MXPA97005300A - Propionic acid b-ditiofosforilado in lubrican - Google Patents

Abstract

A description is given of compositions comprising A) a lubricant, a metalworking liquid or a hydraulic fluid, in particular a base oil of the group consisting of mineral, vegetable and synthetic oils (for example poly-alpha-olefinoesters); From 0.005% to 1.0% by weight of a compound of the formula (See Formula) in which R1 and R2 independently of each other mean C3-C18 alkyl, C5-C12 cycloalkyl, C5-C6 cycloalkylmethyl, C9- bicycloalkylmethyl C10, C9-C10 tricycloalkylmethyl, phenyl or C7-C24 alkylphenyl together are (CH3) 2C (CH2) 2, and R3 is hydrogen or methyl and if desired C) other oil additives customary for the groups consisting of antioxidants , metal passivators, rust inhibitors, dispersants, detergents, viscosity index improvers, depressurization agents, defoamers, solid lubricants and other antiwear additives

Description

PROPIONIC ACID B-DITIOFOSFORILADO IN LUBRICANTS. The present invention relates to compositions comprising a lubricant (preferably an industrial oil or a grease), a fluid for working metals or hydraulic type and at least one β-dithiophosphorylated propionic acid of the formula I, mentioned below. Modern lubricants are formulated with additives that work well as protection against high pressure wear and corrosion and act as antioxidants [W.J. Bartz (editor) et al., "Additive für Schmierstoffe" (expert-Verlag 1994)]. Typical in this context are zinc dialkyldithiophosphate that combine antioxidant properties with those of combating wear under high pressure. In more recent times attempts have been made to replace these additives, which contain heavy metals, virtually metal-free compounds, since this is ecologically more beneficial and exerts a positive effect on the durability of the catalysts for exhaust fumes of the internal combustion engines. Currently in the industry there is a need to have metal-free and ash-free additives. The esters of the type can be obtained: (i-pr = isopropyl) under the trade name Irgalube ® 63. In addition, the North American specification 4,333,841 describes mercaptoacetic acid dithiophosphorales and their salts as additives for lubricants. The bis-dithiophosphoric acid derivatives are described in British specification GB-A 2,267,493 as additives for lubricants. For the same purpose the European specification EP-A 98 809 [CA 101: 55323 s] proposes salts of the formula (RO) 2 P (S) S (CH 2) n (C (O) OM in which M = Li, K , Na or HNR US-A 5,362,419 discloses as acid intermediates of the formula (RO) 2 P (S) S (CH 2) 2 C (0) OH to prepare glycol esters which are suitable as additives for lubricants, such as Example (RO) 2P (S) (CH2) 2C (0) OCH2 (CHOH) CH20H (see also H. Zinke, R. Schumacher, Wear 179 (1-2) (1994) 45-8 [CA 122: 85158t] It has surprisingly been found that the β-dithiophosphorylated propionic acids, on which the propionates mentioned above are based, are in themselves, even at very low concentrations, outstanding high-pressure and wear-fighting agents. the invention to compositions (preferably free of zinc and ash) comprising: A) A lubricant or fuel, a fluid for working metals or a hydraulic fluid, especially an oil or gra an industrial oil, in particular a base oil of industrial oil or fat, in particular a base oil of the group consisting of mineral, vegetable and synthetic oils (for example poly-α-olefin or ester); B) At least one compound of the formula in which R? and R2 independently from each other represent alkyl of C3-C18, C5-C12 cycloalkyl, C5-C6 cycloalkylmethyl, C8-C10 bicycloalkylmethyl, C9-C10 tricycloalkyl ethyl, phenyl or C7-C24 alkylphenyl or together are (CH3) 2C (CH2) 2 and R3 is hydrogen or methyl, and if desired, C) other additives for customary oils, for example from the groups consisting of antioxidants, passivators for metals, rust inhibitors, dispersants, detergents , viscosity index improvers, pour point depression agents and other antiwear additives. Within the context of component B), x