EP0267875B1 - High-temperature lubricant - Google Patents

Description

The present invention relates to lubricant or hydraulic oil compositions containing, as additives, a mixture of an oil-soluble, optionally benzo-condensed 5-ring heterocycle with a tautomeric 2-mercapto-1,3-heteroatom-aza group and a phosphorus compound, and the use of these mixtures as Additives in lubricants or hydraulic oils.

Mineral and synthetic lubricants are usually added to improve their performance. In order to improve the wear protection properties, high-pressure and wear-reducing additives are added to the lubricants. These are required to have a non-corrosive effect on the metal parts to be lubricated and to have good heat resistance.

Various types of zinc dialkyldithiophosphates (ZDTP) are used worldwide as wear protection additives.

The use of optionally benzo-fused 5-ring heterocycles with a tautomeric 2-mercapto-1,3-heteroatom-aza group and optionally further nitrogen atoms in the ring system as lubricant additives is known. However, these generally show insufficient wear protection properties, especially at higher temperatures.

In DE-A 2,605,655 aminobenzothiazole disulfides, such as e.g. Morpholinobenzthiazole disulfide, in combination with ZDTP as a lubricating oil or. Fuel additives described.

US Pat. No. 3,966,623 describes the synergistic mixture of mercaptobenzothiazole-amine salts with 2,5-dimercapto-1,3,4-thiadiazole disulfides as corrosion inhibitors in lubricating oils.

EP-A 150,957 also describes the use of mercaptobenzothiazole-amine salt solutions in excess amine to improve the antioxidative and anticorrosive properties of power transmission fluids. Furthermore, from US-A 3,779,919 rhodamine-amine salts are known as additives for improving the load-bearing capacity of synthetic turbine oils.

Finally, US Pat. No. 4,589,991 describes a process for the production of a lubricating oil, according to which a benzothiazole amine salt is produced and per mole of benzothiazole amine salt by means of 1 or 3 to 5 moles of a benzene mono-, di or triester with the lubricating oil is made miscible.

It has now been found that mixtures of oil-soluble 5-ring heterocycles which have a tautomeric 2-mercapto-1,3-heteroatom aza group and are optionally benzo-condensed, or their amine salts with various derivatives of phosphoric acid, thio , Dithio- or trithiophosphoric acid esters and phosphorus acid esters have particularly good wear-reducing properties, in particular at higher temperatures, and at the same time have a reduced P content in the mixtures.

• a) ein oder mehrere Schmiermittel oder Hydrauliköle auf der Basis von Mineralöl oder synthetischen Oelen und
• b) 0,05 bis 5 Gew.-%, bezogen auf das Gesamtgewicht der Schmiermittel-bzw. Hydraulikölzusammensetzung, eines Gemisches aus
• 1) mindestens einer Verbindung der Formel I oder II,
  
  
  worin Y -O-, -S-, -NH- oder -NR⁹-, mit R⁹ gleich C₁-C₁₂-Alkyl, und Z -CR⁸- oder -N- sind, ferner R¹ Wasserstoff, C₁-C₁₂-Alkyl, C₁-C₄-Alkoxy, C₂-C₂₄-Alkoxycarbonyl oder Nitro, R² Wasserstoff oder unsubstituiertes oder durch -OH substituiertes C₁-C₂₄-Alkyl, R³ Wasserstoff, C₁-C₂₄-Alkyl oder C₂-C₂₄-Alkenyl, R⁴ C₁-C₂₄-Alkyl oder C₂-C₂₄-Alkenyl, oder R³ und R⁴ zusammen einen Rest -C(R¹⁰)=N-CH₂-CH₂- bedeuten, wobei R¹⁰ Wasserstoff, C₁-C₇-Alkyl oder C₂-C₁₇-Alkenyl ist; weiter R⁵ Wasserstoff, -SH oder C₁-C₂₂-Alkyl, R⁶ Wasserstoff, R⁷ Wasserstoff, oder R⁶ und R⁷ zusammen eine direkte Bindung, R⁸ Wasserstoff oder C₁-C₂₂-Alkyl oder Phenyl oder R⁷ und R⁸ zusammen carbonyl sowie a die Werte 0 oder 1 bis 2 darstellen und
• 2) mindestens einer Verbindung der Formeln III oder IV,
  
