Note: Descriptions are shown in the official language in which they were submitted.
2264R-01
BASIC METAL DIHYDROCARBYLPHOSPHORODITHIOATES
INTRODUCTION TO THE INVENTION
This invention relates to basic metal dihydroca-
rbylphosphorodithioates which impart effective antiwear
properties and antioxidant properties to functional fluids
such as lubricants, and to fuels. The invention also
relates to a method for preparing basic mixed metal
dihydrocarbylphosphorodithioates.
Alkali metal hydroxides and specifically sodium
hydroxide have been used in the preparation of various
metal dihydrocarbylphosphorodithioates, such as zinc
dialkyldithiophosphates. Stoichiometric amounts of the
alkali metal hydroxides have been reacted with phosphorus-
containing acids to form salts; these salts can subse-
quently be reacted with zinc chloride and the like to
prepare the desired dihydrocarbyldithiophosphate. Such
methods and variations thereof are illustrated in U.S.
Patents 2,794,780 to Wystrach et al; 2,797,238 to
20 Miller et al; 3,843,530 to Niedzielski; and 4,123,370 to
Meinhardt. U.S. Patent 2,797,238 to Miller et al
discloses the preparation of various phosphinodithioic
metal compounds, including zinc compounds, utilizing a
stoichiometric amount of sodium hydroxide.
~ ;~9~8 ~
U.S. Patents 3,347,790 and 4,089,793 to Meinhardt
disclose generally the preparation of various zinc
dialkyldithiophosphate compounds, including "normal" or
"neutral" compounds and "basic" compounds.
U.S. Patent 4,094,800 to Warne discloses a basic zinc
dialkyldithiophosphate derived from primary alcohols
containing from about 6 to about 20 carbon atoms.
In U.S. Patent 4,466,895 to Schroeck metal salts of
one or more dialkylphosphorodithioic acids are disclosed
that contain specific alk~l groups.
Mixed metal salts of dialkylphosphorodithioic acidsand carboxylic acids are disclosed in U.S. Patent
4,308,154 to Clason et al.
The ammonia catalyzed preparation of zinc dihydro-
carbyldithiophosphates is disclosed in U.S. Patent4,377,527 to Sabol et al.
U.S. Patent 4,495,075 to Buckley discloses a method
for preventing the precipitation of zinc dialkyldith-
iophosphates, which contain a high percentage of lower
alkyl group, from functional fluids.
The preparation of a mixture of zinc salts of
O,O-dialkyldithiophosphoric acids are disclosed in U.S.
Patent 4,101,428 to Crawford.
Lubricants containing zinc dithiophosphates which
exhibit both antiwear and antioxidant properties are
disclosed in U.S. Patent 3,290,246 to Perotti et al.
U.S. Patent 2,552,570 to McNab et al, U.S. Patent
4,582,920 to Bridges, and European Patent 24146, granted
October 9, 1985 to Exxon Research and Engineering Company,
each disclose copper salts of phosphorus- and
sulfur-containing acids.
Other salts, and processes for their production, are
the subjects of U.S. Patents 3,428,662 to
Millendorf et al, 3,595,792 to Elliot et al, 4,085,053 to
Caspari, 4,376,711 to Shaub, and 4,392,966 to Schlicht.
'7
Basic zinc O,O-dialkylphosphorodithioates are
discussed in papers by: Burn et al, "The Structure of
Basic Zinc O O-Dialkyl Phosphorodithioates," Chemical
Communications, No. 17, pp. 394-396 (1965); Wystrach et
al, "Basic Zinc Double Salts of O, O-Dialkyl
Phosphorodithioic Acids, "Journal of Organic Chemistry,
Vol. 21, pp. 705-707 (1956); and Burn et al, "EXAFS
Determination of the Structure of Basic Zinc OO-Di-n-butyl
Phosphorodithioate" Journal of the Chemical Society,
Chemical Communication, pp. 982-984 (1986).
SUMMARY OF THE INVENTION
In accordance with the present invention, a novel
method for preparing basic mixed metal dihydrocarbyl-
phosphorodithioate compounds and complexes has been
discovered. Further in accordance with the invention,
novel basic, multiple metal complexes of the dialkyl-
phosphorodithioates have been developed. Still further in
accordance with the present invention, it has been found
that the basic mixed metal dialkylphosphorodithioates and
complexes thereof are useful as highly effective antiwear
and antioxidant additives for functional fluids, including
lubricant and fuel compositions. Still further in
accordance with the present invention, a method for
preparing basic mixed metal dihydrocarbylphosphorodi-
thioates in the absence of a catalyst or promoter isprovided. Still further in accordance with the invention,
various functional fluids, including lubricants, automatic
transmission fluids, hydraulic fluids and the like,
comprising basic mixed metal dihydrocarbylphosphorodithio-
ates and complexes thereof of the present invention areprovided.
~&~
In accordance with one aspect of the invention, a
basic metal dihydrocarbylphosphorodithioate is prepared by
reacting (A) at least one dihydrocarbylphosphorodithioic
~ r
acid, or a normalA acid metal salt thereof, with tB) at
least one metal salt thereof, with (B) at least one metal
oxide or hydroxide, wherein the metal is zinc, copper,
nickel, chromium, iron, cobalt, manganese, calcium,
barium, antimony, lead, aluminum, or tin in the presence
of (C) a catalytic amount of at least one alkali metal or
alkaline earth metal hydroxide , oxide, carbonate, or
halide, wherein the metal of (C) is different from the
metal of (B).
These and other aspects of the invention will become
more clear to those skilled in the art upon the reading
and understanding of the following specification.
DETAILED DESCRIPTION OF THE INVENTION
A novel method for preparing basic metal dihydro-
carbylphosphorodithioates and complexes thereof has been
developed. In one embodiment of the invention, the method
involves employing a catalytic amount of: at least one
alkali metal hydroxide, oxide, carbonate or halide; or at
least one alkaline earth metal hydroxide, oxide, carbonate
or halide, or mixtures thereof. The method further
involves reacting at least one dihydrocarbylphosphoro-
dithioic acid or the normal or acid metal salt of at leastone of these acids with a metal oxide, or hydroxide,
wherein the metal is selected from zinc, copper, nickel,
chromium, iron, cobalt, manganese, barium, calcium, lead,
antimony, aluminum or tin in the presence of a catalytic
amount of at least one alkali metal hydroxide, oxide,
halide or carbonate, or alkaline earth metal hydroxide,
oxide, halide or carbonate; or mixtures thereof. It
should be recognized that the metal of the catalyst will
not be the same as the metal of the metal-containing
8i~7
-- 5 --
reactant, e.g , when the reactant is a calcium or barium
salt.