and R 2 independently of each other are preferably C 3-20 alkyl C 5 -C 6 cycloalkyl or C 7 -C 18 alkylphenyl. Within the context of component B) R? and R 2 are, with particular preference, i-propyl, 1-butyl or 2-ethylhexyl and R 3, with particular preference, hydrogen. When R ± and R2 in the above formula I are C3-C18 alkyl they are straight or branched chain radicals. Examples of these are 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 and 1-methylundecyl. R? and R2 as C5-C12 cycloalkyl may be for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or cyclododecyl. Cyclopentyl and cyclohexyl, especially cyclohexyl, are preferred. Ri and R2 'as C5-C6 cycloalkylmethyl are cyclopentylmethyl and in particular cyclohexyl ethyl. R ± and R2 as C9-C10 bicycloalkylmethyl are for example decalinylmethyl. As C8-C10 tricycloalkylmethyl R? and R2 preferably have the meaning of a group of the formula formula Examples of alkylphenyl are methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, isopropylphenyl, t-butylphenyl, di-t-butylphenyl and 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 fluids or metalworking fluids, preferably in hydraulic oils and transmission fluids. The use according to the invention includes the protection of metal parts that must be lubricated to protect them against mechanical wear (high pressure protection and wear) including an anticorrosive effect. Accordingly, the present invention also relates to the method for improving the service properties of liquid lubricants for working metals and hydraulic fluids, which comprise adding to them the compounds of formula I. The above-mentioned fuel lubricants (for example the oils and industrial greases), metalworking fluids and hydraulic fluids according to component A) are based, for example, on mineral or synthetic oils or their mixtures. The lubricants are familiar to the expert and they are described in the corresponding technical literature, for example Dieter Klamann "Schmierstoffe und Verwandte Produkte" (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch" (Dr. Alfred Hüthig-Verlag, Heidelberg, 1974) and in "Ullmanns Enzyklopádie der technischen Chemie", vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977). Lubricants are especially oils and greases, based for example on a mineral oil. The oils are preferred. Another group of lubricants that can be used comprises vegetable or animal oils, fats, tallow and waxes or their mixtures with each other or with the mineral or synthetic oils mentioned above. Examples of vegetable and animal oils, fats, tallow and waxes are palm kernel oil, palm oil, olive oil, rapeseed oil, rapeseed oil, rapeseed oil, linseed oil, peanut oil, soybean oil, cottonseed oil, sunflower oil, pumpkin seed oil, coconut oil, corn oil, resin oil, hazelnut oil and mixtures thereof, fish oils, slaughtered animal tallow such as beef tallow, cow's foot oil and bone oil as well as their modified, epoxidized and sulfoxidated forms, for example epoxidized soybean oil. Mineral oils are based particularly on hydrocarbon compounds. Examples of the synthetic lubricants comprise lubricants based on carboxyl esters of aliphatic or aromatic type, or also polymeric esters, polyalkylene oxides, phosphoric esters, poly-a-olefins or silicones, on a diester of a dibácic acid with a monohydric alcohol , for example the dioctyl sebacate or dinonyl adipate, on a triester of trimethylolpropane with a monobic acid or with a mixture of such acids, for example trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, on a tetraester of pentaerythritol with an acid monobasic or with a mixture of such acids, for example pentaerythritol tetracaprylate, or on a complex ester of monobacic and dibasic acids with polyhydric alcohols, for example a complex ester of trimethylolpropane with caprylic acid and sebacic acid or a mixture thereof . Particularly suitable examples other than mineral oils are poly-a-olefins, lubricants based on esters, phosphates, glycols, polyglycols and polyalkylene