DE2034383A1 - Mixtures of synthetic esters and their uses - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENTANWÄLTE 8 MUNICH 2. HILBLESTRASSE

<f

Df. Brg Dipl.-lnp. Stapf, 8 Manchen 2, HHblestroB «20 Your writing Our sign

Lawyer file 19 Be / Sch

Ethyl Corporation Richmond / USfc

date

10.

"Mixed synthetic esters and their uses"

With the development of gas turbines for airplanes, which operate under top performance at extremely high altitudes, lubricants have become necessary that can withstand the extremely high temperatures, -the io dleeenMaeohinen occur for a longer time and di · and «r« r ~ \ since · with dtn «rather lower Ttoperaburen remain fluid,

Ca ··? 283

009113/19It

to which these machines are exposed in arctic regions or occur if the machine is switched off during the flight. The machine manufacturers and the operators who handle these machines require a lubricant that has an exceptionally low viscosity at low temperatures and at the same time has a satisfactory lubricating viscosity at higher temperatures. In the period from about 19 ² K) to 19 £ 5> ester lubricants were developed primarily for the early turbo engines. The development of these lubricants is described in publications such as Zorn, "Esters as Lubricants ¹¹ , available from the Air Documents Division, T-2 AMC Microfilm No. RC-718 F-18614, Dayton, Ohio, July 194-7. Until recently The lubrication of turbojet engines was generally satisfactory when using diesters of an aliphatic dicarboxylic acid such as di-2-ethylhexyl sebacate. The airplanes recently put into service or airplanes which are still in development are said to be satisfactory * fly with top i sound velocity and need daherein · j higher performance Turboetr * hltri # bwerk ·. · · Di brings j greater burden hineiohtlich represents stability daa Sohaier-] "ittela and requires the Entwiaklung new Soneiareittal, ■ j dia for diaaan Zwtok can be related -

00901371 »69

ORiGJNAL INSPECTED

The present invention relates to a synthetic ester useful as a lubricant under extreme working conditions. The ester is a mixture of esters consisting mainly of essentially fully esterified trimethylolpropane esters of mixtures of aliphatic C 1-6 conocarboxylic acids and essentially fully esterified dipentaerythritol esters of aliphatic Gn- to O ^ Q monocarboxylic acids.

More precisely, it is a mixture of

(a) from about 1.5 to 2.5 parts of a trimethylol propane ester. from a mixture of aliphatic C ^ - to C ^ o "" Monocarboxylic acids with

(b) from about 0.75 to 1.25 parts of a dipentaerythritol ester from a mixture of aliphatic CL- to C-Q-monocarboxylic acids,

whereby one obtains an Estergemisoh, which as a synthetic Lubricants, especially in turbo engines and turbo jets suitable is·

In summary, oat si oh. hence the present invention sur task geaacati

-synthetic Eetergeaieohe, which are in the field of, medium usable bind,
-High synthetic esters with physical properties

008083/1969

shafts that they use as lubricants for turbo machinery make ideally suitable

- Ester blends with good stability and physical properties that meet the requirements of Navy MIL-L-23699-A Comply with regulations,

to provide.

These goals are achieved by forming a synthetic ester mixture from i

(A) 1.5 to 2.5 parts by weight of an essentially fully esterified trimethylolpropane ester from a mixture of aliphatic G ^, - to C ^ p-monocarboxylic acids, the average number of carbon atoms in the Geraisch of G ₁ , - to C. ^ ₂ acids of 6 to 9 carbon atoms and

(b) 0.75 t> is 1.25 parts by weight of an essentially fully esterified dipentaerythritol ester from a mixture of aliphatic G ^ - to C ^ -monocarboxylic acids, where the average number of carbon atoms in the mixture of C ^ - to G ^ _Q -acids is from 5 to 9.

Trimethylolpropane (TMP) is the compound 1,1,1-trimethylol propane and dipentaerythritol (DiPE) is the monoether formed from two molecules of pentaerythritol »low amounts of mono-

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pentaerythritol and higher condensation products of pentaerythritol can be present.

