiwear or extreme pressure agents ~C)
are typically present in the lubricants and functional fluids at a level of up to about
20% by weight, preferably up ~o about 105~o by weight, based on the total weight of
the lubricant, functional fluid, or grease. Typically, the phosphorus or boron
containing antiwear or extreme pressure agent is present in the lubricants and
functional fluids at a level from about 0.01%, or from about 0.05%, or from about
0.08% by weight. The phosphorus or boron containing antiwear or extreme pressureagent 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, or greater than 0.05% phosphorus.
Examples of phosphorus or boron containing antiwear or extreme pressure
agents (C) include a metal thiophosphate; a phosphoric acid ester or salt theréof; a
., ~,
2~2916~ ~
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phosphite; a phosphorus-containing carboxylic acid, ester, ether, or amide; a borated
dispersant; an alkali metal borate; a borated overbased metal salt; a borated fatty
amine; a borated phospholipid; and a borate ester. The phosphorus acids include the
phosphoric, phosphonic, phosphinic and thiophosphoric acids including dithiophos-
phoric acid as well as the monothiophosphonc acid, thiophosphinic and
thiophosphonic acids.
In one embodiment, phosphorus or boron containing antiwear or extreme
pressure agent (C) is a phosphorus acid ester prepared by reacting one or more
phosphorus acid or anhydride with an alcohol containing from one, or from 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 pentoxide9 phosphorus trioxide,phosphorus tetroxide, phosphoric acid, phosphsrous acid, phosphorus halide, lower
phosphorus esters, or a phosphorus sulfide, including phosphorus pentasulfide, and
the like. 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, and oleyl alcohols, and phenols, such as
cresol. Examples of commercially available alcohols include Alfol 810 (a mixture of
- 20 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 Cl~-C28 primary alcohols having
mostly C20 alcohols as determined by ~LC (gas-liquid-chromatography~); and Alfol22+ alcohols (Cl8-c28 primary alcohols containing primarily C22 alcohols). Alfolalcohols are available from Continental Oil Company.
Another example of a commercially available alcohol mixtures are Adol 60
(about 75% by weight of a straight chain C22 primary alcohol, about 15% of a C
primary alcohol and about 85'o of C~18 and C24 alcohols) and Adol 320 (oleyl alcohol).
The Adol alcohols are marketed by Ashland Chemical.
A variety of mixtures of monohydric fatty alcohols derived from naturally
occurring triglycerides and ranging in chain length of from C8 to C18 are available
from Procter & Gamble Company. These mixtures contain various amounts of fatty
. . ~: ~ '
~29~16g
:
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alcohols containing mainly 12, 14, 16, or 18 earbon atoms. For example, CO-1214
is a faKy alcohol mixture containing 0.5% of Clo alcohol, 66.0% of Cl2 alcohol,
26.0% of Cl~, alcohol and 6.5% of C,6 alcohol.
Another group of commercially available mixtures include the "Neodol"
products available from Shell Chemical Co. For example, Neodol 23 is a rnixture
of Cl2 and Cl3 alcohols; Neodol 25 is a mixture of Cl2 and Cl5 alcohols; and Neodol
45 is a mixture of Cl4 to Cl5 linear alcohols. Neodol 91 is a mixture of Cg, C10 and
Cll alcohols.
Fatty vicinal diols also are useful and these include those available from
Ashland Oil under the general trade designation Adol 114 and Adol 158. The former
is derived from a straight chain alpha olefin fraction of Cll-C14, and the latter is
derived ~rom a Cl5-CI8 fraction.
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.
In another embodiment, the phosphorus or boron antiwear or extreme pressure
agent (C) is a thiophosphorus acid ester or salt thereof. Ihe 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.
In one embodiment, the phosphorus acid ester is a monothiophosphoric acid
ester or a monothiophosphate. Monothiophosphates may be prepared by the reactionof 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 olefin or a sulfur coupled dithiophosphate. Blemental sulfur is a preferred
sulfur source. The preparation of monothiophosphates is disclosed in U.S. Patent4,755,311 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 compositioncontaining a sulfur source, such as a sulfurized olefin. The phosphite may react with
2~29~
-14-
the sulfur source under blending conditions (i.e., temperatures from about 30C. to
about 100C. or higher) to ~orm the monothiophosphate.
In another embodiment, the phosphorus or boron antiwear or extreme pressure
agent (C) is a dithiophosphoric acid or phosphorodithioic acid. The dithiophosphoric
acid may be represented by the formula (R8O)2PSSH wherein each R8 is
independently a hydrocarbyl group containing from about 3 to about 30 carbon atoms,
o~ up to about 18, or to about 12, or to about 8. Examples R8 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.
IllustIative lower allylphenyl R8 groups illclude butylphenyl, amylphenyl, heptyl-
phenyl, etc. Examples of mixtures of R8 groups include: l-butyl and l-octyl;
l-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.
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
phosphoNs acid, anhydride, or lower ester. The epoxide is generally an aliphaticepoxide 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 glycvls having from 1 to
about 12, or from about 2 to about 6, or from 2 or 3 carbon atoms, or aromatic
glycols. Glycols include ethylene glycol9 propylene glycol, catechol, resorcinol, and
the like. The dithiophosphoric acids, glycols, epoxides, inorganic phosphorus
reagents and methods of reacting ~he same are described in U.S. patent 3,197,405and U.S. patent 3,544,465 which are incorporated herein by reference for the;r
disclosure to these.
The following Examples P-l and P-2 exemplify the preparation of useful
phosphorus acid esters.
