Note: Descriptions are shown in the official language in which they were submitted.
Background of the Invention
This invention rel~tes to functional fluid com-
posi.tions having the ability to inhibit and control damage to
mechanical members in contact with these fluid compositions.
A wide variety of functional fluids are known and
utilized for many applications. Functional fluids have been
used as electronic coolants, atomic reactor coolants, diffu-
sionpump fluids, lubricants, damping fluids, bases for grease,
power transmission and hydraulic fluids, heat transfer fluids,
heat pump fluids, refrigeration equipment fluids and as filter
.
~. .
: - :. . , . : :, .:. ., . i , ~
- ~ ' ( C-4217
~07~ 29~
mediums for air conditioning systems.
In many of the functional fluid compositions used for
the above purposes there have been reports of damage to the flui~
during use and to ~echanical members~ especially metallic members
in contact with the fluid, as evidenced by a 105s of weight of
such members, due to the wearing away of metallic partsO Damage
has been reporked i~ aircraft hydraulic systems, gas turbine
bearings, jet turbine control systems, steam turbine bearings,
steam turbine control systems, electrohydraulic control systems
and aerospace control equipment. Damage has also been observed
on such materials as glass, Teflon, Mylar, Plexiglass and members
constructed from other non-metalllc materials.
In those instances where functional rluids are used
in the hydrauIic sys~ems of aircraft and aerospace sy~t~ms, such
systems impose stringent requirements on the hydraulic fluid.
Not only must these hydraulic fluids meet stringent use require_
ments but they must also satisfy FAA and other government require-
ments for fire resistance. Additionally, the hydraulic ~luid
must be capable of performing in ~he hydraulic systesn over an
extended period of time without causing significant damage or
functional impairment to the ~arious conduits, valves, pumps,
and the like, through which the fluid flows in the course o~
such use.
Damage caused by functional fluids contacting valves
and other members has been attributed to the wearing away or
erosion of the enviro~.ent in contact with the functional fluid
* Tr~demar~s - 2 -
~ ` . '
.
- ( ( C-4217
~'7~Z9~
in a hydraulic syste~. Among the many undesira~le results
caused by such damage is a marked decrease in strength of the
structural mechanical parts in the hydraulic system, such as
pumps and valves, along with an alteration of the geomekry of
these parts. Such changes in the case of pumps can cause a
decrease in pumping e~ficiency, and in the case of valves can
cause aulty operations, excessive leakage and even hazardous
conditions.
This damage necessitates costly and time consuming
lQ premature overhaul of mechanical parts. Additionally, metal
removed from comp~nent metallic mechanical parts in contact
with the functional fluid contaminates the rluids, causes
filter clogging and excessive filter replacement, and requi~es
premature draining and replacement of the fluid in the system.
. . .
The metal contamination can also c~use a change in physical and ~`
; chemical properties of the functiona~ fluids.
Metal contaminants can also reduce the oxidative
stability of a fluid, thereby adversely affecting fluid perfor~
mance. In addition, metal contamination of the fluid can ~anifest
itself in nurnerous g~her ways, including viscosity change, in-
creased acid nu~.be~, formation of precipi~ates, decrease i~
chemical stability and discoloration.
Another problem in the industry is the unavoidable con-
tamination of alrcraft and elect~ohydraulic control systems with
~25 chlorirated solvents used to clean the systems and componen~s.
--
1~702~
A detailed discussion of this problem apPeaXs ~n Vickers 22ndFluid Power Conference Re~ort, Oct 30, 1972, Section 4, Pages
25-29. Contamination bychlorinated solvents decreases the '
service li~e of functional fluids and accelerates damage,
causing excess-ve internal leakage in hydraulic systems to a
point of malfunction. No additive heretofore known has sat- '
isfactorily o~ercome the problems associated with clorinated
solvent contamination of functional fluids.
In the past, there have been reports of damage to
valves and other metallic members which contact phosphate
ester fluids. U.S. Patent 2,470,792 proposes to overcome this
damage problem by the inclusion of a small percentage of
water in an aircraft hydraulic system. Unfortunately, while
the presence o~ a small percentage of water reduces certain
types of damage when incorporated in some phosphate ester
hydraulic fluids, the presence of water can have a corrosive
effect as well as an undesirable eEfect on the stability of
the fluid.
U.S. Patent 3,707,501 discloses the use of phos-
phonium compounds to inhibit erosion damage to the metallic
environment containing hydraulic fluids. However, the lu-
bricant compositions require relatively high concentrations
of phosphonium compounds, which are very expensive. In
addition, the phosphonium compounds may contribute to the
destabilization of the functional fluid.
U.S. Patent 3,679,587 discloses alkali salts of
perfluorinated alkyl sulfonic acids as erosion inhibitors.
However, since these compositions are ash containing materials,
high temperature operation could'lead to the formation of
particulate matter in a hydraulic system. ~ ,
--4--
~07~2~1
Summary of the Invention ~ .
In accordance with the pXesent in~ention, a ~:
functional flu~d has been discovered which exhibits enhanced :
low erosion, shear, oxidative and thermal stability, and fire
resistance characteristics, and is particularly suitable for
aircraft hydraul~c applications. This invention comprises ..
the incorporation of a minor percentage of certain ammonium
salts of phosphorus acids into various base stock compositions
so as to produce a functional fIuid capable of inhibiting
damage to the metal environment containing the functional fluid~ ~ ?Detailed Description of the Invention : :
The ammonium salts of the phosphorus acids which -
are useful for incorporation in functional fluids in accord-
ance with the present invention are represented by the follow-
ing formula and description: : -
L
where R, R' and R" can be the same, different or conjoint, and
represent hydrogen, alkyl, aryl, alkaryl, and aralkyl groups ~;
containing from 1 to 30 carbon atoms; R''' represents alkyl,
aryl, alkaryl and aralkyl groups containing from 1-30 carbon
atoms; X represents O or S; Y' and Y" represent alkoxy, alkyl-
thio, alkyl, aryl, alkaryl, aralkyl, aryloxy, arylthio and
alkaryloxy; Z represents oxygen or sulfur; and m = 1 or 2. ;. ;
In a preferred embodiment, m = 1. ;-:~
An alternative embodiment involves the ammonium . ~ :.
ions attached to the phosphorus anion via an alkylene or ~.
arylene group. This forms a zwitterion wherein the ions are .
connected, generally by a carbon or carbon and oxygen chain, .
-5-
. . ~
~; as for example:
R' ~ ~
R N tR )x P \ y" : :
~R'~
wherein R, R' and R''' are as above and R" can be any divalent
connectin~ unit such as CH2, and x can vary from 1 to 10.
