DE1594549A1 - Synthetic lubricants and lubricant additives based on diorthosilicic acid esters - Google Patents

Description

DR.-ING. BY KREISLER DR.-ING. SCHÖNWALD DR.-I NG. TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISLER DIPL-CHEM. CAROLA KELLER DR.-ING. KLDPSCH

Patent application P.15 94 · 54-9.0-4-2 Cologne, September 14, 19? 0 Huhrchemie Aktiengesellschaft; ESk / Se-i - K 1688 Today description ______ ■ ■.

Synthetic lubricants and lubricant additives on Baal's diorthosilicic acid esters

As lubricating oils for jet engines of! '' Aircraft are bislier 3 'I types of esters that differ from dibasic carboxylic acids derive, in use:

Type 1 (3 cSt oils, viscosity over 3 cSt at 98.9 ^O ) esters of two-base acids and of primary branched alcohols, which comply with the IT standard "Military Specification Lubricating Oil, Aircraft Turbine Engine, Synthetic Base" of November 9, 1959 i abbreviated ΜΏ-Ι-7808 D, correspond to and are suitable for turbine air jet engines with speeds up to Hach 1. .

2 (7.5 cSt oils) '' ■

3 cSt oils contain additions of complexes which are produced by reacting half-esters of dibasic acids and monohydric alcohols with polyols (polyglycols) or half-esters of glycols and monobasic acids with dibasic acids. They correspond to the British specification "Dir ec.bi or ale of Engine He search and Development") ment Maberial Specif. "From 16. ' % _: I960,", abbreviated UEHU 248 ?. They are used for turboprop machinery.

Ent or of I'lethylols such as noopentyl glycol, trimethyloipropane odor Ponbaoryfchrib, sogonannbe stabilisiorte Ευ bor. You can

109827/1707 bath

! 594549

due to the increased heat and heat loss in airplanes to su a Flügge sc ^ -. rin & iGko it of about ' Mach 2 inserted.-Earth.

The lubricating oils for Turbirient engines in aircraft nüor.en be usable in a very wide temperature range. This area is enhanced by the ongoing development of Supersonic planes with Iliiggeschwindickeiteii over ilach 2 ο constantly festers. Lubricating oils for aircraft at airspeed to Hach 3 with Üluralauite-EiTJeratitreii from 200 - 2G0 ° On the one hand, they must be able to flow at -! 35 °, in the open temperature start to enable oil pumps at great heights .. and ' on the other hand, temperatures of 4-00 ° and higher must also be used; the küimen, olme withstand thermal "or ouqycTative decomposition.

Some of the esters of ¹ I ¹ Jp 3 can still withstand the high permanent temperatures that occur in hirbine bearings, since their application range is 50-100 ° above that of oils of types 1 and 2, but their viscosity indexes with viscosity indices below 100 are unfavorable. Attempts have been made, their viscosity st enrperatur dependence by Susatz thermally beständiger'Silikone 'or halogenated silicones to improve, but have the former to low oclniiex ⁱ properties and the latter can be corrosive. Isetie high temperature-resistant lubricants such as polyphenyl ether or substituted pyrazines are also not applicable for this purpose, as they are no longer flowable below 0 °. There was thus the need to find lubricants or additives to lubricants which combine excellent hold temperature with good fluidity at extraordinarily low levels of exposure and good lubricity over a very low temperature range.

BATH ORIGINAL

109827/178 7

The invention has set itself the task of special pebbles acid esters as lubricants or lubricant additives develop which meet these requirements and the deficiencies of previously known "ortho and disilicic acid esters, away. the splitting off of substances or of low-boiling ones Proportions of exposure to oxygen in the heat, Heiguiig. for polishing, insufficient wafer loosening compatibility and -näßigec pressure absorption capacity of the oil films img do not own.