Example P-l
Phosphoms pentoxide (64 grams) is added at 58C over a period of 45
minutes to 514 grams of hydroxypropyl O,O-di(4-methyl-2pentyl)phosphorodithioate(prepared by reacting di(4-methyl-2pentyl)-phosphorodithioic acid with 1.3 moles of
propylene oxide at 25C). The mixture is heated at 75C for 2.5 hours, mixed with
2~29~8
-15-
a diatomaceous earth and filtercd a~ 70C. The filtrate contains 11.8% by weightphosphorus, 15.2% by weight sulfilr, and an acid number of X7 (bromophenol blue).
Example P-2
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~C is heated at 85 C for 3 hours and filtered. The filtrate contains 15.35'o by
weight phosphorus, 19.6% by weight sulfur, and an acid number of 126
(bromophenol blue).
Acidic phosphoric acid esters may be further reacted with an amine compound
or 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 lubncating
composition. Alternatively, the salts may also be formed in situ when the acidicphosphorus acid ester is blended with other components to form a fully formulated
lubricating composition.
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
arnines, secondary amines or tertiary amines. Useful amines include those aminesdisclos~l in U.S. Patent 4,234,435 at Col. 21, line 4 to Col. 27, line 50, thesepassages being incorporated herein by reference. The amines have been described
above. Examples of monoamines include methylamine, ethylamine, propylamine,
butylamine, octylamine, and dodecylamine, dimethylamine, diethylamine,
dipropylamine, dibutylamine, methylbutylamine, ethylhexylamine, trimethylamine,
tributylamine, methyldiethylamine, ethyl dibutylamine, etc.
In another embodiment, the amines may be hydroxyhydrocarbyl amines, such
as those represented by the formula
/(RIlO)zH~ . (RIIO)~'H
Rgt~ R107~(R'1)~
whereill: R9 i~ a hydrocarbyl group generally containing from about 6 to about 30
carbon atoms; Rlo is an alkylene group having from about two to about twelve carbon
atoms, or an ethylene or propylene group; R" is an alkylene group containing up to
212~8
-16-
about 5 carbon atoms; y is zero or one; and each ~ is independently a number from
zero to abou~ lû, with the proviso that at least one z is zero.
Useful hydroxyhydrocarbyl amines wherein y in the above formula is zero
include 2-hydroxyethylhexylamirle; 2-hydroxyethyloctylamine;
2-hydroxyethylpentadecylamine;2-hydroxyethyloleylamine;2-hydroxyethylsoyamine;
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 x is at least 2, as for example, 2-hydroxyethoxyethylhexylamine. -
A number of hydroxyhydrocarbyl amines wherein y in the above formula is
zero are aYailable from the Akzo Chemical, under the general ~rade designations
"Ethomeen" and "Propomeen". Specific examples of such products include~
Ethomeen C/15 which is an ethylene oxide condensate of a cocoamine containing
about 5 moles of ethylene oxide; Ethomeen C/20 and C/25 which are ethylene oxidecondensation products from cocoamine containing about 10 and 15 moles of ethylene
oxide, respec~ively; Ethomeen O/12 which is an ethylene oxide condensation product
of oleylamine containing about 2 moles of ethylene oxide per mole of amine;
~thomeen S/15 and S/20 which are ethylene oxide condensation products with
stearylamine 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 condensationproducts of tallowamine containing about ~29 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.
Commercially available examples of alkoxylated amines where y in the above
formula is one include Ethoduomeen T/13 and T/20 which are ethylene oxide
condensation products of N-tallowtrimethylenediamine containing 3 and 10 moles of
ethylene oxide per mole of diarnine, respectively. ~ -
The fatty diamines include mono- or dialkyl, symmetrical or asymmetrical
ethylene diamines, propane diamines (1,2, or 1,3), and polyamine analogs of the
above. Suitable commercial fatty diamines 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).
"Duomeens" are commercially available from Armak Chemical (: o., Chicago,
~ 2 ~
-17-
Illinois. In one embodiment, the secondary amines may be cyclic amines such as
piperidine, piperazine, morpholine, etc.
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
S compound capable of forming a metal salt. E~amples of metal bases include metal
oxides, hydroxides, carbonates, su1fates, borates, or the like. The metals of the metal
base include Group IA, IIA, IB through VIIB, and VIII metals (S:~AS version of the
Periodic Table of the Elements). These metals include the alkali metals, alkaline
earth metals and transition rnetals. In one embodiment, the metal is a Group IIAmetal, such as calcium or magnesium, Group IIB metal, such as zinc, or a Group
VIIB metal, such as manganese. In one embodiment, the metal is magnesium,
calcium, manganese or zinc. Examples of metal compounds which may be reacted
with the phosphorus acid include zinc hydroxide, zinc oxide, copper hydroxide,
copper oxide, etc.
lS In one embodiment, phosphorus or boron containing antiwear or extreme
pressure agent (C) 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(cyclo-
hexyl) dithiophosphate, ~inc di~;sobutyl) dithiophosphate, calcium di(hexyl)
dithiophosphate, zinc isobutyl isoamyl dithiophosphate, and zinc isopropyl secondary-
butyl dithiophosphate.
The following Examples P-3 to P-6 exemplify ~he preparation of useful
phosphorus acid ester salts.
Bxample P-3
A reaction vessel is charged with 217 gMms of the filtrate from Example P-l.
A commercial aliphatic primary amine (65 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- -
60C. 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.
2~2911~8
-18-
Example P-4
The filtrate of Example P-2 (1752 grams) is mixed at 25-82 ' C with 764 grams
of the aliphatic primary amine used in of ~xample P-3. The resulting product has9.95% phosphorus, 2.72% nitrogen, and 12.6% sulfur.
Example P-5
Phosphorus pentoxide (852 grams) is added to 2340 gMms of iso-octyl alcohol
over a period of 3 hours. The temperature increases ~rom room temperature but ismaintained below 65C. After the addition is complete the reaction mixture is heated
to 90C and the temperature is maintained for 3 hours. Diatomaceous earth is a~ded
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 neutrali~ation number
(phenolphthalein).