Representative of the above is:
/ ~ (C~2)2 -- P ~
The following is a listing o~ typical ammonium
salts of phosphorus acids tabulated according to the respect- :
ive ammonium ions and phosphorus ester anions~
Ammonium Ions Phosphorus Ester Anions
Dodecyl trimethyl ammonium Diphenyl phosphate :
~exadecyl trimethyl ammonium Phenyl phosphate (bis-amine
ti salt)
Octadecyl trimethyl ammonium Dimethyl phosphate
Tridecyl trimethyl ammonium Methyl phosphate (bis-amine
salt) :
; Decyl trimethyl ~nmonium Methyl methylphosphonate :~ :
Didodecyl dimethyl ammonium Methylphosphonate (bis-amine
salt) :
Methyl butyl dodecyl ammonium Diethyl phosphate
Dimethyl propyl dodecyl ammonium Ethyl phosphate (bis-amine
~ salt)
:~ Dodecyl ammonium Dioctyl phosphate
Trioctyl ammonium Dibenzyl phosphate ~:
6-
..
~07~)Z~
~mmoniu~ Ions P~o~phorus Ester ~nions
Dioctyl methyl ammonium Diallyl phosphate
Dioctyl dimethyl ammonium Methyl phenyl phosphate
Dodecylbenzyl trimethyl ammonium Bis(octylphenyl~ phosphate
Nonylphenyl trimethyl ammonium Di-n-dodecyl phosphate
Doaecyl dimethyl butyl ammonium Diethyl dithiophosphate ~-
Phenyl dodecyl dimethyl ammonium Di-n-butyl-dithiophosphate
Phenyl trimethyl ammonium Dibenzyl dithiophosphate
Benzyl trimethyl ammonium Diphenyl dithiophosphate :.
Allyl tributyl ammonium Bis(nonyl phenyl) phosphate ~ :
Dimethyl dodecenyl ammonium Dibutyl Phosphate ~ :
tUnsaturated R Group)
Methyl Octylphosphanate
Trimethyl hexadecenyl ammonium s
(Unsaturated R Group) Hexadecyl phosphonate ~ .
Heptadecyl trimethyl ammonium Methyl hexadecyl phosphonate
Trioctyl methyl ammonium Methyl tertiary-butyl
phosphonate ~:
Methyl-alpha-naphthyl phenyl
ammonium Methyl carbomethoxymethyl
phosphonate : `
Cyclohexyl dimethyl ammonium `:
Nonyl trimethyl ammonium ~ ~ .
Tris(n-tridecyl)methyl ammonium ~`
Tris(n-dodecyl)methyl ammonium
Tris (isooctyl)methyl ammonium : :
Dimethylbutylhexadecyl ammonium
Triethylmethyl ammonium :
1,3,5 Trimethyl pyridinium
t /~
CH3 N ~ N - CH3
2-ethylhexyl dimethyl dodecyl ammonium
Dimethylethyl dodecyl an~lonium
~ ~7~
. ` ~ ' .
-. ~
~7~2~g~
Ammonium Ions
Dimethylbutyl dodecyl ammoniurn
Trimethyl dodecyl ammonium
Hexadecyl dimethylethyl ammonium
Tris(dodecyl) butyl ar~nonium
Tetramethyl ammonium
,, .~
`,.
'"'',
'
-7A-
; . ' ~ , I
` ~~4217
( 1 ~7
Amm~ium Ion_
Trimethyl benzyl ammonium
Trimethyl tertiary-octyl phenyl ammonium
4-acetyl N-methyl pyridinium
CGH I 3 C--0 / OEI2 ) 2 ~C~3
O
CH3 ~ CH2- OP(OC6Hs)2
CH f ~ CH2N(Cl2H2s)~CH3)z
l-(N,N-dimethyl)-l-imidazolium
l-(N~N-dimethyl)-l-pyrrazolium
N-methyl oxazolium
lV N-butyl quinolinium
N-methyl pyrrolium
: ~,N-diethyl pyrrolidinium ~:
~-methyl,N-hexyl piperidinium
~-methyl,N-butyl piperidinium
. 15 ~ i50propyl thiazolium
.
N-ethyl~N-methyl phenothiazinium :
Pyridinium
M-methyl pyridinium
Each member of the ammonium ions may be combined
20 . in turn with each member of the phosphorus ester anion in order :
ko generate typical compounds which may be used in this inventionr
For example, particularly preferred ammonium salts of phosphorus
acids are:
'
. ~ .
.: ' ;
(
7029~
Hexadecyl trimethyl ammonium diphenyl phosphate
Decyl trimethyl ammoniu~ diphenyl phosphate
Didodecyl dimethyl ammonium diphenyl phosphate
Dimethyl propyl dodecyl ammonium diphenyl phosphate
Dodecyl ammonium diphenyl phosphate
Dodecylbenzyl trimethyl ammonium diphenyl phosphate
~onylphenyl trimethyl ammonium diphenyl phospha~e
Phenyl dodecyl dimethyl ammonium diphenyl phosphate
; Allyl tributyl ammonium diphenyl phosphate
lQ Trimethyl hexadecenyl ammonlum diphenyl phosphate
Bis(dodecyl trimethyl ammonium)phenyl phosphate
Bis(octadecy} trimethyl ammonium)phenyl phosphate
Bis~phenyl dodecyl dimethyl ammonium)phenyl phosphate
Decyl trimethyl ammonium dimethyl phosphate
: 15 Didodecyl dimethyl ammonium methyl methylphosphonate
Bis(didodecyl dimethyl ammonium~methylphospllonate
Dodecyl trimethyl ammonium dimet'nyl phosphate
: Dodecyl trimethyl ammonium dibenæyl phosphate
.
: Dodecyl trimethyl ammonium methyl phenyl phosphate
Dodecyl trimethyl ammonium bis(nonylphenyl)phosphate
Dodecyl trimethyl an~oniwn diphenyl dithiophosphate
; . . Octadecyl trime~hyl ammonium diphenyl dithiophospha~e
Dioctyl methyl ammonium diphenyl dithiophosphate
Phenyl dodecyl dimethyl ammonium diphenyl dithiophosphate
Dodecyl tr-methyI ammonium diethyl dithiophosphate
Phenyl trimethyl a~onium diethyl dithiophosphate
Dodecyl trimethyl ammonium diallyl phosphate
~odecyl trimethyl ammonium diphenyl phosphate
_ c _ .
.~ ~
. ' ~ ~ ~ . i - .
07~;~9~
Didodecyl dimethyl ammonium di-n-dodecyl phosphate
Dodecyl trimethyl ammonium di-n-dodecyl phosphate
Dioc~yl methyl ammonium dioctyl phosphate .
Trioctyl ammonium dioctyl phosphate
Phenyl trimethyl ammonium me~hyl phe~yl phosphate
Benzyl trim~thyl ammonium methyl phenyl phosphate
Trimethyl hexadecenyl ammonium methyl phenyl phosphate
Bis(trioctyl.ammonium) ethyl phosphate
Octadecyl trimethyl ammoniu~ diphenyl phosphate : :~
.10 Tridecyl trimethyl ammonium diphenyl phosphate
Heptadecyl trimethyl ammonium diph~nyl phosphate
~onylphenyl trimethyl ammonium di-n-butyl-dithiopnosphate
Benzyl trimethyl ammonium dibenzyl dithiophosphate
Hexadecyl trime:thyl ammonium dimethyl phosphate . ~ :
Trioctyl methyl ammonium diphenyl phosphate
Heptadecyl trime~hyl ammonium di.methyl phospha~e
Tris(n-tridecyl)~methyl ammonium diphenyl phosphate
:. Tris(n-dodecyl)methyl ammonium diphenyl phosphat~
Tris(isooctyl)methyl ammonium diphenyl. phosphate
: ~O Dimethylbutylhexadecyl ammonium dibutyl phosphate
Triethylmethylammonium methyl methylphosphonate
1,~,5-trimethyl pyridinium diphenyl phosphate . .
