FUNCTIONAL FLUIDS AND CONCENTRATES CONTAINING ASSOCIATIVE POLYETHER THICKENERS AND CERTAIN METAL DIALKYLDITHIOPHOSPHATES

FLUIDES ET CONCENTRES FONCTIONNELS RENFERMANT UN EPAISSISSANT DE POLYETHER ASSOCIE ET DES DIALKYLDITHIOPHOSPHATES DE CERTAINS METAUX

English Abstract

FUNCTIONAL FLUIDS AND CONCENTRATES CONTAINING
ASSOCIATIVE POLYETHER THICKENERS
AND CERTAIN METAL DIALKYLDITHIOPHOSPHATES
Abstract of the Disclosure
The invention relates to functional fluid concen-
trates and functional fluids which can be prepared by mixing
the concentrates with water. The functional fluid concen-
trate comprises certain basic zinc salts as cloud point
raising additives; a polyether nonionic surfactant; and an
associative polyether thickener.

Claims

The embodiments of the invention in which an
exclusive privilege or property is claimed are defined as
follows:
1. A functional fluid concentrate which com-
prises:
(a) a cloud point raising basic zinc salt
additive having an empirical formula which is
represented by either
(a)
<IMG>
(b) <IMG>
wherein R is a linear or branched alkyl,
alkenyl, aryl, arylakyl, or alkylaryl groups
having from 1 to 24 carbon atoms;
(b) from 0.5 to 10.0 parts by weight of a
polyether nonionic surfactant; and
(c) from 0.01 part to 50.0 parts by weight of an
associative polyether thickener, said weights
based upon 1.0 part by weight of the cloud
point raising additive.
22

2. The concentrate of claim 1 wherein from 0.1
part to 10 parts of a nitrogen-containing, phosphorous-free
carboxylic solubilizer is also used, said weight based upon
1.0 part of the cloud point raising additive.
3. The concentrate of claim 2 wherein compo-
nent (b) is used in an amount of 0.5 part to 5.0 parts by
weight; component (c) is used in an amount of 0.5 part to
5.0 parts by weight; and component (d) is used in an amount
of 0.2 to 3.0 parts by weight, said weights being based upon
1.0 part by weight of the cloud point raising additive.
4. The concentrate of claim 3 wherein a linear or
branched alkanolamine is also used in the concentrate.
5. The concentrate of claim 4 wherein a mixture
of triethanolamine and diisopropylaminoethanol is used as
the alkanolamine component.
6. The concentrate of claim 5 wherein the amount
of triethanolamine used is from 0.5 part to 2.5 parts by
weight and the amount of diisopropylaminoethanol is from 0.5
part to 1.5 parts by weight based upon 1.0 part of the cloud
point raising additive.
7. The concentrate of claim 6 which contains
tolyltriazole in an amount of 0.001 part to 2.0 parts by
weight per 1.0 part by weight of the cloud point raising
additive.
23

8. The concentrate of claim 2 wherein the
surfactant is an ethylene oxide adduct of a mixture
of C12-15 alcohols such that the average molecular weight is
from 300 to 5000.
9. The concentrate of claim 3 wherein the
surfactant is an ethylene oxide adduct of a mixture
of C12-15 alcohols such that the average molecular weight is
from 300 to 5000.
10. The concentrate of claim 4 wherein the
surfactant is an ethylene oxide adduct of a mixture
of C12-15 alcohols such that the average molecular weight is
from 300 to 5000.
11. The concentrate of claim 5 wherein the
surfactant is an ethylene oxide adduct of a mixture
of C12-15 alcohols such that the average molecular weight is
from 300 to 5000.
12. The concentrate of claim 6 wherein the
surfactant is an ethylene oxide adduct of a mixture
of C12-15 alcohols such that the average molecular weight is
from 300 to 5000.
13. The concentrate of claim 2 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of
24

ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
14. The concentrate of claim 3 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of
ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
15. The concentrate of claim 4 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of
ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
16. The concentrate of claim 5 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of

ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
17. The concentrate of claim 6 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of
ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
18. The concentrate of claim 7 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of
ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
19. The concentrate of claim 8 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of
26

ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
20. The concentrate of claim 9 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of
ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
21. The concentrate of claim 11 wherein the
associative thickener has an average molecular weight of
5000 to 40,000 and is prepared by reacting a mixture of
ethylene oxide and propylene oxide in a weight ratio of 3:1
to 10:1 with trimethylol propane and then reacting with an
alpha-olefin epoxide such that the weight percent of alpha-
olefin oxide in the associative thickener is from 1 to 20
percent.
22. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 1 such that about 60 to 99.9 percent by
27

weight of the fluid is water, a freezing point lowering
additive, or both.
23. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 2 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
24. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 3 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
25. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 4 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
26. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 5 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
28

27. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 6 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
28. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 7 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
29. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 8 such that about 60 to 99 percent by weight
of the fluid is water,a freezing point lowering additive, or
both.
30. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 9 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive
or both.
31. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 10 such that about 60 to 99 percent by weight
29

of the fluid is water, a freezing point lowering additive,
or both.
32. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 11 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
33. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 12 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
34. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 13 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
35. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 14 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.

36. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 15 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
37. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 16 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
38. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 17 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
39. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 18 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
40. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 19 such that about 60 to 99 percent by weight
31

of the fluid is water, a freezing point lowering additive,
or both.
41. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 20 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
42. A functional fluid comprising water, a
freezing point lowering additive, or both, and the concen-
trate of claim 21 such that about 60 to 99 percent by weight
of the fluid is water, a freezing point lowering additive,
or both.
32

Description

i7~
1~1S-2
F~NCTIONAL FLUIDS AND CONCENTRATES COMTAINING
ASSOCIATIVE POLYETHER THIC~ENERS
AND CERTAIN METAL DIALKYLDITHIOPEIOSPHATES
.
Background of the Invention
1 Field of the Invention
.
This invention relates to functional fluids and
concentrates thickened with associative polyether thick-
eners. In addition to the associative polyether thickener,
the fluid~ and concantrates also contain a cloud point
raising additive which is a basic zinc salt of the pre-
scribed formulae, a polyether nonionic surfactant, prefer-
ably an alkanolamine, and other optional ingredients.
2. Description of the Prior Art
It is known to formulate functional fluids with
associative polyether thickeners. See, for instance, U. S.
Patents 4,411,819 and 4,312,768. However, the fluids
described in these patents have wear rates of approximately
20 milligrams per hour, and have cloud points of approx-
imately 160F. Because of the high wear, these fluids are
not satisfactory in pumps which operate under severe
conditions such as vane pumps which may operate at high
pressures (greater than 5ao psi), or in systems which may
have sump te~peratures above 150F or localized temperatures

~2~71~
(such as where directional valves are placed) as high as
200F.
Summary of the Invention
The invention relates to functional fluid concen-
trates and functional fluids which can be prepared by mixing
the concentrates with water. The functional Eluids can be
used in hydraulic systems or as metalworking compositions to
cool and lubricate surfaces which are in frictional contact
during operations such as the turning~ cutting, peeling, or
the grinding of metals.
The functional fluid concentrate comprises:
~a) a cloud point raising basic zinc salt
additive having an empirical formula which i9
represented by either
(i) Zn2 ~RO)~PS~] OH~ or
(ii) zn4~(R)2Ps2~ 6 '
wherein R is a linear or branched alkyl,
alkenyl, aryl, arylalkyl, or alkyLaryl groups
having ~rom 1 to 24 carbon atoms, preferably
2 to 20.
-- 2 --