  worin X, X¹ und X² unabhängig voneinander Sauerstoff oder Schwefel sind, R¹¹ und R¹² gleich oder verschieden sind und je C₁-C₁₂-Alkyl, das gegebenenfalls durch -O-, -S- oder -C(O)O-unterbrochen ist, unsubstituiertes oder durch C₁-C₁₂-Alkyl substituiertes Phenyl oder Naphthyl; C₅-C₁₂-Cycloalkyl das gegebenenfalls durch C₁-C₄-Alkyl substituiert ist, oder C₇-C₁₃-Aralkyl, ferner n die Zahlen 1, 2 oder 3, n* die Zahlen 1 oder 2, m die Zahlen 1 oder 2, k die Zahlen 1 oder 2 und b die Zahlen 0 oder 1 bedeuten, wobei im Falle von n oder n* gleich 2 oder n zusätzlich gleich 3, die Reste R¹¹ gleich oder verschieden sind oder zwei Reste R¹¹ zusammen mit den zwei Heteroatomen X¹ und dem P-Atom, an das sie gebunden sind, einen 5- oder 6-gliedrigen Ring bilden können;
  weiter worin M ein k-wertiges Metallkation, ein Proton oder eine Verbindung HN^⊕ R¹³R¹⁴R¹⁵ darstellt, wobei R¹³ Wasserstoff oder unsubstituiertes oder durch -OH substituiertes C₁-C₃₀-Alkyl, R¹⁴ Wasserstoff oder C₁-C₃₀-Alkyl und R¹⁵ C₁-C₃₀-Alkyl oder C₁₈-Alkenyl bedeuten oder R¹⁴ und R¹⁵ zusammen einen Rest -C(R¹⁶)=N-CH₂-CH₂- bilden und R¹⁶ Wasserstoff, C₁-C₁₇-Alkyl oder C₂-C₁₇-Alkenyl ist, mit der Massgabe, dass, wenn m gleich 2 und k gleich 1 ist, zwei verschiedene Reste M möglich sind,

mit der Massgabe, dass Zusammensetzungen enthaltend pro Mol an Verbindungen der Formel I 1 oder mehr Mole an Verbindungen der allgemeinen Formel

wobei n eine Zahl von 1 bis 3 und jedes R₈, unabhängig voneinander, eine Alkyl-, Cycloalkyl-, Aryl-, Aralkyl- oder Alkarylgruppe darstellt, ausgeschlossen sind.The present invention relates to a composition containing

• a) one or more lubricants or hydraulic oils based on mineral oil or synthetic oils and
• b) 0.05 to 5 wt .-%, based on the total weight of the lubricant or. Hydraulic oil composition, a mixture of
• 1) at least one compound of the formula I or II,
  
  
  wherein Y is -O-, -S-, -NH- or -NR⁹-, with R⁹ being C₁-C₁₂-alkyl, and Z are -CR⁸- or -N-, furthermore R¹ is hydrogen, C₁-C₁₂-alkyl, C₁- C₄-alkoxy, C₂-C₂₄-alkoxycarbonyl or nitro, R² is hydrogen or unsubstituted or substituted by -OH C₁-C₂₄-alkyl, R³ is hydrogen, C₁-C₂₄-alkyl or C₂-C₂₄-alkenyl, R⁴ C₁-C₂₄-alkyl or C₂ -C₂₄-alkenyl, or R³ and R⁴ together represent a radical -C (R¹⁰) = N-CH₂-CH₂-, where R¹⁰ is hydrogen, C₁-C₇-alkyl or C₂-C₁₇-alkenyl; further R⁵ hydrogen, -SH or C₁-C₂₂-alkyl, R⁶ hydrogen, R⁷ hydrogen, or R⁶ and R⁷ together a direct bond, R⁸ hydrogen or C₁-C₂₂-alkyl or phenyl or R⁷ and R⁸ together carbonyl and a the value 0 or 1 to 2 and
• 2) at least one compound of the formulas III or IV,
  
  wherein X, X¹ and X² are independently oxygen or sulfur, R¹¹ and R¹² are the same or different and each C₁-C₁₂ alkyl, which is optionally interrupted by -O-, -S- or -C (O) O-, unsubstituted or phenyl or naphthyl substituted by C₁-C₁₂ alkyl; C₅-C₁₂-cycloalkyl which is optionally substituted by C₁-C₄-alkyl, or C₇-C₁₃-aralkyl, furthermore n the numbers 1, 2 or 3, n * the numbers 1 or 2, m the numbers 1 or 2, k the Numbers 1 or 2 and b denote the numbers 0 or 1, where in the case of n or n * equal to 2 or n additionally equal to 3, the radicals R¹¹ are identical or different or two R¹¹ radicals together with the two heteroatoms X¹ and the P atom to which they are attached can form a 5- or 6-membered ring;
  further wherein M is a k-valent metal cation, a proton or a compound HN ^⊕ R¹³R¹⁴R¹⁵, where R¹³ is hydrogen or unsubstituted or substituted by -OH C₁-C₃₀-alkyl, R¹⁴ hydrogen or C₁-C₃₀-alkyl and R¹⁵ C₁-C₃₀-alkyl or C₁₈-alkenyl or R¹⁴ and R¹⁵ together form a radical -C (R¹⁶) = N-CH₂-CH₂- and R¹⁶ is hydrogen, C₁-C₁₇-alkyl or C₂-C₁ken-alkenyl, with the proviso that if m is 2 and k is 1, two different radicals M are possible,

with the proviso that compositions containing per mole of compounds of the formula I 1 or more moles of compounds of the general formula

where n is a number from 1 to 3 and each R₈, independently of one another, represents an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group.

Represent R¹, R⁹, R¹¹ and R¹² C₁-C₁₂-alkyl, it is straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert. Butyl, straight chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

Are R¹⁰ and R¹⁶ C₁-C₁₇ alkyl, it is straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl and heptadecyl.

If R⁵ and R⁸ are C₁-C₂₂-alkyl, they are straight-chain or branched alkyl radicals, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl and docosyl.

