DE1594482A1 - Polyphenyl ether mixtures - Google Patents

Description

800 North Lindbergh Boulevard, 66 St.Louuls, Missouri, USA.

"Polyphenyl-ether-Misohungen"

This invention relates to functional fluids, im In particular, it creates new functional fluids, which are mixtures of ester-based fluids and polyphenyl ether include.

The use of functional fluids as a lubricant for aircraft propulsion engines, such as nozzle assemblies that require tile ability at low temperatures · The lubricant must be at least enough liquid "one to read free movement of machine parts in AnIaasen in vice

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Outside temperatures drop until, say, at least O ⁰ F (-17.8 ⁰ O) allow. On the other hand Masohinen high speed, such as in jet propulsion units characterized in that they as about 500 ⁰ F (26O ⁰ G) work as high temperatures, and the lubricant must of course be stable at operating temperatures. A minimum shelf life of 50 to 100 hours should be available before the lubricant has deteriorated to such an extent that it must be drained and replaced with new material.

The polyphenyl ether fluids have been found to be good for use as functional fluids are suitable for uses that require stability at high temperatures. They have unusual thermal and oxidative stability. In addition, these fluids have excellent lubricity and resistance to foaming.

The polyphenylene ethers have a very wide Flüssigkeitsbereioh, up to those of 800 ⁰ F (427 ° G) or higher are sufficient for the liquid phase of temperatures below 100 ⁰ F (37 -8 ⁰ C). The meta-linked variety has a particularly wide range of liquids, and it has been found that a mixture of about 65 (by weight -) ^ m-bis (m-phenoxyphenoxy) benzene, 30 # m- ^ Jm-plienoxyphenoxy) (p -

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phenoxyphenoxy_} 7-benzene u ^ 5 $ m-bis (p-phenoxyphenoxy) benzene provides a preparation which is to under ordinary room temperature liquid, while retaining thermal stability up to about 800 ⁰ F (427 ° C). However, if the pour point of this mixture, is at 'which its viscosity above 500,000 centistokes, at about 40 ⁰ F (4.4 ⁰ C), so that the use of this material, where cold start of the engine is required, is practically not feasible.

It is an object of this invention to provide improved functional fluid formulations.

A particular object of this invention is that it provides functional liquid formulations, wherein these formulations comprise polyphenyl ether based liquids which have an improved liquid operating temperature range.

These and other objects will become apparent from the following description and claims.

It has now been found that mixtures of polyphenyl ethers and liquids of the ester lubricant base are functional Create liquid preparations which have an advantageous liquid range and which especially, when using antioxidant additives like the one below

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are carried out, also have unexpected oxydation stability at high temperature. These functional liquid preparations are particularly suitable for use as lubricants in machines such as jet drives, which increase the flowability in the liquid phase, together with oxidative stability, over a range such as from O ⁰ F (-17.8 ⁰ O) to 500 ⁰ I ¹ (26O ⁰ O) require.

The polyphenyl ethers cannot generally be mixed with liquids on any other basis : For example, they do not dissolve more than about 5% by weight of mineral oil. Attempts to mix silicones with the phenyl ether based liquids have shown that only a few of this class of liquids are miscible with the polyphenyl ethers and still to a limited extent. It has been found, however, that the polyphenyl ethers can be combined with other liquids on an oxygen-containing carbon-containing basis to form homogeneous liquids

create which have favorable properties.

It has been found that the mixing of sster-based liquids with polyphenyl ethers results in an unexpected redaction level of the viscosity of the ethers. The viscosities of the mixtures are not the arithmetic mean of the ingredients and in fact the dursfc.

the introduction of the system induced reduction in the 10 9824/1326

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The ether viscosity is even greater than that of a logarithmic one Effect can be attributed. Such mixtures can be made with a liquid range, the one required for use as a lubricant when the masohine must be capable of one Carry out a cold start and also work at elevated temperatures, with the ether: ester ratio can be used in the range of 25:75 to 75:25. These mixtures, which contain a substantial proportion of polyphe ~ contain nyl ethers, desirably have orhöhte Oxidation stability at high temperatures, compared to the ester components it contains. The percentage the increase in viscosity on exposure of the mixtures to the oxidative conditions at increased Temperatures are reduced to a sufficient extent to make these mixtures act as functional fluids Working temperatures usable where the ester itself cannot be used.

Particularly advantageous oxidative stability at high temperature is achieved by mixing 25 to 75% by weight of polyphenyl ethers with 75 to 25% by weight of neopentyl polyol ester base fluids. These mixtures "remain clear and free of unpleasant or inadmissible solids during the oxidative decomposition. In addition, it was found that these meowages unexpectedly en-fc-

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accommodating to certain antioxidant additives are.