~ N-methyl~ N-butyl piperidinium dibutyl phosphate
.. ~ CH3~ CH3 =(C3H,C)zPOz-~2
! 25 2-ethylhexyl dimetnyl dodecyl. ammoniu~ diphenyl phosphate
Dimethylethyl dodecyl ammonium diethyl phosph~te
-- 10--
::~
'~
'~ ' ' ~ '
~07~Z~l
Dime~hyl butyl dodecyl ammon.ium dibutyl phosphate
Trimethy]. dodecyl ammonium dimethyl methylphosphonate
Hexadecyldimethylethyl ammonium diethyl pho~phate
Tris(dodecyl)butyl ammonium dibutyl phospha~e
Tetramethyl ammonium methyl octylphosphonate
Trimethyl benzyl ammonium methyl octylphosphon~te
Tetramethyl ammonium methyl hexadecylphosphonate
Benzyl trimethyl ammonium methyl hexadecylphosphonate
Tetramethyl ammonium methyl tertiary-butyl-phosphona~e
Benzyl trimethyl ammonium methyl tertiary-butyl-phosphonate
Tetramethyl ammonium methyl carhomethoxymethylphosphonate
Benæyltrimethyl ammonium methyl carbome~hoxymethylphosphonate
Trimethyl tertiary-octylphenyl ammonium diphenyl phosphate
Trimethyl-tertiary-octylphenyl ammonium methyl me~hylpho3phonate
TYimethyl tertiary-octylphenyl ammonium bis(nonylphenyl~phosphate
TeLramethyl ammonium ~is(nonylphenyl)phosphate.
Benzyltrimethyl a~monium bis(nonylphenyl) phosphate
CgHI7-CloH2l0-C~ CH3 (C6HsO)2P02~
.
: ''
CgH 17 -C 1 oH2l0-C ~ MCH3 (CgH 19CBH~O ) 2P0z- .
. .
~8HI7-cloH2lo-c ~ \~CH3 (cHso)(cH3)po2- .
o
CH30-C~ NCH3 (c_Hso)2po^
"
CH~0-C~ CH3 ~C~HIgC~H~0~2PO2-
CH~G-C~ NCH3 (CH3Q)(CH3!P02-
1~ .
1070Z91
The quaternary ammonium salts of diesters of phosph~ric
acid which con~ain no N-H bonds can be prepared by known means
as outlined in British Patent 1,199,015 (1970) and in the Preprints ;
of the Symposi~ on Deposit, Wear, and Emission Control ~y Lubri~
~5 cants and Puel Additives presented in the Division of~Petroleum.
Chemistry of the American Chemical Society~ N.~. City Meeting, ~
Sept. 7-12, 1~5g, page A-llO. These methods includeo l :
1 1. Reaction o an amine with a triester of phosphoric l: ~.
acid in which the triester alkylates the amine. These reactions
; 10 ~sually take place above ~o-60D and can be run neat or in alcohol
. solv~nts. All ~olatile species are then removed by distillation :
- to leave behind the phosphoric acid diester salt of a que~ernary
,~ ' .; .
; ammonium cation.
RsN T R'O P(O?(OR")2 ~ R3NR~ OP(O)~ORI~)2
1~ Rl is preferably of the benzyl, allyl, or lower alkyl (aspecially
metnyl) type. R" may be alkyl, aryl, alkaryl, aralkyl, etc.
`: 2. Reaction of the phosphor~ acid diester with a
1 '
quaternary am~onium hydroxide to generate the salt in a neutraliza
tion reaction and then removal or the water liberated.
.~ 20 (RO)2 P(O)(OH) ~ R~(OH) ~ R4~ VP(O)(OR)2 ~ H20
3. Reaction of the quaternary ammonium halide with the
sodium or po~assium salt of the phosphoric acid diester and ex-
traction of th~ phosphate with a solvent such as acetone to ena~le
removal o~ the sodium or pot~ssium chloride.
~RO)2 ~0) (O) Na + R4N Cl :
R4~ OP(O)(OR)2 ~ ~aCl
~ . -
:;.. ~ :
,; ~ ,~ -, . .
( C-4217
~7~
Erosion exhibited by hydraulic fluids has been r~lated
to the electrical properties of the fluid in Boeing Scientific
Research Laboratories Document Dl-82-03~7. It has been proposed
that erQsiOn caused by hydraulic fluids can be controlled by
eliminating ionic impurities present in the fluid, or by signi-
ficantly increasing the conductivity of the 1uid.
Both appro.aches have been explored with some degree
of success. This is surprising due to the fact that eliminating
ionic impurities actually lowers the conductivity. This appears
to indicate two contradictory approaches to the. problem o~ :
ameliorating damage caused by erosior.t. Recent experiments have
::~ shown that the elimination of ionic impurities by filtration
through an activated clay will control erosion caused by a phosphat~
ester hydraulic fluid. However, this is not a practical solution
. 15 since erosion beyins again soon after the filtration is dis- :
continued. In addition, filtration on aircraft is virtually
impossible.
The addition of ammonium salts of phosphorus acids to
various base stocks has been found to effectively inhibit dama~e.
Furthermore, conductivity measurements of these 1uids containing
ammonium salts o- phosphorus acids indicated increased conductivity.
: It is too early to conclusively attribute conductivity as an
explanation of .he mechanismJ or for evaluating the effectiveness
of damage inhibi~ors. However, conductivity does serve as some
indicia, althou~h further research in this area is deemed necessary
and desirable. ;:
Typic_l conductivitles of com~ercial phosphate es~e~
aircraft hydra~.l' ic fluids on the market today vary from about .o~
,:
'~
,
( ~ ~7
to about . o6 micromhos/centimeter.
Functional fluid comp~itions to which the ammonium salt of
phosphorus acid compositions can be added are referred to as base
stocks. They include, but are not limited to esters and amides of
i phosphorus acids, mineral oil and synthetic hydrocarbon oil base
stocks, hydrocarbyl silicates, siliconesJ aromatic ether and
thioether compounds, chlorinated biphenyl, monoesters~ dicarboxylic
acid esters, esters of polyhydric compounds, polv~lkylene ether
qlycols and al_ohols as well as ~heir es~ers.
O The conc~ntration o~ ammonium salts of phosphorus acids
in the functional fluid is adjusted in terms of the particular
` system and the functional fluid to inhibit and control damaye.
Thu~, it has been found that the additive response, ~hat is, the
concentration ol an ammonium salt of phosphorus acid required to
inhibi~ and contxol dama~e of a base stock varies according to the
base stock or blends of base stock~ employed.