In a preferred embodiment, the acids used for the esterification to the trimethylolpropane ester consist of at least 90 wt. % from a mixture consisting essentially of pentane, hexane, octanoic and decanoic acids. In a further embodiment, the acid portion of the ester consists essentially of normal aliphatic monocarboxylic acids. By "essentially normal" it is to be understood that the main portion of the acid mixture consists of normal or straight-chain acids 90 $ of aliphatic acids normal *

In a particularly preferred embodiment, the trimethylolpropane ester is essentially completely esterified Trimethylolpropane ester of a mixture of essentially normal aliphatic monocarboxylic acids consisting of at least 9Cl% by weight of a mixture comprising essentially from about 20 to 50% by weight of hexanoic acids, about to 48% by weight of octanoic acids, and about 25 to 35% # Contains decanoic acids and the dipentaerythritol ester

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is a substantially fully esterified dipentaerythritol esters of a mixture of substantially normal aliphatic monocarboxylic acids, which consists at least 90 wt.% of a mixture consisting essentially of about 30 to 60 wt. # pentanoic acids, about 8 to 20 wt.% hexanoic , about 15 to 32 wt. # ootanic acids and about 10 to 25 wt. # decanoic acids.

The two synthetic ester components of the mixture are prepared separately by known processes. The hindered polyol (trimethylolpropane or dipentaerythritol) is generally mixed in suitable proportions with the desired aliphatic monocarboxylic acid mixture and subjected to esterification conditions. There should be enough acid equivalents in the acid mixture to esterify at least substantially all of the hydroxyl radicals in the oil. A slight excess of the acid mixture is generally used, although a large excess is not recommended because it is after the esterification or if the product is one too; should have a high acid number, must be removed. The removal of large amounts of unreacted acids is not economical and emulsions are difficult to form. rig. Generally from 1 to 1.25 equivalents of the acid mixture are used for each hydroxyl equivalent of the polyol.

As stated above, the esters are prepared by subjecting the polyol-acid mixture to esterification conditions. Esterification conditions are to be understood as meaning that the reaction is carried out under conditions generally known to the person skilled in the art in order to cause an organic carboxylic acid and an alcohol to form an ester with the elimination of a molecule of water. It is conveyed thereby, in general, that the mixture, the organic carboxylic acid-and the polyol contains, heated a temperature in the range of about 75 to 3QO ⁰ C is used. The reaction is preferably carried out at a temperature so high that the water formed is distilled off, but is not so high that the decomposition of the reactants or products is caused. The removal of the water is often facilitated by incorporating a water-insoluble azeotropic solvent in the reaction mixture. Suitable solvents include aliphatic or aromatic hydrocarbons. The aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and the like are particularly useful. When these are used, the esterification is generally carried out at a boiling point of the mixture and the water is removed from the distillate by means of phase separation. After the esterification has ended, the solvent is returned to the reaction mixture. If higher temperatures are used using an azeotropic solvent. ■■■ - ■■ ''. -8- ■

009883/1969

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are applied, the reaction can be carried out under such a pressure that the boiling point of the mixture the desired reaction temperature is raised «,

The rate of esterification can be increased by adding an esterification catalyst to the mixture. Acid or acidic catalysts are particularly useful for this. These catalysts include sulfuric acid, phosphoric acid, p-toluenesulfonic acid, sodium bisulfate, potassium bisulfate, sulfonated polystyrene-acid ion exchange resins, and the like. Other useful etalysers include esters of titanium or zirconium such as tetraalkyl titanates or zirconates (for example tetraethyl titanate, tetrabutyl titanate, tetra propyl zirconate, etc.) "Metal oxides such as zinc oxide, aluminum oxide and the like can also be used," The catalyst range is not critical, but should be sufficient to promote a reasonable rate of esterification _o A useful range is from O _φ 00.1 to 5 Gew _e # _? based on the weight of the reaction mixture. A preferred catalyst concentration is from 0 _s 1 to 3

The esterification is durohgef ührfc ₈ to the hydroxyl number of the mixture to about 10 unt © r is reduced "After the ester various treatments may have been subjected to removal under desired material _Q Lösmngstnitt; ©!

009883/1969

or excess aliphatic carboxylic acids can be removed by heating the ester, preferably under vacuum, to a temperature high enough to distill them off. Temperatures from 100 to 250 ^° C. and a vacuum below 50 torr, preferably below 10 torr, are usually sufficient. Residual acid can be removed by washing the ester with an aqueous base such as sodium hydroxide or sodium carbonate. The ester can also be washed first with an aqueous base before the solvent is distilled off. This process indicated in the acetate allows the residual water to be removed with your solvent. Further drying of the ester can be effected by treating it with any known drying agent such as anhydrous sodium sulfate. It is generally desirable to treat the Endester for further treatment with an absorbent such as activated clay, alumina or activated charcoal, to üpurensäuren and other impurities to remove *

