DE2046368A1 - Additive for lubricant mixture - Google Patents

Description

Esso Research and (Prio 24 October 1969 Engineering Company G.B. 52217/69 - 725?)

Linden, NJ / V.St.A. Hamburg, September 15 L97O

Additive for lubricant mix

The present invention relates to additives for Lubricant mixtures.

Lubricant mixtures should reduce the friction between moving parts to a minimum, generally more viscous lubricants provide better separation of the moving parts in the relevant working temperatures, if this Parts are pressed against each other under load. On the other hand, highly viscous lubricants show in comparison low-viscosity lubricants of the same chemical composition have several disadvantages, such as a greater tendency to decompose under the action of heat ™ and non-volatile deposits how to form coke. These difficulties occur in particular with bearings for turbine cores in gas turbine! on, but also in other contexts.

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To overcome these difficulties, relatively low viscosity lubricants have been used which at higher temperatures, there is less tendency for non-volatile decomposition products to deposit However, mixtures are generally less resilient. The resilience is there in general

in relation to the kinematic viscosity and it is advisable to provide such mixtures with additives, see below, in order to improve the load-bearing capacity.

According to the invention, an additive for lubricant mixtures is now proposed which consists of the combination consists of two components, of which component A is a neutral hydrocarbon phosphate and component B is a neutral alkylamine hydrocarbon phosphate, wherein at least one dialkylamine is Monokohlenwaeseretoffphoephat.

Derivatives of phosphoric acid in which all three replaceable hydrogen atoms are called neutral phosphates each phosphoric acid molecule are substituted.

Each alkylamine radical of component B can have 8 to 18 carbon atoms and preferably 10 to 14 carbon atoms have and the alkyl radical can be in at least one of the

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Alkylamine radicals can be a tertiary alkyl radical.

The hydrocarbon radicals of component B can be alkyl radicals or aryl reserves with 31 to 9 carbon atoms * The hydrocarbon radicals are preferably aliphatic C ₁ to Cjj

The hydrocarbon radicals of component A can be the same and can be different and can be either alkyl, aryl, or aralkyl radicals.

Preferably, the proportion of component A is greater than the proportion of component B, wherein component A may constitute from 50 to 97.5 Oew.it and preferably from 85 to 97.5 wt.% Of the additive.

In addition to components A and B, the additive according to the invention can also contain a metal deactivator, to prevent corrosion of the metal associated with the additive in the lubricant, further an antioxidant may be present to prevent oxidation of the lubricant mixture; further Antifoam agents can be added.

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20A6368

The additives according to the invention result in a surprising one Improvement in terms of the resilience of lubricants, so that it is now possible to use lubricants to be used that are less prone to the deposition of non-volatile constituents at elevated temperatures, without reducing the load-bearing capacity of the parts that move towards one another and are to be lubricated.

Accordingly, the invention also encompasses a lubricant mixture which consists of a major portion of a lubricant and contains a smaller proportion of the lubricant additive mentioned.

The lubricant can be of any type, for example a hydrocarbon or a polyether but preferably at least one ester, which esters are so-called "hindered" esters, in which a quaternary carbon atom is either in the beta position in the alcohol radical or in the ester bond and / or in the acid radical or radicals in the alpha position in relation to the ester bond.

The ester lubricant can be measured at 99 ° C Viscosity of 7 cSt or less, such as

2 to 6 and, for example, about 3.3 cSt. Although

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the lubricant behaves in such a way Viscosities and correspondingly low axes can have - since in general at a given Lubricant the resilience raife stei Viscosity is improved ~ the eg lubricant mixture has load-bearing properties that surprisingly high 3ind compared to my smear medium, and unexpectedly large in comparison mi ': combinations of the lubricant, which is either component A alone or contains component B alone.

Component A can be 1 to * S QeKoJ and preferably Make up 1.5 to 2.5 wt. * Of the lubricant mixture, while component B makes up 0.025 to 1.0 and preferably 0.05 to 0.25 percent by weight of the total mixture.

In the following several lubricant mixtures are intended for Explanation of the advantages of the additives according to the invention are described.

Two basic lubricants with different viscosities but of the same chemical composition were investigated to determine the load capacity.

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A lubricant I was used as the starting lubricant 1 once which had a viscosity of ^ι } ./$ cSt at 99 ° C and which was a tetraester of pentaaryihritol which was esterified with a mixture of C ^ - to Cn-Mcno ^ nrbonsaursn, while the other lubricant II had a viscosity of 3.3 oSt at 99 ° C. and consisted of an ester solution consisting of 92 wt and 8 wt.? Neopentyl glycol dipelargonate.