Are R², R³ and R⁴ C₁-C₂₄-alkyl, it is straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl , straight-chain or branched pentyl, hexyl, heptyl, octyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl tricosyl and tetracosyl.

R¹³, R¹⁴ and R¹⁵ represent C₁-C₃₀-alkyl, so it is straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.- Butyl, straight chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl tricosyl, tetracosyl, pentacyl, pentacyl, pentacyl.

If R² and R¹³ represent hydroxy-substituted alkyl, it is mono- or polysubstituted hydroxy-substituted alkyl, with simple substitution the hydroxyl group preferably being terminal. In particular, it is 2-hydroxyethyl.

R¹¹ and R¹² represent C₁-C₁₂ alkyl which is interrupted by -O-, -S- or -C (O) O-, the hetero atom or the C (O) O group can be in any possible position are located, and the C₁-C₁₂-alkyl radical can be interrupted one or more times, the interruption can be done both by the same or different heteroatoms and by C (O) O groups. An interruption is preferred.

R¹⁰ and R¹⁶ are C₂-C₁₇ alkenyl and R³ and R⁴ C₂-C₂₄ alkenyl are straight-chain or branched alkenyl radicals which contain one or more, but preferably a double bond, such as vinyl, allyl, n-butenyl , 1,3-butadienyl, i-pentenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, 2-nonyl-2-butenyl, tetradecenyl, pentadecenyl, hexadecenyl and 8-heptadecenyl. In addition, R³ and R⁴ as alkenyl can also mean, for example, 2-octadecenyl, oleyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl and tetracosenyl. 8-heptadecenyl and oleyl are preferred.

R¹ as C₁-C₄ alkoxy can e.g. Be methoxy, ethoxy, isopropoxy or n-butoxy.

R¹ as C₂-C₂₄ alkoxycarbonyl contains 1-24 carbon atoms in the alkyl part and can e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or 2-ethylhexyloxycarbonyl.

R¹¹ and R¹² represent phenyl or naphthyl substituted by C₁-C₁₂-alkyl, the phenyl or naphthyl radical can be substituted one or more times, but preferably one to two times; C₁-C₁₂-alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched nonyl or dodecyl.

R¹¹ and R¹² are C₅-C₁₂-cycloalkyl, for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl, preferably cyclohexyl.

R¹¹ and R¹² represent C₅-C₁₂-cycloalkyl substituted by C₁-C₄-alkyl, it can be a single or multiple substitution, but is preferably a simple substitution; such as methylcyclohexyl, trimethylcyclohexyl, butylcyclohexyl or propylcyclopentyl.

R¹¹ and R¹² are C₇-C₁₃ aralkyl, for example benzyl, 1- or 2-phenethyl, 3-phenylpropyl, α, α-dimethylbenzyl, 2-phenylisopropyl, 2-phenylhexyl, benzhydryl or naphthylmethyl, but preferably around benzyl.

If M is a k-valent metal cation, then in the case of k equals 1, it is, for example, Li ^⊕ , Na ^⊕ , K ^⊕ and, in the case of k equals 2, it is, for example, Mg² ^⊕ , Ca² ^⊕ , Ba² ^⊕ , Zn² ^⊕ . However, the preferred metal cation M is Zn² ^⊕ .

A preferably represents the values 0 or 1 to 1.25, but particularly preferably 0 or 1.2.

Compositions are preferred in which in the compounds of the formulas I or II Y is oxygen or sulfur, but in particular sulfur.

Also preferred are compositions in which in the compounds of the formula I R¹ is hydrogen or C₁-C₁₂-alkyl, in particular hydrogen or C₁-C₄-alkyl and very particularly R¹ is hydrogen.

Compositions are further preferred in which, in the compounds of the formula I, R 1 is hydrogen and Y is sulfur.

Also of interest are compositions in which Z in the compounds of the formula II denotes -CR⁸-.

Also of interest are compositions in which R Verbindungen in the compounds of the formula II together with R⁷ mean a direct bond, or in which in the compounds of the formula II R⁵ is hydrogen or —SH, in particular hydrogen.

Also of interest are compositions in which in the compounds of the formulas I or II R² is hydrogen or unsubstituted or -OH-substituted C₁-C₄alkyl, in particular hydrogen or methyl; further those in which in the compounds of the formulas I or II R³ is hydrogen, C₈-C₂₄-alkyl or C₈-C₂₄-alkenyl; or in the compounds of the formulas I or II R⁴ is C₈-C₂₄-alkyl or C₈-C₂₄-alkenyl.

Compositions are particularly interesting in which, in the compounds of the formulas I or II, R² is hydrogen and R³ and R⁴ are, independently of one another, C₈-C₂₄-alkyl or C₈-C₂₄-alkenyl; further those in which in the compounds of the formulas I or II R² and R³ are methyl and R⁴ are C₈-C₂₄-alkyl or C₈-C₂₄-alkenyl; or such wherein in the compounds of the formulas I or II R² and R² are hydrogen and R⁴ C⁴-C₂₄-alkyl or C₈-C₂₄-alkenyl.