The aliphatic monocarboxylic acid mixtures which can be used to prepare the esters are mixtures of aliphatic monocarboxylic acids which, in the case of the trimethylolpropane ester component, contain from 4 to 12 and in the case of the dipentaerythritol ester component from 4 to 10 carbon atoms per molecule. The proportion of the individual acids in the mixture

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009883 / 19S9

is set so that, on a mole basis, the average number of the carbon atoms in the acid mixture used to produce the trimethylolpropane ester from 6 to 9 and the average number of carbon atoms in the acid mixture used to make the dipentaerythritol esters from 5 to 9. For example, it has a molar mixture of hexanoic and octanoic acids in equal parts » on a mole basis, an average of 7 carbon atoms per molecule.

The aliphatic monocarboxylic acids can be straight or branched chain be. Examples of typical acids that can be used to make the esters include: n-butyric acid, isobutyric acid, 2-methyl-n-butyric acid, 3-methyl-n-butyric acid, n-pentanoic acid, 2-methyl-n-pentanoic acid, 2-ethyl-n-butyric acid, n-hexanoic acid, 2-methyl-n-hexanoic acid, 2-ethyl-n-pentanoic acid, 3-methyl-n-hexanoic acid, n-heptanoic acid, 2-ethyl-n-hexanoic acid, 2-methyl-n-heptanoic acid, 3-methyl-n-heptanoic acid β, 2,3-01πο * θ7ΐ-π-ββχαη8Μ ^ β, n-octanoic acid, 2-methyl-n-octanoic acid, 2-ethyl-n-heptanoic acid, 2,3-Diaethyl-n-heptanoic acid, n-nonanoic acid, 2-methyl-n-nonanoic acid, 2-ethyl-n-octanoic acid, 2,3-diB »ethyl-n-octanoic acid ·, 2,3,5-trimethyl-n-heptanoic acid, n-decanoic acid, 2-methyl-ndecanoic acid, 2-ethyl-n-nonanoic acid, 2,3-dimethyl- »n-nonanoic acid, n-undecanoic acid, 2-methyl-n-undeoanoic acid, 2-ethyl-ndeoanoic acid, 2,5-dimethyl-n-decanoic acid and n-dodecanoic acid.

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009883/1969 copy

The preferred aliphatic monocarboxylic acids used to make the esters are normal or straight-chain acids. Examples of such acids are n-butyric acid, η-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, n-undecanoic acid and n-dodecanoic acid. The most preferred esters of the acids used to make the trimethylol propane ester are mixtures of n-hexanoic acid, n-octanoic acid and n-decanoic acid " and particularly preferred acids for the preparation of the dipentaerythritol ester are n-pentanoic acid, n-hexanoic acid, n-octanoic acid and n-decanoic acid.

The proportion of the various acids used to prepare the ester mixture components should be such that in the case of the TMP ester, the individual acids contain from 4 to 12 carbon atoms, so that the average acid, on a molar basis, contains from 6 to 9 carbon atoms and in the case of the DiPE esters contain the individual acids from 4 to 10 carbon atoms, so that "the average acid, on a molar basis, contains from 5 to 9 carbon atoms. the # consists of 90 wt. of a mixture consisting essentially of 20 to JO wt.% hexanoic acid, 38-48 wt. # of octanoic acid and 25 to 35 wt.% decanoic acid contains. one particularly sawn '

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copy I.

/ r

vorzugtes mixture of acids for the preparation of the substantially completely esterified DIPE blending component is a mixture having a content of at least 90 wt.% of a mixture consisting essentially of 30 to 60 wt. ° / o pentanoic acid, from 8 to 20 wt. ° / o containing hexanoic acid, from 15 to 32 wt. ° / o octanoic acid and from 10 to 25 wt.% of decanoic acid. As indicated above, the best results are obtained when essentially all of the acids are in the normal configuration.