Thus, or the base stocks useful in the practice of
this invention the concentration of ammonium salts of phosphorus
acid is from about O.Ol percent to a~out 15 perren~ by weight,
O the particular concentration being that amount which will efectivel~-
_ inhibit and con~rol damaye. The preferred additive concentration ~`
is from about 0.1% to about 10% and preferably about 0.025 to
about S weight percent, e~en more preferably, from about 0.1%
~ .
to about 2.0% and preferably about 0.1 to about 0.5 weight
perecent. Therefore, included within the present invention
are compositions comprising a functional fluid and a damage-
; inhibiting amount of an ammonium salt of phosphorus acids,
that ist the ammonium salt is added, in a concentration
sufficien~ to control and inhibit damage. The functional
fluid compositions of this învention can be compounded in
any manner known to those skilled in the art f~r the incorpor-
' . ' .
~70Z~
ation of an additive into a base stock and pxe~erably, by
adding an ammoniumsalt of phosphorus acids to the base stock
; with stirring until a fluid composition is obtained.
As indicated above, the compositions of this in-
;-vention can employ a wide variety of base stocks. Suitable
base stock materials are discussed in detail below.
~-The functional fluid compositions which are suit-
able for use as base stock materials in the present invention
can be esters and amides of an acid of phosphorus represented
;~by the structure:
'` 10 '~
-(Y)a~P ~ (Yl)C R2
; (Y2)b
R
wherein Y is selected from the yroup consisting o~ oxygen,
sulfur and
3 ---
" .~
-N-
:, ,~,. .
Yl is selected from the group consisting of oxygen, sulfur
and
R4
-N-
and Y2 iS selected from the group consisting of oxygen, sul-
fur and
,R5
-N-
:, . . ~.
',,',! R, Rl, R2, R3, R4, and R5 are each selected from the group
consisting of alkyl, alkoxy, aryl, substituted aryl and
substituted alkyl wherein R, Rl, R2, R3, R4 and R5 each can
-; -15-
1~7~Z91 ~ ~
be identical or di~ferent with respect to any other r~dical,
and a, b and c are whole numbers hav~ng a value o~ 0 to 1
and the sum o~ a ~ b ~ c is from 1 to 3.
: Generally, the number of carbon atoms in the alkyl
groups will vary from 1 to 30. Included within the alkyl
groups are the cycloalkyls and alkyl substituted cycloalkyls. .
Typical examples o~ alkyl radicals are as follows:
methyl, ethyl, normal propyl, isopropyl, normal
butyl, isobutyl, secondary butyl, tertiary butyl, normal amyl,
isoamyl, 2-methylbutyl, 2,2-dime-thyl propyl, l-methyl butyl, :~
~ diethylmethyl, 1,2-dimethyl propyl, tertiary amyl, normal hexyl, :
.~ l-methylamyl, l-ethyl butyl, 1,2,2-trimethyl propyl, 3,3-di-
:~ methyl butyl, 1,1,2-trimethyl propyl, 2-methyl amyl, l,l-di-
. . .
-~: methyl butyl, l-ethyl 2-methyl propyl, 1,3-dimethyl butyl,
; isohexyl, 3-methylamyl, 1,2-dimethyl butyl, l-methyl l-ethyl
propyl, 2-ethyl butyl, normal heptyl, 1,1:,2,3 tetramethyl
propyl, 1,2-dimethyl l-ethyl propyl, 1,1,2-trimethyl butyl,
isopropyl 2 methyl propyl, l-methyl 2-ethyl butyl, 1,1-di-
ethyl propyl, 2-methyl hexyl, l,l-dimethyl amyl, l-isopropyl
:~ 20 butyl, l-ethyl 3-methyl butyl, 1,4-d.imethyl amyl, isoheptyl,
; l-methyl, l-ethyl butyl, l-ethyl 2-methyl butyl, l-methyl
;. hexyl, l-propyl butyl, normal octyl, l-methyl heptyl, 1,1-
diethyl 2-methyl propyl, 1,1,3,3-tetramethyl butyl, 1,1-
diethyl butyl r l~,!l-dimethyl hexyl, l-methyl l-ethyl amyl, 1-
methyl l-propyl butyl, 2-ethyl hexyl, 6-methyl heptyl (iso-
octyl~, normal nonyl, l-methyl octyl, 1-ethyl heptyl, 1,1- :
` dimethyl heptyl r l-ethyl l-propyl butyl, 1,1-diethyl 3- :~
>- methyl butyl, diisobutyl methyl, 3,5,5-trimethyl hexyl, 3,5-
., dimethyl heptyl, normal decyl, l-propyl heptyl, l,l-diethyl
hexyl, l,l-dipropyl butyl, 2-isopropyl 5-methyl hexyl and
, . .
... ~ -16
;,~
'1~70Z9~ -
',
Cll - C18 alkyl ~roups such as dodecyl~ t~idecy,l, hex~decyl
and the like. Also included are aralkyl groups, e.g.,
benzyl, alpha- or beta-phenylethyl, alpha-alpha dimethyl
benzyl and the like, with the alkyl portion having from 1
to 30 carbon atoms. Also included are cyclobutyl, cyclohexyl,
cycloheptyl and the like~ ~lso included are alkaryl groups
such as methylphenyl, ethylphenyl
''''`:~ ; ~;;
;:
.
': :
,,
.
: :,.. ~
:'. ,: ": '.
';.' '::
,;
''` ~:
~'
: :
~` :
- . ,, . - . . -
-. . : : . ,
( ( C-4~17 .
. ~ ~7
and the like. Al.so included are alkoxy al~yl such as methoxy ethyl J
ethoxy ethyl, butoxyethyl, butoxy butyl and the like.
Typical examples of substituted alkyl radicals are the
haloalkyl radicals which can be repres~nted ~y the structure:
.
R7 ~:
:i where ~al refers to a halogen, m is less than or equal to 2n+1 and
n may have any value fr~m O to 1~ and R6 and R7 ean be hydrogen~
halo~en such as F3 C~, Br and I, or alk~l radicals. Preferred radicals
are those where Hal is fluoro and include those represented b~ the
" following form~las: .
.: O R6 R6
:, S
' CF3 C_ CF3 CF2 C_
7 R7
, R8 R6
:....................... CF3CH2C- CF3(CF2~2C-
. 1 ~ .
~5 R7 R~
~ 8 R~
; . CF5 tCF2 )3C- CF3(CF2)~C- !
~ R7 R7
~: ~
R6 ~ R6
O ~F3 (CF2)sC- CF3(CFz)eC-
' 1 7
~ ~ R7 R7
, ~ .
.
R~ R~
CFs(~2~s)C- . ~F3 ( C3~7 ) C -
. R~ R~
. . t
~5 ~ P-,(C4 ~ )C- CF3(csHll)c-
.
.
-- ~ ( C_4217
R~ ~6
CF3 (C5HI3 )C~ CF3 (C7HI 5)C_
R~3 R~3
CF3 (C8HI7 )C~ CF3CF2 (C2H5 )C~
~., ' . .
R6 R6
CF3 CF2 ( C3 E~7 ) C--CF3 CF2 ( C 4Hg ~ C--
. ,
: .
R6 R6
CF3CF2(C5HI 1 )C--CF3CF2(C~Hl3 )C-- '
.
