MXPA96001359A - Compounds with (benzo) triazole radicals - Google Patents

Abstract

A description is given of compounds of the formula I, and mixtures thereof, (I), in which Y and Z independently of one another are a radical of the formula (II) or (III) (III) R and R1 independently of one another are hydrogen, C1-C12alkyl, C5-C8cycloalkyl, C1-C4alkyl-substituted C5-C8cycloalkyl, phenyl or C1-C4alkyl-substituted phenyl, R2 is C2-C20alkylene, C5-C8cycloalkylene, a radical of the formula The compounds/mixtures are particularly suitable as metal deactivators for use in lubricants.

Description

COMPOUNDS WITH RADICALS OF (BENZO) TRIAZOL The invention relates to novel compounds which are suitable in particular as metal deactivators and corrosion inhibitors, and have triazole and / or bepzotriazole groups, to mixtures of these compounds to compositions comprising these compounds, or mixtures thereof, and to their preparation and use. 'It is known that copper ions catalyze autoxidation and the formation of peroxide radicals in organic materials. This is also true of the oxidation degradation of lubricants (see Ullmann's Encyclopaedia of Industrial Chemistry, Volume A3, page 104). By the addition of benzotriazole or benzotriazole derivatives, usually together with antioxidants, it is possible to make the decomposition of the lubricant by copper considerably slower. Examples of the compounds currently used in the industry are those of the type: where, for example, R, is hydrogen. R2 and j are 2-ethylhexyl or hydroxyethyl, and Rβ is hydrogen, or methyl (see, for example, U.S. Patent Nos. 4, 683, 071 and 4,701,273). The patent of the United States of America Number No. 5,076,948 describes N-triazole compounds having alkoxy groups. The N-benzotriazole compounds having alkoxy groups are also known from US Pat.

North America Numbers 4,153,565 and 5,032,300. Katritzky et al. Describe compounds that contain two benzotriazal radicals that are joined by means of nitrogen [A.R. Katritzky et al., J. Chem. Soc. Perkin Trans 1987, 791; 19901717; J Heterocyclic Chem. 27 1543 (1990)]. There continues to be a need for active substances that have metal deactivating properties and / or that prevent corrosion. It has now been discovered that the compounds described in more detail below, which contain two (benzo) triazole radicals, have outstanding metal deactivating properties and prevent corrosion. Accordingly, the invention provides compounds of the formula I: where: Y and Z, independently of each other, are a radical of the formula: RyR1 (independently of one another, are hydrogen, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms substituted by alkyl of 1 to 4 carbon atoms, phenyl, or phenyl substituted by alkyl of 1 to 4 carbon atoms, R2 is alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, a radical of the formula: or (CnH2nO) mCnH2n, wherein n is 2, 3, or 4, and m is from 1 to 20, R3 is hydrogen or alkyl of 1 to 4 carbon atoms, and R4 is hydrogen or methyl, and mixtures of these compounds.

The invention also relates in particular to mixtures of the compounds of the formula I just described, wherein the radicals Y and Z are different, with compounds of the formula I wherein the radicals Y and Z are identical. Suitable compounds or mixtures of compounds of the formula I are those wherein: R and R? they are hydrogen, alkyl of 1 to 9 carbon atoms, or phenyl, R 2 is alkylene of 2 to 15 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, a radical of the formula: or (CnH2nO) mCnH2n, where n is 2, 3, or 4, and m is from 1 to 10, and R3 is hydrogen or methyl.

In the compounds of the formula I, R and R? they are preferably identical. In addition, preference is given to the compounds of the formula I wherein: R and R? they are hydrogen or alkyl of 1 to 6 carbon atoms, R is alkylene of 2 to 12 carbon atoms, cyclohexylene, or a radical of the formula: or (CnH2nO) p? CnH2n, where n is 2, 3, or 4 , and it's from 1 to 10, and Rj is hydrogen or meti.