The above filtrate is mixed with 200 gMms 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 Ç0-70C under a pressure of 30 mm Hg. The resulting productmixture is filtered using a diatomaceous earth. The filtrate has 8.58% zinc and
7.03% phosphorus.
Example P-6
Phosphorus pentoxide (208 gMms~ is added to the product prepared by
reacting 280 grams of propylene oxide with 1184 grams of O,O'-di-isobutylphos~
phorodithioic acid at 30-60C. The addition is made at a temperature of 50-60 C and
~he resulting mixture is then heated to 80C and held at that temperature for 2 hours.
The commercial aliphatic primary amine identified in E~ample P-3 (384 grams) is
added to the mixture, while the temperature is maintained in the range of 30-60C.
The reaction mixture is filtered through diatomaceous earth. The filtrate has 9.31%
phosphorus, 11.37% sulfur, 2.50~d nitrogen, and a base number of 6.9 (bromophenol
blue indicator).
In another embodiment, the phosphorus or boron antiwear or extreme pressure
agent ~C) 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 siescribed
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
2~l2~1~8
- 1 9- ~ . ,
carboxylic acids are those having the formula R,2COOH, wherein Rl2 is an aliphatic
or alicyclic hydrocarbyl group preferably free from acetylenic ~msaturation. Rl2generally contains from about 2 up to about 40, or from about 4 up to about 24, or
to up about 12 carbon atoms. In one embodiment, R,2 contains from about 4 up to
S about 12, or from about 6 up to about 8 carbon atoms. In one embodiment, Rl2 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
carboxylic acid is 2-ethylhexanoic acid.
The metal salts may be prepared by merely blending a metal salt of a
dithiophosphoric acid with a metal salt of a carboxylic acid in the desired ratio. The
ratio of equivalents of dithiophosphoric acid to earboxylic 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 û.5
up to about 4.5 to one, or 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 the number of carboxy groups therein.
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 thispurpose is its atomic weight divided by its valence. The temperature at which the
metal salts are prepared is generally between about 30C and about 150C, or up to
about 125C. U.S. Patents 4,3~8,154 and 4,417,990 descAbe procedures for
preparing these metal salts and disclose a number of examples of such metal salts.
These patents are hereby incolporated by reference for those disclosures.
2129~6g ~
.
-20-
In another embodiment, the phosphorus or boron containing antiwear or
extreme pressure agent (C) is a phosphite. The phosphite may be a di- or
trihydrocarbyl phosphite. Generally, each hydr~arbyl group independently has from
1 up to about 24, or from about 2 up to about 18, or up to about 8 carbon atoms.S Examples of specific hydrocarbyl groups include propyl, butyl, hexyl, heptyl, octyl,
oleyl, linoleyl, stearyl, phenyl, naphthyl, heptylphenol, and mixtures of two or more
of thereof. In one embodiment, each hydrocarbyl group is independently propyl,
butyl, pentyl, hexyl, heptyl, oleyl, or phenyl. Phosphites and their preparation are
known and many phosphites are available commercially. Particularly useful
phosphites are dibutyl phosphite, trioleyl phosphite and triphenyl phosphite.
In one embodiment, the phosphorus or boron containing antiwear or extreme
pressure agent (C) is a phosphorus containing amide. The phosphorus containing
amides are prepared by the reaction of one of the above describe phosphorus acids,
prefeIably a dithiophosphoric acid, with an one of the above described unsatuMted
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 containin~ amides are known in the art and are
disclosed in U.S. Patents 4,670,169, 4,770,gO7, and 4,876,374 which are
incorporated by reference for their disclosures of phosphorus amides and their
preparation. ~;
In one embodiment, the phosphorus or boron antiwear or extreme pressure
agent ~C) is a phosphorus containing carboxylic ester. The phosphorus containingcaIboxylic esters are prepared by reaction of one of the above-described phosphorus
acids, preferably a dithiophosphoric acid, and an one of the a~ove describedl unsatu~
rated carboxylic acid or ester. If the ~arboxylic acid is used, the ester may then be ~ ; 3
formed by subsequent reaction of the phosphoric acid-unsaturated carboxylic acidadduct with an alcohol, such as those described herein.
In one embodiment, the phosphorus or boron containing antiwear or extreme
pressure agent (C3 is a reaction product of a phosphorus acid, preferably a ; ~
dithiophosphoric acid, and one of the above described vinyl ethers. ;
2~ 2~ 6~
In another embodiment, the phosphorus or boron containing antiwear or
extreme pressure agent (C) is an alkali metal borate. Alkali metal borates are
generally a hydrated particulate alkali met~l borate which are known in the art.Alkali metal borates include mixed alkali and alkaline earth metal borates. These
alkali metal boMtes are available commercially. Representative patents disclosing
suitable alkali metal borates and their methods of manufacture include U.S.
3,9973454; 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.
In another embodiment, the phosphorus or boron containing antiwear or
extreme pressure agent (C) is a borated overbased metal salt. Borated overbased
compounds are generally prepared by reacting an overbased metal salt, such as a
carbonated overbased metal salt with a boron compound. The boron compounds
include boron oxides, boron acids, boric acid, boron anhydrides, boron amides and
various borate esters, such as mono-, di-, and tri-organic esters of boric acid with
alcohols or phenols. Preferred borate esters are those derived from alcohols having
less than about 8 carbon atoms.
The overbased metal salts include basic salts (i.e., overbased salts) of alkali
or alkaline earth metals with sulfonic acids, carboxylic acids, phenols or organic
phosphorus acids. The phosphorus acids include those prepared by the treatment of
a polyalkene with a phosphorizing agent, such as phosphorus pentasulfide. The most
commonly used metals are sodium, potassium, lithium, calcium, and magnesium. Th~term "basic salt" is used to designate metal salts wherein the metal is present in
stoichiometrically larger amounts than the organic acid radical. The overbased salts
~5 and borated overbased salts are prepared by means known to those in the art.