The radicals R³ and R⁴ as C₈-C₂₄-alkyl are preferably branched C₈-C₂₄-alkyl radicals, in particular those which contain tert.-C atoms, and particularly preferably those with a tert.-C atom in the α position to the N atom to which they are attached. If, for example, NR²R³R⁴ is a primary amine, preference is given to using mixtures of such amines as are commercially available under the name "Primene". For example, the mixture "Primene®81-R" (mainly branched alkylamines with 12 to 15 C atoms) or the mixture "Primene®JM-T" (mainly branched alkylamines with 18 to 24 C atoms) can be used.

Also of interest are compositions in which in the compounds of the formulas I or II R² is 2-hydroxyethyl and R³ together with R⁴ is a radical —C (R¹⁰) = N-CH₂CH₂-, where R¹⁰ is hydrogen, C₁-C₁₇ alkyl or C₂-C₁₇ -Alkenyl, but preferably C₈-C₁₇-alkyl or C₈-C₁₇-alkenyl.

A further embodiment are compositions in which in the compounds of the formulas III or IV R¹¹ is C₁-C₁₂-alkyl, which is optionally interrupted by -O-, -S- or -C (O) O-, or unsubstituted or by C₁ -C₁₂-alkyl, especially C₈-C₁₂-alkyl, substituted phenyl or naphthyl; Cyclohexyl or benzyl, where R¹¹ is preferably C₃-C₁₂ alkyl, which is optionally interrupted by -C (O) O-, or phenyl or nonylphenyl.

An additional embodiment are compositions in which in the compounds of the formulas III or IV R¹² is C₁-C₁₂-alkyl, which is optionally interrupted by -O-, -S- or -C (O) O-, or unsubstituted or by C₁ -C₁₂-alkyl, especially C₈-C₁₂-alkyl, substituted phenyl or naphthyl; Cyclohexyl or benzyl, where R¹² is preferably C₃-C₁₂ alkyl, which is optionally interrupted by -C (O) O-, or phenyl or nonylphenyl.

Also of interest are compositions in which in the compounds of the formulas III or IV X is oxygen, furthermore those in which in the compounds of the formulas III or IV X¹ and X² are oxygen or those in which in the compounds of the formulas III or IV X and X² is sulfur and X¹ is oxygen.

Also of interest are compositions in which in the compounds of the formula III M denotes a proton, Zn²⁺ or HN ^⊕ (R¹³) (R¹⁴) (R¹⁵).

Of particular interest are compositions in which in the compounds of the formula III X and X² are sulfur, X¹ is oxygen, R¹¹ is C₃-C₈-alkyl, n * = 2, m = 1 and M is Zn²⁺; or those in which in the compounds of the formula III X, X¹ and X² are oxygen, R¹¹ is C₂-C₆-alkyl, n * = 1 or 2, m = 2 or 1, and M in the case of m = 1, HN ^⊕ ( R¹³) (R¹⁴) (R¹⁵), and in the case of m = 2, HN ^⊕ (R¹³) (R¹⁴) (R¹⁵) or a proton, with the proviso that at most one radical M is a proton, preferably R¹³ is hydrogen and R¹⁴ and R¹⁵ are independently C₈-C₂₄ alkyl.

Of additional interest are compositions in which X in the compounds of formulas III or IV is sulfur, furthermore those in which in the compounds of formulas III or IV X is sulfur and X 1 and X 2 are oxygen; or those in which, in the compounds of the formulas III or IV, X is oxygen and X¹ and X² are sulfur.

Also of interest are compositions in which in the compounds of the formula III, R¹³ 2-hydroxyethyl and R¹⁴ together with R¹⁵ represent a radical -C (R¹⁶) = N-CH₂-CH₂-, where R¹⁶ is preferably C₈-C₁₇-alkyl or C₈-C₁₇ -Alkenyl means.

Compositions are preferred in which the mixture b) consists of 1) a compound of the formulas I or II and 2) a compound of the formula III.

Compositions are particularly preferred in which in the compounds of the formulas I or II a has the value 0, Y is sulfur or oxygen, but preferably sulfur, and in formula I R¹ is hydrogen and in the compounds of the formula III X, X¹ and X² are oxygen, R¹¹ C₂-C₆-alkyl, n * the numbers 1 or 2, m the numbers 2 or 1 and M in the case of m = 1, HN ^⊕ (R¹³) (R¹⁴) (R¹⁵) and in the case of m = 2, HN ^⊕ (R¹³) (R¹⁴) (R¹⁵) or a proton, with the proviso that at most one radical M is a proton.

Also particularly preferred are compositions in which in the compounds of the formulas I or II a has the value 1 to 1.25, Y is sulfur or oxygen, but preferably sulfur, and in formula I R¹ is hydrogen and in the compounds of the formula III X and X² is sulfur, X¹ is oxygen, R¹¹ is C₃-C₈alkyl, n * is 2, m is 1 and M is Zn²⁺.

Compositions in which mixture b) consists of 1) a compound of the formula I and 2) a compound of the formula III are very particularly preferred.