~;~6S~
(b) a polyether nonionic surfactant, and
(c) an associative polyether thickener.
Preferably the concentrate also contain~ a linear or
branched alkanolamine having 2 to 20 carbon atoms.
Functional fluids can be prepared from the subiect
concentrate by diluting the concentrate with water such that
approximately 60 to 99.9 percent of the fluid will consist
of water. Alternatively, some or all of the water of
dilution may be replaced by a freezing point lowering
additive ~uch as ethylene glycol, propylene glycol, butylene
glycol, diethylene glycol, dipropylene glycol, triethylene
yCGl~ tetraethylene glycol, and ~he like, or mixtures
thereof. Functional fluids prepared with the subject
:
concentrates have viscosities which may exceed 200 SUS àt
100F which is substantially maintained at increased
temperatures. They also have cloud points as high as 205F
and, thus, are able to be utilized ~in~systemo which may have;
sump temperatures or~localized temperatures (auch as might
exist where directional valves are placed) of up to 200F or
20 ~ higher. In the Vicker~ ~ane Pump Test, a widely used test~
of the antiwear properties of a hydraulic ~luid, the fluids ;~
will generally have wear rates of less than 10 mgthour and
~: '
:~
'~
:

;'78~
are likely to have wear rates of less than 5 mg/hour over
long term operations such as 100 hours or more.
Descrip~on of the Preferred Embodiments
The cloud point raising additive is a basic zinc
salt having an empirical formula as set forth previously.
These compounds are commercially available. A method of
preparation i9 described by Wystrach et al, Journal_of
Organic Chemistr~, "Basic Zinc Double Salts of 0,0-dialkyl
Phosphorodithioic Acids," pp. 705-707, (June 1956).
In general, any polyether nonionic surfactant ~can
be used in the practice o this invention provided that it
will mix with the associative thickener, cloud point raising
additive and other ingredients in water. Such polyether
nonionic surfactants are well known in the art. They are
prepared by reacting an alkylene oxide with an active
hydrogen-containing compound to form a molecule having an
average molecular weight of approximately 300 to 10,000,
preferably 500 to 5000, and most preferably 500 to 2000,
which contains a hydrophobe segment and a hydrophile
segment. However, they do not contain a hydrophobe segment
based upon an alpha-olefin epoxide or glycidyl ether
addition as do the associative thickeners described in a
subsequent part of this specification.
Althou~h other polyether nonionic surfactants may
work satisfactorily, three groups of surfactants have been

~2~iS~3 [11
shown to work particularly well. The most preferred group
consists of polyether nonionic surfactants prepared by
reacting a preferably aliphatic alcohol, fatty acid, fatty
acid amide, amine initiator (preferably an alcohol initi-
ator) having about 12 to about 18 carbon atoms, preferably
about 12 to about 15 carbon atoms, with ethylene oxide to
prepare a homopolymer containing the residue of about 5 to
about 100 moles of ethylene oxide. Preferably, about 5 to
about 20 moles of ethylene oxide are reacted with the
initiator to prepare said homopolymer polyether surfac-
tants. Alternatively, block or heteric copolymers can be
prepared using as reactants ethylene oxide and a lower
alkylene oxide, preferably having 3 to 4 carbon atoms. The
residue of ethylene oxide in said polyether copolymer
generally is at least about 70 percent by weight when the
lower alkylene oxide used with ethylene oxide has 3 carbon
atoms. ~'he ethylene oxide residue in the polyether obtained
generally is about 80 percent by weight when a lower
alkylene oxide containing 4 carbon atoms i5 utilized with
ethylene oxide in the preparation of said ethoxylated
surfactant. Preferably, the average molecular weight of
~aid surfactant i5 about 500 to about 2000. Representative
aliphatic alcohol or amine initiators are octadecyl alcohol,
stearyl amine, lauryl alcohol, lauryl amine, myristyl
alcohol or amine, and cetyl alcohol or amine.

