IL46483A

IL46483A - Functional fluids containing ammonium salts of phosphorus acids

Info

Publication number: IL46483A
Application number: IL46483A
Authority: IL
Original assignee: Stauffer Chemical Co
Priority date: 1974-02-11
Filing date: 1975-01-21
Publication date: 1977-11-30
Also published as: ZA75843B; DE2505189A1; FR2260617A1; JPS50115183A; AU7758075A; NO141016C; CH615217A5; IN142832B; NO750423L; DK38975A; SU679151A3; GB1506196A; AR208190A1; FR2260617B1; SE7501453L; CA1070291A; NL7501552A; BE825342A; IT1029652B; NO141016B

Abstract

A hydraulic fluid which is able to limit the wear of mechanical parts coming into contact therewith contains an ammonium salt of a phosphoric acid of the formula <IMAGE> in which the individual symbols have the meaning specified in Claim 1. [GB1506196A]

Description

Functional fluids containing ammonium salts of phosphorus acids STADFFEH CHEMICAL COMPAST C. 44468 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 a damage inhibiting amount of an ammonium salt of a phosphorus acid in accordance with the formula: wherein R, R' , Rn ana R1 ' ' can be the same, different or conjoint and represent hydrogen, alkyl, aryl, alkaryl, and aralkyl groups containing from 1 to 30 carbon atoms; X represents 0 or S; Y' and Y" represent alkoxy, alkylthio, alkyl, aryl, alkaryl, aralkyl aryloxy, arylthio and alkaryloxy; Z represents oxygen or sulfur; and rn = 1 or 2.

Background of the Invention This invention relates to functional fluid composition 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, diffusion ρτ fluids, lubricants, camping fluids, bases for grsas , owe transmission a d hydraulic fluids, heat transfer fluids, 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 fluid during use and to mechanical members, especially metallic members in contact with the fluid, as evidenced by a loss of weight of such members, due to the wearing away of metallic parts. Damage has been reported in 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-metallic materials.

In those instances where functional fluids are used in the hydraulic systems of aircraft and aerospace systems, 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 A ents for fire resistance. Additionally, the hydraulic fluid must be capable of performing in the hydraulic system over an extended period of time without causing significant damage or functional impairment to the various conduits, valves, pumps, and the like, through which the fluid flows in the course of such use.

Damage caused by functional fluids contacting valves and other members has been attributed to the wearing away or erosion of the environment in contact with the functional fluid in a hydraulic system. Among the many undesirable 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 geometry of these parts. Such changes in the case of pumps can cause a decrease in pumping efficiency, and in the case of valves can cause faulty operations, excessive leakage and even hazardous conditions.

This damage necessitates costly and time consuming premature overhaul of mechanical parts. Additionally, metal removed from component metallic mechanical parts in contact with the functional fluid contaminates the fluids, causes filter clogging and excessive filter replacement, and requires premature draining and replacement of the fluid in the system. The metal contamination can also cause a change in physical and chemical properties of the functional fluids.

Metal contaminants can also reduce the oxidative stability of a fluid, thereby adversely affecting fluid performance. In addition, metal contamination of the fluid can manifes itself in numerous other ways, including viscosity change, in- 1 i creased acid number, formation of precipitates, decrease in chemical stability and discoloration.

Another problem in the industry is the unavoidable contamination of aircraft and electrohydraulxc control systems with chlorinated solvents used to clean the systems and components.

A detailed discussion of this problem appears in Vickers 22nd Fluid Power Conference Report, Oct. 30, 1972 , Section 4 , Pages 25- · Contamination by chlorinated solvents decreases the service life of functional fluids and accelerates damage, causing excessive internal leakage in hydraulic systems to a point of malfunction. No additive heretofore known has satisfactorily overcome the problems associated with chlorinated 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, ^70,792 proposes to overcome this damage problem by the inclusion of a small percentage of water in an aircraft hydraulic system. Unfortunately, while the presence of 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 effect on the stability of the fluid.

U.S. Patent 3 ,707 , 501 discloses the use of phosphonium compounds to inhibit erosion damage to the metallic environment containing hydraulic fluids. However, the lubricant compositions require relatively high concentrations of phosphonium compounds, which are very expensive. In addition, the phosphonium compounds m contribute to the destabilization of the functional fluid.

U.S. Patent 3 , 67 * 587 discloses alkali salts of per-fluorinated 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. fluid has been di shear, oxidative and thermal stability, and fire resistance charac-^ teristics, and is particularly suitable for aircraft hydraulic 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 fluid capable o inhibiting damage to the metal environment containing the functional fluidc Detailed Description of the Invention The ammonium salts of the phosphorus acids which are useful for incorporation in functional fluids in accordance with the present invention are represented by the following formula and description: 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 0 or S; Y' and Y" represent alkoxy, alkylthio, alkyl, aryl, alkaryl, aralkyl, aryloxy, arylthio and alkaryloxy; Z represents oxygen or sulfur; and m=l or 2. In a preferred embodiment, m=l.

An alternative embodiment involves the ammonium ions attached to the phosphorus anion via an alkylene or arylene group. wherein R, R' and R' ' ' are as above and R" can be any divalent connecting unit such as CH2) and x can vary from 1 to lO.