glycols, as well as their mixtures with water. Industrial oils, greases, metalworking fluids and hydraulic fluids can be prepared on the basis of the same substances as described for lubricants. In many cases, the compositions involved are also emulsions of such substances in water or other liquids. The lubricant compositions according to the present invention are used for example in internal combustion engines, for example in motorized vehicles equipped, for example, with Otto, Diesel, two-stroke, Wankel or orbital engines. Component B is also suitable as an additive for fuels in motor vehicles equipped with engines of the specified type. The compounds of the formula I are soluble without problem in lubricants, fuels, liquids for working metals and hydraulic fluids and therefore are particularly suitable as additives for lubricants, liquids for working metals and hydraulic fluids. The compositions advantageously include from 0.005% to 1.0% by weight of a compound of the formula I, preferably from 0.005% to 0.1% by weight, and in particular from 0.005% to 0.05% by weight. The compounds of the formula I can be introduced into the fuel lubricants in a manner known per se. The compounds are soluble, without problem, for example in oils. It is also possible to prepare a so-called master batch that can be diluted with the corresponding lubricant to use concentrations in a cup with which they are consumed. In such cases concentrations of more than 1% by weight are also possible. The lubricants or fuels, the metal working and hydraulic fluids, stabilized according to the invention, can additionally include other additives that are added to further improve the basic properties of those formulations: these additives include antioxidants, metal passivators, other rust inhibitors, viscosity index improvers, depression agents for the pour point, solid lubricants, dispersants, detergents, defoamers, other high-pressure additives, anti-wear additives and additives that reduce the coefficient of friction. These additives are added in the usual amounts that in each case are in the range of 0.01% to 10.0% by weight. The following text presents an example of such additives: Examples of phenolic antioxidants: 1.1. Alkylated monophenols for example 2,6-di-ter. Und-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-ter. -butyl-4-ethylphenol, 2,6-di-ter. -butyl-4-n-butylphenol, 2,6-di-tert.-butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (a-methyl-cyclohexyl) -4, 6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexyphenol, 2,6-di-ter. -butyl-4-methoxymethylphenol, straight or branched chain nonylphenols, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-eleventh-1'-yl) phenol , 2, 4, dimethyl-6- (1-methylhepta-ten-methyl-1-yl) phenol, 2,4-dimethyl-6-methyl-methyl-1-yl) phenol and mixtures thereof. 1.2 Alkyltiomethyl-enols, for example 2,4-di-octythiomethyl-6-ter. -butylphenol, 2,4-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol. 1.3 Hydroquinones and alkylated hydroquinones, for example 2, 6-di-ter. -but il-4-methoxy-enol, 2, 5-di-ter. - butylhydroquinone, 2,5-di-ter. -a to ilhydroquinone, 2,6-dif-enyl-4-octadecyloxyphenol, 2,6-di-ter. -butyl hydroquinone, 2, 5-di-ter. -butyl-4-hydroxyanisole, 3, 5-di-ter. -butyl-4-hydroxyanisole, 3, 5-di-ter. -butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert.-butyl-4-hydroxyphenyl) adipate. 1.4. Tocopherols, for example, high, beta, gamma or delta-tocopherol and their mixtures (vitamin E). 1.5 hydroxylated thiodiphenyl ethers. for example 2f2'-thiobis (6-tert.-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert.-butyl-3-methylphenol) , 4,4'-thiobis- (6-tert.-buty-1-2 -methyl-enol), 4,4'-thiobis (3,6-di-sec. -amymphenol), 4,4'-bis ( 2,6-dimethyl-4-hydroxy-enyl) -disulfide. 1.6 Alkylidenebisols, for example 2,2'-ethylenebis (6-tert.-butyl-4-methylphenol), 2,2'-methylenebis (6-tert.-butyl-4-ethylphenol), 2,2'- methylenebis [4-methyl-6- (alba-cyclohexylphenol), 2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert.-butylphenol) , 2,2 '-ethylidenebis (4,6-di-tert.-but i lf enol), 2,2'-ethylidebis (6-tert.-butyl-4-isobutyl-enol) 2, 2 '-methylenebis [6- (a-methylbenzyl) -4-nonylfolol], 2,2'-methylene-bis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert.-butyl-enol), 4,4'-methylenebis (6-tert.-butyl-2-methylphenol), 1, 1-bis (5-ter. -but i 1 -4-hydroxy-2-methyl-1-phenyl) butane, 2,6-bis (3-tert.-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1, 3-tris (5- ter-butyl-4-hydroxy-2-methyl-phenyl) -butane, 1,1-bis ((5-tert-butyl-4-hydroxy-2-methyl-phenyl) -3-n-dodecyl-mercaptobutane, ethylene glycol bis [ 3-3-bis (3 'tert.-butyl-4' -hydroxyphenyl) butyrate], bis (3-tert.-butyl-4-hydroxy-5-methylphenyl) dicyclopentadine, bis [2- (3 ' -ter. -but il-2 '-h id roxi-5' -methylphenyl) -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.-buyl-4-hydroxy-2-methylphenyl) -4 -n -dodecylmercaptobutane, 1,1,5, 5-tetra (5-tert.-butyl-4-hydroxy-2-methyl) enyl) -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-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5-di-ter. -butylbenzylmercaptoacetate, tris (3,5-di-tert.-butyl) -amino, bis (4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephine, bis (3, 5-di-ter) .butyl-4-dimethylbenzyl) di thioterephthalene, bis (3, 5-di-tert.-butyl-1-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-ter. -butyl-4-hydroxybenzyl ercaptoacetate. 1.8 Hydroxybenzylated malonate, for example dioctadecyl 2,2-bis (3,5-di-tert.-butyl-2-hydroxybenzyl) alonate, dioctadecyl 2- (3-tert.-butyl-4-hydroxy-5-methylbenzyl) -malonate, di-dodecyl-mercaothiethyl-2, 2-bis (3,5-di-tert.-butyl-4-hydroxybenzyl) -malonate, di [4- (1, 1,3, 3-tetramethoxybutyl] 2, 2-bis (3,5-di-tert.-butyl-4-hydroxybenzyl) -alonate 1.9 Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert.-butyl-4-) hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert.-butyl-4-hydroxybenzyl) -2,3,5,6-tetramet-1-ene, 2,4, 6-tris (3, 5-di-tert.-butyl-4-hydrobenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert.-butyl) -4-hydroxybenzyl) phenol 1.10 Triazine compounds, for example 2,4-bisoctylmercapto-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-ter. but i 1-4 -hidroxif enoxi) -1, 3, 5-triaci na, 2, 4, 6-tris (3, 5-di-ter. -butyl-4-hydroxyphenoxy) -1,2, 3-triacine, 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- triac ina, 1,3,5-tris (3,5-di-tert.-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3-tris (3,5-dicyclohexyl- 4-hydroxybenzyl) -isocyanurate. 1.11 Benzylpholophones, for example dimethyl-2, 5-diTER. -butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-ter. -butyl- 4-hydroxybenzylphosphonate, dioctadecyl 3, 5-methylbenzylphosphonate, the calcium salt of the 3,5-di-ter monoethyl ester of acid. -butyl- 4-hydroxybenzylphosphonic. 1.12 Acylaminophenols, for example 4-hydroxylauranylide, 4-hydroxystearanilide, octyl N- (3,5-di-tert.-butyl-4-hydroxyphenyl) carbamate. 1.13 Esters of ß- (3, 5-di-tert.-butyl-4-hydroxyphenyl) propionic acid, ß-f-5-ter acid. -butyl-4-hydroxy-3-methylphenyl) pro ionic. ß- (3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid, 3,5-di-ter acid. -buty 1-4-hydroxyphenylacetic acid or β-f-5-ter acid. -butyl-4-hydroxyphenyl) -3-thiabutyric acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) -isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane , 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane, glycerol and the tranesterification products based on natural triglycerides for example coconut oil, rapeseed oil, sunflower oil or rapeseed oil 1.14 Amides of ß- (3,5-di-tert.-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert.-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert.-butyl-4-hydroxyphenylpropionyl) trimethyldiamine, N, N'-bis (3, 5-di-tert.