DE1644916A1 - Functional liquid preparations - Google Patents

Description

DR. EULE DR. BERG DIPL.-ING. STAPF

PATENTANWÄLTE 8 MÜNCHEN 2. HILBL.ESTRASSE 2O J 6 4 4 9 * | Q

Dr. Owl dr Berg Dipl.-Ing. Stapf 8 Munich 2, Hilblestraße 20 Your character quieter characters Date Λ <»I ··» »· 1QC7

Attorney's file: 14 728

MONSAHSQ COMPANY
St. LOUiS ₉ Missouri / U «SA

Puncture fluid preparations.

The present invention relates to new phenoxy and l'hio- * Functional ones containing phenoxyazobenzene compounds Liquids with improved oxidative stability and especially preparations »that have a functional® liquid-

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speed and a stabilizing amount of an azo-y compound include.

many different materials were considered functional Liquids used and functional fluids were used for a wide variety of purposes. Such liquids are called electronic cooling oils, refrigerants for nuclear reactors, effusion pump liquids synthetic detergents, steaming liquids, raw materials for grease, iLraft transmission fluids iHydraulic Liquids ;, heat transfer fluideiij Mold release agent in metal injection molding processes and as an IFiI-termedium has been used for air conditioners. Because of the variety of uses and different tmgsn of the functional fluids will be Properties depend on that of a good functional fluid evaluated, whereby the respective application purpose a functional fluid with a special class of Requires properties «

The use of functional fluids as lubricants tel »in particular all lubricants for jet engines has now proven to be the most difficult area of application shown. To the extent that the working temperatures for lubricants have increased »is © g iajmsr more difficult

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Will usually find lubricants at these high levels ! Temperatures function properly for a satisfactorily long period of time. So are the requirements for A jet engine lubricant following Me fluid should be stable at both high and low temperatures have, show no foam formation, have good storage stability and on metal parts that are with the Are in contact with liquids, do not have a corrosive effect. Such liquids should also have adequate temperature-viscosity properties and have satisfactory lubricity, that is, the lubricants should not at the very high temperatures to which they are subjected become, become too thin, and again do not and should not become too fat even at low 'temperatures at the same time be able to exhibit good lubricity over such a range of temperatures. aside from that Such lubricants should not contain deposits that would impair the proper operation of a jet engine could, form.

As the working speed and working height of jet engine carriers increases, so do they Lubrication problems due to the increased working temperatures and higher hunting pressures, which is a 3? Length of the increased Are thrusts required to achieve high speeds and greater heights. JYes the herewith

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bound working conditions become increasingly difficult, the useful life of the functional fluid is shortened, which is primarily due to its lack of oxidation stability above 500 ° £ '/ approx. 260 ⁰ O. In general, since the operating conditions of a jet engine have become more severe, the temperatures of the engine increase and oil temperatures in the range of 600 ⁰ Ji ¹ / approx. 320 ⁰ C and higher occur.

The useful life of any lubricant can be determined based on many criteria such as the extent of viscosity increase, the extent of corrosion of the lietal surfaces in contact with the lubricant, and the extent of deposits. Many ways of improving the lubricant and thus of delaying or preventing the effects that shorten the useful life of a lubricant are known to those skilled in the art. In practice, it is common practice to »add small amounts of other materials or additives to the lubricants in order to influence one or more of the properties of the basic lubricant, but it is difficult to find additives, especially after the working temperatures have increased. which even then still take over the function for which they are intended and added and at the same time no other problems, such as increased corrosion and deposits in

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the machine or the engine.

As can be seen from the temperature characteristics of a jet engine mentioned above, a functional liquid can reach temperatures of up to 6UO ⁰ I ¹ ZCa. 320 ⁰ G and higher, which can lead to oxidative and thermal degradation of a lubricant! The stabilization of lubricants at these high working temperatures through the use of additives is an extremely complex and difficult problem since antioxidants that have been used in lubricating oil formulations, such as phenol and amine derivatives, are formed at such high temperatures decompose of deposits and debris. In addition, such decomposition products can promote oxidation at high temperatures and, in the case of a lubricant, cause an increased degree of oxidative degradation. It is therefore a fundamental requirement for an antioxidant intended for use in a lubricant at high temperature that it perform the desired puncture without the formation of sludge and debris, thus it is of particular importance that a functional fluid provide improved oxidative properties. Resistance without the formation of sludge and deposits in the various functional systems and in the. previously described areas of application «