Representative of the above is: The following is a listing of typical ammonium of phosphorus acids tabulated according to the respective ammonium ions and phosphorus ester anions: Ammonium Ions Phosphorus Ester Anions Dodecyl trimethyl ammonium Diphenyl phosphate Hexadecyl trimethyl ammonium -Phenyl phosphate (bis-amine Octadecyl trimethyl ammonium Dimethyl phosphate Tridecyl trimethyl ammonium Methyl phosphate bis-amine Decyl trimethyl ammonium Methyl methylphosphonate Didodecyl dimethyl ammonium Methylphosphonate (bis-amine Methyl butyl dodecyl ammonium Diethyl phosphate Dimethyl propyl dodecyl ammonium Ethyl phosphate (bis-amine s Dodecyl ammonium Dioctyl phosphate Trioctyl ammonium Dibenzyl phosphate Dioctyl methyl ammonium Diallyl phosphate Dioctyl dimethyl ammonium Methyl phenyl phosphate Dodecylbenzyl trimethyl ammonium Bis(octylphenyl ) phosphate Dodecyl dimethyl butyl ammonium Diethyl d thiophosphate Phenyl dodecyl dimethyl ammonium Di-n-butyl-dithiophosphc Phenyl trimethyl ammonium Dibenzyl dithiophosphate Benzyl trimethyl ammonium Diphenyl dithiophosphate Allyl tributyl ammonium Bis( nonyl phenyl) phosphate Dimethyl dodecenyl ammonium Dibutyl Phosphate (Unsaturated R Group) Methyl Octylphosphonate Trimethyl hexadecenyl ammonium (Unsaturated R Group) Hexadecyl phosphonate Heptadecyl trimethyl ammonium Methyl hexadecyl phosphonat= Trioctyl methyl ammonium Methyl tertiary-butyl phosph Methyl-alpha-naphthyl phenyl Methyl carbomethoxymethyl ammonium 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 inium 2-ethylhvex_yl7dimethyl dodecyl ammonium Dimethylethyl dodecyl ammonium Dimethylbutyl dodecyl ammonium Trimethyl dodecyl ammonium Hexadecyl dimethylethyl ammonium Tris( dodecyl) butyl ammonium Tetramethyl ammonium ( Ammonium Ions Trimethyl benzyl ammonium Trimethyl tertiary-octyl phenyl ammonium 4-acetyl N-methyl pyridinium CH3 CH2- 0P(0C6H5)a CH^ CH2 (C12H25)(CH3)2 l-(N,N-dimethyl )-l-imidazolium l-(N,N-dimethyl )-l-pyrrazolium N-methyl oxazolium N-butyl quinolinium N-methyl pyrrolium N,N-diethyl pyrrolidinium N-methyl jN-hexyl piperidinium N-methyl ,Ν-butyl piperidinium N-isopropyl thiazolium N-ethyl j -methyl phenothiazinium Pyridinium N-methyl pyridinium Each member of the ammonium ions may be combined in turn with each member of the phosphorus ester anion in order to generate typical compounds which may be used in this invention For example, particularly preferred ammonium salts of phosphorus Hexadecyl trimethyl ammonium diphenyl phosphate Decyl trimethyl ammonium diphenyl phosphate Didodecyl dimethyl ammonium diphenyl phosphate Dimethyl propyl dodecyl ammonium diphenyl phosphate Dodecyl ammonium diphenyl phosphate Dodecylbenzyl trimethyl ammonium diphenyl phosphate Nonylphenyl trimethyl ammonium diphenyl phosphate Phenyl dodecyl dimethyl ammonium diphenyl phosphate Allyl tributyl ammonium diphenyl phosphate Trimethyl hexadecenyl ammonium diphenyl phosphate Bis(dodecyl trimethyl ammonium)phenyl phosphate Bis (octadecyl trimethyl ammonium)phenyl phosphate Bis(phenyl dodecyl dimethyl ammonium)phenyl phosphate Decyl trimethyl ammonium dimethyl phosphate Didodecyl dimethyl ammonium methyl methylphosphonate Bis ( didodecyl dimethyl ammoniu )methylphosphonate Dodecyl trimethyl ammonium dimethyl phosphate Dodecyl trimethyl ammonium dibenzyl phosphate Dodecyl trimethyl ammonium methyl phenyl phosphate Dodecyl trimethyl ammonium bis (nonylphenyl) phosphate Dodecyl trimethyl ammonium diphenyl dithiophosphate Octadecyl trimethyl ammonium diphenyl dithiophosphate Dioctyl methyl ammonium diphenyl dithiophosphate Phenyl dodecyl dimethyl ammonium diphenyl dithiophosphate Dodecyl trimethyl ammonium diethyl dithiophosphate Phenyl trimethyl ammonium diethyl dithiophosphate Dodecyl trimethyl ammonium diallyl phosphate Didodecyl dimethyl ammonium di-n-dodecyl phosphate Dodecyl trimethyl ammonium di-n-dodecyl phosphate.

Dioctyl methyl ammonium dioctyl phosphate Trioctyl ammonium dioctyl phosphate Phenyl trimethyl ammonium methyl phenyl phosphate Benzyl trimethyl ammonium methyl phenyl phosphate Trimethyl hexadecenyl ammonium methyl phenyl phosphate Bis (trioctyl ammonium) ethyl phosphate Octadecyl trimethyl ammonium diphenyl phosphate Tridecyl trimethyl ammonium diphenyl phosphate Heptadecyl trimethyl ammonium diphenyl phosphate Nonylphenyl trimethyl ammonium di-n-butyl-dithiophosphate Benzyl trimethyl ammonium dibenzyl dithiophosphate Hexadecyl trimethyl ammonium dimethyl phosphate Trioctyl methyl ammonium diphenyl phosphate Heptadecyl trimethyl ammonium dimethyl phosphate Tris(n-tridecyl ) methyl ammonium diphenyl phosphate Tr s (n-dodecyl )methyl ammonium diphenyl phosphate Tris( isooctyl )methyl ammonium diphenyl phosphate Dimethylbutylhexadecyl ammonium dibutyl phosphate Triethylmethyla monium methyl methylphosphonate 1,3»5—trimethyl pyridinium diphenyl phosphate N-methyl, N-butyl piperidinium dibutyl phosphate 2-ethylhexyl dimethyl dodecyl ammonium diphenyl phosphate Dimethylethyl dodecyl ammonium diethyl phosphate Dimethyl butyl dodecyl ammonium dibutyl phosphate Trimethyl dodecyl ammonium dimethyl methylphosphonate Hexadecyldimethylethyl ammonium diethyl phosphate Tris( dodecyl )butyl ammonium dibutyl phosphate Tetramethyl ammonium methyl octylphosphonate Trimethyl benzyl ammonium methyl octylphosphonate Tetramethyl ammonium methyl hexadecylphosphonate Benzyl trimethyl ammonium methyl hexadecylphosphonate Tetramethyl ammonium methyl tertiary-butyl-phosphonate Benzyl trimethyl ammonium methyl tertiary-butyl-phosphonate Tetramethyl ammonium methyl carbomethoxymethylphosphonate Benzyltrimethyl ammonium methyl carbomethoxymethylphosphonate Trimethyl tertiary-octylphenyl ammonium diphenyl phosphate Trimethyl tertiary-octylphenyl ammonium methyl methylphosphonate Trimethyl tertiary-octylphenyl ammonium bis (nonylphenyl )phosphat Tetramethyl ammonium bis ( nonylphenyl )phosphate Benzyltrimethyl ammonium bis( nonylphenyl ) phosphate C8H17-C10H2 (CeH50)2P02- 0 The quaternary ammonium salts of diesters of phosphori acid which contain no N-H bonds can be prepared by known me n^ as outlined in British Patent 1 , 119 , 015 ( lS7o ) and in the Prepri of the Symposium on Deposit, Wear, and Emission Control by Lubri cants and Fuel Additives presented in the Division of Petroleum Chemistry of the American Chemical Society, N. Y. City Meeting, Sept. 7-12 , 1 9, page A-llO. These methods include: 1. Reaction of an amine with a triester of phosphoric acid in which the triester alkylates the amine. These reactions usually take place above kO-6o° and can be run neat or in alcoho solvents. All volatile species are then removed by distillation to leave behind the phosphoric acid diester salt of a quaternary ammonium cation.

