EP0819754A1 - Beta-dithiophosphorilated propionic acid in lubricants - Google Patents

Abstract

Composition comprises: (A) a lubricant or fuel, metal processing fluid or hydraulic fluid; (B) a compound of formula (I) (where, R1 and R2 = 3-18C alkyl, 5-12C cycloalkyl, 5-6C cycloalkylmethyl, 9-10C bicycloalkylmethyl, 9-10C tricycloalkylmethyl, phenyl, 7-24C alkylphenol or together are a group of formula (CH3)2C(CH2)2; and R3 = H or methyl; and optionally (C) further usual additives. Also claimed is a process for improving the properties of lubricants, hydraulic fluids or metal processing fluids by adding the above composition (I).

Description

The present invention relates to compositions which contain a lubricant (preferably an industrial oil or a fat), a metal working or a hydraulic fluid and at least one β-dithiophosphorylated propionic acid of the formula I described below.

sind unter dem Handelsnamen lrgalube™ 63 erhältlich. Ferner sind in US 4,333,841 dithiophosphorylierte Mercaptoessigsäuren und deren Salze als Schmierstoffzusätze beschrieben.Additives are added to modern lubricants, which perform tasks such as high-pressure and wear protection, corrosion protection and antioxidation effects [WJ Bartz (Editor), et al., "Additives for lubricants" (expert-Verlag 1994)]. Zinc dialkyldithiophosphates, which combine antioxidative and high-pressure and wear protection effects, are of particular importance. In recent times, efforts have been made to largely replace these heavy metal additives with metal-free compounds, because this is environmentally friendly and has a positive effect on the service life of the exhaust gas catalysts of internal combustion engines. There is currently a need in the industry for metal-free and ash-free additives. Type of ester:

are available under the trade name lrgalube ™ 63. Furthermore, US 4,333,841 dithiophosphorylated mercaptoacetic acids and their salts are described as lubricant additives.

Bis-dithiophosphoric acid derivatives are described in GB-A 2'267'493 as lubricant additives. For the same application, EP-A 98,809 [CA 101: 55323 s] salts of the formula (RO) ₂ P (S) S (CH ₂ ) _n (C (O) OM, M = Li, K, Na, HNR, US-A 5,362,419 describes as intermediates acids of the formula (RO) ₂ P (S) S (CH ₂ ) ₂ C (O) OH for the production of glycol esters suitable as lubricant additives, such as (RO) ₂ P (S) ( CH ₂ ) ₂ C (O) OCH ₂ (CHOH) CH ₂ OH (see also H. Zinke, R. Schumacher, Wear 179 (1-2) (1994) 45-8 [CA 122: 85158 t]).

Surprisingly, it was found that the β-dithiophosphorylated propionic acids on which the above-mentioned propionic acid esters are based, even at very low concentrations, are excellent high-pressure and wear protection agents.

• A) einen Schmier- oder Kraftstoff, eine Metallbearbeitungs- oder eine Hydraulikflüssigkeit, insbesondere ein Industrieöl oder ein Fett, vor allem ein Grundöl aus der Gruppe der mineralischen, pflanzlichen oder synthetischen (wie z.B. Poly-α-olefin- oder Esteröle) Öle;
• B) mindestens eine Verbindung der Formel
  
  worin
  • R₁ und R₂ unabhängig voneinander C₃-C₁₈-Alkyl, C₅-C₁₂-Cycloalkyl, C₅-C₆-Cycloalkylmethyl, C₉-C₁₀-Bicycloalkylmethyl, C₉-C₁₀-Tricycloalkylmethyl, Phenyl, C₇-C₂₄ Alkylphenyl oder zusammen (CH₃)₂C(CH₂)₂ bedeuten, und
  • R₃ Wasserstoff oder Methyl ist, und gegebenenfalls
• C) weitere übliche Öladditive, z.B. aus den Gruppen der Antioxidantien, Metall-Desaktivatoren, Rost-Inhibitoren, Dispergatoren, Detergentien, Viskositätsindexverbesserer, Stockpunkterniedriger und weiteren Verschleißschutzadditive.

The invention therefore relates to compositions (preferably free of zinc and ash) containing

• A) a lubricant or fuel, a metalworking or a hydraulic fluid, in particular an industrial oil or a fat, especially a base oil from the group of mineral, vegetable or synthetic (such as poly-α-olefin or ester oils) oils;
• B) at least one compound of the formula
  
  wherein
  • R ₁ and R ₂ independently of one another are C ₃ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₅ -C ₆ cycloalkylmethyl, C ₉ -C ₁₀ bicycloalkylmethyl, C ₉ -C ₁₀ tricycloalkylmethyl, phenyl, C ₇ -C ₂₄ alkylphenyl or together mean (CH ₃ ) ₂ C (CH ₂ ) ₂ , and
  • R _{3 is} hydrogen or methyl, and optionally
• C) further customary oil additives, for example from the groups of antioxidants, metal deactivators, rust inhibitors, dispersants, detergents, viscosity index improvers, pour point depressants and other wear protection additives.