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It has now been found that the oxidative stability and the useful life of fluids functional, even under the most about 32O ⁰ C and higher given in jet engines and other machines or i'rägern with working temperature s in the range 600 ⁰ I ¹ / strict conditions, can be largely increased by adding to the functional fluids one or more azo compounds of the formula

wherein a and b are integers from 0 to 5, R and R _{1 are} each an alkyl, substituted alkyl, aryl, substituted aryl, amino, substituted amino, cyano, nitro, halogen, sulfon , Carboxyl, carboalkoxy, phenoxy, substituted phenoxy, phenylmercapto, substituted phenylmercapto, alkoxy and / or hydroxy1 group, and if a or b has a value of 2 to 5, any two radicals R or iL bonded to adjacent carbon atoms within the phenylene ring together form a carbocyclic or substituted carbocyclic ring. can form.

Mixtures of such compounds can also be added will.

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The functional liquids to which an azo compound to create the preparations according to the invention can be added, hereinafter referred to as starting material or base material, include, but are not limited to polyphenyl ether, polyphenyl thioether, mixed polyphenyl-ether-thioethers, phenozybiphenyls, Phenylmereapto-biphenyls, mixed phenoxyphenylmercapto- "biphenyls and mixtures thereof. In addition, in the context of the present invention, the phenyl and phenylene groups in the above-described base material partially or completely by a heterocyclic group, such as thiophene and / or be replaced by pyridine.

Even if it is the incorporation of some foreign element can change the properties of a functional liquid in a basic material, but the concentration becomes an azo compound in the base material adjusted to the special © system and the base material, which in this system to create inventive Functional liquid preparations are used, where the base material contains the azo compound in sufficient quantity to improve its oxidation stability, without critical properties of the base material disadvantageous To affect · In general, it has been found that the preferred additive concentrations are an azo compound for the basic material described above in general

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from about 0.001 percent by weight to about 10 percent by weight, preferably from about 0.05 weight percent to about 5 weight percent.

Therefore, the present invention also includes preparations comprising a base material and a stabilizing amount of an azo compound, i.e. an azo compound is added in a concentration that improves the oxidative stability of the base material sufficient. The functional liquid preparations This invention can be used in any manner known to those skilled in the art for incorporating an additive into a Base material, for example by adding an azo compound to the u-round material while stirring until it is homogeneous Liquid preparation is obtained.

Typical examples of azo compounds are azobenzene, azoditoluene, 4-dimethylamino-azobenzene, 2,2'-diphenoxyazobenzene, 4-phenyl-azobenzene, 3 »3 ^f -diphenoxy-azobenzene, 4-amino-azobenzene, 4-ii-phenylamino -azobenzene, 4,4'-diphe- • noxy-azobenzene, 2,2'-diphenylmercapto-azobenzene, 3,3 '-' diphenylmercapto-azobenzene, 4 »4'-diphenylmercapto-azobenzene, 4,4'-dimethoxy- azobenzene, 3,3'-diphenyl-azobenzene, 3-phenyl-azobenzene, 3,3'-alpha-cumyl-azobenzene, 2,2'-azonaphthalene, 3,3 ^f -trifluoromethyl-azobenzene, 2,2'-trifluoro -

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methyl-azobenzene, 4-gyano-azobenzene, 4-J-nitro-azobenzene, 4.4 ^l -dibromo-azobenzene, 4- ± 5rom-azobenzene, m, m'-azobenzenedicarboxylic acid, m-azobenzene-carboxylic acid, mjm'-azobenzenesulfonic acid, m-azobenzenesulfonic acid and u-emics thereof.