- : :
lo ~ : CF3 (CG~13 )C~ CF3CF2(C8H1~ )C--
- R~3 R6 ::
t
C~?3 ( CFZ 12 ( C2H~ ) C_ CF3 t CF2 ) 2 ( C3~ ? ) C~
6 ~ R6
GF3 ( CFZ ) 2 ( CSH9 ) C_ CF3 ( CF2 ) 2 ( C 5H 1 1 ) C-
15~ R~ R~ .
CF3(cF2)2(c6Hl3)c- CF3tcF2)2(c7Hl5)
. R6 : : R6
. I . 7
~ CF3 ( C~2 ) 2 ( C8M 17~ j C~ ~ CF3 ( C~2 ) 3 ( C2H 5 ) C_
.. :.... ~ : . ,
R~ ~ R6
. i
CF3 (CF2 )2(C8H17 )C~ - ~CF3 (CF2 )3 (CaHS )C-
::: :
R6 R6
:: : ': '
CF3 (CF2 )3 ( (:~3H7 jC~ ~ CF-~ (CF2 )3 ( C4~9 )C-
:: :
18 -
.. .
:~ .
~: : :
- :
- . . ~ . . . , ; -, .. . .
070 ~
~o Ro
Cl~3(CF2 j 3 t C5~ l l ) c- ~ C~3(CFzJ3(C~Hl3)c~
R~ Ra
` '~t
~3(CF2)q(C7~{l5)G~ . CF3(CF~33(C~,Hl7)C~
. ~ R6 ~ .
-.CF3(CF2)~.(C2~s)c~ CF3~CF2)~(C3~17)C-
I
CF 3( CF2)~(C~Hg)C~ CF3(CF2j~C5H~)C-
'
R6 R6
' 10 CF3(CF2)4(C3X~3)C- ' . CF3(CFz)~(C7Hl5~~
... : , .
R6
~ . r
::- CF3(CF2)~(C~H~7)C- ~F3tcFz~s(c2~l5)c-
.: : R~, R6
.. , , . ,, I .
~ CF3~CF2)5(Cç.H~C- ~ ~F3(CF2)s(C Hg)C-
;15 ~ ,. . ; . R6
F3(C~2)s(Csxll)c- :~ C~3(cF2)s(c6Hl3)c-
Ro . . : R6
s . ,
CF3(CF;~)5(C7Hl53C- ' . . CF3~cF2)s(c~3Hl7
CF3C(C3H7)2~ CF3C(C4~l9)2-
. 20 CF3C(CH3~2- : CF3C~2Hs)2~
~her~ R~ an~ ~7 have ~heir aforedes~ribed significance~
:
. The~halogenated alkyl radicals can be primaryJ
secondary or terti3ry.
.
. Other suitable fluorine-containing radicals
,~25 include fluo~inate~l alkoxyalkyl radiczls particularly thos~
. . . .
.rcprescnt~d b; th~ ~ollo~ing formulas:
.
., ., 1 ~ ~ . ~ "
~7~29~
. XG
' C,~H50C~ .CF;,CF2C- C3H-,OC~i21~ CF2C-
, ~ :
R7 . R7
- ~
, . .
R6 : R~ `
I .1
;C~H9~H2CF2CF2C- .C5H~1C~I2CF2CF2C- .
.
~` . R7 .R7
.
.; RB . RG
t . I :.:
C6H130C~2CF2C~2C_ . C2HSOCH2C~2CF2CF2C- :
: - R7 .. ~
R ~6 !
, ~, C3~7OCH2CF2CF2CF2C- . C~LHgOCHzCF2CF2CF2C~
."`~ . I . I
R7 . ` R~
.
: . R~ R~
,
C ,Hl lOCHzCF2CF2CF2C~ C~Hl30G~2G~2CF2CF2C-
~;5 ~ R7 ` R7
',:' ' ' . . ~ :~
~ R6 ` R6 -
. . I . I .
C2H50CH2(CFZ)~C_ . ` C3H70CIIZ(CF2~C-
.. . . I
; . R7 ~7
. .
.. ..
6 ~ . ` ' . Ra ; .:
~ . C~H90CH2(~F2)~C- ` C5H11QC~2(CFZ)~C_
: - R7 R7 `
. . , . - . . .
- ' ' ' ' ' ' ~ . ' ' '.' '
R~
C 6H i 30CH~ ( CI~2 ) ., C~
.. I .
.- R7 ~ ` . .
~ . . .
' ' : . . ' ' :
; _ 20_ -
.. . . .. .
.
~L~J76;~25~
where R6 and R7 have their aforedescL~ed si~nif~cance~
It is also contemplated within the scope of this
invention that the hydrogen and the fluorine in the previous-
ly described haloalkyl radicals can be replaced by other
halogens, such as chIorine or bromine. :~
; Typ~cal examples of aryl and substituted aryl
radicals are phenyl, cresyl, xylyl, halogenated phenyl,
~: alkoxylated phenyl, cresyl and xylyl in which the available
~; hydrogen on the aryl or substituted aryl is partially or
totally replaced by a halogen, o-, m- and _- trifluoromethyl-
phenyl, o-, _- and ~-2,2,2-trifluoroethylphenyll o-, m- and
p-3,3,3-trifluoropropylphenyl and o-, m-, and p-4,4,4-tri- :
fluorobutylphenyl. Also included are isopropylphenyl, butyl-
-~ phenyl, alpha-alkylbenzylphenyl and alpha,alpha-dialkylbenzyl- : .
:~ phenyl, e.g. alpha-methylbenzylphenyl, alpha,alpha dimethyl-
benzyl phenyl.
The orthosilicates useful as base stocks include
the tetraalkyl orthosilicates such as tetra(octyl)ortho-
silicates, tetra~2-ethylhexyl)orthosilicates and the tetra-
(isooctyl)orthosilicates and those in which the isooctyl ~ :
radicals are obtained from isooctyl alcohol which is derived
. from the oxo process, and the (trialkoxysilico)trialkyl
orthosilicates, otherwise referred to as hexa~alkoxy) di-
siloxanes, such as hexa(2-ethylbutoxy~ disiloxane and hexa-
. (2-ethylhexoxy) disiloxane.
The pre~erred tetraalkyl or~hosilicates and hexa-
(alkoxy~ disiloxanes are those ~n which the alkyl or alkoxy
.' r -
radicals have from 4 to 12 carbon atoms and in which the
total
-21-
:.~
, ~
1~7~29:~L
- ( :
numbcr o~ carbon a~oms in ~lle ortllosilicatc is ~rom 15 to ~.
- In adclition to ti-e he~a~alkoxy) disiloxanes r~e,red
to above, othcr he~a(alkoxy) disilo,;anes can be use~ in which : :
the aliphati radical o~ th~ alko~y groups are for exan.ple~
l-ethylpropyl, l "-dimethylbuty~ methylpentyl, l-n~ethyl- .
. hexyl, l-ethylpenLy~, 2-butylhe.~yl and I~met~yl-4 ethyl.oct~rl.
Th~ orthosilicates and alkoxy polysiloxanes can be
represented by th~ general structure: .