The amount of the triraethylolpropane ester component and the dipentaerythritol ester component used is adjusted to prepare the mixture so that from 1.5 to 2.5 parts by weight of trimethylolpropane ester are used for each 0.75 to 1.25 parts of dipentyerythritol ester. Ester mixtures with superior physical properties are generally obtained when from about 1 _ton 9 to 2.2 parts by weight of triraethylolpropane ester are used for every 0.9 to 1.1 parts by weight of dipentyerythritol ester. When using this narrowly defined ratio of triethylolpropane ester to dipentaerythritol ester, best results are obtained when the trimethylolpropane ester component is an essentially fully esterified trimethylolpropane ester of an essentially normal aliphatic monocarboxylic acid mixture with a content of at least 90% by weight of a mixture that is at least about 20 to 30 wt.% hexanoic acid, un-

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009883/1969

contains about 38 to 48 wt. Octanoic acids and about 25 to 35 wt .% decanoic acids containing about 30 to 60 wt.% Pentansäura} is approximately 8 to 20 wt.% hexanoic, about 15 to 32 wt. # octanoic acids and about 10 to 25 wt.

A particularly preferred class of Esterschmiermitteln this invention is a mixture of about 1.9 to 2.2 parts by weight of a substantially completely esterified Trimethylolpropanesters a substantially normal aliphatic monocarboxylic acid mixture, -. Essentially of about 24 to 28 wt% hexanoic acid, contains about 41 to 45 weight percent octanoic acid and about 29 to 33 weight percent decanoic acid, and from 0.9 to 1.1 weight parts of a substantially fully esterified dipentaerythritol ester of a substantially normal aliphatic monocarboxylic acid raw containing substantially from about 45% to 55% by weight of pentanoic acid, about 11 to 15% by weight of hexanoic acid, about 18 to 24% by weight of octanoic acid and about 13 to 18% by weight of decanoic acid.

The following examples serve to explain in which Way the esters are made »All parts are

009883/1989

Parts by weight, unless otherwise stated »

example 1

Herste Settin g F a TMP ester

Equipped with Äührwerk ₉ thermometer in a reaction vessel, üa? Hitzungsraitteln and with a Dean-Stark water trap, 67 parts of trimethylolpropane, 235 parts were introduced a Säuregemisehs, consisting essentially of 26 wt _o $ hexanoic _y 4-3 wt _o # octanoic acids and 31 wt _e # Decansauren consists * the acids were substantially normal, "this purpose I70 parts of xylene and 6 parts were then rjatriumbisulfat added" the mixture was maintained for 8 hours at reflux, during which time the collected in the separator, water was removed _β to this time had the infrared analysis a hydroxyl content of less than 0.1 $ of ₉ what the finished Yeresterung indicating _o the mixture was then cooled, diluted with an equal volume of diluted petroleum ether, was extracted twice with 1Obigem alkali and then with Masser to washed to neutrality ₀ the solution dried over anhydrous calcium sulphate and filtered. The petroleum ether = solvent i-iurd © by heating the Geraiseas to un- =

ο
fahr 100 G © ntfornt and the remaining volatile material

was dareli heating the mixture to about 130 ° 0 at a Dpuok under Q "25 Torr abd © stilli @ rt ₀ The remaining © TMP ~ Ests3? vnird © filters and delivers © © ia © n Misonajasats

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009883/1989

for making the ester blends of this invention.

Example 2 Production of the MPE ester

In that used in Example 1 Eeaktionsgefaß 220 parts of n-pentanoic acid and 220! Parts of mixtures% decanoic acids were essentially 26 wt.% Hexanoic, 43 wt. # OGtansäuren and 31 wt. Containing introduced. The acids

- ■■ ..... ■■■ ■. ■■ M

were essentially normal overall. 143 parts of dipentaerythritol and 2 parts of p-toluenesulfonic acid in 180 parts of xylene were added to this mixture. The mixture was refluxed for 72 hours, during which time water was continuously removed in the water trap. After this time, infrared analysis showed a hydroxy content of less than 0.1% by weight. The mixture was then cooled, diluted with an equal volume of petroleum ether, washed twice with 10% alkali and then with water until neutral. It was then dried over anhydrous M calcium sulfate and filtered. The P.etroläther was distilled off under a! Liquid temperature of about 100 ° C and the remaining volatile material is removed by heating to about 130 G ⁰ at a vacuum of 0.25 Torr. Lastly, the product was filtered to give a DiPE blend suitable for making the ester blends of this invention.

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009883/1969

example

This example shows the preparation of a TMP ester blend component without using a catalyst.