Examples of borated overbased compounds include borated overbased sodium
~: - " .: ~
alkylbenzene sulfonate, sodium borated overbased polybutenyl (Mn=gSO) substituted ~:
succinate, ~md borated overbased magnesium alkylbenzene sulfonate.
Patents describing overbased salts, methods of making the salts and
components for making the same include U.S. Patents 2,501,731; 2,616,911;
'`'-' ~ '
;` ~129~8
-22~
?,777,874; 3,384,S85; 3,320,162; 3,488,284 and 3,629,109. The disclosure of these
patents are hereby incorporated by reference. Borated overbased compositions,
lubricating compositions contain the same and methods of preparing borated
ove~ased compositions are found in U.S. Patents 4,744,920, 4,792,410, and PCT
publicationWO88/03144. Thedisclosureofthesereferencesareherebyincorporated
by reference.
In another embodiment, the phosphorus or boron antiweiar or extreme pressure
agent (C) is a borated fatty amine. The borated amines are prepared by reacting one
or more of the above boron compounds, such as boric acid or borate ester, with afatty amine, e.g. an amine having from about four to about eighteen carbon atomsThe borated fatty amines are prepared by reacting the amine with the boron
compound at about 50C to about 300C, preferably about 100C to about 250C,
and at a ratio of 3:1 to 1:3 equivalents of amine to equ;valents of boron
compound.
In another embodiment, the phosphorus or boron containing antiwear or
extreme pressure agent (C) is a borated epoxide. The borated fatty epoxides are
generally the reaction product of one or more of the above boron compounds, withat least one epoxide. The epo7dde is generally an aliphatic epoxide having at least 8,
or at least about 10, or at least about 12, up to about 24, or up to about 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 about 14 to about 16 carbonatoms and from about 14 to about 18 carbon atoms. The borated fatty epoxides aregenerally known and are disclosed in U.S. Patent 4,584,115. This patent is
incorporated by reference for its disclosure of borated fatty epoxides and methods for
preparing the same.
In another embodiment, the phosphorus or boron containing antiwear or
extreme pressure agent (C) is a borated phospholipid. The borated 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, ; ~
:,";', '''. ',','".'
2~2915~
such as reaction products of carboxylic acrylating 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
S 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.
The reaction of the phospholipid, the boron compound, and the optional
components usually occurs at a temperature from about 60C, or about 90C up to
about 200(:, up to about 150C. The reaction is typically accomplished in about0.5, or about 2 up to about 10 hours. aenerally, from one equivalent to about three
equivalents of the phospholipid are reacted with each boron atom of the boron
compound. An equivalent of phospholipid is determined by the number of
phosphorus atoms in the phospholipid. The equivalent of boron compound is
determined by the number of boron atoms in the boron compound. When the
combination includes additional components, one atom of the boron compound is
reacted with from one to about three equivalents of the combination. The equivalents
of the combination is determined by the total equivalents of the phospholipid and the
additional component.
Lubricants
As previously indicated, the combination of a dithiocarbamate compound (A)
and an organic polysulfide (B) is 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
' '..' '' ''' ' "'
2~29168
-2~-
engines and turbines and the like. Automatic or manual transmission fluids9 transa~le
lubricants, gear lubricants, including open and enclosed ge~r lubricants, tractor
lubricants, metal-working lubricants, hyd~aulic fluids and other lubricating oil and
grease compositions can also benefi~ from the incorporation therein of the composi-
tions of the present invention. They may also be used in lubricants for wirerope,
walking cam, way, rock drill, chain and conveyor belt, worm gear, bearing, and rail
and flange applications.
The combination of the dithiocarbamate containing compound and the organie
polysulfide may be used in lubricants or in concentrates. The concentrate may
contain the combination or other components used in prepadng 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 diseussed below. In one embodiment, the concentrates contain from about
0.01%, or from about 0.1%, or from about 1% up to about 70% or up to about 80%,
even up to about 90% by weight of the combination.
The dithiocarbamate compound (A) and the organic polysulfide (B) may be
present in a final product, blend, or concentrate in any amount effective to act as an
antiwear, antiweld, and/or extreme pressure agent in lubricating compositions.
Generally ~he components are each independently present in the lubricating compo~
si~ion in an amount from about O.01%, or from about O. 1%, or from about O.5 %, or
from about 1% up to about 10%, or up to about 5% by weight. In one embodiment,
when the components are used in oils, such as gear oils, they are each preferably
present in an amount from about 0.5%, or from about 1%, or from about 1.5% up
to about 8%, or up to 5%, by weight of the lubricating composition. When the
dithiocarbamate compound and the organic polysulfide are used in hydraulic fluids,
they are each generally present in an amount from about 0.01%, or from about 0.3%
up to about 2%, or up to about 1 % by weight of the hydraulic fluid.
In one embodiment, the lubricating composition contains less than about 2%,
or less than about 1.5%, or less than about 1.0%, or less than about 0.5% by weight
of reaction product of a polyisobutenyl substituted succinic anhydride and a
~2~8
-2~-
ps)lyaLlcylene polyamine. In another embodiment, the lubricatin~ compositions, such
2S gear lubricants, contain less than 2%, or less than 1.5%, or less than 1% by
weight of a dispersant, such as those described herein. The dispersants may include
carboxylic dispersants, amine dispersants, Mannich dispersants, post-treated
S dispersants and polymeric dispersants.
The lubricating compositions and methods of this invention employ an oil of
lubricating viscosity9 including natural or synthetic lubricating oils and mi~tures
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. Patent
4,582,618 (column 2, line 37 through column 3, line 63, inclusive3, herein incorpo~
rated by reference for its disclosure to oils of lubricating viscosity.