R3N ÷ R'O P( 0)(0R")2 → R3NR' 0P( 0)(0R")2 R' is preferably of the benzyl, allyl, or lower alkyl (especiall methyl) type. R" may be alkyl, aryl, alkaryl, aralkyl, etc. 2. Reaction of the phosphoric acid diester with a quaternary ammonium hydroxide to generate the salt in a neutrali tion reaction and then removal of the water liberated.

(R0)2 P( 0)(0H) + R4N(0H) → R4 ΘNΘ0P(0){0R)2 + H20 5· Reaction of the quaternary ammonium halide with t sodium or potassium salt of the phosphoric acid diester and extraction of the phosphate with a solvent such as acetone to ena removal of the sodium or potassium chloride.

(R0)2 P( 0 ) ( 0 ) ΘNaΘ + R4NΘ CIΘ R N ΘΘ 0ΨP( 0)(0R)2 4- NaCl Erosion exhibited by hydraulic fluids has been related to the electrical properties of the fluid in Boeing Scientific—, Research Laboratories Document Dl-82-03½7. It has been proposed that erosion caused by hydraulic fluids can be controlled by eliminating ionic impurities present in the fluid, or by significantly increasing the conductivity of the fluid.

Both approaches 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 of ameliorating damage caused by erosion. Recent experiments have shown that the elimination of ionic impurities by filtration through an activated clay will control erosion caused by a phosp ester hydraulic fluid. However, this is not a practical solutio since erosion begins again soon after the filtration is discontinued. 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 damage. Furthermore, conductivity measurements of these fluids containin ammonium salts of phosphorus acids indicated increased conductiv It is too early to conclusively attribute conductivity as an explanation of the mechanism, or for evaluating the effectivenes of damage inhibitors. However, conductivity does serve as some indicia, although further research in this area is deemed necess and desirable.

Typical conductivities of commercial phosphate ester . .

Functional fluid compositions to which the ammonium salt of phosphorus acid compositions can be added are referred to as kaj^, stocks. They include, but are not limited to esters and amides of phosphorus acids, mineral oil and synthetic hydrocarbon oil base stocks, hydrocarbyl silicates, silicones, aromatic ether and thioether compounds, chlorinated biphenyl, monoesters, dicarboxylic acid esters, esters of polyhydric compounds, polyalkylene ether glycols and alcohols as well as their esters.

The concentration of 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 damage.

Thus, it has been found that the additive response, that is, the concentration of an ammonium salt of phosphorus acid required to inhibit and control damage of a base stock varies according to the base stock or blends of base stocks employed.

Thus, for the base stocks useful in the practice of this invention the concentration of ammonium salts of phosphorus acid is from about 0.01 percent to about 15 percent by weight, the particular concentration being that amount which will effective inhibit and control damage. The preferred additive concentratio is from about 0.025 to about 5 weight percent, more preferably, from about 0,1 to about 0.5 weight percent." Therefore, included v.'ithin the present invention are compositions comprising a functional fluid and a damage-inhibiting amount of an ammonium salt of phosphorus acids, that is, the ammoniu salt is added, in a concentration sufficient to control and inhibit damage. The functional fluid compositions of this invention can be compounded ation of an additive into a base stock and preferably, by adding an ammonium salt of phosphorus acids to the base stock w ith stirrip* until a fluid composition is obtained.

As indicated above, the compositions of this invention can employ a wide variety of base stocks. Suitable base stock materials are discussed in detail below.

The functional fluid compositions which are suitable for use as base stock materials in the present invention can be esters and amides of an acid of phosphorus represented by the structure: O II R-(Y)a-P-(Yi)c-¾ wherein Y is selected from the group consisting of oxygen, sulfur and R3 t -N- Y: is selected from the group consisting of oxygen, sulfur and R4 -N- and Υ≥ is selected from the group consisting of oxygen, sulfur and • Rs -N- R, R:, R? , R3, R4 and R5 are each selected from the group consisting of alkyl, alkoxy^ aryl, substituted aryl and substituted aL v.'herein R, Ri , R≥, R3 , 4 and R5 each can be identical or differerrfe- with respect to any other radical, and a, b and c are whole number£ having a value of 0 to 1 and the sum of a+b+c is from 1 to J. r n atoms in the a k cycloalkyls and alkyl substituted cycloalkyls. Typical examples of alkyl radicals are as follows: methyl ethyl, normal propyl, isopropyl, normal h isobutyl, secondary butyl, tertiary butyl, normal amyl, isoar.y 2~methylbutyl , 2,2-dimethyl propyl, 1-methyl butyl, diethylme 1,2-dimethyl propyl, tertiary amyl, normal hexyl, 1-methylamyl ethyl butyl, 1,2, 2-trimethyl propyl, 3,3-dimethyl butyl, 1,1.2 trimethyl propyl, 2-methyl amyl, 1,1-dimethyl butyl, 1-ethyl 2 methyl propyl, 1,3-dimethyl butyl, isohexyl, 3-methylamyl, 1,2 dimethyl butyl, 1-methyl 1-ethyl propyl, 2-ethyl butyl, normal heptyl, 1 , 1 , 2,3-tetramethyl propyl, 1,2-dimethyl 1-ethyl propy 1,1, 2-trimethyl butyl, 1-isopropyl 2-methyl propyl, 1-methyl 2 ethyl butyl, 1,1-diethyl propyl, 2-methyl hexyl, 1,1-dimethyl amyl, 1-isopropyl. butyl, 1-ethyl 3-niethyl butyl, 1,^-dimethyl amyl, isoheptyl, 1-methyl 1-ethyi butyl, 1-ethyl 2-methyl buty 1-methyl hexyl, 1-propyl butyl, normal octyl, 1-methyl heptyl . 1,1-diethyl 2-methyl propyl, 1, 1,3,3-tetramethyl butyl, 1,1-diethyl butyl, 1,1-dimethyl hexyl, 1-methyl 1-ethyl amyl, 1-rce 1-propyl butyl, 2-ethyl hexyl, 6-methyl heptyl (iso-octyl), no nonyl, Γ-methyl octyl, 1-ethyl heptyl, 1,1-dimethyl heptyl, 1- ethyl 1-propyl butyl, 1,1-diethyl 3-wethyl butyl, diisobutyl methyl, 3,5, 5-trimethyl hexyl, 3, 5-dimethyl heptyl, normal decr 1-propyl heptyl, 1,1-diethyl hexyl, 1,1-dipropyl butyl, 2-isop 5-methyl hexyl and Cn-Cig alkyl groups such as dodecyl, trid hexadecyl and the like. Also included are aralkyl groups, e.g. benzyl, alpha- Or beta-phenylethyl, alpha-alpha dimethyl benzy! and the like, with the alkyl portion having from 1 to carbc: Also included are e clob t l c clohexyl, cycloheptyl and the 1 and the like. Also included are alkoxy alkyl such as methoxy etl^l, ethoxy ethyl, butoxyethyl, butoxy butyl and the like.