The reaction vessel of Example 1 were 134 parts of TMP and 475 parts of an essentially normal acid mixture consisting essentially of 26 weight "$ hexanoic, 43 wt.% Octanoic acids and 31 wt.% Decanoic acids was introduced. The mixture was then rapidly heated to 188 ⁰ O ⁰ O and slowly to 240, having been removed during this time, water in the water trap. The heating was continued for 8 hours at a temperature of 240 to 250 0, after which time the infrared analysis showed that the hydroxyl "content was less than 0.5 wt. $" The mixture was cooled, diluted with 400 parts of hexane and with washed with aqueous alkali. It was then washed with water until neutral and dried over anhydrous calcium sulfate. It was filtered and the hexane and other volatiles were removed by heating and then by reducing the pressure with gentle heating to 1JO ⁰ O and reducing the pressure to approximately 0.5 Torr.

Example 4

This example illustrates the preparation of a DiPE ester blend component without the use of a catalyst,

-17-009883 / 1969.

ίο

The reaction vessel of Example 1 were 59.33 parts of dipentaerythritol, 165 parts of an essentially normal öäuregemischs, consisting essentially of 50 wt. $ _ Pentanoic acids, 13 wt. ° /> hexanoic, 21.5 wt.% Octanoic acids and 16.5 Wt. $ Decanoic acids were supplied. With stirring, the mixture was heated rapidly to 165 ° C. and then to 233 ° C. over a period of 2.25 hours while continuously removing water in the water trap. The mixture was then heated slowly during the following 5 hours at 244 ⁰ C, after which the Infrarοtanalyse showed the esterification was completed. It was then cooled, diluted with 100 parts of hexane and washed with 10% aqueous alkali. It was then washed with water until neutral and dried over anhydrous sodium sulfate. The mixture was then filtered and hexane and the other volatiles were distilled off by heating to 130 ° C. at 0.5 torr. The final product was treated with a mixture of activated alumina and bleaching charcoal and then filtered through a filter containing a "Celite" filter pad. The product is a useful blend formulation for the ester blends of this invention.

Further fully esterified TMP and DiPE blending components can easily be prepared according to the above procedures, for which one simply determines the amounts and types of

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009883/1969

2 (

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used aliphatic monocarboxylic acids within the, already described parameter changes.

Example 5

Lined glass in a reaction vessel, 9.4 parts of trimethylolpropane, 2.15 parts of xylene and 32.9 parts Säuregemiseh, consisting essentially of 26 weight _'o # n-hexanoic acid, 4-3 wt.% N-octanoic acid and 31 weight . % n-decanoic acid was introduced .. The mixture was heated to reflux (150 ⁰ G) with stirring and refluxed for 7 hours while water was removed from the distillate. The temperature reached 251 ⁰ O, It was then cooled and diluted with 30 parts of hexane. It was then washed with 10 parts of a 10% aqueous alkali and a second time with 5 parts of a 10% aqueous alkali. "It was then washed with water until it was neutral, dried over 5 parts of anhydrous sodium sulfate and filtered" 0.5 part of activated alumina was added and the mixture was stirred for 10 minutes. The volatile constituents were ^{distilled off at a liquid temperature of 160 °} C. and 73 torr. Finally, the ester was filtered to yield a useful TMP ester blend component.

Example 6

In a glass-lined reaction vessel were 6, $ 6 Parts of dipenta @ rythritol, 1.33 parts of xylene and 20 parts of one

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Acid mixture consisting essentially of 50 wt.% N-pentanoic acid, 13 wt.% N-hexanoic acid, 21.5 wt. # N-octanoic acid and 15.5 wt. # N-decanoic acid was introduced. The mixture was heated at reflux (15O ⁰ C) with stirring, and the RücMluß continued for 11 hours while continuously removing water from the distillate. The temperature reached 245 ⁰ C. The mixture was then cooled und4it 16.5 parts hexane diluted. It was washed with 8 parts of 10 # aqueous alkali (sodium hydroxide) and a second time with 4 parts of 10 # aqueous alkali. Then, it was washed with water until the mixture became neutral, and then it was dried over 5 parts of anhydrous sodium sulfate and filtered. Hexane was distilled off at a temperature of 129 ° C. and then 0.25 part of activated alumina was added. The distillation of the volatile components was continued up to 140 ^° C. while the pressure was reduced to 4 torr. Final filtration provided a useful DiPE ester blend component.