The term "catalytic amount," as used herein, denotes
an amount of a material which promotes the efficient
reaction of a dihydrocarbylphosphorodithioic acid, or
salt, with a metal-containing reactant to form a basic
salt; in general, a catalytic amount contains about 0.001
to 0.05 equivalents of an alkali or alkaline earth metal,
per equivalent of phosphorus in the acid or its salt.
~nother embodiment of the invention involves the
preparation of basic metal dihydrocarbylphosphorodithio-
ates by contacting a normal or acid metal salt of a
dihydrocarbylphosphorodithioic acid with a metal-
containing reactant in the absence of a catalyst or
promoter. This aspect of the invention has been found to
be particularly useful for preparing basic metal
dillydrocarbylphosphorodithioates where the hydrocarbyl
groups are aryl, aralkyl or long chain alkyl (e.g.,
greater than 24 carbon atoms).
As still another aspect of the invention, basic,
multiple metal complexes of dialkylphosphorodithioic acids
have been developed and may be represented by the follow-
ing general formula:
[Z]d[(RO)2Pss]yMaxb (I)
wherein M and X represent different metal cations selected
from the group consisting of zinc, copper, chromium, iron,
copper, manganese, calcium, barium, lead, antimony, tin
and aluminum; Z is an anion selected from oxygen,
hydroxide and carbonate; R is independently a linear or
branched alkyl group of 1 to about 200 carbon atoms, or a
substituted or unsubstituted aryl group of 6 to about 50
carbon atoms; a and b are integers of at least one and are
dependent upon the respective oxidation states of M and X;
y is a whole integer which is dependent upon the oxidation
states of M and X; and d is an integer of 1 or 2.
As used herein, the terms "hydrocarbyl" or `'hydro-
carbon-based" denote a radical having a carbon atom
directly attached to the remainder of the molecule and
having predominantly hydrocarbon character within the
context of this invention. Such radicals include the
following:
(1) Hydrocarbon radicals; that is, aliphatic, e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cyclo-
alkenyl), aromatic, aliphatic- and alicyclic-substituted
aromatic, aromatic-substituted aliphatic and alicyclic
radicals, and the like, as well as cyclic radicals wherein
the ring is completed through another portion of the
molecule (that is, any two indicated substituents may
together form an alicyclic radical).
(2) Substituted hydrocarbon radicals; that is,
radicals containing non-hydrocarbon substituents which, in
the context of this invention, do not alter the predomi-
nantly hydrocarbon character of the radical. Those
skilled in the art will be aware of suitable substituentsj
examples are halo (particularly chloro and fluoro),
alkoxy, mercapto, nitro, nitroso, sulfoxy, and other
groups.
(3) Hetero radicals; that is, radicals which, while
predominantly hydrocarbon in character within the context
of this invention, contain atoms other than carbon present
in a chain or ring otherwise composed of carbon atoms.
Suitable hetero atoms will be apparent to those skilled in
the art and include, for example, nitrogen, oxygen and
sulfur.
Terms such as "alkyl-based radical," "aryl-based
radical" and the like have meaning analogous to the above
with respect to alkyl and aryl radicals and the like.
The preferred radicals are usually hydrocarbon, that
is, composed most often of carbon and hydrogen atoms, and
are straight- or branched-chain alkyl.
By "basic" metal phosphorodithioate, it is intended,
for the purposes of the present invention, to include
8 ~'~
those salts and/or complexes that have a higher ratio of
equivalents of total metal to equivalents of the
dihydrocarbylphosphorodithioic acid moiety r than that of
the corresponding "neutral" or "normal" salt and/or
complex. Partially neutralized dihydrocarbyl phospho-
rodithioic acids, denoted "acid salts" herein, have a
lower ratio of equivalents than that of the "Neutral" or
"normal" salts. More specifically, a "neutral" or "normal"
zinc phosphorodithioate has one equivalent of zinc per one
equivalent of the phosphorodithioic acid moiety, i.e., a
1:1 ratio in this case. The corresponding "basic" zinc
phosphorodithioate has more than one equivalent of zinc
per one equivalent of the phosphorodithioic acid moiety,
e.g., in certain instances the equivalent ratio will be
4:3 of zinc to phosphorodithioate.
In a preferred embodiment of the present invention,
the salts and/or complexes of the present invention are
derived from oxides or hydroxides of a metal selected from
the group consisting of Zn, Cu, Ca, Ba, Ni, Cr, Fe, Co,
Mn, Sn, Sb or mixtures thereof. In a most preferred
embodiment, metal oxides are used and the metal is
selected from Zn, Cu, Ca, Sb, Co or mixtures thereof.
Also in a preferred embodiment, the catalyst used in
the method of the present invention is calcium hydroxide,
potassium hydroxide or sodium hydroxide. In a most
preferred embodiment, the catalyst is sodium hydroxide.
In a further preferred embodiment, the hydrocarbyl
groups of the phosphorodithioic acid are, independently,
linear or branched alkyl groups of 1 to about 200 carbon
atoms or substituted or unsubstituted aryl group of 6 to
about 50 carbon atoms. Representative of such alkyl or
aryl groups include octyl, butyl, pentyl, propyl, oleyl,
heptyl, hexyl, heptylphenyl, dodecylphenyl, nonylphenyl,
cresyl and the isomers thereof. In a more preferred
embodiment, the total number of carbon atoms in the
dihydrocarbylphosphorodithioate moiety is at least 8. In a
most preferred embodiment, the hydrocarbyl groups are,
lZ988 ~7
independently, selected from isooctyl, isopropyl,
4-methyl-2-pentyl and heptylphenyl.
