COMPOSITIONS FLUIDES INHIBITRICES D'OXYDATION ET PROCEDE DE PREPARATION CONNEXE

OXIDATION INHIBITED FLUID COMPOSITIONS AND A PROCESS FOR THE PREPARATION THEREOF ABSTRACT OF THE DISCLOSURE

Abrégé anglais

OXIDATION INHIBITED FLUID COMPOSITIONS AND
A PROCESS FOR THE PREPARATION THEREOF
ABSTRACT OF THE DISCLOSURE
Fluid compositions useful to serve as oxidation
inhibited functional fluids, and a process for the
preparation thereof, are provided. Such fluid
compositions comprise a colloidal dispersion of an
aromatic ether represented by the formula
<IMG>
wherein R1, R2, and R3 independently are phenyl,
biphenyl, and terphenyl and n is an integer of from
zero (0) to 5, and an oxidation inhibiting amount of an
alkali metal salt of oxalic acid.

Revendications

-30-
WHAT IS CLAIMED IS:
1. A fluid composition comprising a colloidal
dispersion of:
(a) an aromatic ether represented by the
formula
<IMG>
wherein R1, R2, and R3 independently are phenyl,
biphenyl, and terphenyl and n is an integer of from
zero (0) to 5, and
(b) an oxidation inhibiting amount of an
alkali metal salt of oxalic acid,
the fluid composition being characterized by being
transparent when subjected to visual inspection with
white light shining through the fluid composition at a
180° angle to the line of sight.
2. The fluid composition of Claim 1 wherein
the aromatic ether is a polyphenyl ether.
3. The fluid composition of Claim 2 wherein
the polyphenyl ether is a mixture of five-ring
polyphenyl ethers having the nonterminal phenylene
rings linked through oxygen in the meta and para
positions.
4. The fluid composition of Claim 3 wherein
the mixture of five-ring polyphenyl ethers comprises a
composition, by weight, of 64-65% m-bis(m-phenoxy-
phenoxy)benzene, 30-32% m-[(m-phenoxyphenoxy)(p-
phenoxyphenoxy)]benzene, and 3-6% m-bis(p-phenoxyphen-
oxy)benzene.

-31-
5. The process of Claim 4 wherein the mixture
of five-ring polyphenyl ethers comprises a composition,
by weight, of 64% m-bis-(m-phenoxyphenoxy)benzene, 32%
m-[(m-phenoxyphenoxy)(p-phenoxyphenoxy)]benzene, and 4%
m-bis(p-phenoxyphenoxy)benzene.
6. The fluid composition of Claim 2 wherein
the polyphenyl ether is a six-ring polyphenyl other.
7. The fluid composition of Claim 6 wherein
the six-ring polyphenyl ether is bis[m-(m-
phenoxyphonoxy)-phenyl ] ether.
8. The fluid composition of Claim 1 wherein
the aromatic ether is a phenoxybiphenyl.
9. The fluid composition of Claim 8 wherein
the phenoxybiphenyl is selected from the group
consisting of o-phenoxybiphenyl, p-phenoxybiphenyl, and
mixtures thereof.
10. The fluid composition of Claim 1 wherein
the aromatic ether is a bis(biphenylyl) ether.
11. The fluid composition of Claim 10 wherein
the bis(biphenylyl) ether is selected from the group
consisting of bis(o-biphenylyl ) ether, bis(p-
biphenylyl) ether, bis(o-biphenylyl)(p-biphenylyl)
ether, and mixtures thereof.
12. The fluid composition of Claim 1 wherein
the aromatic ether is a diphenoxybiphenyl.
13. The fluid composition of Claim 12 wherein
the diphenoxybiphenyl is selected from the group
consisting of 4,4'-diphenoxybiphenyl, 3,4-
diphenoxybiphenyl, and mixtures thereof.
14. The fluid composition of Claim 1 wherein
the aromatic ether is selected from the group
consisting of phenoxyterphonyls and
diphenoxyterphenyls.

-32-
15. The fluid composition of Claim 14 wherein
the aromatic ether is a phenoxyterphenyl.
16. The fluid composition of Claim 15 wherein
the phenoxyterphenyl is 4-phenoxy-m-terphenyl.
17. The fluid composition of Claim 14 wherein
the aromatic ether is a diphenoxyterphenyl.
18. The fluid composition of Claim 17 wherein
the diphenoxyterphenyl is 4,4'-diphenoxyterphenyl.
19. The fluid composition of Claims 1, 2, 3,
4, 5, 6, or 7 wherein the colloidal dispersion of the
alkali metal salt of oxalic acid in the aromatic ether
has a concentration of from about 0.20 mmol to about
2.50 mmols of alkali metal salt of oxalic acid per kg
of fluid composition.
20. The fluid composition of Claim 19 wherein
the concentration of the alkali metal salt of oxalic
acid is from about 0.30 mmol to about 2.00 mmols per kg
of fluid composition.
21. The fluid composition of Claim 1 wherein
the alkali metal of the alkali metal salt of oxalic
acid is selected from the group consisting of sodium
and potassium.
22. The fluid composition of Claim 21 wherein
the alkali metal of the alkali metal salt of oxalic
acid is potassium.

-33-
23. A process for the preparation of an
oxidation inhibited fluid composition comprising:
(a) mixing an aromatic ether represented by
the formula
<IMG>
wherein R1, R2, and R3 independently are phenyl,
biphenyl, and terphenyl and n is an integer of from
zero (0) to 5, and an alkali metal precursor compound
convertible under alkali metal precursor compound
conversion conditions into an alkali metal salt of
oxalic acid,
(b) heating the aromatic ether/alkali metal
precursor compound mixture from Step (a) at an elevated
temperature in the presence of molecular oxygen or a
molecular oxygen-containing gas and for a time
sufficient to convert the alkali metal precursor
compound into an alkali metal salt of oxalic acid and
form a colloidal dispersion of the aromatic ether and
an oxidation inhibiting amount of the alkali metal salt
of oxalic acid, and
(c) separating any noncolloidally dispersed
solid material from the colloidal dispersion to thereby
recover the oxidation inhibited fluid composition,
the fluid composition being characterized by being
transparent when subjected to visual inspection with
white light shining through the fluid composition at a
angle to the line of sight.
24. The process of Claim 23 wherein the
aromatic ether is a polyphenyl ether.

-34-
25. The process of Claim 24 wherein the
polyphenyl ether is a mixture of five-ring polyphenyl
ethers having the nonterminal phenylene rings linked
through oxygen in the meta and para positions.
26. The process of Claim 25 wherein the
mixture of five-ring polyphenyl ethers comprises a
composition, by weight, of 64-65% m-bis(m-
phenoxyphenoxy)benzene, 30-32% m-[(m-phenoxyphenoxy)-
( p-phenoxyphenoxy)]benzene, and 3-6% m-bis(p-
phenoxyphenoxy)benzene.
27. The process of Claim 26 wherein the
mixture of five-ring polyphenyl ethers comprises a
composition, by weight, of 64% m-bis(m-
phenoxyphenoxy)benzene, 32% m-[(m-phenoxyphenoxy)(p-
phenoxyphenoxy)]benzene, and 4% m-bis(p-phenoxyphen-
oxy)benzene.
28. The process of Claim 24 wherein the
polyphenyl ether is a six-ring polyphenyl ether.
29. The process of Claim 28 wherein the six-
ring polyphenyl ether is bis[m-(m-
phenoxyphenoxy)phenyl] ether.
30. The process of Claim 23 wherein the
aromatic ether is a phenoxybiphenyl.
31. The process of Claim 30 wherein the
phenoxybiphenyl is selected from the group consisting
of o-phenoxybiphenyl, p-phenoxybiphenyl, and mixtures
thereof.
32. The process of Claim 23 wherein the
aromatic ether is a bis(biphenylyl) ether.