The individual TMP and DiPE ester components can following the general procedures of Examples 3 and 4, however can be prepared using different acid mixtures shown in the tables below. The used Acid amount is based on using 134 parts TMP in the TMP ester table and 136 parts DiPE in the DiPE ester table. The aliphatic monocarboxylic acids are

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003883/1969

identified in the table by the following letters:

a. n-butyric acid b. Isobutyric acid C. »-Pentanoic acid d. 2-methyl-n-butyric acid e. η-hexanoic acid f. 2-methyl-n-pentanoic acid G. 2,2-diethyl-n-butyric acid H. 2-ethyl-n-butyric acid i. n-heptanoic acid d 2-methyl-n-hexanoic acid k. 2,2-dimethyl-n-pentanoic acid 1. n-octanoic acid τη. 2-methyl-n-heptanoic acid η. 2,2-dimethyl-n-hexanoic acid 0. 2-iithyl-n-hexanoic acid n-nonanoic acid q 2-methyl-n-octanoic acid r. n-decanoic acid S. 2-ethyl-n-octanoic acid t. 2,2-dimethyl-n-octanoic acid U. n-undecanoic acid V. 2-methyl-n-decanoic acid W. 3-ethyl-n-nonanoic acid X. n-dodecanoic acid

y. 2,2-Diinethyjbn-decanoic acid z. 2-ethyl-n-decanoic acid

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009883/1969

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ιη ιη ιη

- 21 -

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009883/1969

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00988371969

TJo

Mixtures useful as lubricants of this invention are prepared using the TMP esters and DiPE esters from the preceding tables in the following Mixes ratio given in table.

Table III Mixed Esters

mixture TMP ester "A" DiPE ester K " I. 25O parts 1I ₁ ) Il 75 pieces " 1IJ ₁ Il II 150 parts ¹¹ B " 125 pieces "H" - ^ III 200 parts IIQII 100 parts J " IV ' 225 pieces "E" 75 parts ^u IIQ.l V 190 parts UJjUI 110 parts "H" VI 210 parts "B" 100 parts "L" VII 230 parts i'D " 110 parts K " VIII 160 parts "E" 90 pieces " 11JU IX 170 parts ItJiIl 110 parts HQ tr X 210 parts 120 parts

Similarly, many other useful ester scaffolds can be obtained by using other combinations of the TMP- and DiPE ester can be mixed. In the same way you can further useful esters can be obtained if the amount of the ester of each type is within the range of 1.5 to 2.5 parts of TMP ester for every 0.75 to 1.25 Ie of DiPE ester changes.

009883/1969

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Ester blends, the preparation of which has been described herein, have physical properties that make them ideally suited for use as lubricants for jet engines. The Air Force MIL-L-23699-A specifications call for: Viscosity at 21Q ⁰ F (98.9 ⁰ O), 5 to 5.5 es; Viscosity at 100 ⁰ F (37.8 ⁰ C), it is greater than 25 and viscosity at -40 ⁰ F (-40 ⁰ C), 13 000 where max. Of the prepared mixtures, the physical properties shown in the following table were found .

Table IV

Ester 1. 21O ⁰ F
(98.9 ⁰ C) viscosity (it) VI No. 70 parts of EMP ester
from example 3
30 parts DiPE
Ester von'Bei
game 4 5.02 100 ⁰ F
(37.8 ° C) -40 ° F
(-40 ⁰ C) 144 - 24.82

2. 67 parts TMP ester from Example 3 33 parts DiPE ester from Example 4 5.14 25.67 6150

3. 68.3 parts of TMP ester of Example 5 31.7 parts of DiPE ester of Example 6 5.03 24.69 - 5839 146.5

Although the viscosities of the ester mixtures 1 and

100 ⁰ F viscosities are in the preceding table slightly below 25 os, experiments have shown that this value _t

-25-009883 / 1969

. - 25 ■ -.-

above 25 it can rise if normal formulation additives to be added to the esters. Typical examples of this Additives are given later.

Further mixtures of those prepared in Examples 1 to 6 Esters are easily made by mixing the esters in the proportions described above.

Attempts were made to demonstrate the stability of the ester blends of this invention under high temperature oxidative conditions. Refers to these experiments, "Oxidative stability tests" can be carried out in such a way that firstly the Esterschmiermittel formulated in such a manner that it 0.8 wt.% Dioctyldiphenylamine, 0.8 wt. "^ Phenyl-.alpha.-naphthylamine, -0 , 04 .Gew. # Benzotriazole and 2.0 Gew. ^ Tricresylphosphat contain Then 100 ml of samples are logged in test containers with copper and steel plates, oie are ^{heated to 204 ° 0 (40Q 0} F) and air is through the liquid with 5 1 / hour 72 hours of pearls. Then the weight loss of the section © and also the acid number, the increase in viscosity, the appearance and the content of peritane-insoluble substances are determined. With the above mixed ester lubricants vmrdsn. the following results are obtained.