It was' now found that this ₅ 2Jiel by lubricants

on the basis of voijtiefjelsatireestern is achieved, the DiorthokieselGäureöter the general lOxrniel

A (OOi) ₂ (OE) _6- ^ _{n + 311} -) (OE ¹ ) _n (0E ") _m

s ", alone or in Genisch with other lubricant known per se and contain Zusatsstoffen wherein A pentaerythritol di-carboxylic ester or Dipentaerytlirit-tetra-carbonsäureeste.r-Eeste, E ^ Folyo cyalkylenglykolätherreßte 1 - M- üthers oxygen atoms, E ¹ Alkjrlreste with melir as 3 carbon atoms and E "denote esters of monopentaerythritol tri-carboiic acid esters or of dipentaerythriii-penta-carboxylic acid esters, while η values from O - 6 and m can assume values from 0-2, and the carboxylic acid proportions of the A- and E "groups are derived from saturated monocarboxylic acids with more than 2 carbon atoms and the substituents E, E ¹ and S" present in the molecule can be the same or different from one another. "

Diorthosilicic acid esters in which η and ei '= O oreren = 3 and m - O or η = 2 or 3, m = 1 or 2 and η + m is not higher than ¹ V are particularly suitable.

109827/1787 bath

_ Z ₁ . -

Particularly suitable as A groups are pentaerythritol di- (3 ₅ 5) 5-trimethylliexaiiat) - or - (2-ethylhe3: anate) residues, and as R groups diethylene glycol n-butyl ether residues, as R ¹ - Groups are alkyl radicals of 8 or more carbon atoms, primarily isodecyl radicals and, as R "groups, pentaerythritol (3,5? 5-trimethylhes: anate) radicals.

The esters according to the invention can according to any conventional Process in a manner analogous to the previously known diorthosilicic acid esters are produced * e.g. by converting stoichiometric mixtures of the corresponding water-resistant alcohols, ether alcohols and pentaerythritol di- or tri-isononanate with one or two free hydrosyl groups with gaseous silicon tetrachloride DBP 1 184 855 or DAS 1 180 359 (patent application R 52 696 IVb / 12o).

Can UiJpen The starting materials for the A and R ¹¹ -Gx ¹ eg by "esterification of 1 mole of pentaerythritol and of 2 or 3 moles of 3,5? ^5-T 3? Ethylhexanoic in and be prepared by subsequent distillation distribution. This pentaerythritol di-isononanate, pentaerythritol tri- and pentaerythritol tetra-isononanate are formed

3,515-trimethylhexanoic acid and 2-ethylhexanoic acid expediently by hydroformylation of the corresponding olefins (Oxo synthesis) and air oxidation of the reaction products be won.

In Tables 1 and 2, the properties became as follows Esters compiled according to the invention: ■ - ■ "

Pentaerythritol-di-3,5,5-trimethylhexanate-diorthosilicic acid-hexa-isodecyl-ester,

II Pent aerythritol-di-3,5,5-trimethylhexanate-diorthosilicic acid-hexa- [ diethylene glycol n-buthyl ether] ester,

III pentaerythritol di-3,5,5-trimethylhexanate diorthosilicic acid e-tri- [diethylene glycol.-n-butyl ether] -tri- [iso de eyl] ester,

IV Pentaerythritol-di-355,5-trimethylhexanate-diorthosilicic acid-di- [pent aerythritol tri- (3,5,5-trimethylhexanate)] - tetra- [diethylene glycol n-butyl ether] ester,

V Pentaerythritol-di ^^ jS-trimethylhexanate-diorthosilicic acid-m, ono- [pentaerythritol-tri- (3,5,5-trimethylhexanate)] -penta- [diethylene glycol-n-butyl ether] -ester _}

VI Pentaerythritol-di-3 _J 5,5-trimethylhexanate-diorthosilicic acid-mono- [pent aerythritol-tri- (3,5,5-trimethylhexanate)] -tri- [diethylene glycol-n-butylether] -di (isodecyl) - ester,

VII Pentaerythritol-di-3,5,5-trimethylhexanate-diorthokieseisäure- [pent aerythritol tri- (3,5,5-trimethylhexanate)] tri- (isodecyl) di (diethylene glycol n-butyl ether) ester.

They were in the bubble column reactor according to the method of the DAS 1,180,359 at temperatures of 67 - 75 ⁰ O prepared.

For comparison, the following were also listed in Table 1:

VIII Average values of complex esters /

IX Phenyl-methyl-silicone oil. A ,. Molar ratio of phenyl to methyl group 0.75 ^?