With respect to the multiple metal complexes of the
present invention, it has been found that the complex
includes at least two different metals where one metal is
included as the oxide or hydroxide and the other metal is
included in the form of a salt of a phosphorodithioic
acid, generally in a 1:3 molar ratio. More specifically,
one mole of a metal oxide, for example, is complexed with
3 moles of a neutral metal dihydrocarbylphosphorodi-
thioate. This ratio, of course, may vary dependent upon
the ratio of reactants used to prepare the complex and the
like.
A presently preferred basic salt for use in
lubricating compositions is a mixed zinc and copper salt
of a dihydrocarbylphosphorodithioic acid. This salt can
be conveniently prepared by reacting a normal or acid zinc
salt of the acid with a cuprous compound, such as cuprous
oxide, in the presence of a catalytic amount of a material
such as sodium hydroxide.
When the method of the invention is carried out in
the absence of a catalyst, the reaction is conducted by
contacting a metal dihydrocarbylphosphorodithioate with a
metal oxide. The metal of the phosphorodithioate and the
metal of the oxide may be the same or different and
preferably are, independently, Zn, Cu, Ca, Sb and Co.
This embodiment of the invention is most effective in
preparing "basic" metal dihydrocarbylphosphorodithioates
where at least one hydrocarbyl group is aralkyl, e.g.,
heptylphenyl or dodecylphenyl, or is long-chain alkyl,
e.g., greater than 24 carbon atoms.
The following examples are provided to illustrate
various salts/complexes prepared by the method of the
present invention as described above. These examples are
provided for illustrative purposes only and are not to
serve as a limitation on the scope of the invention, such
scope being set out solely in the appended claims.
lZ~38~7
_ 9 _
EXAMPLE I
354 grams of zinc oxide and 225 grams of diluent oil
were charged to the reaction container. At ambient
temperature, 5.28 grams of a 50~ sodium hydroxide solution
was charged with stirring to the reaction container.
After which, 1,982 grams of zinc O,O-isobutyl/amyl (65:35)
dithiophosphate was charged to the reaction container.
After the initial exotherm, the reaction container was
heated to 80C and held at that temperature for 5 hours.
The material was vacuum stripped at 100C and lOmmHg.
After filtering, 1,773 grams of product resulted.
EXAMPLE II
1,030 grams of zinc diheptylphenyldithiophosphate,
1.6 grams of a 50~ sodium hydroxide solution, 50 grams of
water and 32.1 grams of zinc oxide were charged to a
reaction container with stirring. This mixture was heated
to 80C and held at that temperature. After filtering,
982.1 grams of product was produced.
EXAMPLE III
To a reaction container was charged 369 grams of zinc
oxide and 309 grams of diluent oil. With stirring 4.8
grams of S0~ sodium hydroxide solution was charged to the
reaction container. After the addition was complete,
2,472 grams of zinc diisooctyldithiophosphate was charged
to the reaction container. The reaction container was
heated to 80C and held at that temperature for 5 hours.
After vacuum stripping at 100C and 20mmHg, the material
was filtered to yield 2,383 grams of product.
- 10 ~
EXAMPLE IV
A reaction container was charged with 147 grams of
zinc diisooctyldithiophosphate, 4.1 grams of calcium
hydroxide and 10 grams of water. The mixture was heated
to 95C and maintained at that temperature for 5 hours.
The mixture was vacuumed stripped under reduced pressure
at 110C. Final product yielded 148 grams after filtering
through diatomaceous earth filter aid.
EXAMPLE V
A reaction container was charged with 1,945 grams of
zinc dialkyldithiophosphate (the alkyl groups are a 65/35
mixture of isobutyl/primary amyl respectively), 77 grams
of calcium hydroxide, 22 grams of water and 700 grams of
toluene. This mixture was stirred and heated to 80C and
maintained at the temperature for S hours. The contents
were then vacuum stripped at 100C and lOmmHg. The
product was filtered through diatomaceous earth filter aid
yielding 2,000 grams of product.
EXAMPLE VI
The same procedure in the previous examples was
followed utilizing 11 grams of calcium hydroxide, 10 grams
of water and 291.4 grams of zinc dialkyldithiophosphate
(the alkyl groups were a 65/35 mixture of isobutyl/amyl
respectively). 250 grams of product was obtained.
38 ~'7
EXAMPLE VII
A reaction container was charged with 1,000 grams of
zinc diisooctyldithiophosphate, 26.88 grams of copper (I)
oxide, 2.54 grams of a 50% sodium hydroxide solution and
S 25.4 grams of distilled water. This mixture was heated
with stirring to 80C and maintained at that temperature
for 2.5 hours. The reaction mixture was then vacuumed
stripped at 100C and 15mmHg. The mixture was then
filtered through diatomaceous earth filter aid to obtain
1,022 grams of product.
EXAMPLE VIII
A reaction container was charged with 30.1 grams of
copper oxide, 2.0 grams of a 50% solution of sodium
hydroxide, 25 grams of water and 350 grams of zinc di-
alkyldithiophosphate (the alkyl groups are a 65t35 mixtureof isobutyl/amyl respectively). This mixture was heated
to 100C and maintained at that temperature for 1.5 hours.
The mixture was then vacuum stripped and filtered through
diatomaceous earth filter aid to give 320 grams of
product.
EXAMPLE IX
The procedure for the above examples was followed to
prepare the following product which was prepared from 34
grams of zinc oxide, 18 grams of copper (I) oxide, 33
grams of diluent oil and 256 grams of a dialkyldithiophos~
phoric acid (the alkyl groups are a 60/40 mixture of
methylamyl/isopropyl, respectively). The addition of
..
-` 129~8~7
these reactants took place over a period of 1.5 hours
where the temperature was maintained at less than 60C.
After the addition was complete, the mixture was heated to
75C and maintained at that temperature for 4.5 hours.
After filtering through diatomaceous earth filter aid, 270
grams of product was obtained.
EXAMPLE X
The same procedure was followed as with the previous
examples where the following reactants were used to
10prepare the desired product. 483 grams of a l:1.1
equivalents mixture of diisooctyldithiophosphoric acid and
copper (I) oxide, 13.43 grams of zinc oxide and 9.6 grams
of distilled water. From this reaction mixture was
obtained 450 grams of product.