Compositions are particularly preferred in which in the compounds of the formula I a has the value 1 to 1.25, Y is sulfur, R¹ is hydrogen, R² is hydrogen, R³ is hydrogen or C₈-C₂₄-alkyl and R⁴ C₈-C₂₄-alkyl and are in the Compounds of the formula III X and X² sulfur, X¹ oxygen, R¹¹ C₃-C₈-alkyl, n * the number 2, m the number 1 and M Zn²⁺.

The components of the mixtures b) which can be used according to the invention are known. The heterocyclic compounds are commercially available or can be easily prepared from commercially available products by generally known methods of organic chemistry. Your amine salts are obtained in the usual way by adding the corresponding amine (salt formation). The amine can also be used in excess (a> 1). The preparation of the phosphorus compounds is described, for example, in Houben-Weyl, "Methods of Organic Chemistry", Volume 12, Part 2, 4th edition, G. Thieme Verlag, Stuttgart 1964, on pages 53-77, 143-210, 226-274, 299-376 and 587-748. Their amine salts are prepared analogously to those of the heterocyclic compounds.

Mixtures b) are prepared by methods known per se, for example by simple mixing. For example, 2-mercaptobenzothiazole can be incorporated into a commercially available amine phosphate (phosphoric acid mono- / diester amine salts).

Mixtures b) are liquid, but of different viscosity. They are excellent as excellent wear protection additives for lubricants and hydraulic oils, preferably for lubricants. The mixtures according to the invention are particularly effective at high temperatures.

wobei n eine Zahl von 1 bis 3 und jedes R₈, unabhängig voneinander, eine Alkyl-, Cycloalkyl-, Aryl-, Aralkyl- oder Alkarylgruppe darstellt, ausgeschlossen sind.The present invention therefore furthermore relates to the use of mixtures of 1) at least one compound of the formulas I or II and 2) at least one compound of the formulas III or IV as wear-reducing additives to lubricants or hydraulic oils, with the proviso that the lubricants or Hydraulic oils containing 1 or more moles of compounds of the general formula per mole of compounds of the formula I

where n is a number from 1 to 3 and each R₈, independently of one another, represents an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group.

Mixtures b) are sufficiently soluble in lubricants and hydraulic oils and are used in a concentration of 0.05 to 5% by weight, preferably in a concentration of 0.1 to 3% by weight, based on the total weight the lubricant or hydraulic oil composition used.

The ratio of 1): 2) is e.g. from 10: 1 to 1:10, preferably from 5: 1 to 1:10, particularly preferably from 2: 1 to 1: 5, in particular from 1: 1 to 1: 3.

The mixtures can be added to the lubricant as such, or the components such as 2-mercaptobenzothiazole-amine salts and the phosphorus compound can be prepared separately and the Lubricants are added separately in the formulation. In the case of highly viscous mixtures, dilution with an appropriate base oil, for example, offers a favorable form of assembly.

The lubricants or hydraulic oils in question are familiar to the person skilled in the art and e.g. in the "Lubricant Paperback" (Hüthig Verlag, Heidelberg, 1974) resp. in "Ullmann's Encyclopedia of Technical Chemistry", vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).

In addition to mineral oils, e.g. Poly-α-olefins, ester-based lubricants, phosphate esters, glycols, polyglycols and polyalkylene glycols.

The lubricants can additionally contain other additives which are added in order to further improve the basic properties of lubricants and hydraulic oils; these include antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, high-pressure additives and other wear protection additives.

Examples of phenolic antioxidants 1. Alkylated monophenols

2,6-di-tert-butyl-4-methylphenol
2,6-di-tert-butylphenol
2-tert-butyl-4,6-dimethylphenol
2,6-di-tert-butyl-4-ethylphenol
2,6-di-tert-butyl-4-n-butylphenol
2,6-di-tert-butyl-4-iso-butylphenol
2,6-di-cyclopentyl-4-methylphenol
2- (α-methylcyclohexyl) -4,6-dimethylphenol
2,6-di-octadecyl-4-methylphenol
2,4,6-tri-cyclohexylphenol
2,6-di-tert-butyl-4-methoxymethylphenol
o-tert-butylphenol

2. Alkylated hydroquinones

2,6-di-tert-butyl-4-methoxyphenol
2,5-di-tert-butyl hydroquinone
2,5-di-tert-amyl hydroquinone
2,6-diphenyl-4-octadecyloxyphenol

3. Hydroxylated thiodiphenyl ether

2,2ʹ-thio-bis- (6-tert-butyl-4-methylphenol)
2,2ʹ-thio-bis- (4-octylphenol)
4,4ʹ-thio-bis- (6-tert-butyl-3-methylphenol)
4,4ʹ-thio-bis- (6-tert-butyl-2-methylphenol)