X phenyl-methyl-silicone oil.Bj molar ratio phenyl to Methyl group Ί, 3)

⁺ ) Gunderson, Hart, Synthetic Lubricants, Heinhold P. Corp. New Yo3k, 1962, p. 197

⁺⁺ ) Gunderson, Hart, Synthetic Lubricants, p. 275, and! Great,

Verlag Chemie 1960, pp. 291 and 292

109827/1787

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SAD ORIG / NAL

" ^R 7 ~

The origins are high molecular weight silicic acid esters boil over 2? 0 ° at 1 Torr, or. over 210 ° at 0.01 torr or at 4-90 ° "at 760 Torr. Hire ElaEna points are above

2? 5 ° ■

The esters according to the invention with a relatively high viscosity and low temperature dependence are evaluated according to their viscosity properties by comparisons with other corresponding lubricants, where in addition to the viscosity, the viscosity temperature constant is expedient (VTC) is taken into account as a value meter.

The esters I to III show in comparison with the usual Complex esters of type 2, the average values of which are also given in Table 1, have a higher viscosity, Their temperature dependence has the same characteristics; Ester II has even more favorable properties. If you use this Esters according to the invention instead of the complex esters to "increase the viscosity of dibasic esters for the production of 7.5 cSt oils according to DEED 24θ?" Due to their higher viscosity with lower admixture the same or better effect.

The esters IV to VIl with pentaerytliritol tri-isononanate hests as substituents are with the diethyl-phenyl-silicone oils to compare, in which the heat-resistant wedge by the incorporation of phenyl groups; improved and the Risk of crosslinking or gel formation is limited. The pentaerythritol di-isononanate diortliosilicic acid ester IV to VII reach the low in their viscosity data with regard to the level of toughness and temperature resistance phenylated methyl-phenyl-siliconols and are even sometimes superior to them (see Table 1) -

BAOORlGiNAt-

In view of their high viscosity, the silicic acid esters of the invention exhibit excellent cold properties on. The specified pour points are due to the high toughness of the esters and are not due to deposition caused by solid substances.

The pentaerythritol di-isononana.t-diorthosilicic acid esters according to the invention are generally more stable to oxidation than the ester oils of type 1, 2 and 3.

The high-boiling esters according to the invention are surprisingly heat-resistant; gel formation occurs when heated above 300 ° in air not on. The esters according to the invention with E substituents of 8 and more carbon atoms are water-resistant, especially in the case of steric shielding of the SiOC bond.

The oil films formed from the claimed silicic acid ester also have a high load-bearing capacity. as The benchmark for the pressure absorption capacity is the welding test measured in the four-ball apparatus (VKA) according to Boerlage, which is 170/180 kg for the new esters. The first number here means the highest possible load in kg, the the tested oil film can withstand one minute without change. The second number denotes the load at the welding of the balls takes place. The one listed in Table 2 Values are the data of the dibasic esters of type 1 to 3 used for comparison, the methyl-phenyl- and the mineral lubricating oils. Thereafter, the oxidation-stable and heat-resistant silicic acid esters surpass the Invention of the comparative oils.

109827/1787

15-9 A 549

Table 2

Welding values of pentaerythritol di-isononanate diorthosilicic acid ester measured in the four-ball apparatus

Ester - 3.6 (48 cSt) No. Welding test
Load kg Pentaerythritol di-isononanate (10.4 cSt) diorthokieseisäureester A (4 cSt) I. 170/180 B (Il cSt) II - 170/180 unalloyed smear oil (11 cSt) III 170/180 Silicone oil cSt) IV 170/180 V 170/180 VI 170/180 VII 170/180 dibasic esters, type 1 (3 150/160 Most complex type 2 160/170 stabilized esters, type 3, 150/160 ■ at 160/170 98.8
Oz ^ 150/160 ^U O 120/130

BATH

- 10 -

109827/1787

The Pent8.erythrit-di-isononanat ~ diorthokieselsäui? Eester can be mixed depending on their viscosity .in "any proportion with known suitable as a lubricant. Substances. It is advantageous to mix them with up to 75% of other lubricants, for example with Hineralschmierölen, Diearbonsäureestern, organo silicon compounds other structure PoIyphenylätherölen and Phosphorsäureestern. due to its oxidation stability, long-term heat resistance, lubricity lind viscosity data including their fluidity at low temperatures, they improve the ψ properties of its oil components. they are effective in an extended temperature range, that is stable at high temperatures, lubricious and sufficiently viscous and flowable at low temperature «

The esters of the invention can be used as oxidation stable thickeners for the production of 7 »5 cSt oils instead of Complex esters are used. 'This is where the esters are used based on their viscosity in amounts of 25 to 75 / ό, ' on the amount of the total mixture.