The temperature has proven to be critical as far as the high temperature oxidation stability of neopentyl polyol base fluids is concerned. At 425 ⁰ F (218 ⁰ O) an inhibited trimethylolpropane ester is only slightly by exposure to a stream of air at a rate of 96 liters per hour (G-Underson, et al, eds, "Synthetic Lubricants", Reinhold, 1962, Page 395) decomposed. At 50O ⁰ I ¹ (260 ⁰ C), however, the same liquid usually doubles in viscosity within 24 hours at an air flow rate of 5 1 per hour.

It has been found that the present mixtures of neopentyl polyol esters Mt polyphenyl ethers have a unique and decisive increase in oxidative stability through combination with an (alkanedionato) cobalt coordination compound. The 500 ⁰ I * (260 ⁰ O) oxidative stability of the mixtures combined with such cobalt compounds is markedly superior to that of a mixture which contains the inhibitor which is used in the ester which the results stated above are used. Unexpectedly, other metal pejitiandionates do not have a single antioxidant effect, and they have a "pro" effect in mixtures

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It was also found that combinations of a cobalt alkanedionate with an aromatic amine compound effective antioxidant for the specified mixtures are. The useful amines include polyarylamines and polyaryliden ** polyamines, which are at least two Contain benzene nuclei.

Thus, preparations are made according to the present invention which not only have the fluidity at ⁰ ° F (-17.8 ⁰ G) and including, as they lack the Polyphenyläthern but also oxidative stability at 500 ⁰ F (260 ⁰ C) ₁ as esters Keopentyl polyol-the missing, possess and which are suitable in an unusual way, as lubricant for Strahlautriebssysteme that require the ability of cold start to flow temperatures of about 500 ⁰ F (26O ⁰ O) to work ·

The polyphenyl ethers used in the formulations of this invention have from 5 to 7 benzene rings and from 1 to 6 oxygen atoms with the determined oxygen atoms connecting the benzene rings in chains like etheric fertilizers. One or more of the benzine triages in these polyphenyl ethers can be hydrooarbyl-substituted. For thermal stability, the hydrocarbyl substituents must be free of QH ₂ and all- sufficient , including the preferred options. Substjttuenteii lower

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saturated hydrocarbon residues (1 to 6 carbon atoms) such as methyl and tertiary butyl, and preferred aromatic substituents are aryl radicals such as phenyl, Tolyl, t-butyl-phenyl and alpha-cumyl. In the latter The trap carries the one with the hydrocarbyl substituent

connected

Benzene ring to the total number of benzene rings

in the molecule. Polyphenyl ether, which is exclusively from chains of 3 to 7 benzene rings, with at least 1 oxygen atom, which the specified benzene rings in the Chains such as an iither bond connect, exist, they have a particularly desirable thermal stability.

Examples of poly phenyl ethers containing aliphatic carbon which are used as high temperature base x ^? Liquids are suitable are 3-ring polyphenyl ethers, such as 1- (p-methylphenoxy) -4-phenoxybenzene and 2,4-diphenoxy-1-methylbenzene, 4-ring polyphenyl ethers, such as bis / p- ( p-kethylphenoxy) -phenyl7-ether and bis / j? - (p-tert.i3utylphenoxy) -phenyl7-ether and so on.

Ψ Polyphenyl ethers, which consist exclusively of benzene rings and include ether oxygen atoms that connect the named rings, are characterized in an exemplary manner by the triphenoxybenzenes and aryl- buttuated polyphenyl-ethers, such as biphenylyl-phenoxyphtnyl-ether, biphenylyl- oxyphenyl-phenoxyphenyl-etaitr,

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Biphenylyl ether, dibiphenylyloxybenzene, bis (Biph.enylyloxyphenyl) ether, Bis phenoxy diphenyl and the like.

A preferred class of polyphenyl ethers are those which consist of benzene rings linked in a chain by oxygen atoms, such as ether bonds between each ring, of the formula GgHp-OC GgH, O-) _n -CgHc, in which η oine _o indicates Number from 1 to 5 is.

Examples of the polyphenyl ethers that come into consideration in this class are the bis (phenoxyphenyl) ethers (4 bensol rings ve.iei.nt in a chain through 3 oxygen atoms), v; obei explained for the ^ e dis (m Phenoxyphenyl) ether. jjie bis (i'henoxyphenoxy) benzenes are particularly valuable in the present context. Explanatory for such aind ni-bis (m-jrhenoxyphenoxy) -benzene, m-bis (p-phenoxyplienoxy) -benzene, o-bisCo-1-phenoxyphenoxy) -benzene and so on, Veiter also include the polyphenyl ethers that come under consideration here the bis (phenoxyphenoxyphenyl) ethers, such as bis ^ m- (i: i-phenoxyphenoxy) -phenyl7-; lther, bis / jp- (p-phenoxyphenoxy) phenyl7-ether and m- (m-phenoxyphenoxy) -phenyl-m - (o-phenoxyphenoxy) phenyl ether and bis (phenoxyphenoxyphenoxy) benzene, such as ni-bis ^ - (ia-phenoxyphenoxy) -phenoxv7'-benzene _t p-bis / p- (ia-phenoxyphenoxy) -phenoxv7-benzene and m-

a.