~.~657~1~
Another preferred group of polyether nonionic
surfactants is ethoxylated alkyl phenol~ having 1 to about
20 carbon atoms in the alkyl group and preerably an average
molecular weight of about 400 to about 2000. These are
derived from reaction of an alkyl phenol with ethylene oxide
to produce a homopolymer. Alternatively, a block or heteric
copolymer can be prepared by reacting ethylene oxide and a
lower alkylene oxide, preferably having 3 to 4 carbon atoms,
with an alkyl phenol. The alkyl phenol preferably has about
4 to about 20 carbon atom~ in the alkyl group. Preferably,
the ethoxylated alkyl phenols are derived from the reaction
of said alkyl phenol with ethylene oxide or ethylene oxide
and at least one lower alkylene oxide, preferably having 3
to 4 carbon atoms, provided that the ethoxylated polyether
copolymer surfactant obtained thereby contains at least 60
percent to abaut 96 percent by weight of ethylene oxide
residue. The ethoxylated homopolymer alkyl phenols contain
the residue of about 5 to about 100 moles of ethylene
oxide. Representative alkyl phenols useful in the prepara-
tion of alkoxylated alkyl phenol surfactants are octyl-
phenol, nonylphenol, dodecylphenol, dioctyphenol, dinonyl-
phenol, dodecylphenol and mixtures thereof.
The final group o~ preferred polyether nonionic
surfactant~ consist~ of ethylene oxide adduct~ o sorbitol
and sorbitan mono-, di-, and triesters having average
- 6 -

~L2~;5~
molecular weights of 500 to 5000, preferably 500 to 2000.
These suractants are well known in the art. These surfac-
tants are generally prepared by esterifying 1 to 3 moles of
a fatty acid and then Eurther reacting with ethylene
oxide. The fatty acids usually contain from 10 to 20 carbon
atoms, preferably 12 to 18 carbon atoms. Alternatively, a
block or heteric copolymer can be prepared by reacting
ethylene oxide and a lower alkylene oxide, preferably having
3 to 4 carbon atoms with the fatty acid ester. Preferably
the surfactants are prepared by the reaction of the ester
with ethylene oxide or ethylene oxide and at least one lower
alkylene oxide preferably having 3 to 4 carbon atoms
provided that the ethoxylated polyether copolymer surfactant
obtained thereby contains from about 20 percent to about 90
percent hy weight of ethylene oxide residue. The ethoxy-
lated homopolymers contain the residue of about 5 to about
100 moles of ethylene oxide. They are commercially sold
under the INDUSTROL~ trademark. Particularly useful are
INDUSTROL~ L20-S, INDUSTROL~ 020-S, INDUSTROL S20-S,
INDUSTROL~ 68, and INDUSTROL~ 1186.
The concentrate generally contains about 0.5 to
about 10.0 parts by weight of the polyether surfactant,
preferably about 1.0 to about 5.0 parts by weight per 1.0
part by weight of the cloud point raising additive.

gl26~
~ he associative polyether thickeners which are
used in the subject concentrates and functional fluids are
relatively new in the art and are disclosed in U. S.
Patents 4,288,639; 4,312,775; and 4,411,819. I'hese
th iC ke n e r s a r e p r e p a r e d b y f i r s t
reacting ethylene oxide or ethylene oxide and generally at
least one lower alkylene oxide with at least one active
hydrogen-containing compound and subsequently reacting
therewith at least one long chain aliphatic alpha-olefin
epoxide or glycidyl ether. The long chain alpha-olefin
epoxide or glycidyl ether has a carbon chain length of about
12 to about 18 aliphatic carbon atoms. The proportion of
alpha-olefin epoxide or giycidyl ether present in the
polyether thickener is ge~erally l to about 20 percent by
weight, based upon the total weight of the thickener.
The associative polyether polyol thickeners may be
readily prepared by modifying a conventional non-associative
polyether aqueous thickener by reacting it with an alpha-
olefin epoxide or glycidyl ether having about 12 to about 18
carbon atoms or mixtures thereof. The conventional non-
associative polyether polyol thickener can be an ethylene
oxide~derived homopolymer or a heteric or block copolymer of
ethylene oxide and at least one lower alkylene oxide
preferably having 3 to 4 carbon atoms. The ethylene oxide
i~ used generally as a reactant in the proportion of at
- 8 -