Typical examples of round materials, which round materials suitable for this invention are represented through connections of the jacket

wherein A, A ₁ , A ₂ and a, each chalcogen with an atomic number of 8 to 16, X, A ^ ₁ X ₂ , X, and X. each is hydrogen, an alkyl, haloalkyl, halogen, phenyl, Represent alkaryl, hydroxyl, alkoxy, aralkyl and / or substituted aralkyl ur group, w, y and ζ denote integers each with a value from υ to 8, ο an integer with a value from 1 to 4, d a whole bald with one

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Value from 1 to 5 and e is an integer with a value of 0 or 1, provided that when e is 0, y can have a value of 1 to 2. Typical examples of such base materials are 2 to 7 singles containing o-, m- and p-iOlyphenyl ethers and mixtures thereof, polyphenylthioether and mixtures thereof, mixed polyphenylether-thioether compounds in which at least one of the by A, A ₁ , Ap and A, represented ecogenes is different from any of the other alkogens, phenoxybiphenyls, phenylmercaptobiphenyls, mixed phenoxyphenylmereaptobiphenyls, and mixtures thereof. In the framework of the present invention, phenyl and phenylene groups of the base material described above can also be partially or completely replaced by a heterocyclic group such as thiophene and / or pyridine.

Typical examples of rolyphenyl ethers, ie if A, A ₁ , Ap and A- are building material and e has a value of 1, those are those which have all their ether bonds in the meta division, since the whole meta -bound ethers for many purposes because of their wide liquid range and high thermal stability, which are most suitable, ^ s, however, mixtures of .folyphenyl ethers, ie either isomeric mixtures or mixtures of homologous ethers to achieve certain properties , for example low consolidation points,

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be used. Examples of possible polyphenyl ethers are the bis (phenoxyphenyl) ethers, for example bis (m-phenoxyphenyl) ethers, the bis (phenoxyphenoxy) benzenes, for example m-bis (m-plienoxyphenoxy) benzene, m-bis (p-phenoxyphenoxy ) benzene, o-bis (o-phenoxyphenoxy) benzene, the bis- ^ phenoxyphenoxyphenyl) ethers, for example bis ^ ~ m- (m-phenoxyphenoxy) phenyl ^ -ä ^ her »bis / ~ p- (p-phenoxyphenoxyphenyl 7 -ä- ~ bh.eT, m- ^ f (m-phenoxyphenoxy) (o-phenoxyphenoxy) / -ether and the bis (phenoxyphenoxyphenoxy) benzenes, for example m-bis ^ m-Cm-phenoxyphenoxy) phenoxy J / benzene, p -bis ^ ~ p- (m-phenoxyphenoxy) phenoxy__7 ^ e ^nz ol »m-bis / 'm- (p-phenoxyphenoxy) phenoxy benzene and 1 ^» ^'i'riphenoxybenzene. In addition, mixtures of polyphenyl ethers can be used in the context of the present invention. For example, have a look mixtures of polyphenyl ethers _s in which the non-terminal phenylene rings (ie, those rings that are in the above structural formula of usable PoIyphenyläther in brackets by oxygen atoms in the meta and para positions are attached, as a lubricant to be particularly Proven suitable because such mixtures have lower solidification points, thus creating formulations with extended fluid ranges. Of the mixtures with only meta and para bonds, a preferred polyphenyl ether mixture of this invention is the mixture of 5-hing polyphenyl ethers, the non-terminal phenylene rings being replaced by oxygen atoms in

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the meta and para positions are bound and made up about 65 percent by weight m-bis (m-phenoxyphenoxy) benzene,

30 weight percent m- ^ ~ "(m-phenoxyphenoxy) (p-phenoxyphenoxy27 benzene and 5 weight percent m-bis zusammeneetzen (p-phenoxyphenoxy) benzene. Am Such a mixture Terfestigt to j at about -1O ⁰ P / ca, 24 ⁰ C, whereas the three components solidify individually at temperatures above room temperature,

i Examples of substituted polyphenyl ethers are 1-t.p-methylj phenoxy) -4-phenoxybenzene, 2,4-diphenoxy-i-methylbenzene,

bis ^ / 'p- (p-methylphenoxy) phenyl_ _i 7- ^ä "fc ^{: a} er, bis ^ ~ p- (p-tert-butylphenoxy / phenyl ^ T-ether and mixtures thereof.