Because of their viscosity and low temperature behavior, the request claimed heat-resistant esters as the sought-after Hisfa components for stabilized dibasic esters, for esters of type 5, the VI values of which are in part below 100.

The partly highly viscous pentaerythritol di-isoiionanat-diorthosilicic acid ester can also be advantageous with high-boiling, low-viscosity diorthosilicic acid esters, such as with the after the patent application R 38 337IVc / 23c (patent. ... ...) Diethylene glycol diorthosilicic acid esters, the oxyalkylene glycol alkyl ether residues contain, mixed and earth. The resulting silicic acid ester mixture ■■ has a V: ü. ~ - viscosity temperature behavior with Vl values above 1 ^ 0, lower

- ii -

1 09827 Π 787

15945A9

Cold viscosity .en imd. Stoclqmnkte and remarkably favorable wear and tear like '. They are suitable as lubricating oils with a wide range of applications in high temperature applications. claimed turbine drive values.

Example 1 ν ■. '-

A reaction vessel marked as Elasensäulenreafctor.gekemarkes consists of a glass tube with an inner "width of 69 mm and a height of 550 % * & as well as with a frit 2 (Jenaer devices glass grain size 2) inserted at the bottom and is provided with a thermometer 7. Das Vessel was filled with 333 S pentaerythritol di-isononanate as the hydroxy ester, 417 S isodecanol and 427 g of diethylene glycol n-butyl ether, all of which had previously been dried ^{to a water content below 0.1 c} / o Silicon tetrachloride on an evaporator tube 4, which was preheated to 80 °. The vapors of the silicon tetrachloride were sucked in by a third 2 under a vacuum of 180 Torr via line 6 in which a condenser 5 is switched on. which essentially consisted of the evolving hydrochloric acid, a column of bubbles formed at a height of 40 cm. The alcohol mixture, preheated to 40 °, heated up h by the heat of reaction to 49 °. In 90 minutes, 272 g of silicon tetrachloride were passed in and reacted, the reaction vessel was brought to 110 ° over a period of 2 hours and the dissolved hydrogen chloride was removed from the reaction mixture under a vacuum of 20 torr while the reaction was complete, laughing after this treatment the Beilstein reaction was negative. The amounts added in excess and unreacted were in an amount of 132 g im. Distilled vacuum from 0.01 Torr to 225 °. Pentaerythritol di-isononanate fell as the residue of the distillation

- 12 -

108827/1787

diorthosilicic acid tri- (diethylene glycol n-butyl ether) tri- (isodecyl) ester (Ester III) in an amount of 1105 g

20th

a density & £ 1.02 at. The silicon content found was 4.02%, the calculated 3 »94 %» The viscosities of the ester were at 98.9 °: 23.2 cSt, at 37.8 °: 125.5 cSt. The viscosity index was 146 and the viscosity temperature constant was 0.813. The flash point was 275 °

Example 2

A mixture of dried alcohols or hydroxy esters, consisting of 208 g of pentaerythritol di-isononanate, 278 g of pentaerythritol tri-isononanate, was poured into the reaction vessel 1 shown in the figure with a clear width of 63 mm and a height of 480 mm -3 g of diethylene glycol n-butyl ether and 158 g of isodecanol. 170 g silicon tetrachloride were dosed and evaporated in the evaporator coil 4. The vapors were drawn into the reaction vessel through the frit 2 under a vacuum of 180 torr. The alcohol mixture, preheated to 40, was heated to 56 ° by the heat of reaction in the bubble column. The reaction was complete after 100 minutes. The dissolved hydrogen chloride was removed from the reaction mixture heated to 110 ° under a vacuum of 20 torr while passing in nitrogen. The Beilstein reaction was then negative. The excess and unreacted fractions were distilled off in an amount of 110 g at 0.01 torr up to 252 °. In an amount of 863 g, pentaerythritol di-isononanate diorthosilicic acid [pentaerythritol tri-isononanate] tri- (diethylene glycol n-butyl ether) di (iso-, decyl) ester (ester VI) was obtained from the distillation . The silicon content found was 3.18 % of the calculated 3.08 %. The density d ^ ° was 1.001. The viscosity values were at 98.9 °: 27.0 cSt, at 37.8 °: "241.1 cSt. The viscosity index was 127, (Uo viscosity temperature could be 0.888 : Stoclipttnlct at -30 °.

