CA1070291A - Functional fluid containing ammonium salts of phosphorus acids - Google Patents

Abstract

FUNCTIONAL FLUIDS CONTAINING AMMONIUM
SALTS OF PHOSPHORUS ACIDS

Abstract of the Invention A composition and method for inhibiting damage in a functional fluid by incorporating therein damage inhibit-ing amount of an ammonium salt of a phosphorous acid in accordance with the formula:

Description

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. ~ , ~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, .

. . ~

~; 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 ~:

..

~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 ,, .~

`,.
'"'', ' ; . ' ~ , 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 ::~
'~
'~ ' ' ~ ' ~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~ .

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 " .~
-N-:, ,~,. .
Yl is selected from the group consisting of oxygen, sulfur and -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_ , 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~
~., ' . .

CF3 CF2 ( C3 E~7 ) C--CF3 CF2 ( C 4Hg ~ C--. , : .

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-::: :

:: : ': ' CF3 (CF2 )3 ( (:~3H7 jC~ ~ CF-~ (CF2 )3 ( C4~9 )C-:: :

.. .
:~ .
~: : :
- :
- . . ~ . . . , ; -, .. . .

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-' ' 10 CF3(CF2)4(C3X~3)C- ' . CF3(CFz)~(C7Hl5~~
... : , .

~ . 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 :.~
, ~

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

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, ..
. , .. . . . . .

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 - : ?
'', ~ [)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 ~' , ~ - : .: . - . i, .; , :i 107~2~
.

phosph~te to ~ phosphate estex h~dxaulic ~luid inhibitS dama~e to hydraulic Systems.

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.
;., . ,, .. :, 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 ~ . . . _ _ 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.

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:

~- ~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.

., . ~
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_ .,.

--, - :

Claims (64)

The embodiments of the invention in which an ex-clusive property or privilege is claimed are defined as follows:

1. A method of operating a hydraulic pressure device wherein a displacing force is transmitted to a displaceable number by means of a hydraulic fluid comprising a major amount of base stock material selected from the group consisting of the esters and amides of an acid of phosphorus, mineral oils, synthetic hydrocarbon oils, ortho silicate, alkoxy polysiloxanes, silicones, polyphenyl ethers, polyphenyl thioethers, chlorinated biphenyls, esters of dicarboxylic acids and monohydric alcohols, esters of mono carboxylate acids and monchydric alcohols and esters of monocarboxylic acids and polyhydric alcohols and mixtures thereof, polyalkylene ether alcohols and esters thereof, and blends thereof; and a wear inhibiting amount of an ammonium salt of phosphorus acids in accordance with the formula:

where R, R', R" and R''' can be the same, different or con-joint and represent hydrogen, alkyl aryl, alkaryl or aralkyl group containing from 1 to 30 carbon atoms, X represents oxy-gen or sulfur, Y' and Y" represent lower alkoxy, lower alkyl, phenyl, lower alkylphenyl, phenyl lower alkyl, phenoxy and lower alkylphenoxy, Z represents oxygen, and m = 1 or 2.

2. The method of Claim 1 where m = 1.

3. The method of Claim 2 wherein said base stock material is selected from the group consisting of esters and amides of an acid of phosphorus, mineral oils, synthetic hydrocarbon oils and blends thereof.

4. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is hexadecyl trimethyl ammonium diphenyl phosphate.

5. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is decyl trimethyl ammonium diphenyl phosphate.

6 The method of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diphenyl phosphate.

7. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecylbenzyl trimethyl ammonium di-phenyl phosphate.

8. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is nonylphenyl trimethyl ammonium di-phenyl phosphate.

9. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is allyl tributyl ammonium diphenyl phosphate.

10. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is bis(dodecyl trimethyl ammonium) phenyl phosphate.

11. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is decyl trimethyl ammonium dimethyl phosphate.

12. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trim ethyl ammonium dibenzyl phosphate.

13. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium methyl phenyl phosphate.

?4. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium bis(nonyl-phenyl) phosphate.

15. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diphenyl dithiophosphate.

16. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is phenyl dodecyl dimethyl ammonium di-phenyl dithiophosphate.

17. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diallyl phosphate.

18. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is nonylphenyltrimethyl ammonium di-n-butyl dithiophosphate.

19. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is benzyl trimethyl ammonium dibenzyl dithiophosphate.

20. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is hexadecyl trimethyl ammonium dimethyl phosphate.

21. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is trioctyl methyl ammonium diphenyl phos-phate.

22. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is heptadecyl trimethyl ammonium dimethyl phosphate.

23. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is tris(n-tridecyl) methyl ammonium diphenyl phosphate.

24. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is dimethylbutylhexadecyl ammonium di-butyl phosphate.

25. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is triethylmethylammonium, methyl, methyl-phosphonate.

26. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is 1,3,5-trimethyl pyridinium diphenyl phosphate.

27. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is N-methyl, N-butyl piperidinium dibutyl-phosphate.

28. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is

29. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl dodecyl ammonium dimethyl methylphosphonate.

30. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl octyl-phosphonate.

31. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl benzyl ammonium methyl octylphosphonate.

32. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is benzyl trimethyl ammonium methyl hexadecylphosphonate.

33. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl tertiary-butyl phosphonate.

34. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl carbo-methoxy methyl phosphate.

35. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl tertiary-octylphenyl ammoni-um methyl methylphosphonate.

36. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium bis(nonylphenyl) phosphate.

37. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is benzyltrimethyl ammonium bis(nonyl-phenyl) phosphate.

38. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is PO2-.

39. The method of Claim 3 wherein said ammonium salt of a phosphorus acid is

40. In a method for inhibiting damage to a metal en-vironment containing a functional fluid by deploying in a base stock composition of said fluid an effective amount of a damage inhibiting composition, the improvement which com-prises deploying said damage inhibiting composition in accord-ance with the formula:
where R, R', R" and R''' can be the same, different or con-joint and represent hydrogen, alkyl, aryl, alkaryl, and ar-alkyl groups containing from 1 to 30 carbon atoms, X repre-sentso or S, Y' and Y" represent alkoxy, alkylthio, alkyl, aryl, alkaryl, aralkyl, aryloxy, arylthio and alkaryloxy, Z
represents oxygen or sulfur, and m = 1 or 2.

41. The method of Claim 40 wherein m = 1.

42. The method of Claim 41 wherein said damage inhibit-ing composition is deployed in a hydraulic environment con-taminated by organic chlorine.

43. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diphenyl phosphate.

44. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is bis(phenyl dodecyl dimethyl ammonium) phenyl phosphate.

45. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is decyl trimethyl ammonium dimethyl phosphate.

46. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is bis(didodecyl dimethyl ammonium) methylphosphonate.

47. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium dibenzyl phosphate.

48. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diphenyl dithiophosphate.

49. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is phenyl trimethyl ammonium diethyl di-thiophosphate.

50. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diallyl phosphate.

51. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is nonylphenyl trimethyl ammonium di-n-butyl-dithiophosphate.

52. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is tris(n-tridecyl) methyl ammonium di-phenyl phosphate,

53. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is dimethylbutylhexadecyl ammonium di-butyl phosphate.

54. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is triethylmethylammonium methyl methyl-phosphonate.

55. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is 1,3,5-trimethyl pyridinium diphenyl phosphate.

56. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is N-methyl, N-butyl piperidinium di-butyl phosphate.

57. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is .

58. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is trimethyl benzyl ammonium methyl octylphosphonate.

59. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is benzyl trimethyl ammonium methyl tertiary-butyl-phosphonate.

60. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl carbo-methoxymethylphosphonate.

61. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is trimethyl tertiary-octylphenyl ammonium methyl methylphosphonate.

62. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is benzyltrimethyl ammonium bis(nonyl-phenyl) phosphate.

63. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is C6H4O)2PO2-.

64. The method of Claim 41 wherein said ammonium salt of a phosphorus acid is (CH3)PO2-.