-35-
33. The process of Claim 32 wherein the
bis(biphenylyl) ether is selected from the group
consisting of bis(o-biphenylyl) ether, bis(p-
biphenylyl) ether, (o-biphenylyl)(p-biphenylyl) ether,
and mixtures thereof.
34. The process of Claim 23 wherein the
aromatic ether is a diphenoxybiphenyl.
35. The process of Claim 34 wherein the
diphenoxybiphenyl is selected from the group consisting
of 4,4'-diphenoxybiphenyl, 3,4-diphenoxybiphenyl, and
mixtures thereof.
36. The process of Claim 23 wherein the
aromatic ether is selected from the group consisting of
phenoxyterphenyls and diphenoxyterphenyls.
37. The process of Claim 36 wherein the
aromatic ether is a phenoxyterphenyl.
38. The process of Claim 37 wherein the
phenoxyterphenyl is 4-phenoxy-m-terphenyl.
39. The process of Claim 36 wherein the
aromatic ether is a diphenoxyterphenyl.
40. The process of Claim 39 wherein the
diphenoxyterphenyl is 4,4'-diphenoxyterphenyl.
41. The process of Claim 23 wherein the alkali
metal of the alkali metal precursor compound is
selected from the group consisting of sodium and
potassium.
42. The process of Claim 41 wherein the alkali
metal of the alkali metal precursor compound is potas-
sium.
43. The process of Claim 23 wherein the
alkali metal precursor compound is selected from the
group consisting of compounds which are insoluble,
partially soluble, and soluble in the aromatic ether.

-36-
44. The process of Claim 43 wherein the alkali
metal precursor compound is insoluble in the aromatic
ether.
45. The process of Claim 44 wherein the
insoluble alkali metal precursor compound is an alkali
metal carbonate.
46. The process of Claim 45 wherein the alkali
metal carbonate is selected from the group consisting
of sodium and potassium carbonate.
47. The process of Claim 46 wherein the alkali
metal carbonate is potassium carbonate.
48. The process of Claim 43 wherein the alkali
metal precursor compound is partially soluble in the
aromatic ether.
49. The process of Claim 48 wherein the
partially soluble alkali metal precursor compound is an
alkali metal phenate.
50. The process of Claim 49 wherein the alkali
metal phenate is selected from the group consisting of
sodium phenate and potassium phenate.
51. The process of Claim 50 wherein the alkali
metal phenate is potassium phenate.
52. The process of Claim 43 wherein the alkali
metal precursor compound is soluble in the aromatic
ether.
53. The process of Claim 52 wherein the
soluble alkali metal precursor compound is selected
from the group consisting of an alkali metal m-
phenoxyphenate, an alkali metal m-(m-phenoxyphenoxy)-
phenate, and mixtures thereof.
54. The process of Claim 53 wherein the
soluble alkali metal precursor compound is an alkali
metal m-phenoxyphenate.

-37-
55. The process of Claim 54 wherein the alkali
metal m-phenoxyphenate is selected from the group
consisting of sodium m-phenoxyphenate and potassium m-
phenoxyphenate.
56. The process of Claim 55 wherein the alkali
metal m-phenoxyphenate is potassium m-phenoxyphenate.
57. The process of Claim 53 wherein the
soluble alkali metal precursor compound is an alkali
metal m-(m-phenoxyphenoxy)phenate.
58. The process of Claim 57 wherein the alkali
metal m-(m-phenoxyphenoxy)phenate is selected from the
group consisting of sodium m-(m-phenoxyphenoxy)phenate
and potassium m-(m-phenoxyphenoxy)phenate.
59. The process of Claim 58 wherein the alkali
metal m-(m-phenoxyphenoxyphenate is potassium m-(m-
phenoxyphenoxy)phenate.
60. The process of Claim 23 wherein the
aromatic ether/alkali metal precursor compound mixture
has a concentration of from about 1 mmol to about 20
mmols of the alkali metal precursor compound per kg of
aromatic ether.
61. The process of Claim 60 wherein the
concentration of the alkali metal precursor compound is
from about 5 mmols to about 15 mmols per kg of aromatic
ether.
62. The process of Claim 61 wherein the
concentration of the alkali metal precursor compound is
from about 8 mmols to about 12 mmols per kg of aromatic
ether.

-38-
63. The process of Claim 23 wherein the
aromatic ether/alkali metal precursor compound mixture
is heated at a temperature of from about 225° C to
about 300° C for a period of time of from about 3 hours
to about 48 hours.
64. The process of Claim 63 wherein the
temperature is about 280° C.
65. The process of Claim 63 wherein the period
of time is from about 12 hours to about 36 hours.

Description

892~
-1- 43-21(7857)A -
OXInATION INHIBITED FLUI~ COM~ITIONS ~ND
A PROCESS FOR THE PREPARA3ION THEREOF
5BACKGROUND OF THE INVE~IQ~
1. Field of the Invention
This invention relates to fluid compositions
and a process for the preparation of ~uch compositions.
More particularly, this invention relates to fluid
10 compositions comprising a colloidal dispersion of an ~ .
aromatic ether represented by the formula
Rl-O ~ R2-o~ R3 - ~ :
wherein Rl, R2, and R3 independently are phenyl, : .
biphenyl, and terphenyl and n is an integer of from
zero (O) to 5, and an oxidation inhibiting amount of an
alkali metal salt of oxalic acid and a process for the - :
preparation thereof.
The fluid compositions of thi~ invention are
useful in a number of applications requiring fluids .:~
resistant to oxidative and thermal degradation under
use conditions of high stress (such a~ elevated
temperatures of 316- C (600- F) and higher. For
example, the fluid compositions are useful as atomic
reactor coolants, diffusion pump fluids, damping
fluid~, force transmission fluids (hydraulic fluids),
¦ h-at transfer fluids, and synthetic lubricants,
particularly as jet engine lubricants.
2. Description of the Prior Art
Aromatic ethers, particularly polyphenyl
ethers (wherein each of R1, R2, and R3 is phenyl), and
their use as functional fluid compositions are well
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~IJ~892,~
-2- 43-21(7857)A
known in the art. They are oxidatively stable to about
275- c (527' F) and resist pyrolysia to about 445- C
(833' F). However, at temperatures above their
stability limits, the aromatic ethers tend to develop
sludge and thlcken to a degree which adversely af~ects
their high temperature performance. Therefore, a
variety of additives have been proposed and disclosed
in the prior art to stabilize the aromatic ethers
against oxidative dsgradation and thereby extsnd their
operation range.
The susceptibility of the aromatic ethers to ~-
some degree of oxidative stabilization by a variety of -
metals (or their oxides and carboxylates) was reported .-
for polyphenyl ethers by Ravner et al, J. Chem. Eng.
15 ~9~, 8, 591-596 (1963).
U. S. Patent No. 3,245,907 discloses the
stabilization of polyphenyl ethers against oxidative
degradation by the incorporation therein of an
organotin compound repre~ented by the formula
~ -
R~-Sn-X~
and ~
- ~-.
R3-Sn-Sn-R~
- ~
wherein R i8 an alkyl, aryl, aralkyl, aryloxyaryl, ~ -
biaryl, thienyl, and pyridyl group; X is R or a
h~logsn, and m is an integer (whole number) of from 1
to ~.
In ~.S. Patent No. 3,290,247, polyphenyl sther
compositions having improved antioxidant propsrties are
disclosed and claimed. The oxidative stabilization of
''` ''.
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~,.~ ''.' " ' ' . .
"' " . ' .
~.. .. .
~.'','''~.