Typical examples of rhenoxybiphenyl compounds, ie when e has a value of 0 and A, A ₁ , A _? and A, representing oxygen, are 3,3 ^f -diphenoxybiphenyl, 3,2 ^f -diphenoxybiphenyl, 3 % 4 · -diphenoxybiphenyl, 3,4-diphenoxybiphenyl, o-, m- and p-.ehenoxybiphenyl and tri- and tetra- substituted Phenoacybiphenyle · It is also possible that mixtures of the above Phenoacybiphenyle can be used as base materials, such as mixtures with 1-25? i a · mono-Phenoxybiphenyls from 25i "to 15f> of di-itoeiiojQrbiplienyls ait mindeetene a phenoxy group. "in the» eta-position in relation to the phenyl nucleus and from 1 JaIm 4üji of a tri- and / or tetra-substituted phenyl nucleus

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noxybiphenyls.

Typical examples of polyphenylthioathera, ie when a, A ₁ , A ₂ and A ^ are sulfur and e has a value of 1, are o-bis (phenyl mercapto) benzene, m-bis (phenylmercapto) benzene, bis (m-phenylmercaptophenyl ) sulfide, m-phenylmer- ■ captophenyl-p-phenyl mercaptophenyl sulfide, the trisphenyl mercaptobenzenes, such as, for example, 1,2,4- ^f i'risphenylmereaptobenzene, m-bisCp-phenylmercaptophenylmercapto) benzene, m-bis (m-phenylmercaptophenylmercapto) benzene , to £ ~ m- (m-Phenylmercaptophenylmercapto) phenyl_7-sulfide, m ~ (m-Ghlorpheny! mercapto) m-phenylmercaptobenzene, m-Ohlordiphenylsulfid, bis ^ o-Phenylmercaptophenylj-sulfide, m-bisCm-Phenylmeroaptophenylmercapto, -2,3-tris (phenyl mercapto) benzene, o-bis (o-phenyl mercaptopheny! Mercapto) benzene, m-bis (p-phenyl mercaptophenyl mercaptoJbenzene and mixtures thereof.

Typical examples of phenylmeroaptobiphenyls, ie if e has a rfert of ü and A, A ₁ , Ap and A_ represent sulfur, are 3,3'-bis (Pheny! Mercapto) biphenyl, o-, m- and p-phenylmercaptobiphenyl, 3 > 4-Phenylmercaptobiphenyl, 3.2 ^f -Jiphenylmercaptobiphenyl, m-chloro-phenylmercapto-3'-phenylmercaptobiphenyl and mixtures thereof.

Typical examples of mixed polyphenyl-ether-thio- 1098U / 1752 " ^H "

ether, ie. if e has a value of 1 and at least one of the through. A, A- »Ap and A ~ shown here is different from any of the other chalcogens, are, 1-phenylmercapto-2,3-bis (phenoxy) benzene, 2-phenylmereapto-4'-phenoxydiphenyl-sulfide, 2-phenoxy -3'-phenylmereaptodiphenyl-sulfide, 2,2'-Ms ^ phenyl mercapto) diphenyl ether »3 _t 4 * -bistm-! I! Olylmercaptojdiphenyl ether _f 3» 3 '~ bis- (XyIy! Mercapto) diphenyl ether , 3 »4 * -l3is (m-isopropylph.enylmercapto) diphenyl ether, 3» 4 * -Ms (p-tert-butylph.enylmercapto) diphenyl ether, 3,3 * -l3is ( _l m-chlorophenylmercapto) - diphenyl ether, 3,3 * -bis (m-trifluoromethylphenylmercapto) -diphenyl ether, 3,4 * ~ bisCm-perfluorobutylphenylmercapto) -diphenyl ether, 2-m-l'olyloxy-2 '-phenylmercaptodiphenylsulfide, m-phenylmercaptod -ather, 3 »3 * -bis { phenylmercapto) diphenyl-ether, 3» 3'-bis phenoxy) diphenyl-sulfide, 3-phenoxy-3'-phenylmercaptodiphenyl-sulfide, 3-phenylmercapt0-3 ^f -phenoxydiphenyl-ether, 3,4 * -bis ν phenylmercapto) diphenyl ether, m-bis { m-phenylmercaptophenoxy) benzene, 3-phenylmercapto-3 * - (m-phenylmercaptopheny lmeroapto) diphenyl ether and mixtures thereof.