R~ R 1 1 . ,
0 (~m
R8 - - Si-- -O - X _ ()m ~ Rl3
: Q (Q~m
:,' . ' ~10 Rl2 rl '~
~, . . .
wherein ~8~ ~ and Rlo each can b~ al~yl, substituted alkyl,
~; 15 arylS substituted aryl and can be identical or di~ferert with
respec~ to any other radical~ O is oxygen, Si is silicon, X
is a member o~ the group consisting of carbon and.silicon,
m is a whole number having a value of 0 or 1, n is an intege~
having a val~e of from 1 to about 200 or more and when X is
carbo~ m is 0, n is 1 and Rlll Rl2 and Rl3 cach can be
hydrogen, alkyl, substituted alkyl, aryl and substituted aryl.
radicals and when X is silicon m is~l', n is an integer having
a ~alue o~ from~l to:sbout 200 or mor~ and R~l, Rl2 and R19 each
. csn b~ alkyl, subs~ituted ~lkyl, aryl and substituted ~ryl.
- 2S TypicaI examples of substituted aryl radicals are
o-, m- and p-chlorophenyl, o-, m- and p-bromophenyl, o-, m-
~nd ~-~luorophenyl, alpha,alpha,alpha-trichlorocresy~, ~lpha,
alpha5alpha-trifluo~ocresyl, xyly~ ~nd o , m- and p-cresyl.
: . .. . .
~2a - . .. ...
.
~ (~7029~ ~ c~ 7
Typical examples o~ alk~l and haloalkyl radicals are those here.G-
fore described.
The siloxanes or silicones useful as base stocks are
represented by the general structure:
Rls Rl7
; Rl4 - Si - 0 - Si - Rl9
_~l6 ~ Rlg
wherein Rl4, R15J Rl6, Rl7, Rl~, and Rlg can each be alkyl, sub-
stituted alkyl, aryl and substituted aryl radicals and n is a
whole number from about 0 to about 2000 or more. Typical exa.ple-
of alkyl and haloalkyl radicals along with the number of carkon
atoms are those heretofore described. Typical examples of the
~ siloxanes are poly(meLhyl~ siloxane, poly(rnethy7, pheryl) siloxan_.
- poly(methylJ chlorophenyl) siloxane and poly(methyl, ~ tri-
- 15 fluoropropyl) siloxane.
Typical examples of substituted aryl radicals and o-,
m- and p- chlorophenyl, o-, m- and ~-bromophenyl~ o-, m- and p-
fluorophenyl~ alpha,alpha,alpha-trichlorocresyl, alpha ? alpha,
,,
alpha-trifluorocresyl, o-, m- and ~-cresyl and xylyl.
Dicarboxylic acid esters which are suitabl~ as base
stocks are represented by the structure:
O
t, ~,
R20 - O ~ C: - R2 1 - C - O - Rz2
whe~ein R20 and Rz2 are each selected from the group consistir~
of alkyl, substituted alkyl, aryl and substituted aryl and R~
is a divalent radic~l selected from the group consisting of
,.
- 2~ -
.
alkylene and substituted alkylene, and are p~e~ared by este~
ifying dicarboxylic acids such as adipic ac~d, azelaic acid,
: suberic acid, sebacic acid, hydroxysuccinic acid, fumaric
acid, maleic acid, etc., with alcohols such as butyl alcohol,
hexyl alcohol, 2eethylhexyl alcohol, dodecyl alcohol, 2,2- ~ :
dimethyl heptano, l-methyl cyclohexyl methanol, and the like. :~
Typical examples of alkyl, aryl substituted
alkyl and substituted aryl radicals are given above. ~:
Polyesters which are suitable as base stocks are
- represented by the structure~
,., _ O _ - ~
~ o - C - R
CH2
R23 ~ tC ~ )a -CH2 ~ C ~ CH2~ 6
.; CH 2
'` O
: ¦ R 5
wherein R23 is selected from the group consisting of hy~
drogen and alkyl, R24 and R25 are each sèlected from the
group consisting of alkyl, substituted alkyl, aryl and sub-
stituted aryl/ a is a whole number having a value of O to 1, ~.
Z is a whole number having a value of 1 to 2 and when Z is 1,
R26 is selected from the group consisting of hydrogen,
: alkyl acyloxy and substituted acyloxy and when Z is 2, R26
~. ~
: is oxygen, and are prepared by esterifying such polyalcohols .
i- as pentaerythritol, dipentaerythritol trimethylolpropane, `~
trimethy~olethane and neopentyl glycol with such acids as .
:~ propionic, butyric, isobutyric, _-valeric, capric, caproic, n-heptylic
:. caprylic, 2-ethylhexanoic, 2,2-dimethylheptanoic and pelar- ~; `:~ .
-24~ :
~,
~' ' '
~07(;~Z9~
gonic. Typical examples of alkyl~ substituted ~lkyl, aryl
and substituted aryl radic~ls are given above.
Other esters which are also suitable as base
stocks are the ~ono esters.
Another class of compositions which are suitable
as base stocks for this invention are the polyphenyl ethers,
~ polyphenyl th~oethers, or mixtures thereof, as represented
;~ by the structure:
~ r A2- ~ X3
::~ A
;::............................................ 3
~ " ~
~ --~
4
wherein A, Al, A2, and A3 are each a chalcogen having an atomic
: number of 8 to 16, X, Xl, X2, X3, and X4 each are selected ;~
~-. from the group consisting of hydrogen, alkyl, haloalkyl~ halo-
.. gen, arylalkyl and substituted arylalkyl, m, n and o are whole
numbers, each having a value of 0 to 8 and a is a whole number
,, ~: . .
.. having a
. . ,
~' ,,
' '
~ ~25c-
,,
;,:: :'
1071D2~ ~
value of 0 to 1 pro~lded that ~Jhen a is 0, n can have a value of
; 1 ~o 2. Typical examples of alkyl and substituted alkyl radicals
are given above. Typical examples o such base stocks are 2- to
7-ring ortho-, meta- and ~ara- polyphenyl ethers and mixtures
j thereof, 2- to 7-ring ortho~, meta-~ and para- polyphenyl thioethers
and mixtures thereofl mixed polyphenyl ether-thioether compounds
in which at least one of t~e chalcogens represented by A, A1, A2
and A3 is dissimilar with respect to any one of the other chalcogens,
dihalogenated diphenyl ethers, such as 4-bromo-3'-chlorodiphenyl
ethers and bisphenoxy biphenyl compounds and mixtures thereof.
Hydrocarbon oils including mineral oils deri~ed from
petroleum sources and synthetic hydrocarbon o1ls are suitable base
stocks. The physical characteristics of functional f1uids derived
~ from a mineral oil are selected ~n ~he basis of the requirements
L5 of the fluid syst~ms and therefore this invention includes as
base stocks mineral oiis having a wide range of viscosities and
volatilities such as naphthenlc base, paraffinic base and mixed
base mineral oils.