EXAMPLE XI
A one liter reaction container was charged with 32
grams of diluent oil and 25 grams of zinc oxide. 200
grams of di-4-methyl-2-pentyldithiophosphoric acid were
added dropwise to the reaction mixture over a period of
one hour. This mixture was then heated to 65C and
maintained at that temperatuxe for one hour. After this
one-hour period, 22 grams of manganese carbonate were
added to the reaction mixture. This addition was followed
by the addition of an additional 60 grams of di-4-methyl-
2-pentyldithiophosphoric acid. This final reaction
mixture was heated to 75C and maintained at that tempera-
ture for 4 hours. The reaction mixture was then vacuum
stripped at 95C and lOmmHa and filtered through
diatomaceous earth filter aid. 242 grams of the mixed
metal product was obtained.
. :,``'`~ .....
The salts and complexes according to the present
invention, which specific species have been illustrated in
the above Examples I-XI, are versatile additives for
r lubricating compositions and fuels as well as other
5 functional fluids. The compositions of the present
invention are useful additives for imparting antioxidant
properties and antiwear properties to various lubricant
compositions. The complexes, i.e., additives, of the
present invention also find use in functional fluids
10 including fuel compositions, automatic transmission fluids,
hydraulic fluids and the like. The salts and complexes of
the present invention may also be used as curing agents for
epoxy resins and the like.
The additives of the present invention may be
15 formulated with a functional fluid by the direct blending
of the composition to the particular functional fluid,
e.g., lubricating oil, or it may be formulated with the
functional fluid in the form of a concentrate. Such a
concentrate may be prepared by adding 1% to about 99~ by
20 weight of the composition or additive of the present
invention to a substantially inert, normally liquid organic
diluent or solvent such as benzene, toluene, xylene,
petroleum naphtha, mineral oil, ethylene glycol monomethyl
ether or the like.
The compositions of the present invention, formulated
with the particular functional fluid or concentrate, may
contain other additives and chemistries such as
dispersants, antioxidants and the like. Such other
additives and chemistries include, for example, detergents
and dispersants of the ash-producing or ashless type,
corrosion- and oxidation-inhibiting agents, pour point
depressing agents, extreme pressure agents, color
stabilizers, antifoam agents and VI improvers. These other
additives and chemistries are fully described and disclosed
in U.S. Patents 3,541,014, 4,289,635, and 4,266,945.
X'
8`.~
- 14 -
A preferred dispersant for use with the present
invention is at least one substituted succinic acid or
derivative thereof containing of substituent qroups,
wherein the substituent groups are derived from poly-
alkylene, said polyalkylene being characterized by a Mnvalue of 500 to about 10,000 and a Mw/Mn value of 1.0 to
about 4Ø
It has also been found that the additive compounds of
the present invention are useful in formulating various
lubricant compositions. The salt and/or metal complex
additives of the present invention are useful in both
mineral and synthetic lubricating oils and greases.
Synthetic oils include polyolefin oils (e.g., polybutene
oil, decene oligomer, and the like), synthetic esters
(e.g., dinonyl sebacate, trioctanoic acid ester of tri-
methylolpropane, and the like), polyglycol oils, and the
like. Greases are made from these oils by adding a
thickening agent such as sodium, calcium, lithium, or
aluminum salts of fatty acids such as stearic acid. These
and similar thickening agents are described in U.S. Patents
2,197,263, 2,564,561 and 2,999,066. The oils and greases
of the present invention are prepared by blending an amount
of at least one salt or metal complex additive of the
present invention sufficient to impart antiwear properties
and antioxidant properties into the oil or grease. A
useful concentration may range from about 0.1 to about 5
weight percent.
To further illustrate various functional fluid
compositions, specifically lubricant compositions, com-
prising the salts and complexes of the present invention,the following illustrative examples are provided. It is
again pointed out that the following examples are provided
for illustrative purposes only and are not to place any
limitation on the scope of the invention where such scope
.~.
7 `
- 15 -
is set out only in the claims. All parts and percentages
are by weight.
Typical compositions according to this invention are
listed in the following table.
TABLE I
COMPONENTS A B C D E F
Base Oil 90.37 90.87 92.82 95.0 81.13 83.18
Product of
Example I 2.00
Product of
Example III 0.11 0.11 3.86 2.50
Product of
Example VIII 2.60
Reaction Product
of Polybutenyl
Succinic Anhydride
with Ethylene
Polyamine 3.61 2.50
Reaction Product
of Polybutenyl
Succinic Anhydride
with Ethylene
Polyamine and
Pentaerythritol 2.50
Reaction Product
of Polybutenyl
Succinic Anhydride
with Ethylene
Polyamine and
Carbon Disulfide 2.00 2.00
Reaction Product
of Polybutenyl
Succinic Anhydride
with Ethylene
Polyamine and
Boric Acid 1.00 1.00
8~
- 16 -
Basic Calcium
Alkylbenzene-
sulfonate 1.79 1.79 1.10
Basic ~lagnesium
Alkylbenzene-
sulfonate 1.35 0.65
Reaction Product of
Maleic Anhydride-
styrene Copolymer
with Alcohol and
Amine 3.50 3.50 1.11 0.20
Hydrogenated Styrene-
diene Block Copolymer
Viscosity Improver 9.00
15 Ethylene-propylene
Copolymer Viscosity
Improver 7.00
Sulfurized Fat 0.50
Reaction Product of
an Organo Sulfur Cmpd.
with an Epoxide 0.50 0.50
Sulfurized Olefin 2.50 1.50
Ester of Dimercapto-
thiadiazole 0.17 0.10 0.06
Sulfurized Diels-
Alder Adduct 0.60
Oil Soluble
Phosphorus-Containing
Extreme Pressure Agent 1.47
30 Alkylated Arylamine 0.10 0.10 0.50 0.30
Ethoxylated Fatty
Amine 0.09 0.09
Fatty Amide 0.11 0.10
Fatty Amine 0.39
35 Silicone Anti-
foam Agent 0.042 0.042 0.066 0.006 0.006
The products of the various examples, contained in a
fully formulated lubricating composition as is described
- 17 -
in Table I, were tested with regard to a Timken "OK" load
test as well as a contact pressure test in accordance with
ASTM D 2782, with the exception that in the "OK" load test
the following procedural differences were made:
1. Test cup and block surfaces are merely "wetted"
with test lubricant (approximately 5 drops on block). No
test sample is recirculated over the surfaces during the
test.