In one embodiment, the oil of lubricating viscosity or a mixture of oils 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 100C. In one
embodiment, the lubricating compositions have ~n SAE gear viscosity number of atleast about SAE 65, or at least about SAE 75. The lubricating composition may also
have a so-called multigrade rating such as SAE 7SW-80, 75W-90, 75YV-90, or 80W-
90. Mllltigrade lubricants may include a viscosity improver which is 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-propylenecopolymers, or polybutylene rubbers, including hydrogenated rubbers, such as
styrene-butadiene or styrene-isoprene rubbers; or polyacrylates, including
polymethacrylates. Preferably the viscosity improver is a polyolefin or
polymethacrylate, more preferably polymethacrylate. Viscosity improvers available
commercially include AcryloidrU viscosity improvers available from Rohm & Haas;
2~2~68
-26-
ShellvisTY rubbers available from Shell Chemical; and Lubrizol 3174 available from
The Lubrizol Corporation.
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 SA
crankcase viscosity number of lOW, 20W, or 30W lubricants. The lubricating
composition may also haYe a so called multi-grade rating such as SAE 5W-30, lOW-30, lOW-40, 20W-50, etc. As described above, multi-grade lubricants include a
viscosity improver which is forrnulated with the oil of lubricating viscosity to provide
the above lubricant grades. ~;
Other Aclditives
The invention also contemplates the use of other additives together with the
combination of a dithiocarbamate compound and an organic polysulfide. Such
additives include, for example, detergents and dispersants, corrosion- and
o~cidation-inhibiting agents, pour point depressing agents, extreme pressure agents,
antiwear agents, color stabilizers and anti-foam agents.
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 basie 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.
The dispersants are known in the art and the following are illustrative.
(1) "Carboxylic dispersants" are the reaction products of carboxylic acids
(or derivatives thereof) containing at least about 34 or at least about 54 carbon atoms
and nitrogen containing compounds (such as amine), organic hydroxy compounds
(such as phenols and alcohols), andtor basic inorganic materials. These reactionproducts include imide, amide, and ester reaction products of carboxylic acylating
agents. The carboxylic dispersants are generally prepared by reacting one or more
of hydrocarbyl substituted carboxylic acylating agent with an amine, such as a
2~2~68
-27-
polyethylenepolyamine, or hydroxy containing compound such as an alcohol. The
hydrocarbyl group may be derived from a polyalkene having a number aYerage
molecular weight from about 800 up to about 5000, or up to about 2500. Exarnplesof these materials include succinimide dispcrsants and carboxylic esteT dispersants.
S Examples of these "carboxylic dispersants" are des- ribed in BAtish Patent 1,306,529
and in many U.S. Patents including the following: 3,219,666, 3,316,177, 3,340,28-
1, 3,351,552, 3,381,022, 3,4339744, 3,444,170, 3,467,668, 3,501,405,
3,542,680, 3,576,743, 39632,511, 4,234,435, and Re 26,433.
(2) "Amine dispersants" are the reaction products of relatively high mo-
lecular weight aliphatic or alicyclic halides and amines, preferably polyalkylene
substituted polyamines. Examples thereof are described for example, in the following
U.S. Patents: 3,275,554, 3,438,757, 3,454,555, and 3,565,804.
(3) "Mannich dispersants" are the reaction products of alkylphenols and
aldehydes (especially formaldehyde) and amines (especially amine condensates andpolyallylenepolyamines). The matenals described in thefollowing U.S. Patents areillustrative: 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.
(4) "Post-treated dispersants" are the produt~ts obtained by post-keating the
carboxylic, amine or Mannich dispersants with reagents such as urea, thiourea,
~bon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted suc-
cinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the
like. Exemplary materials of this kind are described in the following U.S. Patents:
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.
(5) "Polymericdispersants"areinterpolymersofoil-solubilizingmonomers
such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with
monomers containing polar substituents, e.g., arninoalkyl acrylates or acrylamides and
poly-(oxyethylene)-substituted acrylates. Polymeric dispersants include esters of
styrene-maleic anhydride copolymers. Examples thereof are disclosed in the
-` 2129~8
-28-
following U.~. Patents: 3,329,658, 3,449,250, 3,519,656, 3,666,730, 3,687,849,
and 3,702,300.
The above-noted patents are incorporated by reference herein for their
disclosures of dispersants.
S Auxiliary extreme pressure agents and corrosion- and oxidation-inhibiting
agents which may be inclulded in the lubricants of the invention are exemplified by
chlonnated aliphatic hydrocarbons, such as chlorinated wax; sulfurized alkylphenol;
phosphosu1furized hydrocarbons, such as the reaction product of a phosphoms sulfide
with turpentine or methyl oleate; metal thiocarbamates, such as zinc dioctyldithioc-
arbamate, and barium diheptylphenyl dithiocarbamate. Many of the above-mentionedextreme pressure agents and corrosion- and oxidation-inhibitors also serve as antiwear
agents.
Pour point depressants are an additive often included in the lubricating oils de-
scribed herein. Examples of useful pour ~int depressants are polymethacrylates;
polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and
aromatie 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. Patents 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.
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.
The following examples relate to lubricating compositions containing the
combination of a dithiocarbamate compound and an organic polysulfide.
- 2129~8
-29~
Example I
A lubricaslt is prepared by incorporating 2 % by weight of the dithiocarbamate
compound prepared by reacting dibutyl amine, carbon disulfide and methyl acrylate ~-
and 2% by weight of the product of Example 1 into a SAE lOW-40 lubricating oil
mixture. ~ -
Example II
A gear lubricant is prepared by incorporating 2.5% by weight of the product
of Example 2 and 2% of the product of Example 1 into an SAE 80W-90 lubricating
oil mixture.