The preferred polyphenyl ethers are those which are theirs

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have total jither bonds in the meta-gradients, because the total-meta-connected ethers are particularly advantageous because of their wide range of fluids and their high thermal stability. However, mixtures of the polyphenyl ethers, either isomeric mixtures or mixtures of homologous ethers, can also be used advantageously in some applications, especially where special properties such as low solidification points are required. Mixtures of polyphenyl ethers in which the non-terminal phenylene rings are connected by oxygen atoms in the meta and para positions are particularly suitable for creating preparations with wide liquid ranges. Of the mixtures that have only meta and para bonds, a preferred polyphenyl ether mixture of this invention is the mixture of bis (phenoxyphenoxy) benzenes wherein the non-terminal phenylene rings are linked by oxygen atoms in the meta and para positions and in Prepared with (by weight) with about 65 $ m-bis (m-phenoxyphenoxy) benzene, 30 # m-ZJm-phenoxyphenoxy) (p-phenoxyphenoxyj7 ~ benzene and 5fo m-bia (p-phenoxyphenoxy) -benzene. Such a mixture

as
solidifies at lower / room temperature (i.e. below about 7O ⁰ F (21.1 ⁰ O)), while the Dra I components individually are almost at temperatures above normal room temperatures.

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The aforementioned 1-olyphenyl ethers can by known Process such as "for example the Ullmann ether synthesis, which in the broadest sense refer to ether-forming reactions, are obtained in which alkali metal phenoxides,. such as sodium and potassium phenoxide with aromatic halides, such as bromobenzene in the presence of a Copper catalyst, such as metallic copper, copper hydroxide or copper salts are implemented.

The high temperature, oxygen-containing, carbonaceous base fluids used in the formulations of this invention can also contain a synthetic ester base fluid. They are liquids of lubricant viscosity and ^{thermally stable to at least about 400 °} F (204 ^° O), being ethers of alcohols which contain at least 4 carbon atoms and which generally contain more than 1 ester group. They can be esters of polyhydric alcohols, polybasic acids or both.

Ester fluids having particularly favorable low-temperature viscosity Eigensohaften which flow easily at temperatures as low as -30 ⁰ F (-34.4 ⁰ G) are created duroh the diesters of dibasisohen acids. Ester lubricants of the dibasic acid ester type are replaced by diesters of long chain dicarboxylic acids such as azelaic. acid with long-chain branched primary alcohols des

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G, to C ₁₀ ... range explained. The synthetic outer hulls just as often include the esters of long-chain monobasic acids, such as pelargonic acid, with glycols such as polyethylene glycols. Complex esters are also formed by combining the dibasic acid half-esters with a glycol, such as a dipropylene glycol, a polyethylene glycol of 200 molecular weight, and so on, conversion and combination of these ¹ IUsigkei th have proven to be valuable and it is also common practice to achieve the desired properties of the final base liquid by wiping the various polyester products. Simple esters, which create suitable liquids, can be given by way of example, for example as bis (2-ethylbutyl) -sebacate, bis (1-ethyl-4-ethyluctyl) -sebscate, bis (2-ethylhexyl) - sebacate, propylene glycol dipelargonate, the esters of acids, v / ie o'ebacic, alainic and adipic acids with complex Gq _-1 , primary branched-chain alcohols, like those produced by the oxo process, lOlynthylene -i, l -,] :: ol 200 bis (2-l.thylliexylsebacat), jiisoamyl adipate, 1,6-iiexajnethylen-glycol-di- (2-ethylhexanoate), bisCDimethylaiuyl) -; .j: elat and se continue.

Ester FJiessmedien with special;.; , siter Cxyd :; tion -, "usually rot.MJidßiTJji ^ keit, - egeniibc-r licjujj j \ -. ί '- .. ■., ■. ■; "tiirei! are bycJ ·

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the neopentyl polyol ester created / The alcohols, from which these esters are derived, have the carbon structure of neopentane with a central carbon atom surrounded by four carbon substituents. Included in the neopentyl polyols are neopentyl glycol, trimethylol ethane, trimethylol propane and pentaerythritol. In general, the base fluids which contain neopentyl polyol esters are the esters with monocarboxylic acids. Such esters are generally more oxidatively and thermally stable than the dibasic acid esters. Useful esters of polyols Feopentyl sohliessen for example, esters of trimethylol propane, neopentyl glycol and pentaerythritol normal, branched-chain and mixed acids which have chain lengths that change from Og to ₁ O O a. For example, series of such esters are triniethylolpropane tri-n-pelargonate, trimethylolpropane tricaprate, trimethylolpropane trioaprylate, and the trimethylolpropane triesters of mixed octanoates and the like.