In component B), R ₁ and R _{2 are,} independently of one another, C ₃ -C ₁₈ alkyl, C ₅ -C ₆ cycloalkyl or C ₇ -C ₁₈ alkylphenyl.

Component B) R ₁ and R ₂ are particularly preferably i-propyl, i-butyl or 2-ethylhexyl, and R _{3 is} hydrogen.

If IR ₁ and R _{2 are} C ₃ -C ₁₈ -alkyl in the above formula, these are branched or unbranched radicals. Examples include propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl , Heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trimethylhexyl or 1-methylundecyl .

R ₁ and R ₂ as C ₅ -C ₁₂ cycloalkyl can be, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. Cyclopentyl and cyclohexyl are preferred, especially cyclohexyl.

If R ₁ and R _{2 are} C ₅ -C ₆ -cycloalkyl-methyl, this means cyclopentylmethyl and especially cyclohexylmethyl.

If R ₁ and R _{2 are} C ₅ -C ₆ -cycloalkyl-methyl, this means cyclopentylmethyl and especially cyclohexylmethyl.

R ₁ and R _{2 are,} for example, decalinylmethyl as C ₉ -C ₁₀ bicycloalkylmethyl. As C ₉ -C ₁₀ tricycloalkylmethyl, R ₁ and R ₂ preferably have the meaning of a group of the formula

Examples of alkylphenyl are methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, isopropylphenyl, t-butylphenyl, di-t-butylphenyl or 2,6 di-t-butyl-4-methylphenyl.

The invention also relates to the use of component B) as additives in lubricants (industrial oils or greases), hydraulic or metalworking fluids, preferably in hydraulic and gear oils. The use according to the invention includes the protection of the metal parts to be lubricated against mechanical wear (high pressure and wear protection) and an anti-corrosion effect. The present invention therefore also relates to a process for improving the performance properties of lubricants, metalworking and hydraulic fluids, characterized in that compounds of the formula I are added to these.

The lubricants or fuels mentioned (such as industrial oils and greases), metalworking and hydraulic fluids of component A) are based, for example, on mineral or synthetic oils or mixtures thereof. The lubricants are familiar to the person skilled in the art and are found in the relevant specialist literature, for example in Dieter Klamann, "Lubricants and Related Products" (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, "The Lubricant Pocket Book" (Dr. Alfred Hüthig- Verlag, Heidelberg, 1974) and in "Ullmann's Encyclopedia of Technical Chemistry", Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).

The lubricants are in particular oils and fats, for example based on a mineral oil. Oils are preferred.

Another group of lubricants that can be used are vegetable or animal oils, fats, tallow and waxes or their mixtures with one another or mixtures with the mineral or synthetic oils mentioned. Vegetable and animal oils, fats, tallow and waxes are for example Tree nut oil and mixtures thereof, fish oils, tallow from slaughter animals such as beef tallow, claw fat and bone oil and their modified, epoxidized and sulfoxidized forms, for example epoxidized soybean oil. The mineral oils are based in particular on hydrocarbon compounds.

Examples of synthetic lubricants include lubricants based on the aliphatic or aromatic carboxyl esters, the polymeric esters, the polyalkylene oxides, the phosphoric acid esters, the poly-α-olefins or the silicones, a diester of a dibasic acid with a monohydric alcohol, e.g. Dioctyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monohydric acid or with a mixture of such acids, e.g. Trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, a tetraester of pentaerythritol with a monovalent acid or with a mixture of such acids, e.g. Pentaerythritol tetracaprylate, or a complex ester of monohydric and dihydric acids with polyhydric alcohols, e.g. a complex ester of trimethylolpropane with caprylic and sebacic acid or a mixture thereof. In addition to mineral oils, e.g. Poly-α-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene glycols, and mixtures thereof with water.

Industrial oils, greases, metalworking fluids and hydraulic fluids can be produced on the basis of the same substances as described above for the lubricants. Often these are emulsions of such substances in water or other liquids.

Lubricant compositions according to the invention find e.g. Use in internal combustion engines, e.g. in motor vehicles, e.g. with engines of the Otto, Diesel, two-stroke, Wankel or orbital type.

Component B is also suitable as an additive for fuels in motor vehicles which are equipped with the engines of the type mentioned.

The compounds of the formula I are readily soluble in lubricants, fuels, metalworking and hydraulic fluids and are therefore particularly suitable as additives to lubricants, metalworking and hydraulic fluids.