Typical examples of substituted alkyl radicals are the haloalkyl radicals which can be represented by the structure: ; Re CnHal2n+1_mHinC(Hal) 29 7 where Hal refers to a halogen, m is less than or equal to 2n+l and n may have any value from 0 to IS, and R& and Ry can be hydrogen, halogen such as F, CI, Br and I, or alkyl radicals. Preferred radic are those where Hal is fluoro and include those represented by the following formulas: R6 Re CF3C- CF3 CF2C- 1 t R7 T Re Re ! CF3CH2C CF3(CF2)2C- t R7 Ry Re Re ■ 1 « CF3(CF2)3C- CF3(CF2)4C- ■ ■■ . ' ■. .' · . .1 : « Rr T Re e ;- . , . ■ i » CF3(CF2)5C- CF3(CF2)6C- R7 R7 Re e CF3(C2HS)C- CF3(C3K7)C- CF3(C0H13)C- CF3(CTH15)C- Re I I CF3(C8H1T)C- ■CF3CF2.(C2H5)C- I I CF3CFa(C3H7 )C- Re' I CF3CF2(C5Hi i )C- CF3CF2(C6H13)C- e t CF3(C6H1 CF3CF2(C8H17)C- e t CF3(CF2)2(C2H3)C- CF3(CF2)2(C3Hr)C- R6 I (CF2)2(C4H0)C- CFaiCFaJaiCsH! i )C- Re I CF3(CF2)2(C6H13)C- CF3(CF2)2(C7H15)C CF3(CF2)2(C8H1T) CF3(CF2)2(C8H1T) CF3(CF2)3(C3H7) I C2H5OCH2CF;>CF2C- OCH2CF2CF2C I C^H90CH2CF2CF2C- iOCHaCFsCFaG t 1 6Hi30CH2CF2CF2C C2H5OCH2CF2CF2CF2C- I Re • 1 I C3H70CH2CF2CF2CF2C- C4H90CH2CFaCF2CF2C- I I Re Re I C5H! 1Oai2CF2CF2CF2C- 3OCH2CF2CF2CF2C- t Re Re t I C2H50CH2(CF2)4C- ,OCH2(CF2)4C- t t Rr e Ra C4 OCH2(CF2)4C- C5H110a{2(CF2)4C- I I R7 " R7 Re 1 C6H 3OCH2(CF2) C- ( - ( where a and R7 have their aforedescribed significance.

It is also contemplated within the scope of this invention that the hydrogen and the fluorine in the previous described haloalkyl radicals can be replaced by other halcze such as chlorine or bromine.

Typical 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 p_- trifluoromethyl phenyl, o-, m- and £-2,2,2- rifluoroethyIphenyl, o-3 - and R~ t 3,3-trifluoroprop lphenyl and £-, m-, and £- , , ½-tri£li butylphenyl. Also included are isopropylphenyl , butylphenyl alpha-alkylbenzylphenyl and alpha, alpha-dialkylbenzylphenyl, e.g. alpha-methylbenzylphenyl, alpha, alpha dime hylbenzyl rr The orthosilicates useful as base stocks include t tetraalkyl orthosilicates suc as tetra(octyl)orthosilicates tetra(2-ethylhexyl)orthosilicates and the tetra( isooctyl) orthosilicates and those in which the isooctyl radicals are obtained from isooctyl alcohol which is derived frorr. the o:c process, and the ( rialkoxysilico) rialkyl orthosilicates, otherwise referred to as hexa(alkoxy) disiloxanes, such as hexa(2-ethylbutoxy) disiloxane and hexa(2-e hylhe>:oxy) . disiloxane. ·.''? The preferred tetraalkyl orthosilicates and hexa-(alkcxy) disiloxanes are those in which the alkyl or alkoxy number of carbon atoms in the orthosilica c is from 16 to 60.

In addition to the hexa(alkoxy) disiloxanes referral to above, other hexa(alkoxy) disiloxanes can be used in which the aliphatic radical of the alkoxy groups are for example, 1-ethylpropyl, 1, J-dimethylbutyl, 2-methylpentyl, 1-methyl- hexyl, 1-ethylpentyl, 2-butylhexyl and 1-me hyl-^-ethyl.octyl .

The or hosilicates and alkoxy polysiloxanes can be represented by the general structure: wherein Rg, and R1o each can be alkyl, substituted alkyl, aryl. substituted aryl and can be identical or different with respect to any other radical, 0 is oxygen, Si is silicon, X is a member of the group consisting of carbon and silicon, m is a whole number having a value of 0 or 1, n is an integer having a val.o of from 1 to about 200 or more and when X is carbon, m is 0, n is 1 and Rn, R12 and R13 each can be hydrogen, alkyl, substituted alkyl, aryl and substituted aryl. radicals and when X is silicon m is-i, n is an integer having a value of from 1 to about 200 or more and Rn, R12 and R13 each can be alkyl, substituted alkyl, aryl and substituted aryl.

Typical examples of substituted aryl radicals are _o-, m- and £-chlorophenyl, o-, m- and jo-bromophenyl, _o-, m- Typical examples of alkyl and haloalkyl radicals are those hereto¬ fore described.