4. Alkylidene bisphenols

2,2ʹ-methylene-bis- (6-tert-butyl-4-methylphenol)
2,2ʹ-methylene-bis- (6-tert-butyl-4-ethylphenol)
2,2ʹ-methylene-bis- [4-methyl-6- (α-methylcyclohexyl) phenol]
2,2ʹ-methylene-bis- (4-methyl-6-cyclohexylphenol)
2,2ʹ-methylene-bis- (6-nonyl-4-methylphenol)
2,2ʹ-methylene-bis- (4,6-di-tert-butylphenol)
2,2ʹ-ethylidene-bis- (4,6-di-tert-butylphenol)
2,2ʹ-ethylidene-bis- (6-tert-butyl-4-iso-butylphenol)
2,2ʹ-methylene-bis- [6- (α-methylbenzyl) -4-nonylphenol]
2,2ʹ-methylene-bis- [6- (α, α-dimethylbenzyl) -4-nonylphenol]
4,4ʹ-methylene-bis- (2,6-di-tert-butylphenol)
4,4ʹ-methylene-bis- (6-tert-butyl-2-methylphenol)
1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane
2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol
1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercatobutane
Ethylene glycol bis [3,3-bis (3ʹ-tert-butyl-4ʹ-hydroxyphenyl) butyrate]
Di- (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene
Di- [2- (3ʹ-tert-butyl-2ʹ-hydroxy-5ʹ-methyl-benzyl) -6-tert-butyl-4-methyl-phenyl] terephthalate.

5. Benzyl compounds

1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene
Di- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide
3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester
Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate
1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester calcium salt.

6. Acylaminophenols

4-hydroxy lauric anilide
4-hydroxy stearic anilide
2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine
N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.

7. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

with mono- or polyhydric alcohols, such as with

8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid

with mono- or polyhydric alcohols, such as with

9. amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid,

such as
N, Nʹ-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine
N, Nʹ-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine
N, Nʹ-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

Examples of aminic antioxidants:

N, Nʹ-di-isopropyl-p-phenylenediamine
N, Nʹ-di-sec-butyl-p-phenylenediamine
N, Nʹ-bis (1,4-dimethyl-pentyl) -p-phenylenediamine
N, Nʹ-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine
N, Nʹ-bis (1-methyl-heptyl) -p-phenylenediamine
N, Nʹ-diphenyl-p-phenylenediamine
N, Nʹ-di- (naphthyl-2) -p-phenylenediamine
N-isopropyl-Nʹ-phenyl-p-phenylenediamine
N- (1,3-dimethyl-butyl) -Nʹ-phenyl-p-phenylenediamine
N- (1-methyl-heptyl) -Nʹ-phenyl-p-phenylenediamine
N-cyclohexyl-Nʹ-phenyl-p-phenylenediamine
4- (p-toluenesulfonamido) diphenylamine
N, Nʹ-dimethyl-N, Nʹ-di-sec-butyl-p-phenylenediamine
Diphenylamine
4-isopropoxy-diphenylamine
N-phenyl-1-naphthylamine
N-phenyl-2-naphthylamine
octylated diphenylamine
4-n-butylaminophenol
4-butyrylamino-phenol
4-nonanoylamino-phenol
4-dodecanoylamino-phenol
4-octadecanoylamino-phenol
Di- (4-methoxyphenyl) amine
2,6-di-tert-butyl-4-dimethylamino-methyl-phenol
2,4ʹ-diamino-diphenylmethane
4,4ʹ-diamino-diphenylmethane
N, N, Nʹ, Nʹ-tetramethyl-4,4ʹ-diamino-diphenylmethane
1,2-di - [(2-methylphenyl) amino] ethane
1,2-di (phenylamino) propane
(o-tolyl) biguanide
Di- [4- (1ʹ, 3ʹ-dimethylbutyl) phenyl) amine
tert-octylated N-phenyl-1-naphthylamine
Mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines.

Examples of metal passivators are:

for copper, for example:
Triazole, benzotriazole and their derivatives, salicylidene-propylenediamine
Salts of salicylaminoguanidine.

Examples of rust inhibitors are:

• a) Organic acids, their esters, metal salts and anhydrides, for example:
  N-oleoyl-sarcosine, sorbitan mono-oleate, lead naphthenate, dodecenylsuccinic anhydride, alkenylsuccinic acid half-ester, 4-nonylphenoxy-acetic acid.
• b) nitrogen-containing compounds, for example:
  • I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates.
  • II. Heterocyclic compounds, for example:
    Substituted imidazolines and oxazolines.
• c) phosphorus-containing compounds, for example:
  Amine salts of phosphoric acid partial esters.
• d) sulfur-containing compounds, for example:
  Barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates.

Examples of viscosity index improvers are:

Polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polybutenes, olefin copolymers, styrene / acrylate copolymers.

Examples of pour point depressants are:

Polymethacrylate, alkylated naphthalene derivatives.

Examples of dispersants / surfactants are:

Polybutenylsuccinic acid imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.

Examples of wear protection additives are:

Compounds containing sulfur and / or phosphorus and / or halogen, such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphates, chlorinated paraffins, alkyl and aryl disulfides.

In the examples below, parts and percentages are by weight unless otherwise specified.

Examples 1-9:

The amine salts listed in Table 1 below are obtained by combining the corresponding molar proportions of the heterocyclic mercapto compound with an amine.

Examples 10-14: Analogously to Examples 1-9, the mixtures given in Table 2 are obtained by adding a corresponding phosphorus compound to a heterocyclic mercapto compound.