The synthetic hydrocarbon oils include but are not
~0 limited to those oils derived from oligomerization of olefins such
as polybutenes and oils derived from high or alpha-olefin.~ o~ from
4 to 20 carbon ato~s such as by acid catalyzed dimeri3ation and then
:.
oligomerization using mixtures of aluminum alkyls and titanium
,
~ halides as catalysts, or Fxi~del-Crats catalysts~ or peroxide
~ ~ catalysts.
Chlorinated biphenyls and terphenyls are also ~seul as
; base stocks~
.. :
The fluid compositions o~ this invention when utilized
as a functional ~luid can also contain acid acceptorsl dyes? pour
d~
. . , ,~ ~
~070Z91.
point depressants, thickeners~ antioxid~nts anti~oa~ a~ents,
viscosity index i~provers such as polyalkyl acrylates, poly-
alkyl methacrylates, polycyclic polymers, polyurethanes,
polyalkylene oxides and polyesters, lubricity agents, water and
the like.
It is also contemplated that the base stocks as
aforementioned can be utilized singly or as a blend contain-
ing two or more base stocks in varying proportions. The
base stocks can also contain-other fluids which include, in
`~ 10 addition to the functional fluids, desired fluids derived
from coal tar products, synthetics, and synthetic oils, e.g.,
alkylene polymers (such as polymers of propylene, butylene,
etc., and mixtures thereof), alkylene oxide type polymers
( e.g., propylene oxide polymers), and derivatives, including
alkylene oxide polymers prepared by polymerizing the alkylene
oxide in the presence of water or alcohol, e.g., ethyl
alcohol, alkyl benzenes, (e.g., monoalkyl benzene such as do-
decyl benzene, tetradecyl benzene, etc.) and dialkyl benzene ;~
(e.g., n-nonyl 2-ethyl hexyl benzene); polyphenyls, (e.g., bi-
phenyls and terphenyls), halogenated benzene, halogenated
lower alkyl benzene and mono-halogenated diphenyl ethers.
. , .
Howevex, in the preferred form of the present
invention, the ammonium salt of phosphorus acid composition
of the present invention is combined with a phosphate ester
:; . .
; functional fluid base stock. The base stock will consist
primarily of trialkylphosphates being present in amounts
from 50 to 95% byweight and preferably from 60 to 90% by - -
weight. The trialkylphosphates which give optimu~ results -
are those wherein each of the alkyl groups contain fxom 1 to
carbon atoms, preferably from 3 to 12 carbon atoms and
~27-
,~
. - "
': '
j . . ,, . ., . . . . ~ .
~070Z9~ :~
more pre~erably, from 4 to 9 caxbon atoms. The alkyl ~roups
are preferably of straight chain configuration. A single
trialkyl phosphate may contain the alkyl group in all three
positions or may possess a mixture of different alkyl groups.
Mixtures of various trialkyl phosphates can be used. Suitable
species of trialkyl phosphates which may be employed as the
base stock composition include tripropyl phosphates, tributyl ~
phosphates, trihexyl phosphates, trioctyl phosphates, dipropyl ~i
octyl phosphates, dibutyl octyl phosphates, dipropyl hexyl
phosphate, dihexyl octyl phosphate, dihexyl propyl phosphate,
and propyl butyl octyl phosphate. ~ ~;
The trialkyl phosphates can be combined with tri-
aryl phosphates or mixed alkyl aryl phosphates. Preferred
triaryl phosphates are tricresyl phosphate, cresyl diphenyl
phosphate, trixylenyl phosphate, tertiary-butylphenyl phenyl phos-
phates, ethylphenyl dicresyl phosphata or isopropylphenyl di~
phenyl phosphate, phenyl-bis-(4-alpha-methylbenzylphenyl) -
. ~
phosphate, diphenyl decyl phosphate, diphenyl octyl phosphat~
methyl diphenyl phosphate, butyl dicresyl phosphate and the
like. In one preferred embodiment, a base stock containing
primarily trixylenyl phosphate is employed. The triaryl ~`~
: , . ,
phosphates function as a thickener for the trialkyl phosphates.
Thus the amount of triaryl phosphate may xange between 0 to
35% by weight. The preferred range of the triaryl phosphates ~`
will be from about 5 to about 30% by weight of the composition.
Conventional polymeric thickeners or viscosity
index (VI) improvers may be blended with the mixture of tri~
alkyl and triaryl phosphate material to achieve the desired ~;
viscosity. Typical thickeners used may be polyacrylates, -~
polymethacrylates, polyethylene oxides, polypropylene oxides,
-28-
..
. ,
.. . . . . .
107~;~91
pol~esters and the like.
Preferably, a polyester based upon an azelaic acid
and a diol such as propylene glycol, and the like, in the
range of .3 to 20% by weight is used as the thickener.
;; Combinations of antioxidants and/or acid acceptors
in amounts ranging from about .1 to about 5~ by weight may
also be incorporated into the functional ~luid composition,
such as, epoxides and/or aminesO The combination of 3,4-
epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate and
phenyl-alpha naphthylamine has been found to be very effective.
Corrosion inhibitors such as benzotriazole, quinizar-
in or the like in an amount ranging between 0.001 and 0.5~
by weight can be added to the mixture and thoroughly blended
; therewith. A dye in a concentration range between 5 and 20
parts per million can be added to the composition and blended
. . .
therewith in a conventional manner~ Effective amounts of a
silicone antifoaming agent can also be incorporated into the
composition and are usually most effective in an amount ranging
,: , .
between 5 and 50 parts per million.
The functional fluids of this invention can contain
.. . ~ .
up to about 1~ by weight of water. It is preferred, however,
to maintain water levels below 0.6 weight percent, and most prefer-
,~ .
ably below about 0.3 wei~ht percent.
The invention can be illustrated by the following
- non-limiting examples.
; In the examples and throughout the specification,
all parts and percentages are by weight, unless otherwise noted. -
;~ EXAMP~E 1
A base stock consisting of 78.98 weight percent of
tributyl phosphate and 9.70 weight percent of mixed cresyl and
2 9--
- : ?
'',
~ [)702~1
xylenyl phosphates With a viscosit~ of app~oxi~ately 220 ~ay-
bolt Universal Seconds at 100F. is com~ined with 9.00 weight
percent of a polyester thickener, Plastolein~ 9789 sold by
Emery Industries. Thereafter, 1.0 weight percent of 3,4- ~ ~
epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate and ~ ,
1.0 weight percent of phenyl alpha-naphthlamine are blended
into this mixture. Then 0.02 weight percent of ben~otri~
azole is thoroughly blended therewith along with conventional
dye and antifoam ayent in the amount of 20 parts per million
and 15 parts per million, respectively. Thereafter, dodecyl
trimethyl ammonium diphenyl phosphate is blended into the
mixture at various addition levels including 0.1% and 0.3% `
by weight.