Example III ~ ~ -
A gear lubricant is prepa~ed by incorporating 2 % by weight of the ~ ~ ~
- . ~ .
dithiocarbamic compound of Example I, 1.9% by weight of the product of Example
1; 1.5% by weight of the product of Example P-3 into an SAE 80W-~0 lubricating
oil mixture.
ExamRle IV
A lubricant is prepared as described in F,xample III except a SAE lOW-40
lubricating oil mixture is used in place of the SAE 80W-90 lubricatin~ oil mixture.
~xample V
A gear lubricant is prepare by incolporating 2.2% by weight of a
dithiocarbamate compound prepared by reacting diamylamine, carbon disulfide and
acrylamide, 2% by weight of the product of Example 1, and 1% by weight of a
borated overbased compound prepared by reacting bonc acid with a sodium overbased
allyl benzene sulfonic acid, having a metal ratio of 19, into an SAE 80W-90
lubricating oil mixture.
Example VI
A lubricant is prepared as described in Example V except 0.8% by weight of
a borated dispersant prepared by a reacting boric acid with the reaction product of a
polybutenyl (Mn 950) substituted succinic acylating agent and a polyalkylene
polyamine is included in the lubricant.
'' '' ~ ' ~
.~ . -: -
, . . . ~ .
. .
,.
-
212~168
:
-30
Example VII -
A hydraulic fluid is prepared by incorporating 0.5% by weight of the
dithiocarbamate compound of Example V, 0.1% by weight of the product of Example
1, 0.005% by weight tolyltriazole, and 0.25% by weight of 2-6-di-tertiary butyl -
phenol into a hydraulic base stock lubricating oil mixture.
Example VIII
-
A oil based metalworking fluid is prepared by incorporating 2.5% parts by
weight of the dithiocarbamate compound of Example I and 2.5% by weight of the
product of Example 1 into a metalworking lubricating oil mixture.
Qrease
Where the lubricant is to be used in the form of a grease, the lubricating oil
generally is employed in an amount sufficient to balance the total grease composition
and, generally, ~he grease compositions will contain various quantities of thickeners
and other additive components to provide desirable properties. The dithiocarbamate
compound and the organic polysulfide are each independently present in an amountfrom about 0.5% up to about 10%, or from about 1% up to about 5% by weight.
A wide variety of thickeners can be used in the preparation of the greases of
this invention. The this kener is employed in an amount from about 0.5 to about 30
percent, and preferably from 3 to about 15 percent by weight of the total greasecomposition. Including among the thickeners are alkali and alkaline ea~th metal soaps
of fatty acids and fatty materials having from about 12 to about 30 carbon atoms.
The metals are typified by sodium, lithium, calcium and barium. Examples of fatty
materials include stearic acid, hydroxysteanc acid, stearin, oleic acid, palmitic acid~
rnyristic acid, cottonseed oil acids, and hydrogenated fish oils.
Other thickeners include salt and salt-soap complexes, such as calcium
stearate-acetate (U.S. Patent 2,197,263), barium stearate-acetate (U.S. Patent
2,564,561~, calcium stearate-caprylate-acetate complexes (U.S. Patent 2,999,066),
calcium salts and soaps of low-intermediate- and high-molecular weight acids and of
nut oil acids, aluminum stearate, and aluminum complex thickeners. Useful
thickeners include hydrophilic clays which are treated with an ammonium compound
;'''~ '.
--
:::
2 3 ~ 6 ~
-31-
to render them hydrophobic. Typical ammonium compounds are tetraalkyl
arnmonium chlorides. These clays are generally crystalline complex silicates. These
clays include bentonite, attapulgite, hectorite, illite, saponite, sepiolite, biotite,
vermiculite, zeolite clays and the like.
Example G-l
A ~rease is prepared by incorporating 0.5 % by weight of the dithiocarbamat~
compound of Example I and 0.5% by weight of the product of Example 1 into a
Southwest Petr~chem Lithium 12 hydroxy base grease.
Example G-2
A-~rease is prepared by incorporating 0.25 % by weight of the dithiocarbamate
compoundof Example I, 0.2$% by weight of the product of Example 1, 0.5% by
weight of the product of Example P-3, and 1% by weight of tolyltriazole into a
Southwest Petro-Chem Lithium 12 hydroxy base grease.
Aquçous Compositions
~he invention also includes aqueous compositions characterized by an aqueous
phase with the combination of the dithiocarbamate compound an~ the organic
polysulfide dispersed or dissolved in said aqueous phase. The water-based functional
fluids may be in the form of solutions; or micelle dispersions or microemulsionswhich appear to be true solutions. Preferably, this aqueous phase is a continuous
aqueous phase although, in some embodiments, the aqueous phase can be a
discontinuous phase.
- These aqueous compositions usually contain at least about 25% by weight
water. Such aqueous compositions encompass both concentrates containing about
25% to about 80% by weight, or from about 40% to about 65% water; and water~
based functional fluids containing generally over about 80% by weight of water. The
concentrates generally contain less than about 50%, or less than about 25%, or less
than about 15%, and or less than about 6% hydrocarbon oil. The hydrocarbon oil
may be one or more of the above oils of lubricating viscosity. The water-based
functional fluids generally contain less than about 15%, or less than about 5%, and
or less~than about ~% hydrocarbon oil. The dithiocarbamate compound and the
: ~ ~
2 1 2 ~
-32-
organic polysulfide are each indepeindently present in tbe aqueous compositions in an
amount from about 0.2%, or about 0.5%~ or about 0.75% up to about 10%, or to
about 5%, or to about 2.5% of the aqueous composition.
These eoncentrates and water-based functional fluids can optionally include
S other conventional additives commonly employed in water-based functional fluids.
These other additives include surfactants; thickeners; oil-soluble, water-insoluble
functional additives such as antiwear agents, extreme pressure agents, dispersants,
etc.; and supplemental additives such as corrosion-inhibitors, shear stabilizing agents,
bactericides, dyes, water-softeners, odor masking agents, antifoam agents and the
likei.