-but i 1-4 -hydroxy-enylpropionyl) hydraz ina. 1.15 Ascorbic acid (vitamin C) 1.16 Antioxidants of the amine type, for example N, N'-diisopropyl-pf-enylenediamine, N, N'-di-sec-butyl-pf eni lendiamine, N, N'-bis (1, 4 -dime ti 1 f in i 1) -p-phenylenediamine, N, N'-bis (l-ethyl-3-methyl-pentyl) -pf enilendiamine, N, N'-bis (1-methyl-heptyl) - pf enilendiamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di- (naf-2-yl) -pf enilendiamine, N-isopropyl, N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl-p-p-eneylenediamine, N- (1-methylhethyl ) -N'-f-enyl-p-enylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl -pf enilendiamine, diphenylamine, N-allidifenylamine, 4-isopropoxy-dif-enylamine, N-phenyl-1-naphthylamine, N- (4-tert.-octylphenyl) -l-naphthylamine, N-phenyl-2-naphthylamine, octylate diphenylamine, for example p, p'-di-tert.-octyldifenyl-amine, 4-n-butylated indole, 4-butyrylamino-enol, 4-nonanoylamino-enol, 4-dodecanoylamino-enol, 4-octadecanoylamino -f enol, di- (4-methoxyphenyl) -amine, 2,6-di-tert.-butyl-4-dimethylamino-methylphenol, 2,4'-dia-ino-diphenylmethane, 4,4'-diamino- diphenylmethane, N, N, N ', N' -tetramethi4-4, 4'-diamino-diphenylmethane, 1,2-di- [2-methyl-phenyl) -amino] -ethane, 1,2-di- (phenylamino) ) propane, (o-totyl) biguanide, di [4-1 ', 3' -dimethyl-butyl) -phenyl] amine, N-phenyl-1-naphthi laminate ter Oltylated, a mixture of ter-butyl / ter. monoalkylated and dialkylated octyldiphenylamines, a mixture of monoalkylated and dialkylated nonildiphenylamines, a mixture of monoalkylated and dialkylated dodecyldiphenylamines, a mixture of monoalkylated and dialkylated isopropyl / isohexyldiphenylamines, mixtures of ter. - monoalkylated and dialkylated butylphenylamines, 2, 3, dihydro-3, 3-dimethyl-4H-l, 4-benzothiazine, phenothiazine, a mixture of ter. -butil / ter. -octyl-phenothiazines monoalkylated and dialkylated, a mixture of monoalkylated and dialkylated ter-octyl-phenothylazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-l, 4-diaminobut-2-ene, N, N - bis - (2, 2, 6, 6-tetramethylpiperidin-4-yl) hexamethi lendiamine, bis- (2, 2, 6, 6-tetramethylpiperidin-4-yl) sebacate, 2, 2, 6, 6-tetramethylpiperidin -4-one, as well as 2,2,6,6-tetramethylpiperidin-4-ol. Examples of other antioxidants: aliphatic or aromatic phosphites, thiodipropionic acid or thiodiacetic acid esters or dithiocarbamic or dithiophosphoric acid salts, 2, 2, 12, 12-tetramethyl-5,9-dihydroxy-3,7,1-trithiatridecane and 2, 2, 15, 15-tetramethyl-5, 12-dihydroxy-3,7,10,14-tetrathiahexadecane. Examples of metal passivators, 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'- methylenebisbenzotriazole; Mannich bases in the margin of benzotriazole or tolutriazole as l- [di (2- e t i lhex i 1) ami nome t i 1 t or lu t r i a z o 1 and l- [di (2-ethylhexyl) aminomethyl] -benzotriazole; alkoxyalkylbenzotriazoles, such as l- (nonyloxy ethyl) -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 as l- [di (2- ethylhexyl) aminomethyl] -i, 2,4-triazole; alkoxyalkyl-1,2,4-triazoles such as 1- (1-butoxyethyl) -1,2,4-triazole and the 3-amino-1,2,4-triazoles acylated. c) Imidazole derivatives, for example 4,4'-methylenebis (2-undecyl-5-methyl-imidazole), bis [(N-methyl) imidazol-2-yl] carbinol-octyl ether. d) Sulfur-containing heterocyclic compounds, for example 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and its derivatives; 3, 5-bis [di (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one. e) Amino compounds, for example, salicylidenepropylenediamine, salicylaminoguanidine and their salts. Examples of rust inhibitors are: a) Organic acids, their esters, metal salts, amine salts and anhydrides, for example alkyl- and alkenylsuccinic 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 dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid and their amine salts, and also N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, alkenyl succinic anhydrides, for example dodecenylsuccinic anhydride, 2- (2-carboxyethyl) -l-dodeceyl-3-methylglycerin and its salts, especially the sodium and triethanolamine salts. b) Nitrogen-containing compounds, for example: i. The aliphatic or primary, secondary or tertiary cycloaliphatic amines and the amine salts of the organic and inorganic acids for example oil soluble alkylammonium