The siloxanes or silicones useful as base stocks are represented by the general structure: wherein R , Ri5, ie, Ri7j Ri8 an< Rio, 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 example of alkyl and haloalkyl radicals along with the number of carbon atoms are those heretofore described. Typical examples of the siloxanes are poly(methyl) siloxane, pol (methyl, phenyl) siloxan poly(methyl, chlorophenyl ) siloxane and poly(methyl, 7,5,3-tri- 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-, - and j -cresyl and xylyl.

Dicarboxylic acid esters which are suitable as base stocks are represented by the structure: 0 0 I) It R20 - O - C - R21 - C - O - R22 wherein R20 and R22 a^e each selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl and R≤ · C-4217 ( alkylene and substituted alkylene, and are prepared by esterifyii? dicarboxylic acids such as adipic acid, azelaic acid, suberic aci sebacic acid, hydroxysuccinic acid, fumaric acid, maleic acid, et with alcohols such as butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, dodecyl alcohol, 2,2-dimethyl heptanol, 1-methyl cyclo-hexyl 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 repre sented by the structure: wherein R23 is selected from the group consisting of hydrogen and alkyl, 2 and R25 are each selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl, a is a whole number having a value of 0 to 1, Z is a whole number having a val of 1 to 2 and when Z is 1, R2e is selected from the group consist!, of hydrogen, alkyl acyloxy and substituted acyloxy and when Z is 2, R26 is oxygen, and are prepared by esterifying such polyalcohol olethane and neopentyl glycol v/ith such acids as propionic, butyric, isobutyric, n-valeric, capric, caproic, n-heptylic, caprylic, 2-^ ethylhexanoic, 2, 2-dimethylheptanoic and pelargonic. Typical exair.p of alkyl, substituted alkyl, aryl and substituted aryl radicals are given above.

Other esters which are also suitable as base stocks are the mono esters.

Another class of compositions which are suitable as base stocks for this invention are the polyphenyl ethers, poly-phenyl thioethers, or mixtures thereof, as represented by the structure: wherein A, A] , A∑, and A3 are each a chalcogen having an atomic number of 8 to ΐβ, X, Xi, X2, X3 and X4 each are selected from the group consisting of hydrogen, alkyl, haloalkyl, halogen, 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 value of 0 to 1 provided that when a is 0, n can have a value of 1 to 2» Typical examples of alkyl and substituted alkyl radicals are given above. Typical examples of such base stocks are 2- to 7-ring ortho-, meta- and para- polyphenyl ethers and mixtures thereof, 2- to 7-ring ortho- , meta-, and para- polyphenyl thioether and mixtures thereof, mixed polyphenyl ether-thioether compounds in which at least one of the chalcogens represented by A, Ax , As and A3 is dissimilar with respect to any one of the other chalcogen dihalogenated diphenyl ethers, such as ^-bromo-31 -chlorodiphenyl ethers and bisphenoxy biphenyl compounds and mixtures thereof.

Hydrocarbon oils including mineral oils derived from petroleum sources and synthetic hydrocarbon oils are suitable base stocks. The physical characteristics of functional fluids derived from a mineral oil are selected on the basis of the requirements of the fluid systems and therefore this invention includes as base stocks mineral oils having a wide range of viscosities and volatilities such as naphthenic base, paraffinic base and mixed base mineral oils.

The synthetic hydrocarbon oils include but are not limited to those oils derived from oligomerization of olefins such as polybutenes and oils derived from high or alpha-olefin.s of from to 20 carbon atoms such as by acid catalyzed dimerization and the oligomerization using mixtures of aluminum alkyls and titanium halides as catalysts, or Friedel-Crafts catalysts, or peroxide catalysts.

Chlorinated biphenyls and terphenyls are also useful as point depressants, thickeners, antioxidants, antifoam agents, viscosity index improvers such as polyalkyl acrylates, polyalkyl 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 containing two or more base stocks in varying proportions. The base stocks can also contain other fluids which include, in addition to the functional fluids, desired fluids derived from coal tar products, synthetics, an 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, inclvtding alkylene oxide polymers prepared by polymerizing the alky lene oxide in the presence of water or alcohol, e0g«, ethyl alcohol, alkyl benzenes, (e.g.. rnonoalkyl benzene such as dodecyl benzene, tetradecyl benzene, etc.) and dialkyl benzene (e.g., n-nonyl 2-ethyl hexyl benzene)? polyphenyls, (e.g., biphenyls and terphenyls) halogenated benzene, halogenated lower alkyl benzene and ono-halogenated diphenyl ethers.

However, 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 sto The base stock will consist primarily of trialkylphosphates being present in amounts from 30 to o by weight and preferably from 6o to °^ ky weight. The trialkylphosphates which give optimum result are those wherein each of the alkyl groups contain from 1 to 20 carbon atoms, preferably from 3 to 12 carbon atoms and more prefer ably, from 4 to carbon atoms. The alkyl groups are preferabp^ of stjraight 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 tri-propyl phosphates, tributyl phosphates, trihexyl phosphates, tri-octyl phosphates, dipropyl octyl phosphates, dibutyl octyl phospha dipropyl hexyl phosphate, dihexyl octyl phosphate, dihexyl propyl phosphate, and propyl butyl octyl phosphate.

The trialkyl phosphates can be combined with triaryl phosphates or mixed alkyl aryl phosphates. Preferred triaryl phos phates are tricresyl phosphate, cresyl diphenyl phosphate, trixyle phosphate, tertiary-butylphenyl phenyl phosphates, ethylphenyl di-cresyl phosphate or isopropylphenyl diphenyl phosphate, phenyl-bis ( 4-alpha-methylbenzylphenyl ) phosphate, diphenyl decyl phosphate, diphenyl octyl phosphate, methyl diphenyl phosphate, butyl dicresy phosphate and the like. In one preferred embodiment, a base stock containing primarily trixylenyl phosphate is employed. The triary phosphates function as a thickener for the trialkyl phosphates. T the amount of triaryl phosphate may range between 0 to 35/& ¾ weig The preferred range of the triaryl phosphates will be from about 5 to about 5~ Conventional polymeric thickeners or viscosity index (V improvers may be blended with the mixture of ti_jralkyl and triaryl phosphate material to achieve the desired viscosity* Typical thic oxides, polypropylene oxides, polyesters and the like.