The surfactants that are useful in the aqueous compositions of the invention
can be of the cationic, anionic, nonionic or amphoteric type. Many such surfactants
of each type are known to the art. See, for example, McCutcheon's "Emulsifiers &Detergents", 1981, No~th American Edition, published by McCutcheon Division, MC
Publishing Co., Glen Rock, New Jersey, U.S.A., which is hereby incorporated by
reference for its disclosures in this regard. Spec;fic nonionic surfactant types include
alkylene oxide treated products, such as ethylene oxide treated phenols and ethylene
oxide/propylene oxide block copolymers, alcohols, esters, such as glycerol esters,
amines, such as the above hydroxy amines, and amides. Examples of surfactants
include allylene oxide treated alkylphenols, sold commercially under the tradename
of Triton~ such as Triton~ X-100, available commercially ~rom Union Carbide
Chemical Company; alkoxylated amines available from Akzo Chemie under the
names ETHODUOMEEN~9 (polyethoxylated diamines), ETHOMEEN~ (poly~
ethoxylated aliphatic amines), ETHOMID~9 (polyethoxylated amides), and ETHO-
QUAD (polyethoxylated quaternary ammonium chlorides); tall oil acids, sold underthe trade name Unitol DT/40 (a~tailable from Union Camp Corp); and the above
described hydroxyhydrocarbyl amines.
Among th~ useful anionic surfactant types are the widely known carboxylate
- soaps, metal organosul~ates, metal sulfonates, metal sulfonylcarboxylates, and metal
phosphates. Useful cationic surfactants include nitrogen compounds such as amine
2~29~6~
-33-
oxides and the well-known quaternary ammonium salts. Amphoteric surfactants
include amino acid-type mate~ials and similar types.
Surfactants are generally employed in effective amounts to aid in the dispersal
of the various additives, particularly in the functional additives discussed below of the
invention. Preferably, the concentrates can contain up to about 75% by weight, or
from about 10% to about 75% by weight of one or more of these surfactants. The
water-based functional fluids can contain up to about 15 % by weight, or from about
0.05% to about 15% by weight of one or more of these surfactants.
Often the a~ueous compositions of this invention contain at least one
thickening agent. Generally, these thickening agents can be polysaccharides,
including cellulose ethers and esters, such as hydroxyethyl cellulose and the sodium
salt of carboxymethyl cellulose, synthetic thickening polymers, or mixtures of two or
more of these. Specific examples of such gums are gum agar, guar gum, gum arabic,
algin, dextrans, xanthan gum and the like. A thickener can also be synthetic thicken-
ingpolymers. Representativeofthemarepolyacrylates,polyacrylamides,hydrolyzed
vinyl esters, water-soluble homo- and interpolymers of acrylam;doalkane sulfonates
and other comonomers such as acrylonitrile, styrene and the like.
Preferred thickening agents include the water- dispersible reaction products
formed by reacting at least one hydrocarbyl-substituted succinic acid and/or anhydride
wherein the hydrocarbyl group has from about 8, or about 12, or about 16, up to
about 40, or to about 30, or to about 24, about 1~ ~arbon atoms, with at least one
water-dispersible amine terminated poly(oxyalkylene) or at least one water-dispersible
hydroxy-terminatedpolyoxyallylene. Examplesofwater-dispersibleamine-terminated
poly(oxyallylene)s that are useful in accordance with the present invention are
disclosed in U.S. Patents 3,021,232; 3,108,011; 4,444,566; and Re 31,522. The
diselosures of these patents are incorporated herein by reference. Water~dispersible
amine terminated poly(oxyalkylene)s that are useful are commercially available from
the Texaco Chemical Company under the trade name Jeffamine~. Water-dispersible
hydroxy-terminated polyoxyalkylenes are commercially available from BASF
Wyandotte ~orporation under the tradename "Tetronic" and "Pluronic". Useful hy-
21291~
-34-
droxy-terminated polyoxyalkylenes are disclosed in U.S. Patents 2,674,619 and
2,979,528, which are incorporated herein by reference.
The reaction between the succinic acid and/or anhydride and the amine- or
hydroxy-terminated polyoxyalkyleneis described in U.S. Patent 4,659,492 this patent
S is incorporated herein by reference for its teachings with respect to the use of the
reaction product of a hydrocarbyl-substituted succinic acid or anhydride and
hydroxy-tersninated poly~oxyallylene).
When the thickener is formed using an amine-terminated poly(oxyalkylene3,
the thickening characteristics of said thickener can be enhanced by combining it with
at least one of the above surfactant. When such surfactants are used, the weight ratio
of thickener to surfactant is generally in the range of from about 1:5 to about 5:1,
preferably from about 1:1 to about 3:1.
Typically, the thickener is present in a thickening amount in the aqueous
compositions of this invention. When used, tlle thickener is generally present at a
level of up to about 70% by weight, or from about 20% to about 50% by weight of
the concentrates of the invention. The thickener is preferably present at a level in the
range of from about 1.5% to about 10% by weight, or from about 3% to about 6%
by weight of the functional fluids of the invention.
The functional additives that may also be included in the aqueous systems are
typically oil-soluble, water-insoluble additives which function in conventional
oil-based systems as extreme pressure agents, anti-wear agents, load-carrying agents,
dispersants, friction rnodifiers, lubricity agents, etc. They can also function as
anti-slip agents, film formers and friction modifiers. As is well known, such
additives can function in two or more of the above-mentioned ways; for example,
extreme pressure agents often function as load-carrying agents.