~265~
least 10 percent by weight based upon the total weight of
the polyether thickener. Preferably, about 60 to 99 percent
by weight ethylene oxide is utilized with about 40 to 1
percent by weight of a lower alkylene oxide preferably
having 3 to 4 carbon atoms.
The preferred non-associative polyether thickeners
used to prepare the associative thickeners are prepared by
methods well known in the art. Generally this involves
reacting an active hydrogen-containing compound in the
presence of an acidic or basic oxyalkylation catalyst and an
inert organic solvent at elevated temperatures in the range
of about 50C to 150C under an inert gas pressure, gen-
erally from about 20 to about 100 pounds per square inch
gauge. Generally, both monohydric and polyhydric alcohol
initiators are useful. Useful polyhydric alcohol initiators
are selected from the alkane polyols, alkena polyols, alkyne
polyols, aromatic polyols, and oxyalkylene polyols.
Monohydric alcohol initiators which are useful include
aliphatic monohydric alcohols and alkyl phenols containing
~0 about 12 to about 18 carbon atoms in the aliphatic or alkyl
group. In addition, aliphatic mercaptans having about 12 to
about 18 carbon atoms are useful initiators.
In this manner, heteric, block, and homopolymer
non-associative polyether thickeners, preferably having
average molecular weights of about 1000 to about 60,000,

~2GS780
preferably 5000 to 40,000, are prepared which can be used to
prepare associative polyether thickeners by reacting them
with long chain, aliphatic alpha-olefin epoxidss glycidyl
ether.
Generally, about 0.01 part to about 50.0 parts by
weight, preferably about 0.5 to about 5.0 parts by weight,
of the associative polyether thickener is used per 1.0 part
by weight of the cloud point raising additive~
Nitrogen-containing, phosphorous-free carboxylic
solubilizers may also be used in the subject concentrates
and hydraulic fluids. These are well known in the art and
are disclosed .in U.S. Patents 4,368,133 and 4,481,125.
A lt ho u g h a v a r i e ty o f s u c h c o m p o u n d s
a r e d i s c 1 o s e d i n t h e s e p a t e n ts , ge ne-
r a 1 1 y p re fe r r e d a r e r e ac t i o n p r o d u c ts of
an alkenyl succinnic anhydride and a dialkyl alkanolamine.
The concentra~e generally contains 0.1 part to 10
parts by weight, preferably 0.2 part to 5 parts by weight of
the nitrogen-contalning, phosphorous-free solubilizer, said
weight being based upon 1.0 part by weight of the cloud
point raising additive.
As was mentioned previously, concentrates and
functional fluids preferably contain linear or branched
alkanolamines having from 2 to 20 carbon atoms. Specific
examples of alkanolamines which may be used include:
-- 10 --

~;~6~;~7~
monoethanolamine, diethanolamine, triethanolamine, monoiso-
propanolamine, diisopropanolamine, triisopropanolamine, di-
sec-butanolamine, sec-butylaminoethanol, dimeth~lethanol-
amine, diethylethanolamine, aminoethylethanolamine, methyl-
ethanolamine, butylethanolamine, phenylethanolamine,
dibutylethanolamine, monoisopropylethanolamine, diisopropyl-
ethanolamine, phenylethylethanolamine, methyldiethanolamine,
ethyldiethanolamine, phenyldiethanolamine, dimethylisopro-
panolamine, 2-amino-2-methyl-1-propanol, and 2-amino-2-
ethyl-1,3-propanediol.
Particularly useful are triethanolamine, diethyl-
ethanolamine, diisopropylethanolamine and mixtures
thereof. The alkanolamines are used in amounts of 0.1 part
to 20 parts by weight, preferably 0.5 part to 5.0 parts by
wei~ht per 1.0 part o the cloud point raising additive.
Other optional ingredients which may be used in
the subject concentrates and functional fluids include
corrosion inhibitors such as alkali metal nitrites, nitrate-
s, phosphates, silicates and benzoates. Certain amines,
other than the alkanolamines previously described, may also
be u~eful. The inhibitors can be used individually or in
combinations. Representative examples of the preferred
alkali metal nitrates and benzoates which are useful are as
~ollow~: sodium nitrate, potassium nitrate, calcium
nitrate, barium nitrate, lithium nitrate, strontium nitrate,