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009883/1989

mg Table V acid % Visc. Aus ^ j Pentane * * * Ester Ou Weight loss number Increase
hung see insoluble
Fabrics No, O
0 stole O ₉ 7
0.8 10
14th A.
A. Q _S Q2
. O ₀ O2 1
2 0
0

* This evaluation was made so that A was unchanged and E is very dirty ο

mg / 100 ml sample

These results show that the ester compounds of this invention not only have excellent physical properties

i " -

but also opposite. ^ oil., "ar en oxidative" Be conditions? are stable,

In the manufacture of turbo lubricants. at Verviendun ·.? For the esters according to the invention, it is preferred to add other additives to improve the properties of the lubricants. These include antioxidants, Metali like passivstoren5 extreme pressure agents and _s Anbischaummittel. One area of use Antioxidationsmiti & el is from 0.1 to 5 _s 0 ta _a · l, preferred Antioxidatioosmibt ..;

Phenothiazine

Phenyl ~ a-naphthylamine

Phenyl-ß-naphbhylamine

Dioctyldiphenylanjine

-27-

_ ₂₇ _

3 °

E- Alky! Phenothiazine Dipyridylamine ■ 5-Ethy1-10,1O-diphenylphenazasilane 3,7-Dialkylphenothiazine Diphenylamine

Dinaphthylamine Butyl-α-nap ht hy lam in Ditolylamine

PhenyItolylamine Tolylnaphthylamine dicyclohexylamine diphenyl-p-phenylenediarain 4-tert-butylcatechol 2,6-di-tert-butyl-p-cresol.

Hexyl gallate

Tri-nonylphenyl phosphite polymerized l ^ imethyldihydroquinoline ρ, p'-dioetyldiphenylamine Octylphenyl-ß-naphthylamine Octylphenyl-ar-naphthylamine p-amino-diphenylamine o-aminophenol Hydroxydiphenylamine dodecylaniline 3-pentadecyl-4-aminophenol iO-methyl-J.V-dioctylphenothiazine

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009883/1969

10-n-octyl ~ 3,7-dioctylphenothiazine iO - Pheriyl-3,7-dioctyli) h: enothiazine 10-tolyl ~ 3,7-dioctylphenothiazine

10-Gyanoethyl-3,7 "-cLioctylphenothiazin. 10-Cyanobutyl-3,7-dioctylphenothiazin 1O-Benzyl-3,7 ™ d.iisopropoxyplienot; hiazine 10-Benzyl-3 ₅ 7-<iit ^{| U} 'toxyph ^erio ' tt ^l -iazine

Metal passivators are used in concentrations from 0.001 to 2.0 wt, ^ used «Metal passivators include:

1,4-dihydroxyanthraquinone

I-salicylalate ninoguanidine

Benzotriazole

Benzimidazole

Butylbenzothiazole

Methylene bis-benzotisazole

G ^ j, ^ o-aliphatic carbocyclic salt of I-salicylalarainoguanidine

Polyhydroxyanthraquinone

N, N ^l -disalicylidene ~ 1,2 ~ propanediamine N, N'- ~ disalicylidene-1,2-ethandiaine in ghinizarin

alizarin

Extreme pressure agents are used in concentrations of from 0 ₉ 1 to 5.0 percent by _e ^. Typical high pressure agents are the esters of acids of phosphorus "including triaryl phosphates such as triphenyl phosphate, trioresyl phosphate _? Pheoyldicresyl

«29-

009883/1969 '". ■

- 29 -

phosphate, tritolyl phosphate and the Trialky'lphosphate and Phosphonates such as tri-n-butyl phosphate, tri- (2-ethylhexyl) phosphate, Triraethylcyclohexylphosphat, Tri-butylphosphonat, Tri- (β-chloroisopropyl) phosphonate and the like.

Silicones such as dimethyl silicone, diethyl silicone and the like are in small amounts of about 1 to 50 ppm used for foam inhibition. ·

The following examples illustrate the mixing of lubricants for turbo engines using the esters of these Invention.

Example 7

100 parts of ester no. 1 from Table are placed in a mixing vessel IV given. To this, 1 part of phenyl-a-naphthylamine is added, 1 part of dioctyldiphenylamine, 0.1 part of fatty acid salt of I-salicylalaminoguanidine, 0.02 parts 1,4-dihydroxyanthraquinone, 5 parts of tricresyl phosphate and 5 ppm »based on the total amount, dimethyl silicone. The mixture is stirred until homogeneous, and then passed through a fine filter filtered to give an ester lubricant suitable for lubricating turbine bearings.