Typical examples of a mixed phenoxy-thiophenoxybiphenyl, i.e. if e has a value of υ and one of the halcogenes represented by A, A-, A, and A, is different iat of any of the other uhalogens are kienyl mercaptophenoxybiphenyl, o-phenyl mercaptophenyl-m-

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phenoxyphenoxybiphenyl and mixtures thereof.

In the context of the present invention it is also possible that the aforesaid base materials may be mixed to form any two or more of the above Mixture containing base materials. A typical mixture of a polyphenyl thioether and a mixed one rolyphenyl ether thioether contains about 45 percent by weight up to about 55 percent by weight m-phenoxyphenyl-m-phenylmeroaptophenyl sulfide, from about 25 percent by weight to about 35 percent by weight bia (m ~ phenyl ~ mercaptophenyl) sulfide and of about 18 percent by weight up to about 25 weight percent bis (ia-phenoxyphenyl) sulfide. Particularly useful mixtures contain approximately the above mixtures and m-bis (phenyl mercapto) benzene equal parts by weight of typical examples of polyphenyl thioethers, a mixed itolyphenyl ether-thioether and mixtures containing halogenated polyphenyl ether, Which as a lubricant he inks high temperature conditions are suitable and stating in percent by weight the following:

(1) 5Oj6 m-bia (Phenylmereapto) benzene, 25 # m-Phenoxyplieiqrl-Ä-phenyliaeroaptophenyl-sulfide, 115 & bis (a-Plienoaqrpheiiyl) -eiafid, bis (m-PheiorlBeroaptophenyl) eul fid j

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(2) 50 $ m-bis (Pheny! Mercapto) benzene,

25 $ m-phenoxy-m-phenylmercaptobenzene, 25 ^U A o-Mß (phenylmeroapto) benzene;

(3) 46% m- (m-GJalorphenylmercapto) -m-ph.enylmercapto-

benzene,

31 $ m-bis (Pheny! Mercapto) benzene, 15 ^ o m-phenoxy-m-phenylmercapt obenzol, m-uhlordiphenyl sulfide.

JSb is also possible that any of the respective starting materials described above or mixtures thereof mixed with additives of this invention for creation preparations according to the invention can be used.

The following non-limiting examples illustrate the preparation of an azo compound according to the invention.

example 1

In a 2 liter reaction flask equipped with a stirrer, additional funnel and a reflux condenser, 9 g zinc dust, 12 g of a solution of 5 / sodium hydroxide in water and 6 ml of ethanol were brewed. Then 48 g of m-phenoxynitrobenzene was added to the flask

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added over a period of about 30 minutes. The mixture was heated to the reflux temperature of ethanol and the reaction was continued for an additional 8 hours. The reaction mixture was filtered to remove the zinc dust and the 3j3 ^f -dipkenoxyazobenzene was crystallized out due to the cooling of the ethanol solution. The 3 »3'-diphenoxyazobenzene was crystallized from an acetone ethanol mixture. The 3t3'-Dlpheno3cyazobenzol had the following analysis: 78.1 $ carbon, hydrogen and _Λ 4.83 6 7.60 $ nitrogen?.

Following the procedure of Example 1, additional phenoxy and thiophenoxyazo compounds of the invention can be prepared. 3 »3'-dithiophenoxy-azobenzene is produced by .. the reduction of m-thiophenoxy-nitrobenzene · In addition, 3.3 ^l - (m-phenoxyphenoxy) -azobenzene can be produced by the reduction of 3- (m-phenoxyphenoxy) -nitrobenzene be manufactured.

The azo compound of the example and additional azo compounds were included in the basic materials for determination the oxidative stability of the resulting functional liquid β preparation mixed in.

