DE2200459A1 - Lubricant composition - Google Patents

Description

PAt ENΊαriWXUE

DR. E. WIEGAND DIPL-ING. W. NIEMANN

DR. M. KÖHLER DIPL-ING. C. GERNHARDT 2200459

MUNICH HAMBURG

phone: 555 476 800OMONCHENIS ^. January 197?

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE10

W 40 856/71

Mobil Oil Corporation! New York, N.Y. , (V, St.A.)

Lubricant composition

The invention relates to new lubricant compositions; it relates in particular to lubricants which contain an additive to improve their anti-wear properties. The invention particularly relates to certain neutral phosphate sorbers as an antiwear agent.

It is known that certain types of organic compositions usually exhibit poor anti-wear properties during their use. This is particular the case when organic »lubricants, either oils or fats, are used, such as those based on synthetic hydrocarbons or synthetic esters. On the constant search for substances that give lubricants good anti-wear properties, there are already several organic phosphorus-based antiwear additives have been proposed became. Although many of them are sufficient in certain areas of application, However, the meisberi know one or more Disadvantages, such as a limited solubility, a low temperature:; fcurphasenfcrenimng, insufficient heat and oxidation.

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resistance, insufficient resistance to hydrolysis, rapid additive depletion, corrosion, inadequate protection against wear and undesired by-products on.

The only literature that describes compounds of the type used in the present invention is an article by Ramirez et al in ¹¹ J. Am. Chem. Soc. ¹¹ , 81, 4538 (1959). In this article only the methyl and ethyl members are described and there is no suggestion that these are useful as additives to improve the extreme pressure properties of lubricants.

The invention is a lubricant composition which has a larger proportion of a lubricant and a sufficient amount of a hydrocarboxyphenyl dihydrocarbyl phosphate in which each hydrocarboxy or hydrocarbyl group 1 contains up to about -15 carbon atoms to give it anti-wear properties to rent. The neutral phosphate sweeteners which can be used according to the invention have the general formula

Xn

X) R "

in which R, R ¹ and R ″ are alkyl, isoalkyl and / or cycloalkyl with 1 to about 15 carbon atoms, X is halogen (eg chlorine, bromine, fluorine) or alkyl with 1 to about 6 carbon atoms, η is a number from 0 to of the available positions.

The compounds can be prepared by processes known in phosphorus chemistry. One method that can be used involves the transesterification of a trialkyl phosphite with an alkoxyphenol. This reaction is simply carried out under such conditions that the alcohol formed in the

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Dimensions as it is made is removed. Another method that can be used according to the invention can be d \ irch the following equation can be summarized:

OP (OiOo

(EO) _x P

This method is described by Ramirez et al in "J. Am. Chem. Soc", (1959) »described in more detail.

In general, the neutral phosphate ester lubricants of the invention impart useful anti-wear properties when at a concentration within the range of voij. et v / a 0.1 to about 10 weight percent can be used. The concentration of such a phosphate is preferably from about 0.1 to about 5 wt. This includes mineral and synthetic oils as well as the fats made from them. Synthetic oils are to be understood as meaning synthetic hydrocarbons, polyalkylene oxide oils, polyacetals, polysilicones and the like, as well as synthetic ester oils. The ester oils include not only those made from polycarboxylic acids and monohydroxy alcohols, such as 2-iithylhexylacelate, but also those made from polyhydroxy alcohol, such as pentaerythritol, and a monocarboxylic acid. Of particular importance in connection with the present invention are the hydrogenated compounds. i.chvn

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Polydecenöle Rait a viscosity of between about 2 and about 100 c £ tbei'99 ° C (210 ⁰ F). In general, these can be prepared by polymerizing decene, preferably 1-decene, in the presence of a polymerization catalyst and hydrogenating the product obtained.

As indicated above, the above-mentioned neutral phosphorus phosphate esters according to the invention can also be incorporated into fat compositions will. These greases can be made from a combination of a wide variety of lubricants from the. already enumerated Classes and thickening or gelling agents exist. to such agents include the well-known metallic soaps or salts, which are present in the scouring additive in grease-forming amounts in a dispersed in such an amount as to make up the fat composition obtained give the desired consistency. Other thickeners are e.g. the soap-free thickeners, e.g. surface-modified clays and silicas, aryl ureas, Soot, calcium complexes and similar substances.