The compositions advantageously contain 0.005 to 1.0% by weight of a compound of the formula I, preferably 0.005-0.1% by weight, in particular 0.005-0.05% by weight.

The compositions advantageously contain 0.005 to 1.0% by weight of a compound of the formula I, preferably 0.005-0.1% by weight, in particular 0.005-0.05% by weight.

The compounds of the formula I can be added to the lubricants or fuels in a manner known per se. The compounds are readily soluble in oils, for example. It is also possible to produce a so-called master batch, which can be diluted with the appropriate lubricant to the required concentration depending on the consumption. In such cases, concentrations above 1% by weight are also possible.

The lubricants or fuels, metalworking and hydraulic fluids stabilized according to the invention can additionally contain other additives which are added in order to further improve their basic properties; these include: antioxidants, metal passivators, other rust inhibitors, viscosity index improvers, pour point depressants, solid lubricants, dispersants, detergents, anti-foaming agents, other high-pressure additives, anti-wear additives and friction coefficient reducers. Such additives are added in the amounts customary for this in the range from about 0.01 to 10.0% by weight.

The following are examples of such other additives:

• 1.1. Alkylierte Monophenole, z.B. 2,6-Di-tert-butyl-4-methylphenol, 2-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-(a-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Di-octadecyl-4-methylphenol, 2,4,6-Tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethylphenol, lineare oder in der Seitenkette verzweigte Nonylphenole wie z.B. 2,6-Di-nonyl-4-methylphenol, 2,4-Dimethyl-6-(1'-methyl-undec-1'-yl)-phenol, 2,4-Dimethyl-6-(1'-methyl-heptadec-1'-yl)-phenol, 2,4-Dimethyl-6-(1'-methyl-tridec-1'-yl)-phenol und Mischungen davon.
• 1.2. Alkylthiomethylphenole, z.B. 2,4-Di-octylthiomethyl-6-tert-butylphenol, 2,4-Di-octylthiomethyl-6-methylphenol, 2,4-Di-octylthiomethyl-6-ethylphenol, 2,6-Di-dodecylthiomethyl-4-nonylphenol.
• 1.3. Hydrochinone und alkylierte Hydrochinone, z.B. 2,6-Di-tert-butyl-4-methoxyphenol, 2,5-Di-tert-butyl-hydrochinon, 2,5-Di-tert-amyl-hydrochinon, 2,6-Diphenyl-4-octadecyloxyphenol, 2,6-Di-tert-butyl-hydrochinon, 2,5-Di-tert-butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4-hydroxyphenylstearat, Bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipat.
• 1.4. Tocopherole, z.B. α,-β,-γ,- oder δ-Tocopherol und Mischungen davon (Vitamin E).
• 1.5. Hydroxylierte Thiodiphenylether, z.B. 2,2'-Thio-bis(6-tert-butyl-4-methylphenol), 2,2'-Thio-bis(4-octylphenol), 4,4'-Thio-bis(6-tert-butyl-3-methylphenol), 4,4'-Thio-bis-(6-tert-butyl-2-methylphenol), 4,4'-Thio-bis(3,6-di-sec.-amylphenol), 4,4'-Bis(2,6-dimethyl-4-hydroxyphenyl)-disulfid.
• 1.6. Alkyliden-Bisphenole, z.B. 2,2'-Methylen-bis(6-tert-butyl-4-methylphenol), 2,2'-Methylen-bis(6-tert-butyl-4-ethylphenol), 2,2'-Methylen-bis[4-methyl-6-(a-methylcyclohexyl)-phenol], 2,2'-Methylen-bis(4-methyl-6-cyclohexylphenol), 2,2'-Methylen-bis(6-nonyl-4-methylphenol), 2,2'-Methylen-bis(4,6-di-tert-butylphenol), 2,2'-Ethyliden-bis(4,6-di-tert-butylphenol), 2,2'-Ethyliden-bis(6-tert-butyl-4-isobutylphenol), 2,2'-Methylen-bis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-Methylen-bis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylen-bis(2,6-di-tert-butylphenol), 4,4'-Methylen-bis(6-tert-butyl-2-methylphenol), 1,1,1-Bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-butan, 2,6-Bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-butan, 1,1-Bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)-butyrat], Bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)-dicyclopentadien, Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methyl-phenyl]-terephthalat, 1,1-Bis(3,5-dimethyl-2-hydroxyphenyl)-butan, 2,2-Bis(3,5-di-tert-butyl-4-hydroxyphenyl)-propan, 2,2-Bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butan, 1,1,5,5-Tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)-pentan.