8 9 2 3
-3- 43-21(7857)A
the polyphenyl ethers i9 achieved by incorporating
therein organotin compounds represented by the formula
(I) FnSn~XR')~ -
wherein n is an integer of from 2 to 3, m is an integer
of from 1 to 2, and the sum of m + n is 4; R is an
alkyl group ~referred to in the reference as a radical)
of from 1 to 12 carbon atoms, benzenoid hydrocarbon
groups which are free of olefinic and acetylenic
unsaturation and contains from 6 to 12 carbon atoms,
and aryloxyaryl groups of from 12 to 24 carbon atoms,
and such groups having halogen substituted at the -
benzenoid nucleus; R' is R, paraffinic and
lS haloparaffinic acyl groups of from 2 to 12 carbon ~ .
atoms, the group
.~ ~
-N Z
~... .. J
wherein Z is a necessary member to complete a saturated
heterocyclic group of from 6 to 10 members, the groups
-SnR3 and -arylene-0-SnR3; and X is a chalcogen element
25 having an atomic weight of less than 33, and those -:
represented by the formula
R
_ -Y-X-~n-X- _
_ _ Y
wherein Y is an arylene group of from 6 to 12 carbon
atoms, an arylenealkylenearylene group and
~` ``';:.
'
:::
:
~:~
.,

~ 8923
-4- 43-21(7857)A
alkylenearylenealkylene group having from 1 to 4 carbon
atoms in the alkylene group and from 6 to 12 carbon
atoms in the arylene radical, R and X are as previ-
ously defined, and y is a number of from 10 to lO00 (to
denote the degree of polymerization).
U.S. Patent No. 3,492,229 discloses, inter
, aromatic ether compositions which exhibit
improved oxidation resistance. Such compositions are ~ -
provided by incorporation of organic salts of alkali
metals, antimony, bismuth, and lanthanum into the
aromatic ether basestock. Such compositions reportedly
are useful as ~et engine lubricants, heat transfer -~ ~
fluids and hydraulic fluids. -
Although these prior art aromatic ether
compositions generally exhibit increased oxidation
stability over aromatic ether~ themselves, they, in
general, are limited in their application usefulness as
functional fluids and engine lubricants under high
stress conditions extant in present-day high stress
engines -- jet engines, for example -- as well as
engines currently under development for the next
generation of ~et engines. For example, as the speed
and ~ltitud~ of operation oP jet engine-containing -
vehicles increases, lubrication problems also have
increased because of increased operating temperatures
and higher bear~ng pressures resultinq from the
increa~ed thrust needed to obtain and maintain high
s~ ~ds and altitudes. And as the service conditions
encountered become increasingly severe, the useful life
30 of the functional fluid is shortened, primarily due to -
their deficiency in oxidative stability above about
275- C (550- F). In general, as operating requirements --
of a ~et engine are increased, engine temperatures
:. , -
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`` 2n48923
-5- 43-21(7857)A
increase and oil temperatures in the range of 316- C
(600' F) and higher are encountered. Accordingly,
research efforts are continually being made to define
new or improved fluid compositions, and processes o~
making new and old fluid compositions, particularly
aromatic ether compositions, and most particularly
polyphenyl ether compo~itions, which exhibit increased
oxidative stability and concomitantly are suitable for
use as functional ~luids under use condit~on~ o~ high
stress. The discovery of the fluid compositions of the
instant invention, and the process for the preparation
thereof, therefore, is believed to be a decided advance
in the functional fluid art.
SUMMARY OF THE INVENTION
lS This invention i8 directed to fluid
compositions having increased oxidative stability under
use conditions of high stre6s (such as elevated
temperatures of 316' C ~600- F) and higher) and a
process for the preparation of such fluid compoeitions.
Accordingly, the primary ob~ect of this invention is to
provide fluid compositions having increased resistance --
to oxidative degradation under use conditions of high
stress.
It i~ another primary object of this invention
to provide a process for the preparation of oxidation
inhibited rluid compositions having increased
rosistance to oxidative degradation under use
condition~ of high stress.
These and other objects, aspects, and
advantage~ of the instant invention will become
apparent to thosQ skilled in the art from the
accompanying description and claims.
, . . .
.
~'' '

4~923
-6- 43-21(7857)A
The above primary ob~ct of providing ~ ~ -
oxidation inhibited fluid compositions, as well as ~ ~ .
other related ob~ects, are achieved by fluid
compositions which comprise a colloidal dispersion of:
(a) an aromatic ether represented by the : :
formula :
Rl-O--~- R2-o--~ R3
10 wherein Rl, R2, and R3 independently are phenyl, -
biphenyl, and terphenyl and n is an integer from zero
(Q) to 5, and : - .
(b) an oxidation inhibiting amount of an
alkali metal salt of oxalic acid,
the fluid composition being characterized by being
transparent when sub~ected to visual inspection with
white light ~hining through the fluid composition at a:.
180- angle to the line of sight.
The above additional primary ob~ect of
20 providing a process for the preparation of oxidation ..
inhibited fluid compositions, as well as other related - : -
ob~ects, are achieved by a procass which comprises~
(a) mixing an aromatic ether represented by :-.
ths formula
R1~~~~- R2-o--~ R3
w~ rein R1, R2, and R3 independently are phenyl, ~ -.
biphenyl, and terphenyl and n is an integer from zero ~.`
30 (0) to 5, and an alXali metal precursor compound . .
convertible under alkali metal precursor compound
conversion conditions into an alkali metal salt of
oxalic acid,
s': /. ;. .~ . ~ '
~ ` . . .