2. Test duration is 5 minutes under load.
3. This procedure is run as an "OK" Load test,
determining "OK" Load as in ASTM Test D 2782 except
utilizing the following load increments:
a. "OK" Load is less than or equal to 20 lbs.:
Determine "OK" Load to the nearest 1 lb.
b. "OK" Load is greater than 20 lbs.: Deter-
mine "OK" Load using standard load increments as
described in ASTM Test D 2782.
The results from testing products of the present
invention according to the above test procedure are set
out in Table II below.
TABLE II
Timken Results
OK LoadUnit Press. Wt
No. Sample (lbs.) ~. P
1. Product of 15 16,350 0.05
Example IV
2. Product of 17 7,850 0.05
Example V
3. Product of 15 7,625 0.05
Example VI
lBased on the weight of the phosphorous content on
the sample.
Products of the present invention illustrated in the
above examples were also tested in the copper strip test
in accordance with ASTM D ]30. The results from testing
~2~388~7
- 18 -
products of the present invention according to the above
test procedure are set out in Table III below.
TABLE III
Example No. Copper Strip
V la
VI la
VII 2b-2c
IX la
The invention also includes aqueous compositions
characterized by an aqueous phase with at least one salt
or complex of the present invention dispersed or dissolved
in said aqueous phase. 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,
preferably 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 from about 10% to about 90~ by weight OI at least
one of the salt or complex materials of the invention.
The water-based functional fluids generally contain from
about 0.05% to about 15~ by weight of the salt or complex
materials of the invention. The concentrates generally
contain less than about 50%, preferably less than about
25%, more preferably less than about 15~, and still more
preferably less than about 6% hydrocarbon oil. The
water-based functional fluids generally contain less than
about 15%, preferably less than about 5%, and more prefer-
ably less than about 2% hydrocarbon oil.
These concentrates and water-based functional fluids
can optionally include other conventional additives
commonly employed in water-based functional fluids. These
~.298~7
- 19 -
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, anti-foam agents and
the like.
The concentrates are analogous to the water-based
functional fluids except except that they contain less
water and proportionately more of the other ingredients.
The concentrates can be converted to water-based
functional fluids by dilution with water. This dilution
is usually done by standard mixing techniques. This is
often a convenient procedure since the concentrate can be
shipped to the point of use before additional water is
added. Thus, the cost of shipping a substantial amount of
the water in the final water-based functional fluid is
saved. Only the water necessary to formulate the concen-
trate (which is determined primarily be ease of handling
and convenience factors), need be shipped.
Generally these water-based functional fluids are
made by diluting the concentrates with water, wherein the
ratio of water to concentrate is usually in the range of
about 80:20 to about 99:1 by weight. As can be seen when
dilution is carried out within these ranges, the final
water-based functional fluid contains, at most, an insig-
nificant amount of hydrocarbon oil.
In various preferred embodiments of the invention,
the water-based functional fluids are in the form of
solutions while in other embodiments they are in the form
of micelle dispersions or microemulsions which appear to
be true solutions. Whether a solution, micelle dispersion
or microemulsion is formed is dependent, inter alia, on
the particular components employed.
Also included within this invention are methods for
preparing aqueous compositions, including both concen-
129~38 ~7
- 20 -
trates and water-based functional fluids, containing other
conventional additives commonly employed in water-based
functional fluids. These methods comprise the steps of:
(1) mixing at least one salt or complex additive of
the invention with such other conventional additives either
simultaneously or sequentially to form a dispersion or
solution; optionally
(2) combining said dispersion or solution with water
to form said aqueous concentrate; and/or
(3) diluting said dispersion or solution, or
concentrate with water wherein the total amount of water
used is in the amount required to provide the desired
concentration of the components of the invention and other
functional additives in said concentrates or said water-
based functional fluids.
These mixing steps are preferably carried out using
conventional equipment and generally at room or slightly
elevated temperatures, usually below 100 C and often below
50 C. As noted above, the concentrate can be formed and
then shipped to the point of use where it is diluted with
water to form the desired water-based functional fluid. In
other instances, the finished water-based functional fluid
can be formed directly in the same equipment used to form
the concentrate or the dispersion or solution.
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,
North American Edition, published by McCutcheon Division,
MC Publishing Co., Glen Rock, New Jersey, U.S.A.
Among the nonionic surfactant types are the alkylene
oxide-treated products, such as ethylene oxide-treated
phenols, alcohols, esters, amines and amides. Ethylene
X
- 21 -
oxide/propylene oxide block copolymers are also useful
nonionic surfactants. Glycerol esters and sugar esters are
also known to be nonionic surfactants. A typical nonionic
surfactant class useful with the present invention are the
alkylene oxide-treated alkyl phenols such as the ethylene
oxide alkyl phenol condensates sold by the ~ohm & Haas
Company. A specific example of these is Triton X-100 which
contains an average of 9-10 ethylene oxide units per
molecule, has an HLB value of about 13.5 and a molecular
weight of about 628. Many other suitable nonionic
surfactants are known; see, for example, the aforementioned
McCutcheon's as well as the treatise "Non-Ionic
Surfactants" edited by Martin J. Schick, M. Dekker Co., New
York, 1967.
As noted above, cationic, anionic and amphoteric
surfactants can also be used. Generally, these are all
hydrophilic surfactants. Anionic surfactants contain
negatively charged polar groups while cationic surfactants
contain positively charged polar groups. Amphoteric
dispersants contain both types of polar groups in the same
molecule. A general survey of useful surfactants is found
in Kirk-Othmer Encyclopedia of Chemical Technology, Second
Edition, Volume 19, page 507 et seq. (1969, John Wiley and
Son, New York) and the aforementioned compilation published
under the name of McCutcheon's.
Among the useful anionic surfactant types are the
widely known carboxylate soaps, organo sulfates,
sulfonates, sulfocarboxylic acids and their salts, and
phosphates. Useful cationic surfactants include nitrogen
compounds such as amine oxides and the well-known
quaternary ammonium salts. Amphoteric surfactants include
amino acid-type materials and similar types. Various
- 22 -
cationic, anionic and amphoteric dispersants are available
from the industry, particularly from such companies as Rohm
~ Haas and Union Carbide Corporation, both of America.