The main test method used to determine the oxidative stability of a lubricant is that in Ftdtral

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Test Method, Standard Ho. 791, Method Ho. 5308 Method according to which the lubricant to be tested is converted into the equivalent of certain metals at a certain temperature and oxygen heated and the viscosity increase of the Sohmiermitteis is determined. It can also provide information about the corrosive effects of a lubricant against metals and the extent of sludge and deposit formation are taken »

A variety of functional fluid formulations containing an azo compound were tested according to the above procedure, with the exception that the temperature was set to 65O ⁰ IyOa. 34O kept in place of ⁰ O ^{0 0} 26O G was used, and the metal sample, as depicted in the said method, were steel, copper, silver, titanium, magnesium alloy and aluminum alloy. The viscosity of the liquid before and after the examination was at 100 ° P / approx. 38 ⁰ C determined.

In Table I, the percentage stabilization is determined by the following formula:

? £ stabilization »

_χ

where V _{1 is} the percentage increase in viscosity of the base material, approx. a duration of 24 hours at 650 ⁰ I ¹ /

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340 ⁰ G and V "represents the percentage viscosity increase of the base material plus azo compound after 24 hours at 650 ⁰ ? / 340 ⁰ O.

In Table I, the öruadsatsrial used was a Mixture of 5-hing polyphenyl ether.

Table stabilizer s I i » Yisko» f £ Stabili at Conc sit, An sation game tration rose Mr.: None 3-ew-fS £ K) 0 2 Azobenzene e _s oö 100 6? 3 Azobenzene 0.10 SS 68 4th 4.4 ^f -dibromoazobenzene 1.00 108 bO 5 2,2'-diphenoxyazobenzene 1, OC 121 55.5 6th 3,3 * -Diphenoxyazobenaol 1.00 195 35 7th 2,6-di-tert-butyl-p- 0.90 8th crescent oil 400 ^a -45 ^b m, m -phenoxyphenoxy- 0.64 9 phenol 300 ° -35 ^{b a} β increase in viscosity 0.90 after 18 hours D »/ \ ■. _. . . «. certainly

medium is "

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^c = increase in viscosity determined according to. 21 hours.

A bearing lubrication test modified from MIL-L-27502 was carried out. The test time was 100 hours using an EHDOO bearing. The test conditions for Example 8 were a storage temperature of 600 ^ο ϊ · / θα. 316 ⁰ G, a temperature of 600 ⁰ I ¹ Aa * 316 ⁰ O of the oil in the mass and a ^tt oil-in "temperature of 55O ⁰ P / 288 ⁰ C. The test conditions for example 9 were the same as for Example 8 with the exception that the storage temperature was increased to 65O ⁰ JyOa.343 ° 0. In Table II the base material used was a mixture of 5-ring polyphenyl ether.

Table II

Example Concentration Total End Viscosity No. Stration Rating in OS Weight # (37.8 ° 0)

8 0.00 79.3 20,000 ^d

9 0.93 59.4 1 575 ^e

= Test ended and viscosity determined after 62.5 hours ^β = viscosity determined after 100 hours.

As illustrated by Tables I and II, it can be clearly seen that the incorporation of an azo composition

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Binding of this invention into a base material creates a functional liquid preparation which has a high degree of resistance to oxidative decomposition and thus a largely extended service life. With regard to the extension of the service life, it has now been found that the test method described above agrees very well with the results obtained in tests on an actual scale and in plug-body jet engine bearings and under conditions of practical application. It has been found that the degree of change in viscosity at 100 P / ca. 38 ⁰ C, as measured at the (Pestverfahren, representativ for the amount of extended life which is achieved under actual conditions. Thus, for example, was the reduction to Viskositätszunähme a Preparation to which an azo compound of this invention had been added, approximately three times less than the increase in viscosity of the base material for the same period of time. Of equal importance are the results given with regard to the phenolic antioxidants, these antioxidants for the pachmann Inhibition of oxidative degradation of organic substances is known to be effective. The results in Table I show, with regard to these phenolic antioxidants, that the degree of oxidation of a preparation containing these antioxidants is higher

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is alone than with the pure basic material. The higher one Degree of oxidation with the phenolic antioxidants indicates that a compound acts as a prooxidant can work in systems that work at higher temperatures. Those in the table are of equal importance II listed results * because the bearing lubrication test compares well with the actual gas turbine conditions in measuring the total amount of deposition and viscosity change, which increases in practical use is expected corresponds to. The test of the pure base material had to be carried out at the end of the 62.5 hour period be terminated with a substantial increase in viscosity. The preparations of the invention retained what is desired Temperature / viscosity ratio at and were not too thick with prolonged use, while at the same time for provided excellent lubrication of the mechanical parts in contact with the fluid.