The following are the new anti-wear requirements of the invention Additives explained in more detail. It is clear, however, that the invention is not limited to the following explanations but that these can be modified in a wide variety of ways.

example 1

A solution of 300 g Tributylphoivph.it in 300 ml of benzene was added to a solution of 129 ~ gp Ben?, Ochinon in 500 ml of benzene was added at such a rate that the temperature of this mixture did not exceed 30 ⁰ C. After the addition ,, the solution overnight at Ra \ m temperature set goiMsen and then with diluted HatriuKb, ydro was:; yd exl;> crude: i ERÜ. ] a; icji washing with water and drying with l \ ^T n ...; JO “became

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the benzene layer removed. After distillation was obtained 555 I50 S -p-Butoxyphenyldibutylphosphat, Kp. To 158 ⁰ C / 0.002 mm Hg. The refractive index of the product at 20 ⁰ C ⁽⁰ ng) was 1,4755-

Example e 2-4

Equimolar amounts of trioctyl phosphite, tridecyl phosphite or tridodecyl phosphite were added to the stirred suspensions of p-benzoquinone in benzene. The addition was made at about room temperature without cooling. After the addition of each phosphite, the respective product mixture was heated ^{to 70 ° C. to complete the reaction.} After standing overnight at room temperature, each system was extracted with dilute sodium hydroxide, and the benzene was removed by distillation under reduced pressure.

Evaluation of the products
FZG test

p-Äthoxyphenyldiäthylphosphat was'decengetriebeb'l (in a hydrogenated poly-a mixture of (1) 40% of a hydrogenated Dec ent rimer s having a molecular weight of 515 and a viscosity at 99 ⁰ C (210 ⁰ F) of 4.77 cSt and towards studied (2) 60% of a hydrogenated Decendecameren having a molecular weight of 1450 and a viscosity at 99 ° C (210 ⁰ F) of 40.7 cSt) to its anti-wear activity "in the applied test concerned it is the PZG test according the German industrial standard DIN 51 554. In this steel-on-steel spur gear test, the ability of the oil to pass a maximum number of stages was examined, which is a relative indication of its load-bearing capacity. The specific aim of this test is the early examination and verification of genes

gear oils by determining their ultimate load-bearing capacity and the changes in weight on the gearbox surfaces. By doing Test are left selected gears in the gear oil to be tested at a constant speed and at a fixed initial oil temperature run using the splash lubrication method. The gear oil itself without additive only passed eight stages, the oil plus 1 wt% additive passed twelve stages, which was the maximum possible in this test.

Shell-4-KuKel test

In this standard test, three steel balls are held in a stationary position in a container into which the lubricant composition is added. A fourth ball is placed on a jig so that its speed and pressure can be regulated. This fourth ball is rotated against the other three balls and after the test has ended, the balls are examined for scratches. The size of these scratches indicates the amount of wear. The following table summarizes the results obtained using 1% p-butoxyphenyl dibutyl phosphate in various lubricating oils. The experiments indicated were carried out at room temperature.

Table I.

Base fluid viscosity at RPM pressure time without with

99 0 (210 ⁰ F) in (kg) additional additional

cSt

paraffinic

Mineral oil 13.4 1420 15 1 hour 0.76 0.28

synthetic HC ^a ^ 18.8 1420 15 1 "0.55 0.26 synthetic HC ^ 14.0 I500 90 1 min. 3.2 0.48 ⁰ ^ 21.8 1420 I5 1 hour. 0.52 0.25

sterically hindered

Ester ^; 5.0 1420 I5 1 hour 0.76 0.60

Dicarboxylic acid esters ^, 6 1420 I5 1 "0.41 0.36

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Ca) a 40/60 mixture of a hydrogenated decentrimer and decamer, as indicated above,

(b) a 40/60 mixture of a hydrogenated decene trimer and -decamers as indicated above

(c) polypropylene glycol having a Molekiilargewicht of 2000 and a viscosity bei'99 ° C (210 ⁰ F) of 21.8 cSt

(d) a trimethylolpropane ester of isononanoic acid, molecular weight 596, viscosity at 99 ° C (210 ⁰ P) 5.0 cSt

(e) Diisononyl ester of decanedicarboxylic acid, molecular weight • 482, viscosity at 99 ° C (210 °]?) 5.61 cSt ".