carboxylates and also 1- [N, N-bis (2-hydroxyethyl) amino] -3- ( 4-nonylphenoxy) propan-2-ol. ii. Heterocyclic compounds, for example substituted imidazolines and oxazolines, 2-heptadecenyl-1- (2-hydroxyethyl) -imidazoline. c) Phosphorus-containing compounds, for example the amine salts of partial esters of phosphoric acid or partial esters of phosphonic acid and zinc dialkyldithiophosphates. d) Sulfur-containing compounds, for example barium dinonylnaphthalene sulphonate, calcium petroleum sulfonates, aliphatic alkylthio-substituted aliphatic acid esters of aliphatic 2-sulfocarboxylic acids and their salts, e) Glycerin derivatives, for example: monooleate of glycerin, 1- (alky1-phenoxy) -3- (2-hydroxyethyl) glycerines, 1- (alkylphenoxy) -3- (2,3-dihydroxypropyl) glycerins and 2-carboxyalkyl-1,3-dialkyl glycerines. Examples of the viscosity index improvers are: polyacrylates. polymethacrylates, copolymers of vinylpyrrolidone and methacrylate, polyvinylpyrrolidones, polybutenes, copolymers, copolymers of olefins, copolymers of styrene and acrylate and polyethers. Examples of agents that depress the pour point are: polymethacrylate and the alkylated naphthalene derivatives. Examples of dispersants / surfactants are: polybutenylsuccionamides or their amides, polybutenylphosphonic acid derivatives and the basic sulphonates and phenolates of magnesium, calcium and barium. Examples of antifoams are: silicone oils Examples of solid lubricants are: Teflon ® (or molybdenum sulphide) Examples of additives to control wear are: compounds containing sulfur and / or phosphorus and / or halogen, such as sulfurized olefins and the vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, tricresyl phosphate, chlorinated paraffins, the alkyl and aryl diisulfides, the amine salts of the monoalkyl and dialkyl phosphates., the amine salts of methylphosphonic acid, diethanolamine of methyl phosphonic acid, diethanolaminomethylthyltriazole, di (2-ethylhexyl) -a in methyl-tololitriazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, ethyl [(bisisopropyloxyphosphinothioyl)] propionate , triphenyl thiophosphonate (trifluoride), tris (alkylphenyl) phosphorothioate and mixtures thereof (for example tri (isononylphenyl) phosphorothioate), diphenyl ononylphenylphosphorothioate, isobutylphenyl diphenylphosphorothioate, dodecylamine salt 3-hydroxy-l, 3-thiaphosphetane oxide, 5,5,5-tris [isooctyl 2-acetate] trithiophosphoric acid, derivatives of 2-mer cap t oben z ot iazo 1, such as 1- [N, N bis (2-ethylhexyl) aminomethyl] -2-mercapto-1H-1,3-benzothiazole and ethoxycarbonyl 5-octyldithiocarbamate. The compounds of the formula I and their preparation are already known per se. They serve mainly as intermediaries for various products and applications as described for various products and applications as described for example in V.V. Ovchinnikov et al., Org. React (Tartu) 15 (2) (1978), 194-203 (English) [CA 90: 120801s] and in L.A. Belova et al., Zh. Obshch.Khim 51 (9) (1981) 1982-88 (Russian) [CA 96: 103597m]. The compounds according to the invention are prepared, for example, according to the following equation: These syntheses of β-dithiophosphorylated propionic acid by the addition of dithiophosphoric acid to an acrylic or methacrylic acid are already known and described, for example, in US Pat. No. 5,362,419 (Examples 1 to 11). The following examples 1 to 3 constitute a documentation of the synthesis of some of the β-dithiophosphorylated propionic acids which are used in the compositions according to the invention. The parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 7.2 g (0.1 mol) of acrylic acid at 80 ° C are added in a dropwise fashion over a period of 20 minutes to 21.4 g (0.1 mol) of the O, 0-diisopropyldithiophosphoric acid in 50 ml of toluene. Stirring is continued for 5 hours at 80 ° C. Once the solvent has been separated in a rotary evaporator, the residue is fractionated by column chromatography on silica gel to produce 11.8 g of a yellow, liquid main product (41% of theory).