Further information about anionic and cationic surfactants
also can be found in the texts "Anionic Surfactants", Parts
II and III, edited by W. M. Linfield, published by Marcel
Dekker, Inc., New York, 197~, and "Cationic Surfactants",
edited by E. Jungermann, ~arcel Dekker, Inc., New York,
1976.
These surfactants, when used, are generally employed
in effective amounts to aid in the dispersal of the various
additives, particularly the functional additives discussed
below, in the concentrates and water-based functional
fluids of the invention. Preferably, the concentrates can
contain up to about 75% by weight, more preferably 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, more preferably from about 0.05%
to about 15% by weight of one or more of these surfactants.
Often the aqueous compositions of this invention
contain at least one thickener for thickening said
compositions. Generally, these thickeners can be
polysaccharides, synthetic thickening polymers, or mixtures
of two or more of these. Among the polysaccharides that
are useful are natural gums such as those disclosed in
"Industrial Gums" by Whistler and B. Miller, published by
Academic Press, 1959. Specific examples of such gums are
gum agar, guar gum, gum arabic, algin, dextrans, xanthan
gum and the like. Also among the polysaccharides that are
useful as thickeners for the aqueous compositions of this
invention are cellulose ethers and esters, including
- 23 -
hydroxy hydrocarbyl cellulose and hydrocarbylhydroxy
cellulose and its salts. Specific examples of such
thickeners are hydroxyethyl cellulose and the sodium salt
of carboxymethyl cellulose. Mixtures of two or more of any
such thickeners are also useful.
It is a general requirement that the thickener used in
the aqueous compositions of the present invention be
soluble in both cold (10 C) and hot (about 90 C) water.
This excludes such materials as methyl cellulose which is
soluble in cold water but not in hot water. Such hot-
water-insoluble materials, however, can be used to perform
other functions such as providing lubricity to the aqueous
compositions of this invention.
These thickeners can also be synthetic thickening
polymers. Many such polymers are known to those of skill
in the art. Representative of them are polyacrylates,
polyacrylamides, hydrolyzed vinyl esters, water-soluble
homo- and interpolymers of acrylamidoalkane sulfonates
containing 50 mole percent at least of acryloamido alkane
sulfonate and other comonomers such as acrylonitrile,
styrene and the like. Poly-n-vinyl pyrrolidones, homo- and
copolymers as well as water-soluble salts of styrene,
maleic anhydride and isobutylene maleic anhydride
copolymers can also be used as thickening agents.
Other useful thickeners are known to those of skill in
the art and many can be found in the list in the
aforementioned McCutcheon Publication: "Functional
Materials," 1976, pp. 135-147, inclusive.
Preferred thickeners, particularly when the
compositions of the invention are required to be stable
under high shear applications, are the water-dispersible
reaction products formed by reacting at least one hydro-
12g8~
- ~4 ~
carbyl-substituted succinic acid and/or anhydride
represented by the formula
R CHCOOH or R CHC~
1 ~O
CH2COOH CH2C
\\O
wherein R is a hydrocarbyl group of from about 8 to about
40 carbon atoms, with at least one water-dispersible amine
terminated poly(oxyalkylene) or at least one water-
dispersible hydroxy-terminated polyoxyalkylene. R prefer-
ably has from about 8 to about 30 carbon atoms, more
preferably from about 12 to about 24 carbon atoms, still
more preferably from about 16 to about 18 carbon atoms.
In a preferred embodiment, R is represented by the formula
R"CH=CH-CH-
R'
wherein R' and R" are independently hydrogen or straight
chain or substantially straight chain hydrocarbyl groups,
with the proviso that the total number of carbon atoms in
R is within the above-indicated ranges. Preferably R' and
R" are alkyl or alkenyl groups. In a particularly advan-
tageous embodiment, R has irom about 16 to about 18 carbon
atoms, R' is hydrogen or an alkyl group of from 1 to about
7 carbon atoms or an alkenyl group of from 2 to about 7
carbon atoms, and R" is an alkyl or alkenyl group of from
about 5 to about 15 carbon atoms.
The water-dispersible amine terminated poly(oxyalkyl-
ene)s are preferably alpha omega diamino poly(oxyethyl-
ene)s, alpha omega diamino poly(oxypropylene)poly(oxyethylene) poly(oxypropylene)s or alpha omega
diamino propylene oxide capped poly(oxyethylene)s. The
amine-terminated poly(oxyalkylene) can also be a urea
condensate of such alpha omega diamino poly(oxytheylene)s,
alpha omega diamino poly(oxypropylene) poly(oxyethylene)
poly(oxypropylene)s or alpha omega diamino propylene oxide
capped poly(oxyethylene)s. The amine-terminated poly(oxy-
alkylene) can also be a polyamine (e.g., triamino,
tetramino, etc.) polyoxyalkylene provided it is amine-
terminated and it is water-dispersible.
Examples of water-dispersible amine-terminated
poly(oxyalkylene)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. Water-dispersible
amine te~minated poly(oxyalkylene)s that are useful are
commercially available from the Texaco Chemical Company
under the trade name "Jeffamine".
The water-dispersible hydroxy-terminated polyoxy-
alkylenes are constituted of block polymers of propylene
oxide and ethylene oxide, and a nucleus which is derived
from organic compounds containing a plurality of reactive
hydrogen atoms. The block polymers are attached to the
nucleus at the sites of the reactive hydrogen atoms.