~6$78~
sodium benzoate, potassium benzoate, calcium benzoate,
barium benzoate, lithium benzoate and ~trontium benzoate.
Representative amine type corrosion inhibitors are
morpholine, N-methylmorpholine, N-ethylmorpholine, tri-
ethylenediamine, ethylenediamine, dimethylaminopropylamine,
and piperazine.
The metal deactivators may also be u~ed in the
subject concentrates and functional fluids. Such materials
are well Xnown in the art and individual compounds can be
selected from the broad classes of materials useful for this
purpose such as the various triazoles and thiazoles as well
as the amine derivatives of salicylidenes. Representative
specific examples of these metal deactivators are as
follows: benzotriazole, tolyltriazole, 2-mercaptobenzothi-
azole, sodium 2-mercaptobenzothiaæole, and N,NI-disalicyli-
dene-1,2-propanediamine.
~ he corrosion inhibitors and metal deactivators
are generally u~ed in amounts of Erom about 0.001 part to
5.0 parts by weight, preferably 0.001 part to 0.2 part by
~ weight per 1.0 part of the cloud point raising additive.
The examples which follow will illustrate the
practice of thi~ invention in more detail. ~lowever, they
are not intended in any way to limit its scope. All parts,
proportions, and percentage~ are by weight, and all tempera-
tures are in degrees Fahrenheit unless otherwise ~pecified~
- 12

~2~5~
The follo~ling abbreviations will be used in the
Examples:
AMP - 2~amino-2-methyl-1-propanol
DIPAE - N,N-diisopropyl-2-aroinoethanol
E-69 - a 20 mole ethylene oxide adduct of sorbitan
trioleate
LUBRIZOL*5603 - reaction product of polyisobutenyl succinic
anhydride and an alkanolamine sold by
Lubrizol Corporation
P-45 - a 4 mole propylene oxide adduct of penta-
erythritol
Surfactant A - an ethylene oxide adduct of a mixture
of C -C alcohols having an average
molecular weight of 500 to 600
Surfactant B - a 9 mole ethylene oxide adduct of nonyl-
: phenol
: Surfactant C - a 13 mole ethylene oxide adduct of a
stearic acid
TEA - triethanolamine
: 20 Thickener #l - a non-associative polyether thickener
having an average molecule weight of 23,000
prepared by reacting a mixture of ethylene
oxide and propylene oxide ~using an
ethylene oxide/propylene oxide weight ratio
o~ 7S:25) with trimethylolpropane
- 13 -
* trade mark

~265~81D
Thickener #2 - an associative polyether thickener having
an average molecular weight of approx-
imately 17,000 prepared by reacting a
mixture of ethylene oxide and propylene
oxide (we.ight ratio of ethylene oxide to
propylene oxide of approximately 85:15) to
form a heteric intermediate, and then
reacting the intermediate with approx-
imately 4 to 5 weight percent of a mixture
15 18
alpha olefin epoxides.
TT - tolyltriazole (50 percent solution)
- 14
.: :

~L265~8~
ZDP-l* - zinc dialkyldithiophosphate wherein all R
groups are 2~ethylhexyl
ZDP-2* - zinc dialkyldithiophosphate wherein the R
groups are a mixture of isodecyl isomer~
ZDP-3* - zinc dialkyldithiophosphate wherein the R
groups have an average of 3.8 carbon atoms
ZDP-4* - antimonydialkyldithiophosphate wherein all
R groups are 2-ethylhexyl
ZDP-B - basic zinc salt wherein R is 2-ethylhexyl.
*These zinc compounds are not basic zinc salts and are
represented by the formula:
\ P/ ~ Z n/ \ P /
-- 15 --
. ~ .