BAD ^ 109877 / 17Θ7

Example 3 '

A dibasic ester, bis (isodecyl) adipate _J , was treated with pentaery4; L · rit-di-isononanat-diortnoMeselsä ^ lre-tri - (diethylene glycol-n- "biityl ether) -tri- (isodecyl) ester (ester III ), mixed in a ratio of 55 ϊ Λ5 YoI.% · This ester mixture (hereinafter referred to as mixture 55 / 4-5) can be used as a standard lubricant for propeller turbine air jet engines. Its properties have been compared with those of the starting materials listed in table 3.

Example 4 .

The viscous ester VI of the invention, pentaerythritol di-isononanate diorthosilicic acid mono- [pentaerythritol tri-isononanate] tri- £ diethylene glycol-n-butylether-di-cisodecyl-O-ester with the low viscosity esters A (diethylene glycol diorthosilicic acid hexa- (diethylene glycol n-hutyl ether ester) and B (diethylene glycol diorthosilicic acid hexa- (ethylene glycol butyl ether) ester) in the VoL-VertEltnis 25; 55:20 mixed. Esters A and B were according to the application H 38 337 IVc / 23c (Patent. ... ...). This ester mixture, hereinafter referred to as mixture 25/55/20, is for the same purpose suitable as that obtained in Example 3; its properties were compared with those of the starting mixtures in Table 4 ■ listed. The ester mixtures have a high Viscosity (98.9 °) a low low-temperature viscosity and considerable lubricating effectiveness, »

Example 5

900 g Öktanoly daa through hydroformylation and subsequent Hydrogenation had been obtained from n-1 heptene, and 290 g of pen-

^: BAD ORJGfNÄL

109827/1787

Taerythritol di-isobutyrate as a hydroxy ester was charged as a mixture in the bubble column reactor 1 described in Example 1. Both compounds had previously been dried to a water content of 0.05 %. In the heated to 8O ⁰ C evaporator coil S 4357 of silicon tetrachloride was evaporated and the vapors sucked under a vacuum of 180 Torr by the Pritte 2 in the reaction vessel. The temperature of the alcohol mixture, preheated to 50 ° C., in the bubble column rose to 65 ° C. as a result of the heat of reaction. The reaction had ended after 120 minutes. The hydrogen chloride formed was removed from the reaction mixture heated ^{to HO 0} C under a vacuum of 25 torr while passing in nitrogen. The added in excess and the unreacted components were distilled off in an amount of 267 6 in a vacuum of 0.01 Torr at 202 ⁰ C. The residue from the distillation was pentaerythritol diisobutyrate diorthosilicic acid hexa- (octyl) ester with an average molecular weight of 1058 (calculated average molecular weight 1104) in an amount of 975 g (84 % of theory).

20th

The density ej: was 0.969. The silicon content found was 5.12%, the calculated 5 »04%. The viscosities of the ester were at 98> 9 ° C: 11.25 cSt at 37.8 ⁰ C: 57.0 cSt at -40 ⁰ C 12400 cSt The viscosity index was 152. The pour point was -61 ⁰ C and the flash point at 267 ° C.

Example 6

836 g of decanol, which had been prepared from n-1-rITones by hydroformylation and subsequent hydrogenation, and 243 g of pentaerythritol dipivalinate as the hydroxy ester were mixed in a reaction vessel 1 according to Example 1 with a clearance of 63 mm and a height of 480 mm filled. The alcohols were dried beforehand and still contained 0.04 % water. 272 g of silicon were dosed via the evaporation vessel 4