Examples 15-24: The mixtures shown in Table 3 are prepared by adding compounds from Table 1 to phosphorus compounds.

Example 25: The mixtures b) are tested in a Shell 4-ball apparatus in a paraffinic base oil according to DIN 51350 part 3 at various loads. The wear mark diameter WSD (Wear Scar Diameter) serves as a measure of the wear.

Beispiel 26: Die Verschleissschutzwirkung wird mit einem kommerziellen Schwing-Reib-Verschleissgerät (SRV-Gerät) der Firma Optimol GmbH, München bestimmt. (R. Schumacher et al. ASLE Transaction 26, 1(1983), 94-101).

Example 26: The wear protection effect is determined using a commercial vibration-friction wear device (SRV device) from Optimol GmbH, Munich. (R. Schumacher et al. ASLE Transaction 26 , 1 (1983), 94-101).

This device is based on the following principle: A steel ball (100 Cr 6), on which a force F _N acts, oscillates on a steel cylinder. The ball is fixed in a holder and therefore carries out an oscillating sliding movement. The horizontal and vertical force is determined by a piezoelectric force transducer. Under the present test conditions, the maximum Herz normal stress is 2740 N / mm², the maximum shear stress is 850 N / mm². Ball and cylinder are made from the same tool steel.

A few drops of oil, which contains the compound to be examined in solution, are applied between the cylinder and the ball. The following test conditions are chosen:
Load: 200 N, frequency: 50 Hz, amplitude: 1000 µ,
Temperature: 130 ° C-150 ° C, test time: 2 h.
Test oil: Polyalphaolefin ISO VG 100, S content <1.5 ppm.

To characterize the wear, a cross section is recorded with a stylus (Talysurf from Rank Taylor Hobson, Leicester, England). The integrated cross profile surface serves as a measure of wear. The specified values are a relative measure of wear. The true wear value is calculated by multiplying by the factor F = 2 x 10⁻⁴.

Example 27 : Procedure analogous to example 26.
Test temperatures 100 ° C, 120 ° C, 150 ° C

• 0,75 % Zinkdialkyldithiophosphat (ZDTP)
• 11 % Detergens
• 6 % Viskositätsindexverbesserer

Prüföl II :   Prüföl I + 0,5 % Beispiel 3 Prüföl II enthält somit als Gemisch b) Beispiel 34

Example 28 : Carried out analogously to example 26.
Test temperatures 130 ° C-150 ° C.
Test oil I: Paraffin-based base oil ISO VG 32 with commercially available additives

• 0.75% zinc dialkyldithiophosphate (ZDTP)
• 11% detergent
• 6% viscosity index improver

Test oil II: Test oil I + 0.5% Example 3 Test oil II thus contains mixture b) Example 34

Claims (18)

1. A composition comprising

   a) one or more lubricants or hydraulic oils based on mineral oil or synthetic oils and

   b) 0.05 to 5% by weight, relative to the total weight of the lubricant composition or hydraulic oil composition, of a mixture of

   1) at least one compound of the formula I or II

   

   in which Y is -O-, -S-, -NH- or NR⁹, with R⁹ being C₁-C₁₂alkyl, Z is -CR⁸- or -N- and R¹ is hydrogen, C₁-C₁₂alkyl, C₁-C₄alkoxy, C₂-C₂₄-alkoxycarbonyl or nitro, R² is hydrogen or unsubstituted or OH-substituted C₁-C₂₄alkyl, R³ is hydrogen, C₁-C₂₄alkyl or C₂-C₂₄alkenyl, R⁴ is C₁-C₂₄alkyl or C₂-C₂₄alkenyl, or R³ and R⁴ together are a -C(R¹⁰)=N-CH₂-CH₂- radical, with R¹⁰ being hydrogen, C₁-C₁₇alkyl or C₂-C₁₇alkenyl, and R⁵ is hydrogen, -SH or C₁-C₂₂alkyl, R⁶ is hydrogen, R⁷ is hydrogen or R⁶ and R⁷ together are a direct bond, R⁸ is hydrogen or C₁-C₂₂alkyl or phenyl, or R⁷ and R⁸ together are carbonyl and a has the value 0 or 1 to 2, and

   2) at least one compound of the formulae III or IV

   

   in which X, X¹ and X² independently of one another are oxygen or sulfur, R¹¹ and R¹² are identical or different and are each C₁-C₁₂alkyl which may be interrupted by -O-, -S- or -C(O)O-, unsubstituted or C₁-C₁₂alky1-substituted phenyl or naphthyl, unsubstituted or C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl or C₇-C₁₃aralkyl, and n is the number 1, 2 or 3, n^* is the number 1 or 2, m is the number 1 or 2, k is the number 1 or 2 and b is the number 0 or 1, and, in the case of n or n^* being 2 or also n being 3, the radicals R¹¹ are identical or different or two radicals R¹¹ are identical or different or two radicals R¹¹ can, together with the two heteroatoms X¹ and the P atom to which they are linked, form a 5-membered or 6-membered ring,
   and in which M is a k-valent metal cation, a proton or a compound HN^⊕R¹³R¹⁴R¹⁵, R¹³ being hydrogen or unsubstituted or OH-substituted C₁-C₃₀-alkyl, R¹⁴ being hydrogen or C₁-C₃₀alkyl and R¹⁵ together forming a -C(R¹⁶)=N-CH₂-CH₂- radical and R¹⁶ being hydrogen, G₁-C₁₇alkyl or C₂-6₁₇-alkenyl, with the proviso that, if m is 2 and k is 1, two different radicals M are possible, with the proviso that a composition containing, per mole of a compound of the formula I, 1 or more moles of a compound of the general formula