In the compounds just described, with a particular preference, R and R? they are hydrogen or alkyl of 1 to 6 carbon atoms, and R is alkylene of 2 to 8 carbon atoms, or cyclohexylene, or a radical of the formula: the alkyl radicals of 1 to 12 carbon atoms may be straight or branched chain, and, depending on the number of carbon atoms specified, are, for example, methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, tertiary butyl, pentyl, isopentyl, hexyl, heptyl, octyl. 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, 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, as alkyl preferably has from 1 to 4 carbon atoms, and in particular is methyl. Cycloalkyl of 5 to 8 carbon atoms is, for example, cyclopentyl, cyclohexyl, or cyclooctyl; preferred are cycloalkyl radicals having 5 or 6 carbon atoms, especially cyclohexyl. Cycloalkylene of 5 to 8 carbon atoms can be. for example, cyclohexylene, cyclopentylene, or cyclo-octylene. Preferably it is cyclohexylene. ^ Phenyl substituted by alkyl of 1 to 4 carbon atoms is preferably substituted with methyl or ethyl, and in particular is mesityl, xylyl, or tolyl. The invention also provides a process for the preparation of compounds of the formula I and mixtures thereof, in which process, a triazole of the formula: or a benzotriazole of the formula: or mixtures thereof, (i) is made or reacted with aldehyde R.CHO or RCHO or mixtures of these aldehydes and diols H0-R2-0H, wherein the radicals R, Rj, R2, and R3 are as initially defined, or (ii) if Rj and R are methyl, and R2 and R- are as initially defined, the reaction is performed with divinyl ethers of the formula In this context, it is possible to employ any desired mixtures of compounds of the formulas IV and V, as long as mixtures of these compounds are used to start. In these mixtures, the molar ratio of IV: V is preferably in the range from 1:99 to 99: 1, in particular from 1: 9 to 9: 1, and most especially from 1: 4 to 4: 1. The invention further provides the products or product mixtures obtainable by the above process. The individual species in the mixtures of different compounds of the formula I can be obtained either by using pure, unmixed starting materials, in pure form (cf. Examples 2, 6, 13, below), or they can be isolated from the mixtures by conventional physical separation methods, for example, chromatography. Therefore, since it is possible, for the preparation of the compounds of the formula I and mixtures thereof, to use triazole: and / or benzotriazoles: in any desired proportions, the composition of the mixtures according to the invention depends on the ratio in which the starting materials IV and V are used. The reactivity of the benzotriazole and triazole derivatives in the reactions that are possible for the preparation , is substantially the same. Accordingly, the reaction produces mixtures of compounds of the formula I with identical and different radicals Y and Z, whose composition depends substantially on the concentration of the reactants, and has a substantially statistical distribution of the reaction products. The unspecified site of the free link in the formula II: It is intended to indicate that in each case substitution can occur in position 1 or 2 of benzotriazole, since benzotriazole exists in structures of mesomeric resonance. Examples of suitable methods for the preparation of the compounds of the formula I are the two methods explained below and illustrated in detail in the examples, said methods being familiar in organic chemistry (see AR Katritzky et al., J. Chem Soc. Perkin Trans 1987, 791; 1990 1717; J Heterocyclic Chem. 27 1543 (1990); J. Soc. Perkip Trans. 1989, 639). The benzotriazole and / or the triazole can be reacted with an equal amount of aldehyde and with half the molar amount of a diol of the formula H0-R2-0H. for example, with catalysis by an acid - for example, p-toluenesulfonic acid. Alternatively, (benzo) triazole can be reacted directly with half the molar amount of a divinyl ether of the formula HC = CH-0-R2-0-CH = CH2 (VI) - conveniently the same way with acid catalysis. In this case, the compounds of the formula I are obtained wherein R and R are methyl (see the equation below). The reactions take place, for example, according to the following equation: In this equation, the radicals Y, Z, R, and R to R3 have the definitions given initially, and a and b adopt values from 0 to 2, being the sum of a and b of 2. Condensation can take place in apolar organic solvents with catalytic an acid such as, conveniently, para-toluenesulfonic acid. The compounds can also be prepared in alcohols or in alcohol / water mixtures, for example, in ethanol, methanol, or mixtures thereof with water. Under these conditions, it is also possible to omit the acid catalyst. As mentioned above, the products can be substituted in position 1 or 2 of the benzotriazole system (1- or 2-benzotriazolyl compounds). Separation of any isomers is not necessary, but it can be done by customary methods, for example, chromatography. In practice, it is preferred to use the mixtures obtained directly from the reaction. The starting materials used can be obtained commercially, or they can be prepared by known methods. It should be mentioned that, when benzotriazole methyl is used, it is preferable to use a mixture of benzotriazole 4- and 5-methyl. The compounds according to the invention are surprisingly suitable as metal deactivators and antioxidants for organic materials, especially materials that come into contact with metals or that comprise metal ions as impurities. For lubricants, there is also a distinctive activity against wear. Accordingly, the invention also provides compositions comprising: a) a lubricant, a fluid for metal work, or a hydraulic fluid, or a2) a coating composition, especially a paint or varnish, and b) at least one compound of the invention. Formula I, in which context the compounds of the formula I and mixtures thereof mentioned above as preferred. lead to preferred compositions. The compounds of the formula I contribute to the prevention of the oxidation and decomposition processes, in particular. by bonding copper ions, and therefore deactivating them. Therefore, the invention also provides the use of compounds of the formula I as additives in lubricants, hydraulic fluids, metal working fluids, and coating compositions, especially as metal deactivators and corrosion inhibitors. Lubricants, fluids for metal work, and hydraulic fluids of interest are based, for example, on mineral oils, synthetic oils, or mixtures thereof.