~2~S7~3 03
EX~MPLES
Comparative Example A
A hydraulic 1uid was formulated by mixing 92.75
parts of water with 7.25 parts of a concentrate haviny the
following proportion of ingredients:
Ingredient Parts by Weight
TEA 1.0
DIPAE 0.7
Surfactant A 4.0
TT 0.15
Thickener #2 1.4
The cloud point for the above fluid was 162F.
Example 1
In order to show the effect of adding an additive
within the scope of the subject invention to the formulation
in Comparison Example A, several other hydraulic ~luids were
prepared by adding a metal dialkyldithiophosphate to the
concentrate described in Comparison Example A. ~he ~pecific
~ metal dialkyldithiophosphate and the amount used is given in
~able I. In each case the amount of water used in Compar-
ison Example A was reduced by the amount of the metal
dialkyldithiophosphate used so that the amounts of all
ingredients are based upon 100 parts of fluid.
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~. :

~s7ao
TABLE I
Example AdditiveAmount (pbw) Cloud Point (F)
1 ZDP-3 1.0 181
2 ZDP-l 0.5 195
3 ZDP-l 1.0 206
4 ZDP-2 1.5 200
ZDP-4 1.0 206
Examples 1-5 show that the additives of this
invention effectively raise the cloud point of the subject
hydraulic fluid.
The next Examples, 6-7, illustrate that this
phenomenon occurs when other surfactants are used. In these
Examples, the following proportions of ingredients were
used:
Ingredient Parts by Weight
DIPAE 1.0
TEA O.S
Surfactant B or C 4.0
ZDP-l 1.0
Thickener #2 1.3
:
When Surfactant B was used, the cloud point was 203F. When
Surfactant C was used, the cloud point was 198F.
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.

~2~ q~
Com~arison Example B
For comparison purposes, a fluid was for~ulated
having the formulation of the fluid de~cribed in Comparison
Example A except that 20 parts of Thickener #l waq used
instead of ln4 parts of Thickener #2. (Also, 72.65 parts by
weight of water were used instead of 92.75 parts by
weight.) The fluid had a cloud point of 173F. When l.S
parts by weight of ZDP-l were added, the cloud point of the
fluid was 175C.
This comparison indicates that additives such as
ZDP-l are not effective for raising the cloud point of
fluids containing thickeners such as Thickener ~1 even
though it does raise the cloud point of fluids having
thickeners such as m ickener ~2.
Examples 8-12 will illuqtrate what wear rates are
like for the hydraulic fluids within the ecope of this
invention. The flulds dlsclosed in Table II were formulated
by mixing the concentrate with water. The wear rates were
determined by using the Vickers ~ane Pump Test. The
hydraulic circuit and equipment used were as speclfied in
ASTM D2882 and D2271.
The Vickers Vane Pump Test procedure used herein
specifically requires charging the system with S gallons of
the test fluid and running at temperatures ranging from 100
to 13SF at 750 to 1000 psi pump discharge pressure
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' ~'

~26S~
(load). Wear data were made by weighing the cam-ring and
the vanes of the "pump cartridge" before and after the
test. At the conclusion oE the test run and upon dis-
assembly for weighing, visual examination of the system was
made for ~igns of deposits, varnish, corrosion, etc.
The various components and amounts used in the
fluids are given in Table II along with the wear rate data.
-- 19 --
:

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-- 20 --

Table II StlOWS that using the concentrates and
fluids within the scope of this invention, it is possible to
provide effective resistance again~t wear.
Ex_mple 13
This example will illustrate the use of a ba~ic
zinc salt (ZDP-B) as the cloud point raising additive. The
hydraulic fluid contained the following components and was
prepared as in Example 1:
Component Amount
(parts by weight)
Surfactant A 4.00
Thickener 2 1.70
ZDP-B 0.75
TEA 1.00
DIPAE 0.70
TT 0.15
H20 To 100 partq
The cloud point for the fluid was 200~ and the wear rate
was 3.5 mg/hr over 89 hours.
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