Bxamples of these compounds include the hydroxy-terminated
polyoxyalkylenes which are represented by the formula
H(OH4C2)b(OH6c3)a H N ~ (C3H60)a(c2H4O)b
NCH2C 2
H(OH4C2)b(0H6c3)a (C3H60)a(C2H40)b
wherein a and b are integers such that the collective
molecular weight of the oxypropylene chains range from
about 900 toabout 25,000, and the collective weight of the
oxyethylene chains constitute from about 20~ to about 90~,
preferably from about 25% to about 55~ by weight of the
compound. These compounds are commercially available from
BASF Wyandotte Corporation under the trade name
'7
- 26 -
"Tetronic ". Additional examples include the hydroxy-
terminated polyoxyalkylenes represented by the formula
H0(c2H4O)x(c3H6o)y(c2 4 Z
wherein y is an integer such that the molecular weight of
the oxypropylene chain is at least about 900, and x and z
are integers such that the collective weight of the
oxyethylene chains constitute from about 20% to about 90%
by weight of the compound. These compounds preferably have
a molecular weight in the range of about 1,100 to about
14,000. These compounds are commercially available from
BASF Wyandotte Corporation under the trade name
"Pluronic ". Useful hydroxy-terminated polyoxyalkylenes
are disclosed in U.S. Patents 2,674,619 and 2,979,528.
The reaction between the carboxylic agent and the
amine- or hydroxy-terminated polyoxyalkylene can be carried
out at a temperature ranging from the highest of the melt
temperatures of the reaction components up to the lowest of
the decomposition temperatures of the reaction components
or products. Generally, the reaction is carried out at a
temperature in the range of about 60 C to about 160 C,
preferably about 120 c to about 160 C. The ratio of
equivalents of carboxylic agent to polyoxyalkylene
preferably ranges from about 0.1:1 to about 8:1, preferably
about 1:1 to about 4:1, and advantageously about 2:1. The
2S weight of an equivalent of the carboxylic agent can be
determined by dividing its molecular weight by the number
of carboxylic functions present. The. weight of an
equivalent of the amine-terminated polyoxyalkylene can be
determined by dividing its molecular weight by the number
of terminal amine groups present. The weight of an
equivalent of the amine-terminated polyoxyalkylene can be
determined by dividing its molecular weight by the number
* trade-mark
l~g~ 7
- 27 -
of terminal amine groups present. The number of terminal
amine and hydroxyl groups can usually be determined from
the structural formula of the polyoxyalkylene or
empirically through well-known procedures. The amine/acids
and ester/acids formed by the reaction of the carbo~ylic
agent and amine-terminated or hydroxy-terminated
polyoxyalkylene can be neutralized with, for example, one
or more alkali metals, one or more amines, or a mixture
thereof, and thus converted to amide/salts or ester/salts,
respectively. Additionally, if these amide/acids or
ester/acids are added to concentrates or functional fluids
containing alkali metals or amines, amide/salts or
ester/salts usually form, in situ.
South African Patent 85/0978 may be referred to for
its teachings with respect to the use of hydrocarbyl-
substituted succinic acid or anhydride/hydroxy-terminated
poly(oxyalkylene) reaction products as thickeners for
aqueous compositions.
When the thickener is formed using an amine-terminated
poly(oxyalkylene), the thickening characteristics of said
thickener can be enhanced by combini~g it with at least one
surfactant. Any of the surfactants identified above under
the subtitle "Surfactants" can be used in this regard.
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, the thickener is preferably present at a level of up
to about 70% by weight, preferably 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, preferably from
about 3% to about 6% by weight of the functional fluids of
the invention.
X
1~8~`~7
- 28 -
The functional additives that can be used in the
aqueous systems are typically oil-soluble, water-insoluble
additives which function in conventional oil-based systems
as extreme pressure agents, antiwear agents, load-carrying
agents, dispersants, friction modifiers, 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
milliliters of water at 25 C, but is soluble in mineral oil
to the extent of at least 1 gram per liter at 25 C.
These functional additives can also include certain
solid lubricants such as graphite, molybdenum disulfide and
polytetrafluoroethylene and related solid polymers.
These functional additives can also include frictional
polymer formers. Briefly, these are potential polymer
forming materials which are dispersed in a liquid carrier
at low concentration and which polymerize at rubbing or
contacting surfaces to form protective polymeric films on
the surfaces. The polymerizations are believed to result
from the heat generated by the rubbing and, possibly, from
catalytic and/or chemical action of the freshly exposed
~urface. A specific example of such materials is
dilinoleic acid and ethylene glycol combinations which can
form a polyester frictional 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.
Typically these functional additives are known metal
or amine salts of organo sulfur, phosphorus, boron or
carboxylic acids which are the same as or of the same type
12~ 7
- 2~ -
as used in oil-based fluids. Typically such salts are of
carboxylic acids of 1 to 22 carbon atoms including both
aromatic and aliphatic acids; sulfur acids such as alkyl
and aromatic sulfonic acids and the like; phosphorus acids
such as phosphoric acid, phosphorus acid, phosphinic acid,
acid phosphate esters and analogous sulfur homologs such as
the thiophosphoric and dithiophosphoric acid and related
acid esters; boron acids include boric acid, acid borates
and the like. Useful functional additives also include
metal dithiocarbamates such as molybdenum and antimony
dithiocarbamates; as well as dibutyl tin sulfide, tributyl
tin oxide, phosphates and phosphites; borate amine salts,
chlorinated waxes; trialkyl tin oxide, molybdenum
phosphates, and chlorinated waxes.
Many such functional additives are known to the 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", Volume 12, Second Edition, Interscience
Publishers, New York, 1967, page 575 et seq.; "Lubricant
Additives" by M. W. Ranney, Noyes Data Corporation, Park
Ridge, New Jersey, U.S.A., 1973; and "Lubricant Additives"
by C. V. Smalheer and R. K. Smith, The Lezius-Hiles Co.,
Cleveland, Ohio, U.S.A.
In certain of the typical aqueous compositions of the
invention, the functional additive is a sulfur or chloro-
sul~ur extreme pressure agent, known to be useful in oil-
base systems. Such materials include chlorinated aliphatic
hydrocarbons, such as chlorinated wax; organic sulfides and
polysulfides, such as benzyl-disulfide, bis-(chlorobenzyl)-
~29~ 7
- 30 -
disulfide, dibutyl tetrasulfide, sulfurized sperm oil,
sulfurized methyl ester of oleic acid, sulfurized
alkylphenol, sulfurized dipentene, sulfuri~ed terpene, and
sulfurized Diels-Alder adducts; phosphosulfurized hydro-
carbons, such as the reaction product of phosphorus sulfidewith turpentine or methyl oleate; phosphorus esters such as
the dihydrocarbon and trihydrocarbon phosphites, i.e.,
dibutyl phosphite, diheptyl phosphite, dicyclohexyl
phosphite, pentylphenyl phosphite, dipentylphenyl
phosphite, tridecyl phosphite, distearyl phosphite and
polypropylene substituted phenol phosphite; metal
thiocarbamates, such as zinc dioctyl-dithiocarbamate and
barium heptylphenol dithiocarbamate: and Group II metal
salts of a phosphorodithioic acid, such as zinc
dicyclohexyl phosphorodithioate.