In the remainder of the description of other ester fluids that may be used as the lubricant base batch material suitable and for the production of Misohungen. This invention is useful, for example, on the Contribution by Gunderson and others, "Synthetic Lubricants" (Heinhold 1962) referenced.

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The polyphenylene ether-Mischungeh the present üirfindung consist of a mixture of at least one polyphenylene ether and at least one lubricant E _g ^ er-based liquid, wherein the polyphenylene ether! Part of about 25 to 75 of the Gew.?6 Total mix creates. These mixtures have a dropping point at least as low as about ^{0 0} F (-17 »8 ° C), preferably they have a drop point well below ^{0 0} F and a viscosity below about 25,000 centistokes at ^{0 0} P (-17.8 ⁰ G).

Mixtures of polyphenyl ethers with diesters are illustrative of the mixed liquids of this invention. Preferred compositions of this type include mixtures of bis (phenoxyphenoxy) benzenes with alkane dicarboxylic acid diesters of the formula Alkanol.en ILOOG-Rg-COOR., ^{A> wherein} Dedes of R _1, R ₂ and R, saturated aliphatic hydrocarbons of 4 to ^ 12 0 atoms are. For example, such mixtures are illustrated by mixtures in which 25 to 75% by weight of the total weight is a bis (phenoxyphenoxy) benzene and the remainder is a dialkyl alkanedicarboxylate, such as bis (2-ethylhexyl) sebacate, bis (2-ethylhexyl ) -azelate, bisd-methylcyclohexyl) · ¹ · sebacate, di-Cg-oxo-azelate and di-O _1Q -oxo-azelate, (wherein. the oxo-alcohols are mixtures of branched-chain alcohols made by oxo processes , Cq-oxo alcohol, for example, consists essentially of a mixture of 3 »4-, 3,5- and 4,5-dimethyl-1-hexanol).

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Other mixtures., Which include diesters, can, for example, by combining one or more bis (lhenoxyplieiioxy) benzenes with a fluoroalkyl diester, such as 1, iH-perfluoroheptyl sebacate, with a polyalkylene glycol ester, such as dipropylene glycol dipelargonat and so weitez ', created v / earth. Other useful mixtures can be made by bringing together polyphenyl ethers, such as trisplienoxybenzenes, bis (phenoxyphenyl) -; ■ '. therii, diplienoxybenzenes and the like with jithem, such as bis (1-ethylpropyl ^ adipate, bis (i _t 3-dimethylbutyl) sebacate, l) i (2-ethylhexyl) sebacate and the like or through other combinations of polyphenyl ethers and diesters Lubricant base formulation materials such as those mentioned above.

Further illustrative liquid mini loops of base make-up materials created in accordance with this present invention are the particularly preferred class of compounds of polyphenyl-lithium with Ιϊοο-peiityl polyesters. Examples of this class are bis (phenoxyphenyl) ethers and bis (phenoxyphenoxy) benzenes, which primarily include ethers with beta-oriented 3 substituents, with irimethylolpropane esters, such as tri-n-heptanoate and trineoheptanoate, and with ientaerythritol esters, such as Tetraoaprat and Tetraoaproate uders and so on, others of the i ^ rl; 'uterun. dj'.jji - ;. iidr; : i: jo]; u.jj--

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genes are created by bringing together polyphenyl ethers, such as 1- (p-alpha-gumylphenoxy) -4-phenoxy-benzene, mixed bis (phenoxyphenoxy) benzenes and so on, with neopentyl glycol n-heptanoate, pentaerythritol

Nonantetraester with mixed nitsfeiraniOnl-s-ciLBn acids and similar, as well as through other combinations of polyphenyl ethers with neopentyl polyol ethers, as already stated above. It should also be emphasized that mixtures of different Polyphenyl ether, diester and neopentyl polyoleater fall within the scope of the miscibility preparations of this invention.

Preparations in which an antioxidant additive with combined the base-batch blends of this invention form a particularly preferred embodiment of the presently created preparations. Such preparations are for example by bringing together an auxiliary amount of a (alkanedionate) cobalt coordination -Connection with the polyphenyl ether / synthetisohe Ester-base liquid mixture of the type explained above, drunk.