~)4~9~
-7- 43-21(7857)A
(b) heating the aromatic ether/alkali metal
precursor compound mixture from Step (a) at an elevated
temperature in the presence of molecular oxygen or a
molecular oxygen-containing gas and for a time
effective to convert the alkali metal precursor
compound into an alkali metal salt of oxalic acid and
form a colloidal dispersion of the aromatic ether and
an oxidation inhibiting amount of the alkali metal salt
of oxalic acid, and
(c) separating any noncolloidally dispersed
solid material from the colloidal dlspersion to
thereby recover the oxidation inhibited fluid
composition,
the fluid composition being characterized by being
transparent when subjected to visual inspection with
white light shining through the fluid composition at a
180- angle to the line of sight.
DESCRIPTION OF THE PREFERRED ENBODIMENTS
In accordance with this invention novel fluid
compositions, and a process for the preparation of
same, are provided which are useful as functional
fluids under u~e conditions of high stress. The fluid
compositions co~prise a colloidal dispersion of: -
(a) an aromatic ether represented by the
formula
Rl~~~~-- R2-o----~R3
wherein R1, R2, and R3 independently are phenyl,
biphenyl, and terphenyl and n is an integer from zero
(O) to 5, and
(b) an oxidation inhibiting amount of an
alkali metal salt of oxalic acid,
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.
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2~)48923
-8- 43-21(7857)A
the fluid composition being characterized by being
transparent when sub~eeted to visual inspection with
white light shining through the fluid eomposition at a
180- angle to the line of sight.
The oxidation inhibited ~luid compo~itions are
prepared by a proeess whieh eomprises~
(a) mixing an aromatie ether represented by
the formula
R1-ot-- R2-~ ] n R3
wherein Rl, R2, and R3 independently are phenyl,
biphenyl, and terphenyl and n is an integer from zero
(0) to 5, and an alkali metal preeursor compound
convertible under alkali metal preeursor eompound
conversion eonditions into an alkali metal salt of
oxalie aeid,
(b) heating the aromatie ether/alkali metal
preeursor compound mixture from Step (a) at an elevated
temperature in the presence of moleeular oxygen or a
moleeular oxygen-eontaining gas and for a time . -~
effective to eonvert the alkali metal precursor `.:. .
compound into an alkali metal salt of oxalie aeid and
form a colloidal dispersion of the aromatic ether and~ - :
25 an oxidation inhibiting amount of the alkali metal salt - :
of oxalie aeid, and
(e) separating any noncolloidally dispersed - -
solid material from the colloidal dispersion to -~;
thereby reeover the oxidation inhibited fluid ~`
eomposition,
the fluid co~position being characterized by being -~
transparent when subjeeted to visual inspeetion with :~
~:~
,~
.~, ...
~- '
.. -

~2098923
-9- 43-21(7857)A
white light shining through the fluid composition at a
180- angle to the line of sight.
For purposes of this invention, the term
"colloidal dispersion" means a system in which
particles of colloidal size (roughly between 1
nanometer (nm) and 1 micron (~m) of one state [solid
phase material (alkali metal salt of oxalic acid)~ are
dispersed in a continuous phase of a different state
[liquid phase material (aromatic ether)].
The aromatic ethers suitable for use in the
instant invention are those represented by the formula
R1-----~-- R2-o----~ R3
wherein Rl, R2, and R3 independently are phenyl,
biphenyl, and terphenyl and n is an integer of from
zero (0) to 5. Among the aromatic ethers, the
polyphenyl ethQrs are generally preferred in that they
20 are readily available and exhibit desirable properties
for a wide variety of applications. And among the
polyphQnyl ethers, those having all their ether
linkages in the meta position are in general most
preferred ~ince the all-meta linked ethers are the best
25 suited for many applications because of their wide
liquid range and high degree of thermal stability. v
How ver, mixtures of the polyphenyl ethers, that is,
~ther i~omeric mixtures or mixtures of homologous
eth-r~, ar- also suitable, particularly to obtain
30 certain prop~rties, for example, lower solidification
points.
Among the aromatic ethers, nonlimiting
examples of suitable polyphenyl ethers are diphenyl
i ~..... .
F
.
.~,.. . . .
.
~....... .. .
.

8~23
-lO- 43-21~7857)A
ether (also known as diphenyl oxide), the
diphenoxybenzQnes, for example, m-diphenoxybenzene, the
bis(phenoxyphenyl) ethers, for example, bis(m-
phenoxyphenyl) ether, the bis(phenoxyphenoxy)benzenes,
for example, m-bis(m-phenoxyphenoxy)benzene, m-bis(p-
phenoxyphenoxy)benzene, o-bis(o-phenoxyphenoxy)benzene,
the bis(phenoxyphenoxyphenyl) ethers, for example
bis~m-(m-phenoxyphenoxy)phenyl] ether, bistp-(p-
phenoxyphenoxy)phenyl] ether, [m-(m-phenoxyphenoxy)-
phenyl][o-(o-phenoxyphenoxy)phenyl~ ether, and the
bis(phenoxyphenoxyphenoxy)benzenes, for example,
m-bis[m-(m-phenoxyphenoxy)phenoxy]benzene,
p-bis[p-(m-phenoxyphenoxy)phenoxy]benzene,
m-bis[m-(p-phenoxyphenoxy)phenoxy]benzene.
It al80 ig contemplated that mixtures of the
polyphenyl ethers can be employed in the instant
invention. For example, mixtures of polyphenyl ethers
in which the nonterminal phenyl (phenylene) rings [that
i9, wherein R2, which is enclosed in the bracXets in the
above structural formula representation of suitable
aromatic ethers, is phenyl (phenylene)] are linked
through oxygen atoms in the meta and para positions, -~
are particularly suitable for use in the instant
invention in that such mixtures possess lower
25 solidification points and thus provide fluid ~ ~:
composition~ having wider liquid ranges.
Of these mixtures, that is, those having only
~ta and para linkages, a preferred polyphenyl ether
mIxture for use in the instant invention is the mixture
o~ five-ring polyphenyl ethers where the nonterminal
phenylene rings are linked through oxygen atoms in the
meta and para positions and composed, by weight, of
about 64-65% m-bis(m-phenoxyphenoxy)benzenQ, 30-32% m-
' ~
., . ~ ,
,. ..
.'-
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. '

~i~4892~
-11- 43-21(7857)A
[(m-phenoxyphenoxy)(p-phenoxyphenoxy)]benzene, and 3-
6% m-bis(p-phenoxyphenoxy)benzene, with the proviso
that the sum of the components must egual 100%, with a
mixture composed, by weight, of about 64% m-bis(m-
phenoxyphenoxy)benzene, 32% m-~(m-phenoxyphenoxy)(p-
phenoxyphenoxy)]benzene, and 4% m-bis(p-phenoxyphen-
oxy)benzene being most preferred. Such a mixture
solidifies at about 4~ C (40- F) whereas the three
components solidify individually at temperatures above
normal room temperatures.
In addition to the polyphenyl ethers (wherein
Rl, R2, and R3 are phenyl), suitable aromatic ethers
include those wherein at least one of R~, R2, and R~ is
biphenyl or terphenyl. Nonlimiting examples of such
aromatic ethers are the phenoxybiphenyls, for example,
o-phenoxybiphenyl, m-phenoxybiphenyl, p-
phenoxybiphenyl, the bis(biphenylyl) ethers, for
exampla, bis(o-biphenylyl) ether, bis(p-biphenylyl)
ether, (o-biphenylyl)(p-biphenylyl) ether, the i;
diphenoxybiphenyls, for example, those in which the
phenoxy group~ are attached as sub~tituents on
different aro~atic rings (of the biphenyl moiety), as
in 4,4'-diphenoxybiphenyl, or on the same aromatic
ring, as in 3,4-diphenoxybiphenyl, the `~--
phenoxyterphenyls, for example, 4-phenoxy-m-terphenyl,
and the diphenoxy-terphenyls, including, for example,
in ~ manner similar to that noted for the
diph-noxybiphenyls, those in which the phenoxy groups
are attached as substituents on different aromatic
rings (of the terphenyl moiety), as in 4,4'-diphenoxy-
m-terphenyl, or on the same aromatic ring, as in 3,4-
diphenoxy-m-terphenyl.
.
i . .-
..... .
' ~