Known additives were added to lubricants I and II in the test rivets in order to prevent oxidation of the lubricants and corrosion of the metal surfaces with which the lubricant is in contact. The concentrations of oxidation inhibitor and corrosion inhibitor corresponded to the optimal concentration for the inhibiting effect. In addition, a small amount of about 0.001 wt. a known foam-preventing silicone additive was added. The lubricant each contained 2.00 wt.% Oxydationsinhibitor, 0.07% corrosion inhibitor and from 0.001 wt.% Of anti-foam additive.

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6AD ORIGINAL

The lubricant I would with; r & r ^ ohi ^ ii ^ nnr. Additives consisting of components A and B investigated. Cresy was used as component A, which was aggravated by reacting with a mixture of cresols and phenols.

As component B, an alkylamine flushing substance phate was used used, which is the easily prepared reaction product from a mixture of methyl mono and dihydrogen phosphates with a commercially available alkylamine was obtained. The product known as Alkylaxnin was known under the trade name "Primene 81-R", namely a tertiary aliphatic C ^ -Amiii used «, Component B was made as follows:

3 mol of anhydrous methanol were carefully with 1 mol Phosphorus pentoxide converted according to the following equation.

3CH ₃ OH * P ₂ O ₅ ^ CH ₃ OPO (OH) ₂ + (CH ₃ O) ₂ P (O) OH *

Excess methanol became from the resulting mixture the acid phosphates removed by vacuum distillation,

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If essentially pure monomethyl dihydrogen phosphate is required, 1 mole of trisodium phosphate can be used react with 1 mol of methyl iodide and disodium methyl phosphate, in a mixture with only a small amount of dimethyl sodium phosphate according to the following equation:

Na ₃ POi ₁ * CH ₃ I> CH ₃ O CNaO) ₂ PO * NaI

The reaction product is acidified with hydrochloric acid, whereby the corresponding methyl-substituted acidic phosphates are obtained, which are extracted with ether.

If the final product of the component B be a Dialkylaminmonokohlenwaeserstoffphosphat Soli ₄ containing no Dikohlenwasserstoffalkylaminphosphat so dex * low proportion of Dimethylhydrogenphosphat can be separated from the Dihydrogenmethylphosphat by fractional distillation under reduced pressure. Preliminary investigations have shown, however, that the presence of the monoalkylamine derivative does not call into question the advantages of the additive according to the invention, especially when the dialkylamine derivative makes up the greater proportion of component B.

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Component B was thus obtained from the above-mentioned mixture of acidic methyl phosphates which resulted from the process described first by neutralization with "Primene 81-R", the water present in the product being removed by azeotropic distillation. In the experiments with lubricant I, the reaction product of acidic phosphates and "Primene 81-R" consisted of about 60 parts by weight of dimethyl tert-dodecylamine phosphate and 40 parts by weight of methyl di (tert-dodecylamine) phosphate. That "

Lubricant I was made with and without the addition of the components A and B examined in a standard four-ball testing machine, the following results were obtained.

Try Mr. Lubricants together
settlement mean hertz
load in kg 1 Lubricant I. 26.7 2 Lubricant I + 2 wt.
Cresyl diphenyl phosphate
(Component A) 41.4 3 Lubricant I + O, lWeight
Component B .%
41.7 4th Lubricant I ♦ 2 Qew. ϊ

Component A ♦ 0.1 wt. Component B 47.0

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The improvement of resilience by adding the Component A results from a comparison of Experiments 1 and 2, while a comparison of Experiments 1 and 3 shows that adding component B to lubricant I is even better. Experiment 4 shows one extremely surprisingly good value in proportion previous attempts and shows a mutual influence or a synergistic effect between the different additives, it should also be taken into account that a small increase in load capacity with two Try about a logarithmic relation to result to have. Since there is no reason for the synergistic effect, this represents an improvement in resilience • an extremely surprising effect. The resilience of lubricant I in test no. 4 suggests that the somewhat poorer resilience of the lower viscosity lubricating oil II can be significantly improved, so that it can now be used under such loads for which it was previously not suitable.

Experiments have confirmed that the conclusion drawn from the experiments with lubricant I also applies to the Lubricant II applies. These tests were carried out with a standard IAE gearbox, the lubricant bsw. the lubricant composition at a temperature

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of 110 ° C. The values of the limit load with the

IAE test gears have a simple linear relationship

to each other and are in the following as a percentage

Reference lubricant shown, which is a mixture

of esters from C ₁ J to Cg -dicarboxylic acids with Cg to C _1Q -

Alcohols with a viscosity of 7.5 cSt was so that

much more viscous than Lubricant II in this one

Temperature is. As component A, Triersy! Phosphate was used

used, which is produced analogously to creeyl diphenyl phosphate "

can be provided.