Using the same four-ball test were carried out in the synthetic Hydrocarbon of Table I with a viscosity of 18.8 cSt 1% concentrations of various phosph ^ .testers tested. The tests were run for 1 hour at room temperature at 1420 EPM at 15 kg. In the following table II the results obtained are summarized.

Table II
The tests were carried out with

RO.

.OR ¹
"OR"

additive

none

R; E ¹ and R "= ethyl R, JR ¹ and R" - butyl R, R ¹ and R "= octyl and H" = decyl

R, Ε ¹

.ti * and R "- dodecyl

Wear scratch diameter,

0.55 0.36 0.26 0.28

0.28 0.30

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-a- 22UU459

For the use according to the invention, the additional compounds indicated below can be prepared by the process indicated here. These compounds are those in which B, R ¹ and R "are not the same, for example butoxyphenyldioctyl phosphate, octylphenyldicyclohexylphosphate, lionylphenylbutyloctylphosphate and similar compounds. Examples of such compounds in which the phenyl ring is additionally substituted or are jutboxyphenyldibutyl Butoxyphenyldibutvlphospbat, wherein the l'henylring each Verbi] idung also 1 bit 4 chlorine, Bro.ni- or fluorine atoms, and Athoxyphenyldiath.ylphosphat, Butoxyphenyldibuty! phosphate, or Octylphenyldioctylphosphat Dodecylphenyldidodecylphospbat, wherein the ring portion of each of these compounds by 1 to 4 Niedrigalky! groups, % .B. methyl, iithyl, propyl, butyl, pentyl, hexyl or a combination of halogen and alkyl can be substituted, for example in which the phenyl group also contains 1 to 3 halogen atoms and 1 to 3 lower alkyl groups, the sum of these groups does not exceed the value ^L \.

The present invention has been described above with reference to specific embodiments described, however, it is clear that these have been modified and varied in many respects can without thereby affecting the scope of the present invention is left.

Claims

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Claims (1)

Patent claims 1. A lubricant composition containing an anti-wear agent, characterized in that it is used as an anti-wear agent.
abrasive contains a hydrocarboxyphenyl dihydrocarbyl phosphate in which each hydrocarboxy and hydrocarbyl group contains 1 to 15 carbon atoms. 2. Lubricant composition according to claim 1, characterized
characterized in that it is a phosphate of the general formula
contains Xn 0 p in which H, R 'and R "are alkyl or cycloalkyl groups with 1 to 15
Carbon atoms, X is halogen or C ^ -Cg-alkyl and η is an integer from 0 to the number of available positions. 5. Lubricant composition according to claim 2, characterized in that that in the general formula R, R 'and R "mean ethyl. 4. »Lubricant composition according to Ansxjruch 2, characterized in that that in the general formula R, R 'and R "mean butyl. 5. anti-aging agent compositions; ¹ ; according to imspruch 2, characterized in that in the general formula R, R ¹ and R "Üctyl 2 0 over 8'J 07 I 1 B 6. lubricant composition according to claim 2, characterized in that in the general formula R, R 'and K " Mean decyl. 7. Schiuiejrnittelverbindungen according to claim 2, characterized in that in the general "formula R, R ¹ and R" denote dodecyl groups. 8. Lubricant composition according to any one of claims 1 to 7 »characterized in that it contains the phosphate in an amount of 0.1 to 10% by weight. Hydrocarboxypbenyl dicarbyl phosphate, characterized by the general formula Xn in which R, R ¹ and R ″ denote alkyl or cycloalkyl groups with 3 to 15 carbon atoms, X denotes halogen or C 1 -C 4 alkyl and η denotes an integer from 0 to the number of available positions. 10. Hydrocarboxyphenyldicarbyl phosphate according to claim 9, characterized in that in the general formula R, R ¹ and R "are butyl. 209 «30/1) 88