2~8~3
-12- 43-21(7857)A
In a manner sim~lar to that previously
discussed for the polyphenyl ethers, it also is
contemplated that mixtures of the aromatic ethers, in
general, can be employed in the instant ~nvention. For
example, mixtures of o-phenoxybiphenyl and p-
phenoxybiphenyl and o-bis(biphenylyl) ether and p-
bis(biphenylyl) ether are suitable ~or use in the
instant invention. Such mixtures, in general, possess
lower solidification points and thereby provide fluid
compositions having wider liquid ranges.
The aromatic ethers suitable for use in the
instant invention can be obtained by the Ullmann ether
synthesis which broadly relate~ to ether-forming
reaction of, for example, alkali metal arenoxides (or
arenates) such as sodium and potassium phenoxides (or
phenates) with aromatic halides, for example,
bromobenzene and 4-iodo-4'-bromo-m-terphenyl in the
presence of a copper catalyst such as metallic copper,
copper hydroxides, or copper salts. Detailed
descriptions for the preparation of the polyphenyl
ethers are disclosed in U.S. Patent No. 3,451,061 and
Sax et al, "Preparation and Infrared Absorption Spectra
of Some Phenyl Ethers," J. Org. Chem., 25, 1590-1595
(1960). Detailed descriptions for the preparation of
25 the phenoxyterphenyls (including the multi phenoxy- -
substituted terphenyls) are disclosed in U.S. Patent
No. 4,143,077. Other aromatic ethers, such as, for
ex~Jple, the phenoxybiphenyls, can be prepared as by-
product~ in the caustic hydrolysis of chlorobenzene in
accordance with the detailed description disclosed in
U. S. Patent No. 4,092,364.
Compounds useful as source materials to
provide the alkali metal -- that is, the lithium,
~: . ,. ,: '
..: . .
.~` . - . ~
. ~ .

8 '3 ~ .~
-13- 43-21(7857)A
sodium, potassium, rubidium, and cesium -- salts of
oxalic acid component o~ the fluid co~positions of the
instant invention are not narrowly critical. All that
is necessary i~ that such compounds provide the desired
colloidal dispersion comprising an oxidation inhibiting
amount of the alkali metal salt of oxalic acid in the
aromatic ether. Suitable source material compounds are
compounds convertible at elevated temperatures in the
presence of molecular oxygen or a molecular oxygen-
containing gas -- that is, under eolloidal dispersion
forming conditions -- into the corresponding alkali
metal oxalate~. As such, compounds which are suitable
as source materials to provide th~ alkali metal
oxalates may be considered as precursors of the alkali
metal salts of oxalic acid or alkali metal oxalates.
Typical eompounds include those that are insoluble in
the aromatie ethers, for example, alkali metal
earbonates, those that are partially soluble in the
aromatic ethers, for sxample, alkali metal phenates,
and those that are soluble in the aromatic ethers, for
example, alkali metal phenoxyphenates and alkali metal
phenoxyphenoxyphenates. Among such alkali metal
compounds, thQ potassium salts are generally preferred
in that they are readily available and readily provide
the desired eolloidal dispersion.
The fluid compositions of the instant
in~ention ean be prepared by mixing the aromatic ether
ba~estoek with at least one alkali metal precursor
eo~pound to form a mixture in the form of a slurry,
slurry/solution, or solution, depending upon the
solubility of the alkali metal preeursor eompound in
the aromatic ether basestock.
~`"' ''` ' ' , .
~''~ ,.
,
'"' '''

21~48923
-14- 43-21~7857)A
It will be apparent that the coneentration of
the alkali metal precursor eompound in the aromatic
ether basestock is not narrowly critical and can vary
within fairly wide limits. Indeed, all that is
5 necessary is that the concentration is sufficient to -.
provide the desired eolloidal dispersion o~ the
aromatic ether and an oxidative inhibiting amount of
the alkali metal salt of oxalic acid as hereinafter
discussed. Convenient, albeit nonlimiting,
concentrations range from about 1 mmol to about 20
mmols, preferably from about 5 mmols to about 15 mmols,
and most preferably from about 8 mmols to about 12
mmols of the alkali metal precursor compound per
kilogram (kg) of aromatic ether.
Following the formation of the aromatic
ether/alkali metal precursor eompound mixture, the
resultant mixture i9 sub~eeted to eonditions effeetive
to eonvert the mixture into a colloidal di6persion
eomprising an oxidation inhibiting amount of the alkali
20 metal salt of oxalic acid in the aromatic ether. ~ ~
Noneolloidally dispersed solid material, i~ present, is ~ l-
separated or r moved from the eolloidal dispersion by a
variety of eonventional separation teehniques well
known to thofie skilled in the art, ineluding ~ ~-
filtration, eentrifugation and decantation of the
supernatant eolloidal dispersion from the
noncolloidally dispersed solid material. In a
pr~ferred embodiment, the noneolloidally dispersed
~terlal i- separated from the colloidal dispersion by
filtration through a filter having a pore size
effective to retain such noneolloidally dispersed solid ~;~
material and permit the colloidally dispersed particles
j..... ,.. . ~ . :, - . . . .
,~, .. ;.. .. - . . - :- ~ :
~,.' :.
.
~, . . .

8923
-15- 43-21(7857)A
to pass therethrough to thereby recover the oxidation
inhibited fluid composition.
It will be apparent that the conditions
effective to convert the aromatic ether/alXali metal
precursor mixture to the desired colloidal dispersion
will depend to some extent upon the particular aromatic
ether employed as the basestock and the source material
for the alkali metal salt of oxalic acid. In general,
the mixture i8 heated at a temperature of from about
225' C to about 300- C, preferably about 280- C, in the
presence of molecular oxygen or a molecular oxygen-
containing gas, preferably air, for a period Or from
about 3 hours to about 48 hours, preferably from about
12 hours to about 36 hours, and most preferably from
about 20 hours to about 24 hours. At these conditions
(which may be conveniently referred to as "alkali metal
precursor co~pound conversion conditionsn), the alkali
metal precursor compound employed a~ the source
material for the alkali metal salt of oxalic acid
undergoes an in situ oxidation and is converted into
the corresponding alkali metal salt of oxalic acid.
The resultant alkali metal salt of oxalic acid is
dispersed as colloidal sized particles to form the
desired colloidal dispersion of alkali metal salt of
oxalic acid in ths aromatic ether.
The concentration of the alkali metal salt of
oYalic acid in the aromatic ether is not narrowly
critical and will depend to some extent upon the
particul~r aromatic ether and alXali metal salt of
oxalic acid employed as components of the fluid
composition and the ultimate end use for the fluid
composition. All that is necessary is that the alkali
metal salt of oxalic acid be present as a colloidal
.~
.;. . .~ .
. ~ . ..
.~,"'.'.-~- ,.''~ ' '