Example 8

1000 parts of ester no. 2 are applied to a mixing vessel Table IV, 50 parts trioresyl phosphate, JO parts 3, .7-di-

-30-009883 / 1969

- 30 -

octylphenothiazine, 1 part quinizarine and 0.05 part dimebhyl silicone. The mixture is stirred until homogeneous and then filtered to give a suitably formulated Esb lubricant received.

Example 9

1000 parts of ester are poured into a mixing vessel Table IV, 10 parts of phenyl-a-naphthylamine, 10 parts of dioctyldiphenylamine, 5 parts of benzotriazole and 20 parts of tricresyl phosphate. The mixture is stirred until it is homogeneous and filtered to obtain a synthetic lubricant suitable for use in turbine engines is.

Although the ester genes described here are mainly suitable as lubricants for turbine engines, they are also of particular importance for other uses. For example, they are easily made by fatty acid soaps, such as alkali or alkaline earth metal stearates, thickened with the formation of synthetic ester fats. the Add about 10 to 20 wt. # Lithium stearate to the hot ester provides a usable synthetic ester-based grease upon cooling.

ϋΐθ are also used as plasticizers in the plastics field usable. For example, if you have 5 to 5Q parts of poly-

-31-

009883/1969

- 51 -

Calender grade vinyl chloride resin per 100 parts ester admits, you get a usable flexible product.

"The ester mixtures according to the invention are also useful for "various special uses that a liquid demand that does not freeze and has good flow properties maintains a wide temperature range. For example, they can be used as damping fluids in instruments that have moving parts that make damping necessary, as is the case with compasses «Sie can also be used as a fluid in hydraulic shock absorbers. Another example of their use is their application for spirit levels.

Suitable automatic transmission fluids are readily formulated from the ester mixtures by having a Antioxidants such as phenyl-ß-naphthylamine, an abrasive how tricresyl phosphate and a small amount of methyl silicone is added as a foaming agent.

The esters can also be used to lubricate internal combustion engines, both ignition and diesel engines. For this use they can be used as the only base formulation, or they can be mixed with mineral lining oils to obtain the desired properties at the lowest possible cost. At this

-52- 009883/1969

- 32 -

Typical additives such as zinc dialkyldi-. thiophosphate, calcium sulfonate, barium salts of phosphos? - high molecular weight sulfurized olefins and dispersants such as high molecular weight alkenyl succinimides and succinamides of ethylene polyamines such as tetraethylene pentamine and mixtures thereof can be added.

Claims (3)

Claims ;; 1. Mixtures of synthetic esters suitable for mixing with one or more additives known per se, such as antioxidants, metal passivators, high-pressure abrasives and foam inhibitors, characterized in that they are suitable a) 1.5 to 2.5 parts by weight of an essentially fully esterified trimethylolpropane ester from a mixture of aliphatic Ch-C ₁ ~ monocarboxylic acids, the average number of carbon atoms in the mixture of Ch-C ^ -S ^ acids of 6 to 9 and b) 0.75 to 1.25 parts by weight of an essentially complete esterified dipentaerythriteater from a mixture of aliphatic Ch-C ^ Q-monocarboxylic acids, wherein the average number of carbon atoms in the mixture of C ^ -C ^ Q acids is from 5 to 9, exhibit. 2. Mixtures of synthetic esters according to claim 1, characterized in that a) the Geraisch of the Cjj-C ^ -S & ^ en to at least 90 from a mixture of hexanoic, octanoic and decanoic acids exists and 009883/1989 b) the mixture of C ^ -C ^ acids of at least 90 weight '% of a mixture of hexane Penfcan- _S, Qefcan- and DecansäMren consists _β 3. Mixture of synthetic esters according to one of the criteria 1 and 2 thereby gek.ennzelGh.net ₉ that the acid part of the ester consists essentially of straight-chain aliphatic monocarboxylic acids » ¹ J, Gemiseh sfsitliefeiselier Ester oach other claims 1 that it i-jeifeeAiia O _S O 1 to 5 wt »^ ice Änfciosidationsmifefcels _ß O! ® has OOl ₀ to 2.0 wt.% Of a Eiefcallpassivators ma O". To a Hochdrucfaaiföfc © eichnetj to 3 dadtmsfe gekeiin ^, ·,