Sohliessen the useful cobalt coordination compounds the cobalt (II) - and cobalt (III) -1,3-propanedionates (alkanedionates with oxo groups in beta position), in which the Substituents of the propane-dlon carbon chain hydrocarbons

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hydrogen, free from aliphatic (olefinic and acetylenic) unsaturation, and the dione can contain 5 to 15 carbon atoms. For example, illustrative cobaite compounds are the designated type bis (2,4-pentanedionate) cobalt, tris (2,4-pentanedionate) cobalt, tris (2-ethyl-1-phenyl-1,3-hexanedionate) cobalt, tris (2,4-hexanedionate) cobalt, bis (2,4-hexanedionate) cobalt, tris (515-dimethyl-2,4-hexanedionate) cobalt, tris (5-methyl-2,4-hexanedionate) cobalt, trle (3-benzyl-2,4-pentanedionate) cobalt, bis (2-ethyl-1-phenyl-1,3-butanedionate) cobalt, tris (2-methyl-1-phenyl-1,3-butanedionate) cobalt, tris (1-iaphthyl-1,3- "butanedionate) cobalt, tris (1-phenyl-1,3-butanedionate) cobalt, tris (1,3-diphenyl-1,3-propanedionate) cobalt and similar.

The antioxidant additive used in the lubricant formulations of this invention can be derived from the cobalt alkane dionate exist alone or together with other oxidation-suppressing additives. Is was found that a particularly effective suppression dta oxidative decomposition of the present mixtures of basic batch material produced by combinations of aromatic amines with the cobalt alkanedionate compounds will.

Under an aromatic amine is an amine too. understand what a benzene ring is, Mr the present 1 O 9 8 2 A / 1 3 * 2 6

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Purpose useful amines contain at least two benzene nuclei which are either phenyl radicals or part of a linked ring system such as a naphthyl. The amines useful in the present case include arylamines and arylideneamines in which the benzene nuclei are attached to the amine nitrogen atoms either directly through a carbon atom ring or through a single aliphatic carbon atom. The aromatic amines under consideration here are free of aliphatic (olefinic and aoetylenic) unsaturation, contain from 12 to 36 carbon atoms and "consist of hydrocarbon residues and Araino-stiokstoffatomen, which oxy (oxygen with atoms selected from 0 and H) residues may or may not have as substituents. In general, the amines contemplated in the present Jail will include from 1 to 4 Έ and from 0 to 30 atoms.

Illustrative of the aromatic amines that can be used in the present case are aryl amines, such as ITaphthylamine (alpha- or fr), haphthylenediamine (1,2-, 1,5-, 1,8-), IT-methylß-naphthylömin, benzidine, 2,4 ^I -Diaminobiphenyl, 2-aminobiphenyl, 4-aminobiphenyl, diphenylamine, 4-aminodiphenylamine, H-phenylphenylenediamine _T H-ethyl-alpha-naphthylamine, 2,4-diaminodiphenylamine, 1,2-diphenylethylenediamine, N-benzylaniline, methylenedianiline , 1-aminoanthraoene, 1-amino-

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phenanthrene, di-p-tolylamine, 4-dimethylaminodiphenylamine, Ή , Ii «-diphenylethylenediamine, o-ditoluidine (3,5 * -di amino 4,4'-dimethylbiphenyl), ϊ ^ -phenyl-alpha-naphthy lamin, H- Phenyl-ß-naphthylamine, N-gyolohexyl-alpha-naphthyla.irii η (or ß), ff-p-tolyl-ß-naphthylamine, triphenylamine, H ₁ N ¹ -diphenyl-p-phenylenediamine, di-alpha ~ Naphthylamine, di-B-ITaphthylamine, dibiphenylylamine, NjN'-diphenylbenzidine, p-aminophenyltriphenylmethane, N, Ii '-Dinaphthylme thylenediamine, U, If ^f -Dinaphthyl-p-phenylenediamine, Έ-β ^ -niai-yl-aminocyne ^1- phenyl-p-phenylenediamine and so on.

Examples of arylideneamines which can be used in the present case are N _f N ^f -dibenzylidene-p-phenylenediamine _> Ii ₁ N ¹ -bis- (2,3-dimethylbenzylidene) -p-phenylenediamine, Έ, N'-bis (2-hydroxybenzylidene) -p-phenylenediamine, N, N'-bis (2-ethoxybenzylidene) -p-phenylenediamine, Ii, N'-bis (2-hydroxybenzylidene) -ethylenediamine, IT _f Ii ^f -bis (2-hydroxybenzylidene) -1,2 -propylenediamine, H, M ^l -bis (2-hydroxybenzylidene) -1,3-propylenediamine, K, I < ^l -bis (3-ethoxy-4-hydroxybenzylidene) -1,2-propy ^ enediamine, IS ₉ K * -bis (2-Hydroxy-4-methylbenzylidene) ρ-phenylendiamine, IT-3-methylbenzylidene-3-ootylaniline, Na-hydroxybenzylidene ^ -hexadeoylaniline, N , Έ '-bis (5,5-methylenedioxybeniylidene) -p-phenylenediamine , N, H ^f -bis (2,3-dimethoxybenzylidene) -p-phenylenediamine, N, N ¹ -bis (2-methoxybenzylidene) -p-phenylenediamine, N, Π'-bis (2-hydroxybenzyli-