- ~1)48923
-16- 43-21(7857)A
dispersion at a concentration e~ective to inhibit
oxidative degradation of the aromatic ether. At the
same time, however, the concentration of the
colloidally dispersed alkali metal salt of oxalie acid
must not exceed, or preferably must be less than, the
agglomeration/precipitation threshold for such alkali
metal salt of oxalie aeid in the aromatic ether. In
general, concentrations of from about 0.20 mmol to
about 2.50 mmol8, prererably from about 0.30 mmol to
about 2.00 ~mols, of colloidally dispersed alkali metal
oxalate per kg of fluid composition are sufficient to
impart the desired inhibition of oxidative degradation
to the aromatic ether. However, in the event the
concentration of the colloidally dispersed alkali metal
salt of oxalic acid is greater than the
agglomeration/precipitation threshold value for such
alkali metal salt of oxalie aeid in the aromatie ether,
i~ particular greater than the generally desirable 2.50
mmols/kg upper limit or greater than any other
specified desirable value, fresh aromatie ether may be
added to the fluid eomposition to dilute the fluid
composition to a desirable concentration of choiee.
It will be apparent to those skilled in the --
art that the fresh aromatic ether employed as a diluent
may be the same as, or different from, the aromatie
ether ba~estoek employed initially to prepara the
eolloidal dispersion. A different aromatie ether,
ineluding blends of two or more aromatie ethers, may be
used advantageou~ly as a diluent to aehieve eertain
de~irable properties -- for example, a lower
solidification point for the aromatie ether basestoek
and ultimately the fluid composition.
~;' ~'.. ,'~ ' .,
': - : . ,,
, .. .
.
; -
~ ' ' ' '.- .
.. ' .. . . .
.',' - ''

21~')23
-17- 43-21(7857)A
The following speci~ic examples illustrating
the best currently-known method o~ practicing this
invention are described in detail in order to
facilitate a clear understanding of the invention. It
should be understood, however, that the detailed
expositions of the application of the invention, while
indicating preferred embodiments, are given by way of
illustration only and are not to be construed as
limitinq the invention since variou~ changes and
modifications within the spirit of the invention will
become apparent to those skilled in the art ~rom this
detailed description.
EXAMPLES 1-6
General
(a) Oxidative Stability
The oxidative stability of the fluid
compositions of, and prepared in aeeordanee with, this
invention, as well as that of the aromatie ether
basestock, was determined using a modified Corrosion &
Oxidation (C&O) test as speeified in the military
speeification MIL-L-87100 in accordance with Method
5307 of FED-STD 791. In accordance with this test, the
fluid composition (lubricant) to be tested was heated
over a 48-hour period at a speci*ie temperature t343- C
(650- F), as opposed to the stated standard temperature
of 320- C (608- F] at a dry air flow rate through the ~-
~luid composition of 10 L/hr in the presenee of certain
~ tal specimen speeified as aluminum (bottom), silver,
mild steel, ~-50 steel, Waspaloy (a nickel-based
alloy), and titanium (top) and the viscosity increase
of the fluid composition was determined. In addition,
information a~ to the corrosivity of a fluld
composition to metals may be determined, if desired.
-: -- - - -
~.. ~-. .. :.: . . -
.-,- :. . ..., - ~, :- . .
: . - .- . . ~ . .
, .. .. .
,~

~,148923
`\
-18- 43-21(7857)A
Viscosity measurements were made according to
ASTM Method D445-88 using a Cannon-Fenske modified
Ostwald viQcosimeter. The percentage o~ viscosity
increase was determined by taking the difference in
viscosity of a fluid composition be~ore and a~ter it
was heated, dividing that difference by the original
viscosity and multiplying the quotient by 100.
(b) Storage Stability
The storage stability of the fluid
compositions of this invention, as well as that of the
aromatic ether basestock, was determined using Method
3403 of FED-STD 791, except that the method was
modified to serve as an accelerated storage stability
test. In accordance with this modified test, a sample
of the fluid composition (neat) to be tested was stored
in a loosely capped glass container (usually a small
flask) in an oven maintained at 120-125- C (24a-257- F)
for a period o~ 168 hours or more, up to several ~ -
months. At the end of the storage period, the sample,
without a final centrifugation step, was visually
inspected for turbidity with white light shining
through tha sampl6 at a 180- angle to the line of
sight. Noticeable turbidity at any time during the
test period resulted in the fluid composition being
characterized as having failed the test.
(c) ~ erial Component Identification
The colloidally dispersed solid material -
co~ponent Or the fluid compositions was isolated from
th- fluid composition by mixing the fluid composition
with di~thyl ether and extracting ths fluid
composition/diethyl ether mixture with water, followed
by evaporation of the agueous extract to yield a ~olid ~-
material. The resultant solid material was identified
,:.
.
.,.-,., ,, , , ' .',
. . . - ,

2 (~ 2 3
-19- 43-21(7857)A
as the corresponding alkali metal salt of oxalic acid
(for example, potassium oxalate for potassium precursor
compounds), usi~g standard procedures, by ln~rared
spectra, titration with hydrochloric acid, titration
with permanganate, and ICAP analysis.
EXAMPLE 1 (Comparative)
This Example illustrates a typical prior art
process using soluble potassium salts to stabilize
polyphenyl ethers. The fluid composition was prepared
according to the procedure described in Example 38 of
U.S. Patent No. 3,492,229.
A polyphenyl ether basestock having a
composition, by weight, of:
64% m-bis~m-phenoxyphenoxy)benzene
32% m-t(m-phenoxyphenoxy)(p-phenoxyphenoxy)]-
benzene
4S m-bis(p-phenoxyphenoxy)benzene
was employed. Potassium m-(m-phenoxyphenoxy)phenate
was dissolved in the basestock at two concentration
levels -- 7.40 mmols/kg and 3.12 mmolsJkg. These
fluid compositions were further diluted with additional
polyphenyl ~ther basestock to provide samples at
concentrations of 1.58 mmols/kg and 0.79 mmol/kg. The - ~ -
oxidative stability and the ~torage stability of the
fluid compo~itions were determined as described for the
Oxidative Stability test and the Accelerated Storage
Stability te~t, respectively. The results were as --~
- . ~ -
' "'`~"`.'
;, -
.; -

2~4~923
-20- 43-21(7857)A
C&O R~-ult-
Conc l (Vl-co-ltv m2/-)2 Aq~, Ator~- 8t~bllltv
~gmL~ mmol-~ka ~nl~ia~3 ~ ~ Chang- AD~ear~nc~ Comment
51 7 40 368 0 463 0 ~25 8 Dark browr~ rall~d
ppt ~
2 3.12 364.o 434.o ~19.3 Dark brown Fall~d
~pt 4
3 1.58 ND5 ND5 ND5 D-rltbrown Fall-d
ppt
4 0.79 ND5 ND5 ND5 Tran~parQnt~ P~ d --
..... : , ".
~Potassium m-(m-phenoxyphenoxy)phenate in the ~luid
composition.
2At 38- C (100' F). -
3Stated value x 106.
~After one ~1) week.
5Not determined.
The result~ indicate that the fluid
compositions containing soluble potassium salts
exhibited excellent results in the C&0 tQst at 343- C ;~-~
(650- F). However, except for Sample 4, the fluid
compositions developed clumps of dark brown precipitate
following one (1) week of storage, thereby failing the
Accelerated Storage Stability test. The formation of
th dark brown precipitate further indicates the
lik lihood that such fluid compositions could be prone ~ -~
to ~orming deleterious precipitates under use con~
30 ditions, particularly, high stres~ conditions. - `~
- .
'- . -: `
,...
,
'~ .
~, ,
' '.