Preferably, a polyester based upon an azelaic acid ancl a diol such as propylene glycol, and the like, in the range of .5 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 fluid composition, such as, epoxi and/or. amines. The combination of , ^-epoxycyclohexylmethyl 3 , ^- ■ epoxycyclohexane carboxylate and phenyl-alpha-naphthylamine has be found to be very effective.

Corrosion inhibitors such as benzotriazole, quinizarin 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 d 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 anti foaming agent can als be incorporated into the composition and are usually most effectiv in an amount ranging between a d 50 parts per million.

The functional fluids of this invention can contain up to about V}o by weight of water. It is preferred, however, to main tain water levels below 0.6 weight percent, and most preferably be about 0.3 weight 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 weigh 3 unless otherwise noted.

EXAMPLE I xylenyl phosphates with a viscosity of approximately 220 Saybolt Universal Seconds at 100° F. is combined with 9· 00 weight perc n ^ of a polyester thickener, Plastolein*^ 978Q scid by Emery Industries. Thereafter, 1. 0 weight percent of 3 ,½~epoxycyclohexylmethyl 3 , 4- -^2 epoxycyclohexane carboxylate and 1. 0 weight percent of phenyl aipha-naphthylamine are blended into this mixture. Then 0. 02 weight percent of benzotriazole is thoroughly blended therewith along with conventional dye and antifoam agent in the amount of 20 parts per million, and 15 parts per million, respectively.

Thereafter, dodecyl trimethy 1 ammonium diphenyl phosphate is blended into the mixture at various addition levels including Q. l c and Q. ' ; 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 related equipment required to assure that the apparatus will operate according to the requirements of Section 10. 2 of SAE specification AS 12½ 1 pertaining to the erosion resistance of fire 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 TRIMETHYL LEAKAGE RATE Conductivi ' AMMONIUM DIPEEITYL PHOSPHATE INCREASE ( cc/min/hr. ) (micromhos None 7. 0 0. 021 0. 1 2. 0 0. 10 The test results show that the addition of an effective amount of dodecyl trimethyl phate ester hydraulic fluid inhibits damage to hydraulic systems.

EXAMPLE 2 A similar erosion test was performed on the phosphate ester fluid described in Example 1 with 0. > Leakage Rate Total Chlorine (PPM) Total Test Time (Hrs. ) Increase (cc/min/hr) 44θ 625 730 830 910 This data has been plotted in the figure and illustrates the utility of dodecyl trimethyl ammonium diphenyl phosphate for preventing damage caused to hydraulic system by chlorine contaminate phosphate ester hydraulic fluids.

EXAMPLE 3 An erosion test was performed on a Boeing Material Spec. 3 lie (BMS 311-C) qualified phosphate ester aircraft hydraulic fluicl contaminated with 1000 PPM of chlorine as 1 , 1 , l-trichloro-ethane. After the erosion rate was established, the phosphate este fluid described in Example 1 with 0.3> by weight of dodecyl tri-methyl ammonium diphenylphosphate was added in increments to '-^e, contaminated fluid. The following data was obtained in this test: QUALIFIED BMS 11-C PHOSPHATE ESTER HYDRAULIC FLUID -H0Q0 PPM CHLORINE AS CH3CCI3 Total t. < of Phosphate Ester Fluid Containing by wt. of Dodecyl Trimethyl Ammonium Di- Leakage Rate phenyl Phosphate ^_ Increase (cc/min/hr) None 6.0 20 6.0 35 0.8 50 0 The above results illustrate the utility of a formulati containing dodecyl trimethyl ammonium diphenyl phosphate for arresting the damage caused to hydraulic systems by chlorine con¬ taminated phosphate ester hydraulic fluids.

EXAMPLE In an erosion test similar to that described in Exar: ie 1 the damage causing characteristics of the fluid described in Kxample 1 were completely arrested by the addition of 0,5:¾ by weight of a mixed mono- and bis- (dodecyl ammonium) methyl phospha This test illustrates the utility of mixed mono- and bis- dodecyL ammonium) methyl phosphates for arresting damage caused by phospha ester fluids in hydraulic systems. The conductivity before additi was 0.021 mmhos/cm, after 0.24 mmhos/cm.

EXAMPLE 5 A blend similar to that described in Example 1 was pre contained 0.2 phosphate and methyl phosphonium dimethyl phosphate. These formulations were subjected to stability tests described in Boeing Material Speci¬ fication 311-C. The following results were obtained in these tests: Boeing Thermal Stability Test Test Conditions: 250° F. , l68 hours duration, steel, magnesium, cadmium plated steel, copper, and aluminum present as catalysts.

Viscosity Changefcs) Acid No. Increase Fluid 100° F. 210° F. (mgKOH gT" Base Blend + 0.2 Weight Percent Dodecyl Tri ethyl-a monium diphenyl Phosphate + 0.10 + 0.03 0 Base Blend + 0.2 Weight Percent Trioctyl Methyl Phosphonium Dimethyl Phosphate - 1.11 - 0.^2 1.2 BMS il-C Specification _ + Limits + 1.0 - O.J + 0.5 These tests demonstrate that formulations prepared with dodecyl trirnethyl ammonium diphenyl phosphate as an additive exhibit greater thermal and oxidative stability than formulations prepared with trioctyl methyl phosphonium dimethylphosphate.

EXAMPL 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 0.2-5 of bis( dodecylbenzyl trimethyl ammonium ) phenyl phosphate will exhibit less metal damage than the same fluid without the bis-arr.monium phosphate, EXAMPLE 7 Illustrative Embodiment No. 2 In an erosion test conducted in a manner similar to that described in Example 1 a fluid comprised of approximately 3¾ s'ynthetic hydrocarbon oil such as that manufactured by Royal Lubricants for use in MIL-H-83282 hydraulic fluids, 15£ trimethyl-olpropane triheptanoate, and 0.2- didodecyl dimethyl ammonium dido-decyl phosphate will exhibit less metal damage than the same fluid without the ammonium phosphate.

EXAMPLE 8 Illustrative Embodiment No.

In an erosion test conducted in a manner similar to that described in Example 1, a fluid comprised of approximately mixed alkyl substituted phosphate ester, o aromatic mineral oil, such as sold by Sun Oil Co., 10J¾ pentaerythritol tetra-heptanoate, and 0.2 nonylphenyl trimethylammonium dioctyl phosphat will exhibit less metal damage than the same fluid without the ammonium phosphate.