Test no. Lubricant composition limit load in % at setting 2000 rpm. 6000 rpm.

Lubricant II *

2.0 wt. * Component A 63.4 73.2

Lubricant II +

0.1 wt.% Of component B 90-100 90-100

Lubricant II +

2.0 wt.% Of component A ♦

0.1 wt. * Component B 185

These experimental values show that between the components of the additive according to the invention a synergistic effect occurs, which leads to a considerable improvement in the loading capacity of lubricants based on a lubricant II journey. The load capacity values in this test exceed the load capacity values of the more viscous reference oil exercise a substantial amount.

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8AO ORIGWAL

Furthermore, the high temperature stability of the oil mixtures was determined in a Rolla-Royce stability test, in which samples of the lubricant to be examined were examined for 192 hours in closed stainless steel containers. After 192 hours, the proportion of material insoluble in toluene was determined _3, which is a measure of the amount of non-volatile deposits at the test temperature. Here, the temperature, the so-called. S, temperature is determined, wherein a content of 0.5 wt.% Is obtained of toluene insoluble material. If no sample material provides toluolunlösllches 0.5 wt.%, A theoretical S, temperature can be calculated by interpolation or extrapolation from the content of toluolunlösHohem material. In one, the following values were obtained:

Lubricant S, temperature in ⁰ C Lubricant II + 2.0% wt. Component A 290 Seaming agent II * 2.0 wt. * Component A * 0.1 wt. * Component B 315

These values show that a composition according to the invention BU has fewer deposits of non-volatile

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Material leads at elevated temperatures than, for example the same lubricant II with an addition of the Component A alone.

Component A, as hydrocarbon radicals, can not only have cresyl or phenyl radicals but as a component Other neutral hydrocarbon phosphates that are soluble in the base lubricant can also be used are, with neutral aryl or alkary! phosphates in particular are preferred, although neutral aliphatic phosphates can also be used. Likewise, the hydrocarbon the rest of the component is an alkyl radical, a phenyl or aralkyl radical, but preferably an alkyl radical, wherein the radicals 1 to 9 and preferably 1 to 4 carbon atoms have. As already mentioned, the alkylamine radical 8 to 18 and preferably 10 to 14 carbon atoms and can have a tertiary alkyl radical in each alkylamine radical.

8AD ORIGINAL

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Claims (11)

- ι ft ~ Claims rl / additive for Sehmiermitfcelinischungen, characterized in that it consists of a neutral hydrocarbon phosphate, in which all three replaceable hydrogen atoms of the phosphoric acid are replaced by hydrocarbon residues, and a component 3, which is a neutral alkylate hydrocarbon phosphate wherein there is at least one monocarbon dialkylanine phosphate. 2. Additive according to claim 1, characterized in that the alkylamine radicals of component B 8 bi3 18 and preferably have 10 to 14 carbon atoms. 3 · Additive according to claim 1 or 2, characterized in that at least one of the alkyl radicals of the alkylamine radicals is a tertiary alkyl radical. 4. Additive according to claim 1 to 3, characterized in that the hydrocarbon radicals of component B have 1 to and preferably 1 to 4 carbon atoms and are in particular aliphatic radicals. SAD 109819/2029 5. Addition according to claim 1 to 4, characterized in that that component B consists of a neutral monoalkyl & minihydrocarbyl phosphate consists. 6. Addition according to claim 5, characterized dadureh that the proportion of Monohydrooerbyldialicylaininphosphat in of component B is greater than the proportion of monoalkylamine dihydrocarby! phosphate ο 7. Additive according to claim 1 to 6, characterized * that the proportion of component A is greater than that of component B and is preferably 85 to 97 »5 % . 8. Additive according to claim 1 to 7, characterized in that that it also contains a metal deactivator, an oxidation inhibitor and / or an anti-foaming agent. 9> using an additive according to claim 1 to 8 in a lubricant which maintains einen'Ester corresponds% at least, preferably a quaternary carbon atom, either in the alcohol residue in the beta position to the Esterbindung and / or in the acid radical in alpha position to the Esterbindung BAD OBtQtMAL 109819/2029 10. Use of an additive according to claim 9 in one Lubricant with a viscosity of 5 oSt or less at 99 ⁰ C. 11. Use of an additive according to claim 9 and 10, where the component A is 1 to 1 and preferably 1.5 to 2.5 wt. * Of the oil screed and the component B 0.025 to 1.0 and preferably 0.05 to 0.25 wt of the mix. ue: wy 109819/2029