The composition prepared as above was tested in an
; apparatus consisting of a Boeing 737 trailing edge flap valve
pressurized by a Vickers axial piston pump together with re- i
lated equipment required to assure that the apparatus will
,~
operate according to the requiremen~s of Section 10.2 of SAE
;` specification AS 1241 pertaining to the erosion resistance
of ire resistant aircraft hydraulic fluids. Fluids are
evaluated on the basis of leakage rate increase for the valve
when it is in the closed or null position. The results of
the dodecyl trimethyl ammonium diphenyl phosphate addition
into the phosphate ester fluid are as follows:
- % BY WEIGHT OF DODECYL LEAKAGE RATE
TRIMETHYh ~MMONIUM INCREASE CONDUCTIVITY
; DIPHENYL PHOSPHATE (cc/min~hr.) (micromhos cm)
None 7.0 0.021
0.1 2.0 0.10
0 3 0.0 0.29
The test results show that the addition of an
effective amount of dodecyl trimethyl ammonium diphenyl
~'
-30-
, ~ - : .: . - . i, .; ,
:i 107~2~
.
phosph~te to ~ phosphate estex h~dxaulic ~luid inhibitS dama~e
to hydraulic Systems.
EXAMPLE 2
A similar erosion test was performed on the phosphate
: ester fluid described in Example 1 with 0~3% by weight of do
- '
~` decyl trimethyl ammonium diphenyl phosphate. In this test the
concentration of chlorinatedsolvents was gradually increased ~ ;
~; up to a final level of 2000 parts per million (PPM) of chlorine.
` LEAKAGE RATE
TOTAL CHLORINE TOTAL TEST TIME INCREASE
(PPM) (HRS.) (cc/min/hr)
- _
40 (base level) 440
275 (as CH3CC13) 625 0
444 (sis CH3CC13) 730
938 (as CH3CC13) 830 0
2000 (as CH3CC13 and
~: CF2ClCC12F) 910 0 ~,,-
~, , .
This data has been plotted in the figure and illu-
.
strates the utility of dodecyl trimethyl ammonium diphenyl
phosphate for preventing damage caused to hydraulic systems
;~
~ 20 by chlorine contaminated phosphate ester hydraulic fluids.
;., . ,, .. :,
EXAMPLE 3
An erosion test was performed on a Boeing Material
.; . ~ ~ .
Spec. 311C (BMS 311-C) qualified phosphate ester aircraft hy-
dr~ulic fluid con~aminated with 1000 PPM of chlorine as 1,1,1- - `
trichloroethane. After the erosion rate was 2stablished, the
phospha~e ester ~luid described in Example 1 with 0.3~ by
weight of dodecyl trimethyl ammonium diphenylphosphate was
added in increments to the contaminated fluid. The following
~ . ,
~ data was obtained in this test: ~
'',' ., ' ~
;: ~
~07~2S~
QUALIFIED BMS 311-C PHOSP~ATE ESTER HYDRAULIC F~UID . 1000
~ . . . _ _
PPM CHLORINE AS CH3CC13
TOTAL ~T. % OF PHOSPHAT~ E~TER
FLUID CONTAINING 0.3 BY WT. OF LEAKAGE RATE :
DODECYL T~IME~HYL ~MMONIUM INCREASE
DIPHENYL PHOSPH~TE (cc~ ih/hr)
None 6.0
6.0 ~ :
0.8
o
The above results illustrate the utility of a
formulation oontaining dodecyl trimethyl ammonium diphenyl phos~
phate for arresting the damage caused to hydraulic systems by
. ~ . .
chlorine contaminated phospha~e ester hydraulic fluids.
EX~MPLE 4
: .
In an erosion test similax to that described in
Example 1 the damage causing characteristics of the fluid de-
;.. .
scribed in Example 1 were completely arrested by the addition
of 0.5% by weight of a mixed mono- and bis~ (dodecyl ammonium~
methyl phosphate. This test illustrates the utility of mixed
mono- and bis- (dodecyl ammonium) methyl phosphates ~or arrest- ;~
ing damage caused by phosphate ester ~luids in hydraulic
systems. The conductivity be~ore addikion was 0.021 mmhos/cm,
after 0.24 mmhos/cm.
EXAMPLE 5
A blend similar to tha~ described in Example 1 was
prepared. Two ~ormulations were prepared with this blend.
l'he first contained 0.2 weight percent of dodecyl trimethyl
ammonium diphenyl phosphate and the second contained 0.2 weight
percent o~ trioctyl methyl phosphonium dimethyl phosphate.
These formulations were subjected to stability test described
in Boeing Material Specification 311-C. The following results
were obtained in these tests:
-32-
~- ~07~291 ~ ~
; BOEING THERMA~ 'ST~BI_~T~' TEST
Test Cond~tions: 250QF.~ 168 hours duration, steel,
magnesium, cadmium plated steel, copper, and aluminum present
as catalysts.
ACID NO.
VICOSITY CHANGE (CS) INCREASE
FLUID 10 0 F . 2 I0 ~F .tm~KOH/~
~-~ Base Blend + 0.2 ~eight
Percent Dodecyl Trimethyl-
ammonium diphenyl Phosphate +0.10 *0.03 0
Base Blend ~ 0.2 Weight
Percen~ Trioctyl Methyl
Phosphonium Dimethyl
Phosphate -1.11 -0.42 1.2
~MS 311-C Specification
' Limits ~1.0 -0.3 ~0.5
These tests demonstrate that formulations pre- '
'` pared with dodecyl trimethyl ammonium diphenyl phosphate as
. , ~, .
~' an additive exhibit greater thermal and oxidative stability
' than formulations prepared with triocyl methyl phosphonium ~'
dimethylphosphate. ~ ''
....
EXAMPLE 6 '~
- Illustrative Embodiment No. 1 ~'
:. :
~ In an erosion test conducted in a manner similar
'~ to that described in Example 1 a polyphenyl ether fluid
comprised of mixed meta- and para-pentaphenylene tetroxides
and containing 0.2~ of bis(dodecylbenzyl trimethyl ammonium)
~ ~ .
phenyl phosphate will exhibit less metal damage than the same
fluid without the bis-ammonium phosphate.
EXAMPLE 7
., . ~
Illustrative Embodiment No. 2 ;~
. 30 In an erosion test conducted in a manner similar
to that described in Example 1 a fluid comprised of approx-
' imately 85% synthetic hydrocarbon oil such as;that manufact- -~
,-~ , .
'- ured by Royal Lubricants for use in MI~-H-83282 hydraulic
, :
~:
10702~1
fluids, 15% trimeth~lolpropane trihept~no~te~ ~nd Q.2% di~
dodecyl dimethyl ammonium didodecyl phosphate will exhibit ~ -
less metal damage than the same fluid without the ammonium ~ - .
phosphate. : .
, 'EXAMPLE 8
~ llustrative Embodiment No. 3 :: :
: ~ ~
~n an er~ion test conducted in a manner similar ' : ,
to that described in Example 1, a fluid comprised of approx- ~ -
imately 50% mixed alkylsubstituted phosphate ester, 40% ~
aromatic mineral oil, such as N~SO~ 95, sold by Sun Oil Co.,
10% pentaerythritol tetraheptanoate, and 0O2% nonylphenyl
' trimethylammonium dioctyl phosphate will exhibit less metal ~ ,
.: damage than the same fluid without the ammonium phosphate.
,, ` ~.
O, .. :
,' , ~
: ~
'.`,'. ~`
.. '
: ~
.,` ~'. .
~'', '
:,
,:J
:: -,
- _34_ .,.
--, - :