Claims

C- 217 What is Claimed i.s: t ,

1. A functional fluid which comprises: (1) a major amount of a base stock material selected from the group consisting of the esters and amides of an acid of phosphorus, mineral oils, synthetic hydrocarbon oils, orthosilicates, alkoxy polysiloxanes, silicones, polyphenyl ethers, polyphenyl thioethers, chlorinated biphenyl, esters of dicarboxylic acids and monohydric alcohols, esters of monocarboxylic acids and mono-hydric alcohols, esters of monocarboxylic acids and monohydric alcohols, esters of monocarboxylic acids and polyhydric alcohols, and mixtures thereof, polyalkylene ether alcohols and esters thereof, and blends thereof; and (2) a damage inhibiting amount of an ammonium salt of a phosphorus acid in accordance with the formula: wherein R, R' , R", R' ' ' can be the same, different or conjoint, and represent hydrogen, alkyl, aryl, alkaryl and aralkyl groups containi from 1 to 30 carbon atoms, X represents an oxygen or sulfur atom, Y1 ^ Y" represent lower alkoxy, lower alkyl, phenyl lower alkylphenyl, phenyl lower alkyl, phenoxy and lower alkylphenoxy, Z represents oxygen, and m=l or 2.

2. A composition in accordance with Claim 1 wherein itfen 1.

3. A composition in accordance with Claim 1 wherein said base stock material is selected from the group consisting of c-4217 acid of phosphorus and blends thereof; said esters and amides havmg the formula: o II R-(y) P-(Yl) Rl (T2V wherein Y is selected from the group consisting of oxygen, sulfur R3 -N- Yi is selected from the group consisting of oxygen, sulfur and R4 t -N- Y2 is selected from the group consisting of oxygen, sulfur and Rs t -N- R, Ra , R2, R3, R4 and R5 are each selected from the group con¬ sisting of alkyl, alkoxy, aryl, substituted aryl and substituted a and a, b and c are whole numbers having a value of 0 to 1 such that the sum a+b+c has a value from 1 to 3· . A composition in accordance with Claim J wherein said base stock material comprises a blend of an ester of an acid of phosphorus in combination with a mineral oil. 5· A composition in accordance with Claim 3 wherein said base stock material comprises a blend of an ester of an acid of phosphorus in combination with a synthetic hydrocarbon oil.

6. A composition in accordance with Claim J wherein said ester of an acid of phosphorus is selected from the group con c-4217 37 ' Β

8. A composition in accordance with Claim 7 wherein ^ said trialkyl phosphates are present in an amount between about 30 and about 90 by weight and said triarylphosphates are present in an amount up to about 50$ by weight.

9. A composition in accordance with Claim 7 containing a thickener admixed therewith.

10. A composition in accordance with Claim wherein said ammonium salt is present in an amount between about 0. 01$ and about 10$ by weight.

11. A composition in accordance with Claim 3 wherein said ammonium salt is present in an amount between about 0. 1$ and 2. 0$ by weight.

12. A composition in accordance with Claim containing an acid acceptor.

13. A composition in accordance with Claim 3 containing a dye and a silicone antifoaming agent admixed therewith. 1 . A composition in accordance with Claim containing an antioxidant admixed therewith.

15. The composition of Claim 3 wherein Y' and Y" are independently selected from the group consisting of lower alkyl and phenyl. ΐβ. The composition of Claim 3 wherein said ammonium salt of phosphorus acid is hexadecyl trimethyl ammonium diphenyl phosphate.

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

18. The composition of Claim 5 wherein said ammonium salt of a phosphorus acid is didodecyl dimethyl ammonium diphenyl phosphate.

19. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dimethyl propyl dodecyl ammonium diphenyl phosphate.

20. The composition of Claim wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diphenyl phosph 21o The composition of Claim 1 wherein said ammonium salt of a phosphorus acid is dodecylbenzyl trimethyl ammonium diphen phosphate.

22. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is nonylphenyl trimethyl ammonium diphenyl phosphate.

23. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is phenyl dodecyl dimethyl ammonium diphenyl phosphate.

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

25. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl hexadecenyl ammonium diphenyl phosphate.

26. The composition of Claim 3 wherein said ammoni salt of a phosphorus acid is bis (dodecyl trimethyl ammonium) phenyl phosphate. C- 217

27. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is tris(n-tridecyl ) methyl ammonium di-phenyl phosphate.

28. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is bis(phenyl dodecyl dimethyl ammonium) phenyl phosphate. 2 . The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is decyl trimethyl ammonium dimethyl phosphate.

30. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is didodecyl dimethyl ammonium methyl methylphosphonate.

1. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is bis( didodecyl dimethyl ammonium) methylphosphonate.

32. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium dimethyl phosphate.

3. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium dibenzyl phosphate.

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

35. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium bis(nonyl-phenyl )phosphate. salt of a phosphorus acid is dodecyl trimethyl ammonium diphenyl^ dithiophosphate. 37· The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dimethylbutyl hexadecyl ammonium dibutyl phosphate.

38. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is triethylmethylammonium methyl methylphosphona e. 39° The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is phenyl dodecyl dimethyl ammonium diphenyl dithiophosphate.

40. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diethyl dithiophosphate.

41. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is phenyl trimethyl ammonium diethyl dithiophosphate.

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

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

44. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium di-n-dodecyl phosphate.

5. The composition of Claim 3 wherein said ammonium

46. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is 2-ethylhexyl dimethyl dodecyl ammonium diphenyl phosphate.

7. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is phenyl trimethyl ammonium methyl phenyl phosphate.

48. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is benzyl trimethyl ammonium methyl phenyl phosphate. 49 « The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl hexadecenyl ammonium methyl phenyl phosphate. 50 o The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is bis(trioctyl ammonium) ethyl phosphate. 5 1 o The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is octadecyl trimethyl ammonium diphenyl phosphate. 5 o The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is N-methyl, N-butyl piperidinium dibutyl phosphate. 53 » The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dimethyl butyl dodecyl ammonium dibutyl phosphate.

54. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is nonylphenyl trimethyl ammonium di-n-butyl-dithiophosphate. 55 · The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is benzyl trimethyl ammonium dibenzyl

56. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is hexadecyl trxmethyl ammonium dimethyl phosphate. 57» The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is trioctyl methyl ammonium diphenyl phosphate.

58. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is heptadecyl trxmethyl ammonium dimethyl phosphate. 59» The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is tris(n-dodecyl )methyl ammonium diphenyl phosphate.

60. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is tris( isooctyl )methyl ammonium diphenyl phosphate.

61. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is

62. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is dimethylethyl dodecyl ammonium diethyl phosphate. 63» The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is trxmethyl dodecyl ammonium dimethyl methylphosphonate. 6 , The composition of Claim 3 wherei said ammonium salt of a phosphorus acid is hexadecyldimethylethyl ammonium diethyl phosphate. C-4217

66. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl octylphos-phonate. 6 · The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl benzyl ammonium methyl octyl-phosphonate.

68. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl hexadecyl-phosphonate.

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

70. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl tertiary-butyl-phosphonate. 71· The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is benzyl trimethyl ammonium methyl tertiary-butyl-phosphonate.

72. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl carbo-methoxymethylphosphonate.

73. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is benzyltrimethyl ammonium methyl carbo-methoxymethylphosphonate. . The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl tertiary-octylphenyl ammoniu diphenyl phosphate. C-4217 75· The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl tertiary-octylphenyl ammonium methyl methylphosphonate.

76. The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is trimethyl tertiary-octylphenyl ammonium bis(nonylphenyl )phosphate. 77· The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium bis (nonylphenyl) phosphate. 8· The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is benzyltrimefchyl ammonium bis (nonylpheny phosphate. 79· Th composition of Claim 3 wherein said ammonium salt of a 2~ salt of a ) 2P salt of a P02 820 The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is CH30-C-^^ CH3 (C6H50)2P02~ . 8 · The composition of Claim 3 wherein said ammonium salt of a phosphorus acid is CH3O-C— ^_^NCH3 (CaHiaC6H40)2P02~« 8 o The composition o£ Claim 3 wherein said ammonium salt of a phosphorus acid is CH30-C— ^^NC¾ ( CH3o) (CH3 )P02~ . C-4217

85. 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 hydro carbon oils, ortho silicate, alkoxy polysiloxanes , silicones, poly phenyl ethers, polyphenyl thioethers, chlorinated biphenyls, ester of dicarboxylic acids and monohydric alcohols, esters of mono- carboxylate acids and monohydric alcohols and esters of monocar- boxylic acids and polyhydric alcohols and mixtures thereof, poly- alkylene ether alcohols and esters thereof, and blends thereof; an a wear inhibiting amount of an ammonium salt of phosphorus acids in accordance with the formula: where R, R' , R1' an.1 R' 1 ' can be the same, different or conjoint and represent hydrogen, alkyl aryl, alkaryl or aralkyl group containing from 1 to JO carbon atoms, X represents oxygen or sulfur, Y' and Y" represent lower alkoxy, lower alkyl, phenyl, lower alkyl phenyl, phenyl lower alkyl, phenoxy and lower alkylphenoxy, Z represents oxygen, and m=l or 2.

86. The method of Claim 85 where m=l. 8 » The method of Claim 86 wherein said base stock material is selected from the group consisting of esters and amid of an acid of phosphorus, mineral oils, synthetic hydrocarbon oil V

88. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is hexadecyl trimethyl ammonium diphenyl phosphate.

89. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is decyl trimethyl ammonium diphenyl phosphate.

90. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diphenyl phosphate

91. The method of Claim 87 wherein said ammonium salt op a phosphorus acid is dodecylbenzyl trimethyl ammonium diphenyl phosphate. . The method of Claim 87 wherein said ammonium salt of a phosphorus acid is nonylphenyl trimethyl ammonium diphenyl phosphate. 93· The method of Claim 87 wherein said ammonium salt of a phosphorus acid is allyl tributyl ammonium diphenyl phosphate.

94. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is bis (dodecyl trimethyl ammonium) phenyl phosphate.

95. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is decyl trimethyl ammonium dimethyl phosphate.

96. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium dibenzyl phosphate

97. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium methyl phenyl phosphate.

98. The method of Claim 87 wherein said ammonium salt 99· The method of Claim 87 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diphenyl di^ thiophosphate.

100. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is phenyl dodecyl dimethyl ammonium diphenyl dithiophosphate.

101. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is dodecyl trimethyl ammonium diallyl phosphat

102. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is nonylphenyl trimethyl ammonium di-n-butyl-dithiophosphate. 10^· The method of Claim 87 wherein said ammonium salt of a phosphorus acid is benzyl trimethyl ammonium dibenzyl dithiophosphate. loh The method of Claim 87 wherein said ammonium salt of a phosphorus acid is hexadecyl trimethyl ammonium dimethyl phosphate,,

105. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is trioctyl methyl ammonium diphenyl phosphat

106. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is heptadecyl trimethyl ammonium dimethyl phosphate. 107· The method of Claim 87 wherein said ammonium salt of a phosphorus acid is tris (n-tridecyl ) methyl ammonium diphenyl phosphate. I08. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is dimethylbutylhexadecyl ammonium dibutyl phosphate. C- 217 109· Tne method of Claim 87 wherein said ammonium salt of a phosphorus acid is triethylmethylammonium methyl methyl- V phosphonate. HO. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is 1,3 , 5-trimethyl pyridinium diphenyl phosphat llle The method of Claim 87 wherein said ammonium salt of a phosphorus acid is N-methyl, N-butyl piperidinium dibutyl phosphate.

112. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is [_( C6H5c)2P02~_ 2 .

113. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is trimethyl dodecyl ammonium dimethyl methyl-phosphonate.

114. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl octylphosphonate 115· The method of Claim 87 wherein said ammonium salt of a phosphorus acid is trimethyl benzyl ammonium methyl octylphosphonate. Il6„ The method of Claim 87 wherein said ammonium salt of a phosphorus acid is benzyl trimethyl ammonium methyl hexadecyl-phosphonate.

117. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl tertiary-butyl-phosphonate.

118. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium methyl carbomethoxymeth phosphonate. 46483/2 119· The method of Claim 87 wherein said ammonitun salt of a phosphorus acid is trimethyl tertiary-octylphenyl ammonium methyl methylphosphonate.

120. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is tetramethyl ammonium bis(nonylphenyl )

121. The method of Claim 87 wherein said ammonium salt of a phosphorus acid is benzyltrimethyl ammonium bis(nonylphenyl ) phosphate.

124. A functional fluid composition according to Claim 1, substantially as described herein with reference to the Examples.

125. A method according to Claim 85 substantially as ascribed herein with reference to the Examples.