• 1.7. O-, N- und S-Benzylverbindungen, z.B. 3,5,3',5'-Tetra-tert-butyl-4,4'-dihydroxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetat, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl-mercaptoacetat, Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-amin, Bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthalat, Bis(3,5-di-tert-butyl-4-hydroxybenzyl)-sulfid, lsooctyl-3,5-di-tert-butyl-4-hyd roxybenzyl-mercaptoacetat.
• 1.8. Hydroxybenzylierte Malonate, z.B. Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-malonat, Di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonat, Di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-malonat, Di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-malonat.
• 1.10. Triazinverbindungen, z.B. 2,4-Bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1,2,3-triazin,1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurat, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurat, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazin, 1,3,5-Tris(3,5-dicyclohexyl-4-hydroxybenzyl)-isocyanurat.
• 1.11.Benzylphosphonate, z.B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonat, Diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonat, Ca-Salz des 3,5-Di-tert-butyl-4-hydroxybenzylphosphonsäure-monoethylesters.
• 1.12.Acylaminophenole, z.B. 4-Hydroxy-laurinsäureanilid, 4-Hydroxystearinsäureanilid, N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbaminsäureoctylester.
• 1.13.Ester der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionsäure, β-(5-tert-Butyl-4-hydroxy-3-methylphenyl)-propionsäure, β-(3,5-Dicyclohexyl-4-hydroxyphenyl)-propionsäure, 3,5-Di-tert-butyl-4-hvdroxyphenylessigsäure oder β-(5-tert-Butyl-4-hydroxyphenyl)-3-thia-buttersäure mit ein- oder mehrwertigen Alkoholen, wie z.B. mit Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythrit, Tris(hydroxyethyl)-isocyanurat, N,N'-Bis(hydroxyethyl)-oxalsäurediamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-tri-oxabicyclo-[2.2.2]-octan, Glycerin und Umesterungsprodukten auf der Basis natürlicher Triglyceride aus z.B. Kokosfett, Rapsöl, Sonnenblumenöl oder Rüböl.
• 1.14.Amide der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionsäure, wie z.B. N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylendiamin, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylendiamin, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazin.
• 1.15.Ascorbinsäure (Vitamin C).
• 1.16.Aminische Antioxidantien, wie z.B. N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethyl-pentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methyl-pentyl)-p-phenylendiamin, N,N'-Bis(1-methyl-heptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'-Di-(naphthyl-2)-p-phenylendiamin, N-lsopropyl-N'-phenyl-pphenylendiamin, N-(1,3-Dimethyl-butyl)-N'-phenyl-p-phenylendiamin,N-(1-Methylheptyl)-N'-phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p-Toluol-sulfonamido)-diphenylamin, N,N'-Dimethyl-N,N'-di-sec-butyl-p-phenylendiamin, Diphenylamin, N-Allyldiphenylamin, 4-lsopropoxy-diphenylamin, N-Phenyl-1-naphthylamin, N-(4-tert-Octylphenyl)-1-naphthylamin, N-Phenyl-2-naphthylamin, octyliertes Diphenylamin, z.B. p,p'-Di-tert-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylamino-phenol, 4-Nonanoylamino-phenol, 4-Dodecanoylam ino-phenol, 4-Octadecanoylam ino-phenol, Di-(4-methoxyphenyl)-amin, 2,6-Di-tert-butyl-4-dimethylamino-methyl-phenol, 2,4'-Diaminodiphenylmethan, 4,4'-Diamino-diphenylmethan, N,N,N',N'-Tetramethyl-4,4'-diaminodiphenylmethan, 1,2-Di-[(2-methyl-phenyl)-amino]-ethan, 1,2-Di-(phenylamino)-propan, (o-Tolyl)-biguanid, Di-[4-(1',3'-dimethyl-butyl)-phenyl]amin, tert-octyliertes N-Phenyl-1-naphthylamin, Gemisch aus mono- und dialkylierten tert-Butyl/tert-Octyldiphenylaminen, Gemisch aus mono- und dialkylierten Nonyldiphenylaminen, Gemisch aus mono- und dialkylierten Dodecyldiphenylaminen, Gemisch aus mono- und dialkylierten Isopropyl/lsohexyl-diphenylaminen, Gemische aus mono- und dialkylierten tert-Butyldiphenylaminen, 2,3-Dihydro-3,3-dimethyl-4H-1,4-benzothiazin, Phenothiazin, Gemisch aus mono- und dialkylierten tert-Butyl/tert-Octylphenothiazinen, Gemisch aus mono- und dialkylierten tert-Octyl-phenothiazinen, N-Allylphenothiazin, N,N,N',N'-Tetraphenyl-1,4-diaminobut-2-en, N,N-Bis-(2,2,6,6-tetramethyl-piperidin-4-yl)-hexamethylendiamin, Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-sebacat, 2,2,6,6-Tetramethylpiperidin-4-on, 2,2,6,6-Tetramethylpiperidin-4-ol. Beispiele für weitere Antioxidantien:

Examples of phenolic antioxidants:

• 1.1. Alkylated monophenols , e.g. 2,6-di-tert-butyl-4-methylphenol, 2-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- (a-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as 2,6-di-nonyl, for example -4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) phenol and mixtures thereof.
• 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4 -nonylphenol.
• 1.3. Hydroquinones and alkylated hydroquinones , for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl- 4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di- tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
• 1.4. Tocopherols , e.g. α, -β, -γ, - or δ-tocopherol and mixtures thereof (vitamin E).
• 1.5. Hydroxylated thiodiphenyl ethers , for example 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio-bis (6-tert -butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec.-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
• 1.6. Alkylidene bisphenols , for example 2,2'-methylene-bis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (6-tert-butyl-4-ethylphenol), 2,2'- Methylene bis [4-methyl-6- (a-methylcyclohexyl) phenol], 2,2'-methylene bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene bis (6-nonyl- 4-methylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'- Ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis [6- (a , a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-methylene-bis (6-tert-butyl-2-methylphenol) , 1,1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol , 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3 -n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) - dicyclopentadiene, bis [2- ( 3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl ) -butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4- n-dodecylmercapto-butane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
• 1.7. O-, N- and S-benzyl compounds , for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tridecyl- 4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6) -dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hyd roxybenzyl-mercaptoacetate.
• 1.8. Hydroxybenzylated malonates , e.g. dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate, di- [4- (1,1,3,3-tetramethylbutyl) phenyl] - 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
• 1.10. Triazine compounds , e.g. 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5 -di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5 -triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) - 1,2,3-triazine, 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, 2,4,6-tris (3,5-di- tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
• 1.11.Benzylphosphonates , e.g. dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4 -hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Ca salt of the 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.
• 1.12. Acylaminophenols , for example 4-hydroxylauric anilide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.
• 1.13. Ester of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, β- (3,5 -Dicyclohexyl-4-hydroxyphenyl) propionic acid, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid or β- (5-tert-butyl-4-hydroxyphenyl) -3-thia-butyric acid with mono- or polyhydric alcohols, such as with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl ) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-tri-oxabicyclo- [2.2.2 ] octane, glycerin and transesterification products based on natural triglycerides from, for example, coconut oil, rapeseed oil, sunflower oil or rapeseed oil.
• 1.14. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , such as, for example, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
• 1.15. Ascorbic acid (vitamin C).
• 1.16. Aminic antioxidants , such as, for example, N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di- (naphthyl-2) -p-phenylenediamine, N-isopropyl-N'-phenyl-pphenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine , 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl -1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4- Butyrylamino-phenol, 4-Nonanoylamino-phenol, 4-Dodecanoylam ino-phenol, 4-Octadecanoylam ino-phenol, Di- (4-methoxyphenyl) -amine, 2,6-Di-tert-butyl-4-dimethylamino-methyl- phenol, 2,4'-diaminodiphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di - [(2-methylphenyl ) -amino] -ethane, 1,2-di- (phenylamino) -propane, (o-tolyl) -biguanide, di- [4- (1 ', 3'-dimet hyl-butyl) -phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenylamines, Mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N- Bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6- Tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. Examples of other antioxidants:

Aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamide or dithiophosphoric acid, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,11-trithiatridecane and 2,2,15, 15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane.

• a) Benztriazole und deren Derivate, z.B. 4- oder 5-Alkylbenztriazole (z.B. Tolutriazol) und deren Derivate, 4,5,6,7-Tetrahydrobenztriazol, 5,5'-Methylen-bis-benztriazol; Mannich-Basen von Benztriazol oder Tolutriazol wie 1-[Di-(2-ethylhexyl)aminomethyl)]-tolutriazol und 1-[Di(2-ethylhexyl)aminomethyl)]-benztriazol; Alkoxyalkylbentriazole wie 1-(Nonyloxymethyl)-benztriazol, 1-(1-Butoxyethyl)-bentriazol und 1-(1-Cyclohexyloxybutyl)-tolutriazol.
• b) 1,2,4-Triazole und deren Derivate, z.B. 3-Alkyl (oder Aryl)- 1,2,4-Triazole, Mannich-Basen von 1,2,4-Triazolenwie 1-[Di(2-ethylhexyl)aminomethyl]-1,2,4--triazol; Alkoxyalkyl-1,2,4-triazole wie 1-(1-Butoxyethyl)-1,2,4-triazol; acylierte 3-Amino-1,2,4-triazole.
• c) Imidazolderivate, z.B. 4,4'-Methylenbis(2-undecyl-5-methylimidazol), Bis[(N-methyl)imidazol-2-yl]carbinol-octylether.
• d) Schwefelhaltige heterocyclische Verbindungen, z.B. 2-Mercaptobenzthiazol, 2,5-Dimercapto-1,3,4-thiadiazol, 2,5-Dimercaptobenzthiadiazol und deren Derivate; 3,5-Bis[di(2-ethylhexyl)am ino-methyl]-1,3,4-thiadiazolin-2-on.
• e) Aminoverbindungen, z.B. Salicyliden-propylendiamin, Salicylaminoguanidin und deren Salze.