The functional additive can also be a film former such
as a synthetic or natural latex 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 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 2,913,415 and 2,982,734; and esters of
dimerized fatty acids such as disclosed in U.S. Patent
3,039,967.
12988~7
- 31 -
Specific examples of functional additives useful in
the aqueous systems of this invention include the follow-
ing commercially available products.
TABLE IV
5 Functional Addi- Chemical
tive Trade Name Description Supplier
Anglamol~32 Chlorosulfurized
hydrocarbon Lubrizol
Anglamol 75 Zinc dialkyl
phosphate Lubri~ol
Molyvan L A thiaphos- 2
phomolybdate Vanderbilt
Lubrizol-5315 Sulfurized cyclic
carbo~ylate ester Lubrizol
15 Emcol TS 230 Acid phosphate 3
ester Witco
2 The Lubrizol Corporation, Wickliffe, Ohio, U.S.A.
R. T. Vanderbilt Company, Inc., New York, New York,
U.S.A.
3 Witco Chemical Corp., Organics Division, Houston,
Texas, U.S.A.
Mixtures of two or more of any of the afore-described
functional additives can also be used.
Typically, a functionally effective amount of the
functional additive is present in the aqueous compositions
of this invention.
The term "functionally effective amount" refers to a
sufficient quantity of an additive to impart desired
properties intended by the addition of said additive. For
example, if an additive is a rust-inhibitor, a functional-
ly effective amount of said rust-inhibitor would be an
amount sufficient to increase the rust-inhi~iting charac-
teristics of the composition to which it is added.
Similarly, if the additive is an antiwear agent, a func-
~ R ~
~Z~8`~
- 32 -
tionally effective amount of said antiwear agent would be
a sufficient quantity of the antiwear agent to improve the
antiwear characteristics of the composition to which it is
added.
The aqueous systems of this invention often contain at
least one inhibitor for corrosion of metals. These
inhibitors can prevent corrosion of either ferrous or non-
ferrous metals (e.g., copper, bronze, brass, titanium,
aluminum and the like) or both. The inhibitor can be
organic or inorganic in nature. Usually it is sufficiently
soluble in watex to provide a satisfactory inhibiting
action though it can function as a corrosion-inhibitor
without dissolving in water, it need not be water-soluble.
Many suitable inorganic inhibitors useful in the aqueous
systems of the present invention are known to those skilled
in the art. Included are those described in "Protective
Coatings for Metals" by Burns and Bradley, Reinhold
Publishing Corporation, Second Edition, Chapter 13, pages
596-605. Specific examples of useful inorganic inhibitors
include alkali metal nitrites, sodium di- and tri-
polyphosphate, potassium and dipotassium phosphate, alkali
metal borate and mixtures of the same. Many suitable
organic inhibitors are known to those of skill in the art.
Specific examples include hydrocarbyl amine and hydroxy-
substituted hydrocarbyl amine neutralized acid compound,such as neutralized phosphates and hydrocarbyl phosphate
esters, neutralized fatty acids (e.g., those having about
8 to about 22 carbon atoms), neutralized aromatic
carboxylic acids (e.g., 4-tertiarybutyl benzoic acid),
neutralized naphthenic acids and neutralized hydrocarbyl
sulfonates. Mixed salt esters of alkylated succinimides
are also useful. Particularly useful amines include the
alkanol amines such as ethanol amine, diethanolamine.
Mixtures of two or more of any of the aforedescribed
corrosion-inhibitors can also be used. The corrosion-
X
8i~
- 33 -
inhibitor is usually present in concentrations in which
they are effective in inhibiting corrosion of metals with
which the aqueous composition comes in contact.
Certain of the aqueous systems of the present
invention (particularly those that are used in cutting or
shaping of metal) can also contain at least one polyol
with inverse solubility in water. Such polyols are those
that become less soluble as the temperature of the water
increases. They thus can function as surface lubricity
agents during cutting or working operations since, as the
liquid is heated as a result of friction between a metal
workpiece and work tool, the polyol of inverse solubility
"plates out" on the surface of the workpiece, thus
improving its lubricity characteristics.
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
pùblication "Functional Materials" under the heading
"Antimicrobials" on pages 9-20 thereof. Generally, these
bactericides are water-soluble, at least to the extent to
allow them to function as bactericides.
The aqueous systems of the present invention can also
include such other materials as dyes, e.g., an acid green
dye; water softeners, e.g., ethylene diamine tetraacetate
sodium salt or nitrilo triacetic acid: odor masking
agents, e.g., citronella, oil of lemon, and the like; and
anti-foamants, such as the well-known silicone anti-
foamant agents.
The aqueous systems of this invention may also
include an antifreeze additive where it is desired to use
the composition at a low temperature. Materials such as
ethylene glycol and analogous polyoxyalkylene polyols can
12g~84~
- 3~ -
be used as antifreeze agents. Clearly, the amount used
will depend on the degree of antifreeze protection desired
and will be known to those of ordinary skill in the art.
It should also be noted that many of the ingredients
described above for use in making the aqueous systems of
this invention are industrial products which exhibit or
confer more than one property on such aqueous composi-
tions. Thus, a single ingredient can provide several
functions thereby eliminating or reducing the need for
some other additional ingredient. Thus, for example, an
extreme pressure agent such as tributyl tin oxide can also
function as a bactericide.
While the invention has been described and illus-
trated with reference to certain preferred embodiments
thereof, those skilled in the art will appreciate that
various changes, modifications and substitutions can be
made therein without departing from the spirit of the
invention. For example, different concentration ranges
other than the preferred ranges set forth hereinabove may
be applicable as a consequence of variations in the oil
base stock or the type of engine or the like. It is
intended, therefore, that the invention be limited only by
the scope of the claims which follow.