'~J48923
-21- 43-21(7857)A
EXAMpLE 2
This Example illustrates the preparation of a
colloidal dispersion of an alkali metal oxalate,
potassium oxalate, in an aromatic ether basestock from
an insoluble alkali metal salt, potassium carbonate.
Run 1
The polyphenyl ether basestock (405 g) employed
in Example 1 was charged to a 500 mL round-bottomed
flask fitted with a glass paddle stirrer, a fritted
glass air bubbler, a thermometer, and a bent glass exit
tube and heated while a stream of air [flowing through
a tube packed with anhydrous calcium sulfate
(Drierite)] was passed therethrough at the rate of 75
scc/~in. When the temperature of the polyphenyl ether
basestock had reached 130- C, 0.34 g (0.0025 mol) of
potassium carbonate in the form of coarse granular
powder (primarily larger than 50 mesh ~300 microns
(~m)]) was added, with rapid stirring to thoroughly mix
and suspend the potassium carbonate in the polyphenyl
ether basestock. Heating was continued to raise the
tempsrature of the mixture to 280- C, while maintaining
the passage of air therethrough. The mixture was
maintained at these conditions for 23 hours, after ;-- --
which the air flow was turned off. The mixture was
allowed to cool to 120- C and was filtered through a
Buchner funnel using a glass fiber filter (GF/F filter ~-~
fro~ Whatman) having an effective pore size of 0.7 ~m ~ -
to re~ove noncolloidally dispersed solid-phase mate- - --
r~l. The r~3ultant fluid composition of a colloidal
30 dispersion of potassium oxalate in the polyphenyl ether -~
basestock was shown to have a concentration of 1.17 -~
mmols of potassium oxalate per kg of fluid composition
by titrating three samples (6.1 g, 6.1 g, and 4.5 g) of ~ -
' . ~' "`-
, . . . .
i, - .
' .' ' . . .
:-. .
~'`~"' ' ' " , '.`'.
.... ~ .

8923
-22- 43-21(7857)A
the fluid composition with 0.01 N hydrochloric acld in
water-acetone solvent to the ~irst end point tXH(C00)2]
using bromphenol blue indicator, ~ollowed by averaging
the results obtained for the three samples. The ~luid
composition was diluted with fresh polyphenyl ether
basestock to yield several lower concentrations.
The solid phase material collected in the
Buchner funnel on the filter, as w~ll as that remaining
in the reaction flask, was washed several times with
hot hexane to remove residual polyphenyl ether
basestock and dried. The resultant dry solid phase
material was identi~ied as a mixturs o~ potassium
carbonate (75% by weight) and potassium oxalate (25~ by
weight).
15 Run 2 ;~
The procedure described in Run 1 was repeated
to yield n fluid composition of a colloidal dispQrsion
of potassium oxalate in the polyphenyl ether basestock
at a concentration of 1.67 mmols/kg.
A C&0 test from Runs 1 and 2 was carried out
on the fluid compositions at various concentrations. ~ --
An Accelerated Storage Stability tes~ wa~ carried out
on the Run 2 fluid composition (Sa~ple 6). In ;~
addition, a comparative C&0 test was carried out on the
25 neat polyphenyl ether basestock. The results were a~ ~-
follow~: -
- ~
` ` .`,
,
` , .
.~

~1)48923
-23- 43-21(7857)A
C&0 R-~ult-
conc.l LVl-co~ltv. m2/~2 ACC. Stor~qe Stabllltv
Sam~le mmol~/k~ In~ 3 Fln~13 ~ Ch~no~ AoDe~ranc- Comment
1 0.00~ 12.45 237.6 +1809.0 ND5
26 0.070 12.72 104.7 l723.0 ND5
3~ 0.1~ 12.68 58.1 +358.0 ND5
4~ 0.21 12.70 30.2 +137.0 ND5
56 0.35 12.70 13.33 +5 ND5
67 1.67 12.68 13.S5 +6.9 ~ran-p~r-nt~ P~ d
.. .
lPotassium oxalate tK2(C00)2~ in the fluid composition. -- -
2At 100 C (212- F)-
3Stated valuo x 10 6.
~Neat polyphenyl ether basestock.
5Not determined.
~From Run 1 followinq dilut~on with fresh polyphenyl
ether basestock.
7From Rum 2.
20 8After twenty-thrae (23) weeks. -
The results demonstrate that at a threshold
concentration of about 0.30 mmol/kg, a substantially
constant level Or oxidation inhibition i8 provided.
Howevor, at concentrations bQlow this threshold level,
the degree of oxidation inhibition, although observ-
able, falls off quite rapidly. :~
EXAMpT-~
- - This ~xample illustrates the preparation of a -~
cQlloidal dispersion of an alkali metal oxalate,~`-` ;`
pota-sium oxalate, in an aromatic ether basestock from
a soluble alkali metal salt, potassium m-(m- ;~-
phenoxyphenoxy)phenate. ~ - `
. '.' " ,~ : , ' ' , '' ' ':
'-` ~ ' . . , ' ;:
~''''-'.' ' ' : "
, .

211~8923
-24- 43-21(7857)A
The procedure described in Example 2, Run 1 was
employed except that 1.03 g (0.0033 mol) Or potassium
m-(m-phenoxyphenoxy)phenate (which i9 soluble in the
polyphenyl ether basQstock) was substituted ror the
potassium carbonate and 273 g o~ polyphenyl ether
basestock was employed to yield a solution of potassium
phenoxyphenoxyphenate in the polyphenyl ether basestock
of 12.00 mmols/kg. Following the heating with air at
280- C for 23 hours and filtration, the resultant fluid
composition of a colloidal dispersion of potassium
oxalate in the polyphenyl ether basestock had a --
concentration Or 4.67 mmols/kg.
15 Run 2 ~
The procedure described in Run l was repeated - ~-
except that 1.53 g (0.048 mol) Or potassium
m-~m-phenoxyphenoxy)phenate was dissolved in 404 g of
polyphenyl ether basestock to yield a solution of
potassium m-(m-phenoxyphenoxy)phenate in polyphenyl
ether Or 12 ~mols/kg and the solution was heated rOr 21 `~
hours at 280- C in the presence of air. After
filtration, the resultant fluid composition Or a
colloidal dispersion of potassium oxalate in the -
polyphenyl ether basestock had a concentration of 4.56
mmols/kg. The ~luid composition was diluted with fresh -~
polyphenyl ether basetock to a concentration of 0.70
l/kg.
A C~0 test was carried out on the fluid
compositions from Runs 1 and 2 and an Accelerated
Storage Stability test were carried out on the fluid
compo~ition from Run 2. The results were as follows:
.`~ ~ ,
.~ .
:
. ~ .
.: : .
, ~ - - .