Examples of metal deactivators, for example for copper, are:

• a) benzotriazoles and their derivatives, for example 4- or 5-alkylbenzotriazoles (for example tolutriazole) and their derivatives, 4,5,6,7-tetrahydrobenzotriazole, 5,5'-methylene-bis-benzotriazole; Mannich bases of benzotriazole or tolutriazole such as 1- [di (2-ethylhexyl) aminomethyl)] tolutriazole and 1- [di (2-ethylhexyl) aminomethyl)] benzotriazole; Alkoxyalkyl bentriazoles such as 1- (nonyloxymethyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1- (1-cyclohexyloxybutyl) tolutriazole.
• b) 1,2,4-triazoles and their derivatives, for example 3-alkyl (or aryl) -1,2,4-triazoles, Mannich bases of 1,2,4-triazoles such as 1- [di (2-ethylhexyl) aminomethyl] -1,2,4-triazole; Alkoxyalkyl-1,2,4-triazoles such as 1- (1-butoxyethyl) -1,2,4-triazole; acylated 3-amino-1,2,4-triazoles.
• c) Imidazole derivatives, for example 4,4'-methylenebis (2-undecyl-5-methylimidazole), bis [(N-methyl) imidazol-2-yl] carbinol octyl ether.
• d) sulfur-containing heterocyclic compounds, for example 2-mercaptobenzthiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercaptobenzthiadiazole and their derivatives; 3,5-bis [di (2-ethylhexyl) amo-methyl] -1,3,4-thiadiazolin-2-one.
• e) amino compounds, for example salicylidene-propylenediamine, salicylaminoguanidine and their salts.

• a) Organische Säuren, ihre Ester, Metallsalze, Aminsalze und Anhydride, z.B. Alkyl- und Alkenyl-bernsteinsäuren und deren Partialester mit Alkoholen, Diolen oder Hydroxycarbonsäuren, Partialamide von Alkyl- und Alkenylbernsteinsäuren, 4-Nonylphenoxyessigsäure, Alkoxy- und Alkoxyethoxycarbonsäuren wie Dodecyloxyessigsäure, Dodecyloxy(ethoxy)-essigsäure und deren Aminsalze, ferner N-Oleoylsarcosin, Sorbitan-mono-oleat, Blei-naphthenat, Alkenylbernsteinsäureanhydride, z.B. Dodecenylbernsteinsäure-anhydrid, 2-(2-Carboxyethyl)-1-dodecyl-3-methylglycerin und dessen Salze, insbesondere Na- und Triethanolaminsalze.
• b) Stickstoffhaltige Verbindungen, z.B.:
  • i. Primäre, sekundäre oder tertiäre aliphatische oder cycloaliphatische Amine und Amin-Salze von organischen und anorganischen Säuren, z.B. öllösliche Alkylammoniumcarboxylate, ferner 1-[N,N-bis-(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.
  • ii. Heterocyclische Verbindungen, z.B.: Substituierte Imidazoline und Oxazoline, 2-Heptadecenyl-1-(2-hydroxyethyl)-imidazolin.
• c) Phosphorhaltige Verbindungen, z.B.
  Aminsalze von Phosphorsäurepartialestern oder Phosphonsäurepartialestern, Zinkdialkyldithiophosphate.
• d) Schwefelhaltige Verbindungen, z.B.: Barium-dinonylnaphthalin-sulfonate, Calciumpetroleum-sulfonate, Alkylthio-substituierte aliphatische Carbonsäuren, Ester von aliphatischen 2-Sulfocarbonsäuren und deren Salze.
• e) Glycerinderivate, z.B.: Glycerin-monooleat, 1-(Alkylphenoxy)-3-(2-hydroxyethyl)glycerine, 1-(Alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerine, 2-Carboxyalkyl-1,3-dialkylglycerine.