In addition, Tables I and II clearly illustrate that the azo compounds, at low concentrations, are effective in controlling oxidative degradation of the base material, as evidenced by the degree of stabilization of the formulations of the invention. Stabilization of a base material is of particular importance in the diverse areas of application of functional fluids, as the necessary

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Fluid characteristics over extended periods of time practical application, through the incorporation of an azo compound can be maintained. Incorporation an azo compound in a base material to control the oxidative degradation is of particular importance, there, if liquid decomposition occurs, one such decomposition manifests itself in many ways, to which change in viscosity, increase in acid number, Formation of insoluble materials, increased reactivity and discoloration count. In a fluid system the special properties of a liquid must be maintained in order to be able to operate in the special System in which the fluids are used to maintain. So can viscosity changes caused by liquid decomposition, with polymeric products with high molecular weights in the liquid system. Such high molecular weight products are often found in the base material insoluble, resulting in precipitation or sludge formation of the * insoluble material. Such precipitation and Sludge build-up clogs filters and causes debris to form on moving parts carried by the Liquid are lubricated, build up or lock, causing the parts to be inadequately lubricated and impair the proper functioning. When the liquid decomposes there is an increased chemical

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16U916

Reactivity, as well as an increase in the acid number of the liquid was observed. line such increased chemical reactivity and high acid number sets the respective system _f which contains the liquid, a chemical attack from duroh the liquid, whereby seizure, wear and change of the close tolerances in mechanical parts that are in contact with the liquid occurs . Premature overhaul and repair of the mechanical parts may be a direct result of ^w fluid degradation. It is therefore of particular importance that the base material is stabilized and thus the life of a fluid in a functional fluid system is extended.

As a result of excellent stabilization of functional fluids into which an azo compound is incorporated is, lubrication of gas turbines or jet engines is achieved over extended periods of time. Accordingly, this concerns Invention a new method for the lubrication of gas turbines or jet engines, welehee the supply of bearings and other frictionally stressed parts with a lubricating effective amount of a formulation of this invention includes.

In addition, as a result of the excellent tax and oxidative decomposition using the invention

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according to functional fluid formulations improved hydraulic pressure devices according to this invention are produced, which contain a liquid chamber and an operating liquid in this chamber, these Liquid a mixture of one or more of the base materials described hereinbefore and a smaller one comprises a sufficient amount of an azo compound to stabilize said base material. In such a System, the parts thus lubricated include the friction surfaces of the energy source, namely the pump, valves, " Control pistons and cylinders, fluid motors, and in some cases, for machine tools, guides, tables and slideways. The hydraulic system can be either constant or variable volume.

The pumps can be of various types, including centrifugal pumps, injection pumps, turbine blades, liquid piston gas compressors, piston pumps, especially the variable stroke piston pump, the piston \ pump variable discharge or variable displacement, radial piston pump, axial piston pump, in which a rotatably mounted or reciprocating cylinder block is set at different angles with the piston assembly, for example the Vickers Axial Piston Pump, or in which the mechanism that drives the KoIt ben in one, adjustable with the cylinder block

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Angle stands, gear pump, which is a spur gear, Sohrägverzahnungsgetriebe or herringbone gear, variations internal gears or a screw pump or an impeller pump. The valves can be stop valves, Changeover valves, switching or control valves, Throttle valves, series valves, pressure relief valves, servo valves, check valves, ring valves or relief valves be.

Fluid motors are usually piston pumps with constant or variable discharge that are driven by the Pressure of the hydraulic fluid of the system with the energy supplied by the pump power source, to be caused to route. Such a hydraulic motor can be more variable in connection with a pump Discharge can be used to form a variable speed transmission. It is therefore important that the friction parts of the liquid system, which by the functional fluid is lubricated, protected from damage. Thus, damage causes over-welding of friction parts, excessive abrasion and premature Need to replace the parts with others.