- 15 -

OBfGIHAL 109827/1787

Tetrachloride sucked in vapor form through the frit 2 into the Blasehsäul'enreakt'or, which was under a vacuum of 180 Torr. The bubble column of 48 ° C vorerMtzteii alcohol mixture heated by the heat of reaction at 63 ⁰ O. During the further implementation on the tal period of minutes, this temperature was maintained. Thereafter be about 20 Torr with the introduction of nitrogen: Yllo ^o C of hydrochloric expelled. The added in excess and the unreacted components were g in an amount of 216 in a vacuum of 0.01 Torr at 224 ⁰ O distilled off. Pentaerythritol dipivälinate diorthosilicic acid hexa- (decyl) ester with an average molecular weight of 1260 (calculated average molecular weight 1300) was obtained in an amount of 905 g (87 % of theory). The density dj was 0.930. The silicon content found was 4.4%, the calculated 4.31%. The viscosities of the ester were at 98.8 ⁰ O: 7.0 cSt, at 37.8 ⁰ O: 35.9 cSt, at -40 ⁰ O: 16200 eSt. The viscosity index was 150. The pour point was -57 ⁰ G and the flash point was 278 ⁰ O.

- 16 -

109827/1787

Ia £ e 1

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.20 "iisfcositi
, in
, 98.9 it in cSt
⁰ G
37.8 TI Stook
% 'ίΊοΟΕΠΙ—
rmnkt Reconciled
trest
kg Bis (isodecyl) adipate 0.922 3.66 15.2 ' in the- -68 230 150/160 Ester III 1.02 23.3 125.5 , 146 ' -50 275 iyo / 180 Mixture 55A5 0.969 7.92 43.05 ·. , 144 ....... 62 239 .160 / 170

i;

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ijOoi. Viscous
98.9; sit at ii
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57.8 ι cSt
-54 Yl Stoelü-
pmücb ElaMm-
pixolct Ester YI ■ 1.038 27.0 241.1 - 127 -52 295 Ester A 1.026 5.9 15.5 - 7490 203 -71 253 Ester B 1.023 4.1 13.5 5460 218 -76 210 Gemiscli
25/55/20 6.02 '25, 45 9750 178 -70 235

Claims (23)