Examples of rust inhibitors are:

• a) Organic acids, their esters, metal salts, amine salts and anhydrides, for example alkyl and alkenyl succinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl and alkenyl succinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids such as dodecyloxyacidoxyacid, such as dodecyloxyacidoxyacid (ethoxy) acetic acid and its amine salts, also N-oleoylsarcosine, sorbitan mono-oleate, lead naphthenate, alkenylsuccinic anhydrides, for example dodecenylsuccinic anhydride, 2- (2-carboxyethyl) -1-dodecyl-3-methylglycerol and its salts, especially Na and triethanolamine salts.
• 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, furthermore 1- [N, N-bis (2-hydroxyethyl) amino] -3- (4-nonylphenoxy) propane 2-ol.
  • ii. Heterocyclic compounds, for example: substituted imidazolines and oxazolines, 2-heptadecenyl-1- (2-hydroxyethyl) imidazoline.
• c) phosphorus-containing compounds, for example
  Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc dialkyldithiophosphates.
• d) Sulfur-containing compounds, for example: barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and their salts.
• e) glycerol derivatives, for example: glycerol monooleate, 1- (alkylphenoxy) -3- (2-hydroxyethyl) glycerol, 1- (alkylphenoxy) -3- (2,3-dihydroxypropyl) glycerol, 2-carboxyalkyl-1,3- dialkylglycerols.

Examples of viscosity index improvers are:

Polyacrylates, polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinyl pyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers, polyethers.

Examples of pour point depressants are:

Polymethacrylate, alkylated naphthalene derivatives.

Examples of dispersants / surfactants are :

Polybutenyl succinic acid amides or - imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.

Examples of anti-foaming agents are:

Silicone oils and polymethacrylene.

Examples of solid lubricants are:

Teflon ™ or molybdenum sulfide.

Examples of wear protection additives are:

Sulfur and / or phosphorus and / or halogen-containing compounds such as sulfurized olefins and vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, tricresyl phosphate, chlorinated paraffins, alkyl- and aryldi- and trisulfides, amine salts of mono- and dialkyl phosphates, amine salts of methylphosphonic acid, diethanolaminomethyltolyltriazole , Di (2-ethylhexyl) aminomethyltolyltriazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, 3 - [(bis-isopropyloxy-phosphinothioyl) thio] propionic acid ethyl ester, triphenylthiophosphate (triphenylphosphorothioate), tris (alkylphenyl ) phosphorothioates and mixtures thereof (e.g. tris (isononylphenyl) phosphorothioate), diphenylmonononylphenyl phosphorothioate, isobutylphenyl diphenyl phosphorothioate, dodecylamine salt of 3-hydroxy-1,3-thiaphosphetane-3-oxide, trithiophosphoric acid 5,5,5 -tris [isooctylacetate (2)], derivatives of 2-mercaptobenzothiazole such as 1- [N, N-bis (2-ethylhexyl) aminomethyl] -2-mercapto-1H-1,3-benzothiazole, ethoxycarbonyl-5-octyldithiocarbamate.

The compounds of formula I and their preparation are known per se. They primarily serve as intermediates for various products and applications, e.g. in V.V. Ovchinnikov, et al., Org. React (Tartu) 15 (2) (1978), 194-203 [A 90: 120801s] and in L.A. Belova, et al, Zh. Obshch. Khim 51 (9) (1981) 1982-88 (Russian) [CA 96: 103597 m].

The compounds according to the invention are prepared, for example, according to the following scheme:
CA 90: 120801s] and in LA Belova, et al, Zh. Obshch. Khim 51 (9) (1981) 1982-88 (Russian) [CA 96: 103597 m].

The compounds according to the invention are prepared, for example, according to the following scheme:

This synthesis of β-dithiophosphorylated propionic acid by adding dithiophosphoric acid to acrylic or methacrylic acid is known and is described, for example, in US Pat. No. 5,362,419 (Ex. 1-11). The following examples 1-3 document the synthesis of some b-dithiophosphorylated propionic acids used in the compositions according to the invention. Unless otherwise stated, parts and percentages are by weight.

example 1

21.4 g (0.1 mol) of O, O-diisopropyldithiophosphoric acid in 50 ml of toluene are added within 20 min. 7.2 g (0.1 mol) of acrylic acid were added dropwise at 80 ° C. The mixture is stirred at 80 ° C for 5 h. After the solvent has been stripped off on a rotary evaporator, the residue is fractionated by column chromatography on silica gel: 11.8 g of a yellow, liquid main product (41% of theory) are obtained. Analysis: 37.99% C (calculated 37.75) 6.76% H (calculated 6.69) 22.17% S (calculated 22.39) 10.80% P (calculated 10.82); ³¹ P NMR (relative to H ₃ PO ₄ ): 91.84 ppm.