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den-o-phenylenediamine, iT, II'-bis (3-i-ethoxy-4-hydroxybenzylidene) -p-plienylenediamine, U, K'-bis (3-ethoxy-4-hydroxybenzylidene) -p-plienylenediamine, N - (3-Ethoxy-4-hydroxybenzylidene) -4-dodecylaniline, H, N ¹ -bis (4 ~ phenoxybenzylidene) -p-phenylenediamine, N, L ^rI -dibenzylidene-1, 2-diplienyläthyleridiaüiin, and the like.

The antioxidant compounds are combined with the base liquid to an extent generally between about 0 _f 01 ^ S and 10 / ό, individually or in combination, based on the liquid. Particularly effective amounts depend on the type of additive used in the individual case and the base liquid.

It goes without saying that the present preparations can also include one or a large number of other additives. For example, the Base fluids are combined with lubricity improvers, soft ones are effective to increase the ability to bear stress, to decrease wear and tear or both, with viscosity improvers, such as polyethacrylate-alkyl-windows, with detergents and diapergants and so on.

The invention is illustrated by the following examples, but not restricted to the extent to which the examinations carried out to determine the mif-

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shown auxiliary effects of the additive connections, if with the polyphenyl ether lubricant base I liquid were used as follows

To determine the antioxidant effect of the additive compounds present, air is passed through the heated samples of base fluids and base fluids plus additives, blown through. The percentage change in the (100 ° F) (37>, 8 ° G) viscosity from before to after oxidation is an index for antioxidant effectiveness. The conditions used are temperatures at 500 ° and a Flow rate of 1 liter of air per hour. Samples were taken in the presence or absence of metal wires (silver, copper, aluminum, stainless steel) as a test of the effect on such metals in the event of oxidation.

example 1

This example explains the solutions according to the invention and viscosity properties of the mixtures.

The polyphenylene ether base batch material under discussion is a bis (phenoxyphenoxy) benzene mixture of the preparation

65 $ m-bis (m-phenoxyphenoxy) -benzene 30/4 m- / J-m-phenoxyphenoxy) (p-phenoxyphenoxyJ7-benzene

5 '/ o m-bis (p-phenoxyphenoxy) benzene. 10 9824/1326

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This floating medium is liquid at room temperature, has a viscosity of approximately 350 eentistokes (es) at 100 ⁰ P (37 »8 ⁰ O) and a pour point (viscosity over 500,000 es) at 40 ⁰ E (4.4 ⁰ C).

Viscosity measurements of the mixtures of this ether-base batch material with bis (2-ethylhexyl} sebaoate gives the subsequent results.

Percent viscosity, approx Ester low temperature 100 ⁰ F (37.8 ⁰ O)

none - 350

35 14.000 / 0 ⁰ P (~ 17.8 ° 0) 53

60 13,000 / -3O ⁰ P _n 26

(-34 ⁰ O)

100 838 / -30 ⁰ P. 13th

(-34 ⁰ C)

A mixture of 35 ^ bisd-methyloyolohexyli-sebacate and 55% of the bis (phenoxyphenoxy) -benzene mixture described above had a 10O ⁰ P (37.8 ⁰ C) viscosity of 105 es and a mixture of A5 "/ o resorcinyl dineoheptanoate with 55 $ of the designated bis (phenoxyphenoxy) benzene mixture had a 100 ⁰ P (37.8 ° C) viscosity of 73 es.

Example 2

This example further illustrates mixtures of this invention, with mixtures being given by way of example which contain a neopentyl polyol ester.

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The mixture of bis (phenoxyphenoxy) benzenes described in the above example is mixed with pentaerythritol tetracaprate (here referred to as PE-TOA), pentaerythritol tetracaproate (referred to here as PE-TGO), triethylolpropane trienanthate (here referred to as G-TMP) and with. Another, similar Trim ^% thylol-tri ester combined with mixed alkane ar bonic acids of the approximate G ^ chain length (hereinafter referred to as HK-TICP) to create base-batch mixtures.

Viscosities of these mixtures were measured and subjected to the mixtures the Oxydationstest described above, was performed by exposing the base Ans; fcatz ~ materials to a stream of air content in the rate of 1 liter per hour, 24 hours at 500 ⁰ I ¹ (260 ⁰ G ) in the presence of metal (Al, Cu, Ag, and] Te) wires.

The results are compiled in the following table:

Ester $

no

C-TLIP, 100 / ά

C-TLiP, 50 / S

C-TLIP, 4 5? 6

Viscosity, it

^l / j of the change in viscosity during the oxidation (- 17.8 ⁰ G) (37.8 ⁰ C) test

O ⁰ P

100 ⁰ I ¹

6300 11000

350 15 50 50

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Sater

Viscosity, it.