Patents 1.) Lubricant based on silicic acid esters, thereby characterized in that they have diorthosilicic acid esters of the general formula A (OSi) ₂ (0E) ₆ ^ _{(n + m)} (0H ·) _n (0E ») _m Contained alone or in a mixture with other known lubricants and additives, in which A pentaerythritol dicarboxylic acid ester or dipentaerythritol tetracarboxylic acid ester residues, E polyoxyalkylene glycol ether residues with Λ - 4 ether oxygen atoms, E ¹ alkyl residues with more than 3 carbon atoms and E "denote the best of monopentaerythritol tricarboxylic acid esters or of dipentaerythritol-penta-carboxylic acid esters, while η can assume values from 0-6 and m can assume values from 0-2, and the carboxylic acid proportions of the A and E" groups of saturated monocarboxylic acids with more are derived as 2 carbon atoms and the substituents E, E ¹ and E ″ present in the molecule can be identical to or different from one another. 2.) Lubricant according to claim 1, characterized in that they contain diorthosilicic acid esters in which η as well as m β are 0. 3.) Lubricants according to claim 1, characterized in that they contain diorthosilicic acid esters in which η «3 and m s = 0. 4.) Lubricant according to claim 1, characterized in that that they contain diorthosilicic acid esters in which η = ± 2 or 3, ι ■ 1 or 2 and η + m is not higher than 4. - 19 - 109β27 / 17β7 - 19 - I · ■■■ · :: 5.) Lubricant according to claim 1, characterized in that it diorthokie seisäure ester in the Q-emic with up to 75 % other known lubricants and additives . ^: · I -... · !!;. ■! - .. -'ι 1) μ; i ί_.Π ' ^: ' ■, ·· ■! f '■■''■'■> ■ 'Ί r-.i;. · - ι- - ■ '> ■ · '■ ■' · ·! ■ · ■ ' . 6.) Lubricant according to claim *] to 5, characterized in that that they are known lubricants of low viscosity Diorthosilicates, organosilicon compounds different structure, dibasiscjie ISster, PJiosphorsäure, ^ jIyphenylätheröle, Contains mineral oils alone or in a mixture with one another. 7.) Lubricant according to claim ^ to 6, characterized in that they contain pentaerythritol-di-3,5,5-trimethylhexanate diorthosilicic acid-hexa-isodecyl-es1; he. 8.) Lubricants according to claim 1 to 6, characterized in that they contain pentaerytate, urite-di-3,5,5-trimethylhexanate- diorthosilicic acid-hexa- [ diethylene glycol-n-butyl ether } - ester. 9.) Lubricant according to claim 1 to 6, characterized in that that they are pentaerythritol di-3,5,5-trimethylhexanate diorthosilicic acid tri- [diethylene glycol n-butyl ether] tri- [isodecyl] ester contain. 10.) Lubricant according to claim 1 to 6, characterized in that that they are pentaerythritol di-3,5,5-trimethylhexanate diorthosilicic acid di- [pentaerythritol tri- (3,5,5-trimethylhexanate)] tetra [diethylene glycol-n-butyl ether] ester contain. 11.) lubricant according to claim 1 to 6, characterized in that it pentaerythritol di-3,5,5-trimethylhexanate - 20 - ■ ■ * BATH ORIGINAL 109827Π787 1584549 diorthosilicic acid mono- [pentaerythritol tri- (3,5,5-trimethylhexanate)] penta- [diethylene glycol-n-butyl ether ] esters included. 12.) Lubricant according to claim 1 to 6, characterized in that it pentaerythritol-di-3,5,5-trimethylhexanate diorthosilicic acid-mono- [pentaerythritol-tri- (3,5,5-trimethylhexanate)] - tri- [diethylene glycol- n-butyl ether] di (isodecyl) ester contain. 13 ·) Lubricants according to claims 1 to 6, characterized in that they are pentaerythritol-di-3,5,5-trimethylhexanate-diorthosilicic acid- [pentaerythritol-tri- (3,5,5-trimethylhexanate)] -tri- (isodecyl) -di - (diethylene glycol n-butyl ether) ester contain. 14.) Biorthosilicic acid ester of the general formula A (OSi) ₂ (0R) ₆ _ _{(n + m)} (0R ') _n (0R ») _m wherein A pentaerythritol dicarboxylic acid ester or dipentaerythritol tetra-carboxylic acid ester radicals, R polyoxyalkylene glycol ether radicals with 1-4 ether oxygen atoms, R ¹ alkyl radicals with more than 3 carbon atoms and R "radicals of monopentaerythritol tricarboxylic acid esters or of dipentaerythritol denote, while η can assume values from 0-6 and m from 0-2 and where the carboxylic acid components of the A and R ″ groups are derived from saturated monocarboxylic acids with more than 2 carbon atoms and the R, R ¹ and R "can be the same or different from one another. 15.) The chemical "compound pentaerythritol-di-3,5,5-trimethyl-hexanate-diorthosilicic acid-hexa-isodecyl-ester. - 21 - ' η η Q * i BAD 16 «) The chemical compound pentaerythritol di-3,5,5-trimethyl-hexanate-diorthosilicic acid hexa- [diethylene glycol butyl ether] ester. 17 ·) The chemical compound pentaerythritol-di-3,5,5-trimethy1-hexanate-diorthokieseisäure-tri- [diethylene glycol n-butyl ether] -tri- [isodecyl] -ester. 18.) The chemical compound pentaerythritol-di-3,5,5-trimethyl-hexanate-diorthosilicic acid-di- [pentaerythritol-tri- (3,5,5-trimethy1-hexanate)] - tetra- [diethylene glycol ^ n-butyl ether ] -ester. 19.) The chemical compound pentaerythritol-di-3,5,5-trimethyl-hexanate-diorthosilicic acid-mono- [pentaerythritol-tri- (3,5,5-tri-methy1-hexanate)] - penta- [diethylene glycol-n butyl ether] ester. 20.) The chemical compound pentaerythritol-di-3,5, 5-trimethyl-hexanate-diorthosilicic acid-mono- [pentaerythritol-tri- (3,5 , 5-tri-methy 1-hexanate)] -tri- [diethylene glycol> n-butyl ether] di (isodecyl) ester. 21.) The chemical compound pentaerythritol-di-3,5,5-trimethyl-hexanate-diorthosilicic acid- [pentaerythritol-tri- (3,5,5-trimethy1-hexanate)] - tri- (isodecyl) -di [diethylene glycol] -nbutyl ether) ester. 22.) The chemical compound pentaerythritol di-isobutyrate diorthofcyclic acid hexa- (octyl) ester. 23.) The chemical compound pentaerythrib-di-pivalinat-. diorthosilicic acid hexa- (decyl) ester. BATH ORIGINAL 1098 ^ 7/1787 Blank page