Analysis: 37.99% of C (calculated 37.75) 6.76% of H (calculated 6.69) 22.17% of S (calculated 22.39) 10.80% of P (calculated as 10.82); 31P-NMR (relative to H3P04): 91.84 ppm Example 2. 81.4 g (1.1 mol) of acrylic acid are added dropwise at 70 ° C within 1 hour to 252.4 g (0.1 mol) of the 0.0-diisobutyldithiophosphoric acid and stirring is continued at 70 ° C. for 4 hours. The crude product is dissolved in 500 ml of 2N sodium hydroxide and washed twice with 300 ml of petroleum spirit (boiling range 80 to 110 ° C). The solution is then acidified to a pH of 1 using concentrated hydrochloric acid and subjected to extraction with approximately 150 ml of petroleum spirit. The organic phase is washed with water and concentrated in a rotary evaporator to yield 287.6g of a clear, pale yellow oil with a medium viscosity (91% theory). 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); n20D: 1.5006; NMR-H (in solution of CDCL3, 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. 7.21g (1.1 mole) of acrylic acid in the form of droplets at 75 ° C over a period of 15 minutes is added to 35.5g (0.1 mole) of the O, O-di (2-ethylhexyl) dithiophosphoric acid in 50 minutes. ml of toluene. Stirring is continued at 75 ° C for 5 hours. The mixture is subsequently treated as in Example 1 to yield 21.8 g of a yellowish oil (51% of theory). Analysis: 53.86% of C (calculated 53.62) 9.23 of H (calculated 9.0), 15.77% of S (calculated 15.07) 7.3% of P (calculated 7.26). The advantages of the compositions lie in the anti-wear properties and in particular in the highly favorable properties of load-bearing, especially for hydraulic and transmission fluids with relatively small amounts of β-dithiophosphorylated propionic acids which surprisingly are sufficient. As a result it is possible to minimize any negative side effect as a corrosive character for copper and incompatibility with any calcium compound present (precipitation reactions). In addition, a potential for additional protection against corrosion is provided. It requires hydraulic fluids and transmission fluids that have at the same time very good anti-wear properties (AW) and at the same time a very good load-bearing capacity under extreme pressures (EP). With the use of the known additives of phosphorus and sulfur, free of metals [W.J. Bartz et al., "Additive für Schmierstoffe" (1994), p. 88-116] it is relatively easy to achieve good anti-wear properties. However, it is not very easy to ensure an excellent load carrying capacity, especially for transmissions. The test on the transmission wheel called "FZG" described below is used as a model system for transmission fluids and provides information on its load carrying capacity (see the following example 4). Excellent values in the FZG test (load cap with failure greater than 12) are difficult to achieve with the usual anti-wear additives at low concentrations (less than 0.2%). Nevertheless, it has surprisingly been found that relatively low concentrations of the compounds of the formula I (just from 0.005% to 0.05%) produce FZG values ranging from very good to excellent (see table 1, columns 8 and 10). Example 4. The following formulations were tested in the FZG transmission test (as described in the German standard DIN 51, 354, A / 8.3 / 90) (table 1). This test evaluates the load carrying capacity of lubricants that are used as transmission fluids. Immersed in the lubrication oil of the test, certain transmission wheels run at a constant speed and with a fixed initial temperature of the oil. The load exerted by the gear wheels rises, level after level. From the power level of 4 upwards, after each power level, the change in the flanks of the teeth of the wheels of the gear is established by a description and possibly through a photograph with measurement of the roughness or impression of contrast. The limit load level is one level below the load level in case of failure, ie that level where the flanks of at least 2 gear wheels show a clear damage (cracks or similar).