O ⁰ F _n 100 ⁰ F _n (-17.8 ⁰ C) (37.8 ⁰ C)

$ d.Viscosity change

in the oxidation investigation

HN-TMP, $ 100
M-TMP, $ 45
PE TCO, $ 100
PE-TCO
PE-TCO,
PE- ¹ IGA, $ 100
PE-TCA,

8800

12000 6900

14th

47

25th

51

45.

40

51

1!

$ 100

$ 300

$ 200

Example 3

This example illustrates another embodiment of the base / batch material mixes of this invention.

Misohings are created by matching bis (m-phenoxyphenyl) -ether with trimethylolpropane-trienanthate, as referred to in "Example 2" as C-TMP.

the end
The preparation welohe'80 $ 20 $ ether and ester consists, has a 0 ° F viscosity of 22,000 it and 10O ⁰ F-viscosity of 38 esj at a ratio of 70 $ 30 $ ether and ester has the Baeis approach material -Mieohung has a 0 °? Viscosity of 6800 es and a 100 ° F viscosity of 32 os.

25 -

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Example 4

This example also illustrates other mixture formulations this invention, which by admiring three different basic approaches were made.

Mixtures with a lOO ^ viscosity of 39 os were by combining pentaerythritol tetraoaprate, trimethylolpropane trienanthate ester, referred to above as C-TMP-ester, and the Q-emiaoh described in Example 1 of bis (phenoxyphenoxy) benzenes in the following proportions by weight manufactured:

34: 29 •
• 37 4th 57.5: 28, 1 : 54, 3 59.4: 27 3: 33,

When using the oxidation 'conditions shown in Example 3, it was found that these mixtures in the Viscosity can be approximately doubled at the end of the investigation.

Example 5

This example illustrates manufactured wiped base-batch formulations the invention.

Cobalt (II) bis and cobalt (III) tris (2,4-pentanedionate) are in a corresponding »7el3e in one concentration

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of up to 1 g per 100 g of base liquid, with base mixes combined, which are prepared and labeled in the manner described in Example 3 and which ITeopentyl polyol ester blends with a bis (phenoxyphenoxy) -benzene- (xemisoh. These preparations, which contain coordination compounds are subject to the above-described 500 ° J? -oxidation suppression subject. The viscosity increases substantially less than that of the base batch materials such as this from the numbers in the table shown below evident is:

Ester # Pentanedionato- 10O ⁰ F-TiSkOsIt., Whether evaporation. Oo connection before d. after d. $ $

Under- Under- We ohsuch. seek, be

C-TMP, $ 45 tris- 47 53 13 5.0 O-TMP, $ 45 to 50 65 30 1.0 HH-TMP, $ 45 to- 48 61 27 7.6

In the case of other test purees made with preparations, whereby the preparations contain basia-approach-misohungen, which are produced and marked as described in Example 3, and 1 g / 100 g base batch of freshly made Eobalt-2,4-pentandii5 | oat, results as below are obtained:

Ester # Pentanedionato- 100 ° F viscosity., Ca evaporate. $ Oo connection before after ^ Weoh-

d.Investigation, be

O-TMP, 45? Δ 1 trls- 52 56 8th 3 OK - "> 7 - PE-TOA, $ 70 tris- 56 61 11 2 , 0 09824 / 1326 BATH ORlGJNAl.

159A482

Under the same conditions, the mixture had which 45 $ G-IMP-ester, combined with 1 $ 5-Pbenyl-1Q, 1O-diphenylphenazasilane contained, an initial aviaity of 50 os and an after-study viscosity of 76 os, that means an increase of $ 52 in 24 hours with an evaporation loss from 5 »0 $. The TMP ester mishaps that with 1,3-pentandlonato-sodium-, -ohrom-, -titanium and zinc chelate compounds are combined to form in 24 There were heavy deposits large enough to account for 90% by weight of the sample.

Example 6

This example explains preparations which enlarged Have resistance to oxidation and are made by combining a treated base batch material with a combination of a cobalt ohelate and an aromatic amine.