   

   where n is a number from 1 to 3 and each R₈, independently of the other, is an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group, is excluded.
2. A composition according to claim 1, wherein, in the formula I, R¹ is hydrogen and Y is -S-.
3. A composition according to claim 1, wherein, in the formula II, R⁶ together with R⁷ is a direct bond.
4. A composition according to claim 1, wherein, in the formulae I or II, R² is hydrogen or unsubstituted or OH-substituted C₁-C₄alkyl.
5. A composition according to claim 1, wherein, in the formulae I or II, R² is hydrogen and R³ and R⁴ independently of one another are each C₈-C₂₄alkyl or C₈-C₂₄alkenyl.
6. A composition according to claim 1, wherein, in the formulae I or II, R² and R³ are hydrogen and R⁴ is C₈-C₂₄alkyl or C₈-C₂₄alkenyl.
7. A composition according to claim 1, wherein, in the formulae I or II, R² is 2-hydroxyethyl and R³ together with R⁴ is a -C(R¹⁰)=N-CH₂-CH₂-radical.
8. A composition according to claim 1, wherein, in the formulae III or IV, R¹¹ is C₁-C₁₂alkyl which may be interrupted by -O-, -S- or -C(O)O-, or unsubstituted or C₁-C₁₂alkyl-substituted phenyl or naphthyl, or cyclohexyl or benzyl.
9. A composition according to claim 1, wherein, in the formulae III or IV, R¹² is C₁-C₁₂alkyl which may be interrupted by -O-, -S- or -C(O)O-, or unsubstituted or C₁-C₁₂alkyl-substituted phenyl or naphthyl, or cyclohexyl or benzyl.
10. A composition according to claim 1, wherein, in the formula III, M is a proton, Zn²⁺ or HN^⊕(R¹³)(R¹⁴)(R¹⁵).
11. A composition according to claim 1, wherein, in the formula III, X and X² are sulfur, X¹ is oxygen, R¹¹ is C₃-C₈alkyl, n^* is 2, m is 1 and M is Zn²⁺.
12. A composition according to claim 1, wherein, in the formula III, X, X¹ and X² are oxygen, R¹¹ is C₂-C₆alkyl, n^* is 1 or 2, m is 2 or 1 and M, in the case of m = 1, is HN^⊕(R¹³)(R¹⁴)(R¹⁵) and, in the case of m = 2, is HN^⊕(R¹³)(R¹⁴)(R¹⁵) or a proton, with the proviso that at most one radical M is a proton.
13. A composition according to claim 1, wherein the mixture b) consists of 1) one compound of the formulae I or II and 2) one compound of the formula III.
14. A composition according to claim 13, wherein, in the compounds of the formulae I or II, a has the value 0, Y is sulfur or oxygen and, in the formula I, R¹ is hydrogen and, in the compounds of the formula III, X, X¹ and X² are oxygen, R¹¹ is C₂-C₆alkyl, n^* is the number 1 or 2, m is the number 2 or 1 and M, in the case of m = 1, is HN^⊕(R¹³)(R¹⁴)(R¹⁵) and, in the case of m = 2, is HN^⊕(R¹³)(R¹⁴)(R¹⁵), or a proton with the proviso that at most one radical M is a proton.
15. A composition according to claim 13, wherein, in the compounds of the formulae I or II, a has the value 1 to 1.25, Y is sulfur or oxygen and, in the formula I, R¹ is hydrogen, and, in the compounds of the formula III, X and X² are sulfur, X¹ is oxygen, R¹¹ is C₃-C₈alkyl, n^* is the number 2, m is the number 1 and M is Zn²⁺.
16. A composition according to claim 1, wherein the mixture b) consists of 1) one compound of the formula I and 2) one compound of the formula III.
17. A composition according to claim 16, wherein, in the compounds of the formula I, a has the value 1 to 1.25, Y is sulfur, R¹ is hydrogen, R² is hydrogen, R³ is hydrogen or C₈-C₂₄alkyl and R⁴ is C₈-C₂₄_,alkyl and, in the compounds of the formula III, X and X² are sulfur, X¹ is oxygen, R¹¹ is C₃-C₈alkyl, n^* is the number 2, m is the number 1 and M is Zn²⁺.
18. Use of a mixture of 1) at least one compound of the formulae I or II and 2) at least one compound of the formulae III or IV, according to claim 1, as wear-reducing additives to lubricants or hydraulic oils, with the proviso that lubricants or hydraulic oils containing, per mole of a compound of the formula I, 1 or more moles of a compound of the general formula

    

    where n is a number from 1 to 3 and each R₈, independently of the other, is an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group, is excluded.