Basic formulation: Irganox ® L 1356: 0.3%; Irganox ® L577: 0.1%; Hitec ® 5368: 0.07%; Irgamet ® 399: 0.04% Basic oil: ISO VG 46 from Texaco; 2 AW l: Irgalube ® TPPT (triphenyl thiophosphonates) 3 AW 2: Irga lube ® 63. { e t i l 3 - [bisisopropyloxyphosphinothioyl) thio] propionates} 4 AW 3: liquid mixture of tri [(Alk) aryl] thionophosphates, which consist essentially of tri (nonylphenyl) thiophosphate (as described in the European specification EP 368 803); 5 AW 4: bis (0,0-dialkyl-dithiophosphate) mixture of diphenylamine compounds that can be obtained commercially as Irganox ® L-57, cf. US-5, 073, 278, column 2, line 50 8 Hitec < »536, H23C12-CH (COOH) -CH2-CO-NH-CH2-CH2- N CI7HM l- [bis (2-ethylhexyl) aminomethyl] -4-methylbenzotriazole.

Claims (13)

1. CLAIMS 1. A composition comprising A) a lubricant or fuel as a liquid for working metals or a hydraulic fluid; B) at least one compound of the formula
2. In which RL and R2 independently from each other mean C3-C18 alkyl, C5-C12 cycloalkyl, C5-C6 cycloalkylmethyl, C9-C1 bicycloalkylmethyl, C9-C10 tricycloalkylmethyl, C7-C24 phenyl or alkylphenyl or together they constitute (CH3) 2C (CH2) 2 and R3 is hydrogen or methyl and, if desired, C) other additives for common oils. A composition according to claim 1 containing from 0.005% to 0.01% by weight of a compound of the formula I.
3. 3. A composition according to claim 1 containing from 0.005% - 0.05% by weight of a compound of the formula I.
4. 4. A composition according to claim 1 in which component A) is an industrial oil or a fat.
5. 5. A composition according to claim 1 in which component A) is a basic oil of the group consisting of mineral, vegetable and synthetic oils.
6. 6. A composition according to claim 1 wherein R1 and R2 independently of each other are C3-C18 alkyl, C3-C6 cycloalkyl or C7-C18 alkylphenyl.
7. 7. A composition according to claim 1 wherein Rj ^ and R2 are i-propyl, i-butyl or 2-ethylhexyl, and R3 is hydrogen. A composition according to claim 1 which further comprises C) other oil additives of the groups consisting of antioxidants, metal passivators, rust inhibitors, dispersants, detergents, defoamers, solid lubricants, viscosity index improvers, agents for Depress the pour point and anti-wear additives. A method for improving the service properties of lubricants, hydraulic liquids or metalworking liquids which comprises adding thereto at least one compound of the formula I as described in claim 1. 10. A method according to claim 9 to improve the service properties of hydraulic fluids or transmission oils. 11. A zinc-free composition according to claim 1. 12. An essentially ash-free composition according to claim 1. 13. The use of component B) described in claim 1 as an additive for lubricants, hydraulic fluids or liquids to work metals. SUMMARY OF THE INVENTION A description of compositions comprising A) a lubricant, a metalworking liquid or a hydraulic fluid, in particular a base oil of the group consisting of mineral, vegetable and synthetic oils (e.g. poly-α-olefin) is presented. or esters); B) From 0.005% to 1.0% by weight of a compound of the formula R, 0 P R, 0 OH 1 (. R wherein R1 and R2 independently from each other mean C3-C18 alkyl, C5-C12 cycloalkyl C5-C6 cycloalkylmethyl, C9-C10 bicycloalkylmethyl, C8-C10 tricycloalkylmethyl, phenyl or C? -C alkylphenyl or together are (CH3) 2C (CH2) 2, and R3 is hydrogen or methyl and if desired C) other oil additives common to the groups consisting of antioxidants, metal passivators, rust inhibitors, dispersants, detergents, viscosity index, agents to depress the pour point, defoamers, solid lubricants and other antiwear additives.