The mixture of $ 45 ester-based liquid as it is called 0 — TMP and 55 $ mixed bis (phenoxyphenoxy) benzenes, as described in Example 3, with (2,4-pentanedionato / cobalt bonds and aromatic Amines, as indicated above, combined and the resulting preparations that described above Subjected to 500 ° F oxidation test with results shown in the table below:

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(1) aromatic amine 96 alternation f

Go connection $

"bis-, O, ij $ N- / Ji-aminocyclohexyl) -methyl7-N'- 13 $ phenyl-p-phenylenediamine, 0.55 ^

trIa-> 136 diphenylamine, $ 2 26fo

bis-, V / o I \ T, lii ^! -bis (2-hydroxybenzylidene) - ΛΥ / ο

1,2-propylenediamine, Yfo

bis-, 0.5 $ N, IP-bis (2-hydroxybenzylidene) - 9 ^ϋ / ί

1,2-propylenediamine, 0.75 ^

tris-, 1 ^ N, N ^l -bis (2-hydroxybenzylidene) - 15 / ^

1,2-propylenediamine, 1 ^

(1) to: bis (2., 4-pentanedionato) cobalt, tris: tris (2,4-pentanedlonate) -k "obait.

fit percent by weight based on the weight of the

Basic liquid
change

(2) percent weight at 100 F viscosity, it

(3) Consistency of multiple determinations

While the invention has been described with reference to various particularly preferred embodiments thereof it is clear that modifications and changes can be made without departing from the scope of the invention, which is delimited exclusively as described in the following claims.

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Claims (1)

- 29 claims 1. Preparation characterized in that it is a Mixture of (a) at least one polyphenyl ether and (b) at least one synthetic ester liquid (flowing Medium) wherein component (a) is from 25 to 75 w / o of the total of (a) plus (b). 2. Preparation according to claim 1, characterized in that that the designated ester liquid is a diester. 3. Preparation according to claim 1, characterized in that the designated ester liquid is a neopentyl polyol ester is. 4. Preparation according to claim 1, characterized in that the specified ester liquid is a sebaoate diester is. 5. Preparation according to claim 1, characterized in that that the designated ester liquid is a (Drimethylolpropane-ester is. 6. A preparation according to claim 1, characterized in that the designated praying liquid is a pentaerythritol ester. - 30 - 109824/1326
ORIGINAL BATHROOM 7. Preparation according to claim 1, characterized in that that the "designated polyphenyl ether from 3 to 7 Benzene rings and an oxygen atom between "neighboring Contains benzene rings. 8. Preparation daduroh marked that it (a) at least one bis (phenoxyphenoxy) benzene and (b) at least comprises an ETeopentyl polyol ester in which component (a) from 25 to 75% by weight of the total amount, (a) plus (b) is. 9. Preparation characterized in that it comprises (a) a mixture of bis (phenoxyphenoxy) -benzenes and (b) a trimethylolpropane triester of a monocarboxylic alkanoic acid, which has from 5 to 10 carbon atoms, wherein the component (a ) is from 25 to 75% by weight, ^c / £ of the total amount of (a) plus (b). 10. Preparation characterized in that it comprises (a) a Gemisoh of bis (phenoxyphenoxy) benzenes and (b) trimethylolpropane tri-enanthate, wherein the component (a) from 25 to 75 wt. ^C ß> of the total amount (a ) plus (b). 11.Preparation daduroh marked that it (a) a mixture of big (phenoxyphenoxy) benzenes and (b) one tetra
Pentaerythri is based on a monoarboxylic alkanoic acid BATHROOM ORIGINAL - 31 - 109824/1326 comprises from 5 to 10 carbon atoms - wherein the component (ä) is from 25 to 75 wt. ^ of the total amount (a) plus (b). 12. Preparation according to claim 1, characterized in that that it also contains an anti-oxidation additive comprising a 1,3-propanedionato-cobalt compound. 13. Preparation according to claim 1, characterized in that it also contains antioxidant additives which are an aromatic amine containing at least two benzene nuclei and a 1,3-propanedionato-cobalt compound includes. 14. Preparation according to claim 10, characterized in that it is also an antioxidant additive, which comprises a 1,3-propanedionato-koDalt compound. 15. Preparation according to claim 14, characterized in that that the designated 1,3-propanedionato-cobalt compound is a (2,4-pentanedionato) cobalt compound, 16. Preparation according to claim 15 daduroh characterized, that it is also an aromatic amine, which contains at least two benzene nuclei, as an antioxidant additive, includes. 17. Preparation according to claim 12 characterized thereby- · 1 09 82 A / 1 3J2 6 - 32 - BATH ORIGINAL net that the designated cobalt compound bis (2,4-pentanedionato) cobalt (II) is. 18. Preparation according to claim 12, characterized in that that the designated cobalt compound tris (2,4-pentanedionato) cobalt (III) is. 19 · Preparation according to claim 16, characterized in that · the specified antioxidant additives comprises 18- / J ^ l- aniinocyclohexyl) methyl / ⁷ "- !: '-phenyl-p-phenylenediamine and bis (2,4-pentanedionato) cobalt . 20. Preparation according to claim 16, characterized in that the designated antioxidant additives N, IM '- bis (2 ~ hydroxybenzylidene) -p-phenylenediamine and bis (2,4-pentaneclbnato) -cobalt includes. 109824/1326
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