The term "oil-soluble, water-insoluble functional additive" refers to a
functional additive which is not soluble in water above a level of about 1 gram per
100 parts of water at 25C, but is soluble in mineral oil to the extent of at least 1
gram per liter a~ 25C. These functional additives may also include certain solid
lubricants such as graphite, molybdenum disulfide and polytetrafluoroethylene and
,.: : . . . , , . .................... . :. ....... .
, ,~.,, . . ., ., . . , .. , i , . ., . . ,, .. :,. , "
291~8
relaeed solid polymers. These functional addieives can also include frictinnal polymer
formers, which form materials which are dispersed in a liquid are believed to
polymerize under op~rating condieions. A specific example of such materials is
dilinoleic acid and ethylene glycol combinations which can form a polyester friceional
S polymer film. These materials are known to the art and descriptions of them are
found, for example, in the journal "Wear", Volume 26, pages 369-392, and West
German Published Patent Application 2,339,065. These disclosures are hereby
incorporated by reference for their discussions of ~rictional polymer formers.
Typically these functional addi~ives are known metal or amine sales of organo
sulfur, phosphorus, boron or carboxylic acids which are ehe same as or of the same
type as used in oil-based fluids and are described above.
Many such functional additives are hlown to ehe art. For example,
descriptions of additives useful in conventional oil-based systems and in the aqueous
systems of this invention are found in "Advances in Petroleum Chemistry and
Refining", Volume 8, edited by John J. McKetta, Interscience Publishers, New York,
1963, pages 31-38 inclusive; Kirk-Othmer "Encyclopedia of Chemical Technology",
Yolume 12, Second Edition, Interscience Publishers, New York, 1967, page 575 et
seq.; "Lubricant Additives" by M.W. Ranney, Noyes Data Corporation, Park Ridge,
N.J., U.S.A., 1973; and "Lubricant Additives" by C.V. Smallheer and R.K. Smith,
2û The Lezius-Hiles Co., Cleveland, Ohio, U.S.A. These references are hereby
incorporated by reference for their disclosures of functional additives useful in the
compositions of this invention.
Thé functional additive can also be a film former such as a synthetic or naturallatex or emulsion thereof in water. Such latexes include natural rubber latexes and
polystyrene-butadienes synthetic latex.
The functional additive can also be an anti-chatter or anti-squawk agent.
Examples of the former are the amide-metal dithiophosphate combinations such as
disclosed in West German Patent 1,109,302; amine salt- azomethene combinations
such as disclosed in British Patent Specification 893,977; or amine dithiophosphate
such as disclosed in U.S. Patent 3,002,014. Examples of anti-squawk agents are
21291~
-36-
N-acyl-sarcosines and derivatives thereof such as disclosed in U.S. Patents 3,156,652
and 3,156,653; sulfurized fatty acids and esters thereof such as disclosed in U.S.
Patents 2,913,41S and 2,9829734; and esters of dimeriæd fatty acids such as
disclosed in U.S. Patent 3,039,967. The above-cited patents are incorporated herein
S by reference for their disclosure to anti-chatter and anti-squawk agents~
Typically, the functional additive is present in a functionally effective amount.
The term "functionally effective amount" refers to a sufficient quantity of an additive
to impart desired properties intended by the addition of said additive.
The aqueous systems of this invention often contain at least one optional
inhibitor for corrosion of either ferrous or non-ferrous metals or both. The inhibitor
can be organic or inorganic in nature. Included are those described in "Protective
Coatings for Metals" by Burns and Bradley, Reinhold Publishing Corporation, Second
Edition, Chapter 13, pages 596-605, the disclosure of which relative to inhibitors are
hereby incorporated by reference. Specific examples of useful inorganic inhibitors
include alkali metal nitrites, sodium di- and tripolyphosphate, potassium and
dipotassium phosphate, alkali metal borate ancl mixtures of the same. Specific
examples of organic inhibitors include hydrocarbyl amine and hydroxy-substitutedhydrocarbyl amine neutralized acid compounds, such as neutrali~ed phosphates andhydrocarbyl phosphate esters, neutralized fatty acids, neutralized aromatic carboxylic
acids (e.g., 4-tertiarybutyl benzoic acid), neutralized naphthenic acids and neutralized
hydrocarbyl sulfonates. Particularly useful amines include the alkanolamines such as
ethanolamine, diethanolamine.
The aqueous systems of the present invention can also include at least one
bactericide. Such bactericides are well known to those of skill in the art and specific
examples can be found in the aforementioned McCutcheon publication "Functional
Materials" under the heading "Antimicrobials" on pages 9-20 thereof. Th;s disclosure
is hereby incorporated by reference as it relates to suitable bactericides for use in the
aqueous compositions or systems of this invention.
The aqueolls systems of the present invention can also include such other
materials as clyes, e.g., an acid green dye; water softeners, e.g., ethylene-
21~9168
-37-
diaminete~raacetate sodium salt or nitrilotriacetic acid; odor masking agents, e.g.,
citronella9 oil of lemon; antifreeze additive, e.g.,, ethylene glycol and analogous
polyoxyallylene polyols; and antifoamants, such as the well-known silicone
antifoamant agents.
S Discussion of aqueous compositions and components of aqueous systems
occurs in U.S. Patent 4,707,301, herein incorporated by reference for its disclosure
of aqueous compositions and components of aqueous compositions.
Examples IX-X ~ - -
The following examples relate to aqueous compositions containing the
combination of the dithiocarbamate compound and the organic polysulfide. The
examples are prepared by mixing the components in a homogenizer.
IX X
100 neutral mineral oil 4.0 4.0 ~ ~;
Water 9S.0 95.0 ~ ~-
Reaction product of
diethylethanolamine -~
and a polybutenyl-
(Mn=9S0)-substituted
succinic anhydride 0.8 0.8
~ ~
Dithiocarbamate
of Example I 0.1 0.15
Product of Example 1 0.1 O.OS
. : ~
While the invention has been explained in relation to its preferred embodi-
ments, 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.