Example 2

81.4 g (1.1 mol) of acrylic acid are added dropwise at 70 ° C. to 252.4 g (0.1 mol) of O, O-diisobutyldithiophosphoric acid, and stirring is continued at 70 ° C. for 4 h. The crude product is dissolved in 500 ml of sodium hydroxide 2N and twice Washed 300 ml of mineral spirits (bp 80-110 ° C). Then with conc. Acidified hydrochloric acid to pH 1 and extracted with approx. 150 ml of mineral spirits. The organic phase is washed with water and evaporated on a rotary evaporator: 287.6 g of clear, medium-viscosity, light yellow oil (91% of theory) result. Analysis: 42.02% C (calculated 42.62) 7.29% H (calculated 7.37), 20.29% S (calculated 20.40) 10.2% P (calculated 9.85); n ²⁰ D: 1,5006;

¹ H-NMR (in CDCl ₃ solution, relative to tetramethylsilane):
1.02 ppm (d, 12H), 2.05 ppm (hept, 2H), 2.86 ppm (t, 2H), 3.17 ppm (dxt, 2H), 3.89 ppm (dx hept, 4H).

Example 3

To 35.5 g (0.1 mol) of O, O-di (2-ethylhexyl) dithiophosphoric acid in 50 ml of toluene at 75 ° C within 15 min. 7.21 g (1.1 mol) of acrylic acid were added dropwise. The mixture is stirred at 75 ° C for 5 h. Working up is as in Example 1, and 21.8 g of yellowish oil (51% of theory) are obtained. Analysis: 53.86% C (calculated 53.62) 9.23% H (calculated 9.0), 15.77% S (calculated 15.07) 7.3% P (calculated 7.26)

The advantages of the compositions are good wear protection and especially the very good load-bearing properties - especially for hydraulic and gear oils, whereby surprisingly relatively small amounts of β-dithiophosphorylated propionic acids are sufficient. This can minimize any negative side effects such as corrosivity to Cu and incompatibility with any Ca compounds (precipitation reactions). There is also additional corrosion protection potential.

For hydraulic and gear oils, both very good wear protection (antiwear, AW) and very good load-bearing capacity (extreme pressure, EP) are required.

Excellent values in the FZG test (fault load level> 12) are difficult to achieve with the usual wear protection additives at low application concentrations (less than 0.2%). Surprisingly, however, very good to excellent FZG values are achieved with relatively low concentrations of compounds of the formula I (already 0.005-0.05%) (see Table 1, eighth and tenth columns).

Example 4:

The following formulations were tested in the FZG gearbox test (description in DIN 51.354, A / 8.3. / 90) (Table 1). In this test, the load carrying capacity of lubricants for use as gear oils is assessed. In the splash lubrication process, defined gears run in the lubricating oil to be tested at a constant speed and a specified initial oil temperature. The load on the gears is gradually increased. From force level 4, the change of the tooth flanks is recorded after each force level by description and, if necessary, by photo, roughness measurement or contrast impression. The limit load level is one level below the so-called error load level, at which the flanks of at least two gear wheels have clear damage (cracks or the like).

Claims (13)

Containing composition A) a lubricant or fuel, a metalworking fluid or a hydraulic fluid; B) at least one compound of the formula

wherein R ₁ and R ₂ independently of one another are C ₃ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₅ -C ₆ cycloalkylmethyl, C ₉ -C ₁₀ bicycloalkylmethyl, C ₉ -C ₁₀ tricycloalkylmethyl, phenyl, C ₇ -C ₂₄ alkylphenyl or together mean (CH ₃ ) ₂ C (CH ₂ ) ₂ , and R _{3 is} hydrogen or methyl, and optionally C) other common oil additives. A composition according to claim 1 containing 0.005 to 0.01% by weight of a compound of formula I. A composition according to claim 1 containing 0.005-0.05% by weight of a compound of formula I. A composition according to claim 1, wherein component A) is an industrial oil or a fat. A composition according to claim 1, wherein component A) is a base oil from the group of mineral, vegetable or synthetic oils. A composition according to claim 1, wherein R ¹ and R ^{2 are} independently C ₃ -C ₁₈ alkyl, C ₅ -C ₆ cycloalkyl or C ₇ -C ₁₈ alkylphenyl. The composition of claim 1, wherein R ₁ and R _{2 are} i-propyl, i-butyl or 2-ethyl-hexyl, and R _{3 is} hydrogen. The composition according to claim 1, which additionally contains C) further oil additives from the groups of the antioxidants, metal deactivators, rust inhibitors, dispersants, detergents, antifoams, solid lubricants, viscosity index improvers, pour point depressants and wear protection additives. Process for improving the performance properties of lubricants, hydraulic or metalworking fluids, characterized in that at least one compound of the formula I, as described in claim 1, is added to these. A method according to claim 9 for improving the performance properties of hydraulic fluids or gear oils. Zinc-free composition according to claim 1. Substantially ashless composition according to claim 1. Use of component B) described in claim 1 as an additive for lubricants, hydraulic or metalworking fluids.