The liquid preparations of this invention can also when used as a functional fluid, dyes, pour point depressants, metal deactivators

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_ ₂₇ _ 16U916

gates, acid scavengers, antioxidants, antifoam agents in a concentration sufficient to impart anti-skin properties, such as from about 10 to about 100 parts per million, viscosity index improvers, such as polyalkyl aylates, polyalkyl methacrylates, polycyclic * Polymers, polyurethanes, polyalkylene oxide, substituted and unsubstituted polyphenylene oxides and polyesters, lubricants and the like, contain »

It is also possible within the scope of the present invention that the base materials described above either individually or as a liquid preparation with two or more base materials can be used in varying proportions. The basic materials can also other! liquids which, in addition to the above functional fluids described include fluids derived from carbon products and synthetic fluids contain oils, for example alkylene polymers (such as polymers of propylene, butylene, etc. and the mixtures thereof), alkylene oxide polymers (e.g. propylene oxide polymers) and derivatives, including alkylene oxide polymers, those produced by polymerizing the alkylene oxide in the presence of water or alcohols have been, for example ethyl alcohol, alkyl benzenes (for example mono-alkyl-benzene such as dodecyl-benzene, tetradecyl-benzene etc.) »and dialkylbenzenes (for example n-nonyl-2-ethylhexylbenzene), polyphenyls (for example

109814/1752 _ ₂₈ _

Biphenyls and terphenyls), halogenated benzene, halogenated lower alkyl benzene, halogenated biphenyl and mono-halogenated diphenyl ethers.

the present invention has also been described in terms of various specific examples and embodiments has been, it is not limited to this and can be within the scope of the following claims be practiced in various ways.

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Claims (5)

Claims «1. Functional fluid, in particular heat and power fr means of transmission, including Sehmiermittel * marked by a content of (A) a larger amount of a base material β of (1) polyphenyl ethers, (2) polyphenyl thioethers » (3) mixed polyphenyl ether thioethers, (4) phenyl mercaptobiphenylene, (5) phenoxybiphenylene, (6) mixed phenoxyphenylmereaptobiphenylene and or (7) a base material according to (1), (2), (3), (4), (5) and / or (6), wherein any one of the cyclic rings »namely the phenyl and / or Phenylene rings are replaced by 1 to 5 heterocyclic rings, and (β) mixtures of any combination of (1), (2), (3), (4), (5), (6) and / or (7) and (B) an oxidation stabilizing amount of an or several azo compounds of the formula -30- 1 0 ίΡΊ Λ / 1 7 5 2 wherein a and b are integers from 0 to 5 »R and R ₁ each represent an alkyl, substituted alkyl, aryl, substituted aryl, amino, substituted amino, cyano, nitro, halogen, sulfon, Are carboxyl, carboalkoxy, phenoxy, substituted phenoxy, phenylmercapto, substituted phenylmercapto, alkoxy and / or hydroxyl group, and if a or b has a value from 2 to 5, any two radicals R or R ^ which are bonded to "adjacent carbon atoms within the phenylene ring, can together form a carbocyclic or substituted carbocyclic ring, and Mixtures of these. 2. Preparation according to claim 1, characterized in that the base material is a polyphenyl ether and / or is a mixed polyphenyl ether-thioether. 3. Preparation according to claim 2, characterized in that the azo compound is azobenzene and / or diphenoxyazobenzene is. 4. Oxidation-stabilized functional fluid, in particular 1 o a ■■■ u / 17 5 2 -31- special heat and power transmission media, including Lubricants, characterized in that they contain one or more compounds of the formula X ¹ where c and d are integers with a value from ο to 5, R ₂ and R “alkyl, substituted alkyl, aryl, substituted aryl, amino, substituted amino, sulfonic, carboxyl, carboalkoxy, cyano -, nitro, halogen, phenoxy, substituted phenoxy, phenyl mercapto, substituted phenyl mercapto, alkoxy and / or hydroxyl groups, and X and X ^{1 are} halogens, namely sulfur and / or oxygen, provided that, when X is oxygen, X is bonded in the meta position in the azobenzene ring. 5. Compound according to claim 4 »characterized in that c and d have a value of 0 and X and X represent ¹ oxygen. 1098U / 1752