2~8923
-25- 43-21(7857)A
C~O R--ult~
Conc l ~Vl-co~ltv,_~2/~)2 Acc Stora~- 8t~bllltv
~gmDL~ mmol~/k~ Inltlal3 Flnal3 ~ Chana- A~oar~nc- Comment
1~ 0 70 12 74 13 91 +9 18 Tran~paren~5 P~ d
2~ 4 67 12 73 14 11 +10 80 ND7
'':
lPotassium oxalate ~X2(COO)2] in the fluid composition.
2At 100- C (212- F). -
3Stated value x 10~.
~From Run 2 ~ollowing dilution with fresh polyphenyl
ether basestock.
5After fifteen (15) weeks.
6From Run 1.
7Not determined. However, at the end of the C&0 test, a
crystalline precipitate was present, thereby indicating
that the concentration of potassium oxalate in the
fluid composition was too high to remain stable as a
colloidal dispersion. - ~
EXAM~ 4 ---
Thi~ Example illustrates the preparation of a
colloidal dispersion of an alkali metal oxalate,
potassium oxalate, in an aromatic ether basestock from --
a partially soluble alkali metal salt, potassium -~
phenate.
Run 1
The procedurs described in Example 2, Run 1 was
e~ployed exc~pt that 1.27 g (0.0096 mol) of potassium
pb-n~te (which is slightly soluble in the polyphenyl
~th-r ba6Qstock) was substituted for the potassium
30 carbonate and mixed with 800 g of the polyphenyl ether -
ba~estock in a 1000 mL round-bottomed flask fitted as
described in Example 1, Run 1 to yield a
slurry/solution of potassium phenate in the polyphenyl
~ . , .
~ .
~'' - ' ~ ' .
.: . , .

~i~A~923
-26- 43-21(7B57)A
ether basestock of 12.00 mmols/kg. Following the
heating with air (150 scc/min.) at 280- C for 45 hours
and filtration (at 120-C), the resultant fluid
composition of a colloidal dispersion of potassium
oxalate in the polyphenyl ether basestock had a
concentration of 1.83 mmols/kg. The solid material
collected on the ~ilter consisted primarily of
potassium oxalate, with traces of unidentified
impurities (possibly potassium carbonate or potassium
phenate).
Run 2
The procedure described in Run 1 was repeated
except that 5.30 g (0.040 mol) of potassium phenate was
mixed with 3346 g of polyphenyl ether basestock to
yield a slurry/solution of potassium phenate in
polyphenyl ether of 12 mmols/kg and the slurry/solution
was heated for 23 hours at 280-C in the presence of
air. After filtration, the resultant fluid composition
of a colloidal di persion of potassium oxalate in the
polyphenyl ether basestock had a concentration of 2.67
mmols/kg. The fluid composition wa~ diluted with fresh ~ -
polyphenyl ether ba~estock to provide a concentration
of 0.70 mmol/k~. A C&0 test and an Accelerated Storage - --
Stability test were carried out on the diluted fluid
composition. The results were a~ follows:
~-,
'"'~
.'
: .
:
.-

2~48923
-27- 43-21(7857)A
C&O R--ult-
Conc.l LVl-co~itv. mZ/~2 Acc. Storaae Stab-lltY
SamD1~ mmol-lka ~n~lal3 ~ ~ Chana~ A~D~a~a~c~ Comment
1 0~70 12.4a 13.56 +8.70 Tran-p~r-nt~ P~ d
lPotassium oxalate [K2(COO)2~ in the ~luid composition. --
2At 100- C (212- F). -
3Statad value x 1o6. -~
10 ~After forty-two (42) weeks. --
EXAMPLE 5
This Example illustrates the preparation of a
colloidal dispersion of an alkali metal oxalate, sod$um ~ -
oxalate, in an aromatic ether basestock from a soluble
alkali metal salt, sodium m-phenoxyphenata.
Tha procedure described in Example 2, Run 1 was
employed, excapt that 0.38 g ~0.0018 mol) of sodium m-
phenoxyphenate (which is soluble in the polyphenyl ~ ~ -
ether basestock) was substitutQd ror the potassium
20 carbonate and dissolved in 302 g of the polyph~nyl ~ -
ether baststock to yield a solution o~ sodium m- - ~
phenoxyphenate in the polyphenyl ether basestock of ~---~-;
6.00 mmols/kg. Following the heating with air at 280- --
C for 16 hours and filtration, the resultant fluid
25 composition of a colloidal suspension of sodium oxalate -
in the polyphanyl ether basestock had a concentration
of 0.90 mmol/kg.
-- The ~luid composition was diluted with fresh -
polyphenyl ether basestock to provide a concentration
of 0.70 mmol/kq. A C&O test and an Accele~ated Storage
Stability test were carried out on the diluted fluid
composition. The results were as follows:
~.. ,.~ .,..., , ;
,-

8923
-28- 43-21(7857)A
C~O R-~ult-
Conc 1 ~Vl-co-ltY m2/~2 Acc Stora~e Stabllltv
Samol~ mmol~/k~ L~ al~ ~ ~ Chan~- ADoearanc- Comment
1 0 70 12 51 39 60 +137 00 Transpar~nt4 Pass~d
1Sodium oxalate ~Na2(C00)2] in the ~luid compo~ition.
2At 100- C (212- F).
3Stated value x 10 6
4After nine (9) weeks.
EXAMPLE 6
This Example illustrates the preparation of a
colloidal dispersion of alkali metal oxalate, potassium
oxalate, in an aromatic ether basestock from a soluble
alkali metal salt, potassium m-(m-phenoxyphen-
lS oxyphenate.
The procedure described in Example 3 wasemployed, except that a six-ring polyphenyl ether
basestock, bistm-(m-phenoxyphenoxy)phenyl] ether, was
substituted for the five-ring polyphenyl ether
basestock. Following the heating with air at 280- C
for 21 hours and filtration, the resultant fluid
composition of a colloidal disper~ion of potassium
oxal~te in the polyphenyl ether basestock had a
concentration of 2.09 mmols/kg. --
A portion of the fluid composition was diluted
with fresh polyphenyl ether basestock to provide a
~-cond concentration o~ 1.40 m~ol~/kg. A C&0 test and
~a Accelerated Storage Stability test were carried out
o~ the fluid composition at the two concentrations.
30 The results were as follows: -
~"
,~
.
::~
;:
~s~-

~J~8923
-29- 43-21(7857)A
C60 R--ult-
conc.l(vlsco~lty~ m2/s)2 A~c- storag- 8t~bllitY
Samol~ mmol~/k~Fin~l,3 ~ Ch~ng- Ao ~ ar~nce Con ~ nt --
1 1.~0 24.58 27.02 +9.93 Tr~n-par-nt4 Pa~-d
52 2.09 24.41 27.13 l11.14 sran-par-nt4 Pa~-~d ~:
;..~ " .
lPotassium oxalate tK2(C00)2] in the fluid compo~ition.
2At 100- C (212- F). ;
10 3Stated value x 10~. -
~After thirty-seven (37) day8.
Thus, it is apparent that there has been ~ ~-
provided, in accordance with the instant invention,
fluid compositions that fully satisfy the ob~ects and
advantages set forth hereinabove. While the invention
has been described with respect to various specific -~-
exaDIples and embodiments thereof, it i8 understood that ~--
the invention is not limited thereto and many
alternatives, modification~, and variations will be
apparent to those ~killed in the art in light of the
foregoing description. Accordingly, it is intended to
embrace all such alternatives, modifications, and
variation~ a~ fall within the spirit and broad scope of
the invention. ~-
~ `
~ ..
. . .~,