These are important for the expert in this field, and are described in the relevant technical literature, for example. in Dieter Klamann. "Sch ierstoffe upd Verwandte Produkte" [Lubricants and related products] (Verlag Chemie, Weinheim, 1982), in Sche e-Kobek, "Das Schmiermittei-Taschenbuch" [The Manual of Lubricants] (Dr. Alfred Húthing-Verlag, Heidelberg , 1974), and in "Ullmanns Enzyklopadie der technischen Chemie" [Encyclopedia of Industrial Chemistry of Ullmanp], Volume 13, pages 85-94 (Verlag Chemie, Weinheim, 1977). Lubricants are, in particular, oils and fats based, for example, on a mineral oil. The oils are preferred. An additional group of lubricants that can be used are oils, fats, tallow, and vegetable or animal waxes, or mixtures thereof with one another, or mixtures with the aforementioned mineral or synthetic oils. Examples of oils, fats, tallow, and vegetable and animal waxes are palm kernel oil, palm oil, olive oil, rapeseed oil, rape seed oil, flaxseed oil, peanut oil, oil soybeans, cottonseed oil, sunflower oil, pumpkin seed oil, coconut oil, corn oil, castor oil, walnut oil, and mixtures thereof, fish oils, tallow of slaughtered animals , such as beef tallow, bone oil and beef paw. and the modified, epoxidized forms. and sulfooxides from the same, for example, bean oil from saya epoxiríadp. Mineral oils are based in particular on hydrocarbon compounds.

Examples of the synthetic lubricants include lubricants based on aliphatic or aromatic carboxylic esters, polymeric esters, pallacylene oxides, phosphoric esters, poly-α-olefins or silicones, a diester of a dibasic acid with a monohydric alcohol, for example, sebaceous dioctyl or dinonyl adipate. a triester of trimethylolpropapo with a monobasic acid or a mixture of these acids, for example, trimethylolpropane tripelargonate, trimethylolpropane tricaprylate, or mixtures thereof, a tetraester of pentaerythritol with a monobasic acid or a mixture of these acids, for example, pentaerythrite tetracaprylate, or a complex ester of monobasic and dibasic acids with polyhydric alcohols, for example, a complex ester of trimethylolpropane with caprylic and sebasic acid, or a mixture thereof. Particularly suitable lubricants, in addition to mineral oils, are, for example, poly-α-olefins, ester-based lubricants, phosphates, glycols. polyalkylene glycols and glycols, and mixtures thereof with water. Fluids for metal work and hydraulic fluids can be prepared based on the same substances described above for lubricants. Often, they also comprise emulsions of these substances in water or other liquids. The lubricant compositions according to the invention are used, for example, in combustion engines, for example, in motor vehicles that are adjusted, for example, with Otto spark ignition, diesel engine, two-way engines, Wankel , or orbital. The compounds of the formula I are readily soluble in lubricants, metal working fluids and hydraulic fluids, and therefore, are particularly suitable as additives for lubricants, metalworking fluids, and hydraulic fluids. The compounds of the formula I and / or mixtures thereof can be mixed with the lubricants in a manner known per se. The compounds, for example, are easily soluble in oils. It is also possible to prepare a so-called masterbatch, which can be diluted up to the concentration levels of the application with the appropriate lubricant according to the use. In those cases, concentrations of more than 10 weight percent are also possible. The compounds according to the invention as described above may be present, for example, in amounts of 0.01 to 10 weight percent, conveniently in amounts of 0.01 to 5 weight percent, preferably in an amount of 0.01 to 3 weight. percent by weight, and with a very particular preference, in an amount of 0.01 to 1.5 percent by weight, based on the composition, on the lubricant, on the metal working fluid, or on the hydraulic fluid. In addition to the compounds according to the invention, lubricants, metalworking fluids, and hydraulic fluids may comprise other customary additives. examples being other antioxidants, metal deactivators, oxidation inhibitors, viscosity index improvers, pour point depressants, dispersants / surfactants, and additives for extreme pressure and wear.

The examples of these are: Examples of Phenolic Antioxidants 1. Alkylated monophenols, for example, 2,6-dibutyl tertiary-4-methylphenol, 2-tertiary butyl-4,6-di-ethylphenol, 2,6-tertiary-dibutyl-4-ethylphenol, 2,6-dibutyl-tertiary-4-butyl-normal-phenol, 2.6-tertiary dibutyl-4-i sobuti 1 phenol. 2.6-d ic i cl open ti 1 -4-me t il f enol. 2- (α-methylcyclohexyl) -4,6-dimethylphenal, 2,6-dioctadecyl-4-methylphenal. 2,, 6- tr i c ic 1 ohexi 1 f enol. 2.6-tertiary dibutyl-4-methoxymethylphenol. 2, 6-dinonyl-4-methylphol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2-di methyl-6- (1'-methylheptadec-1'-yl) ) phenol, 2,4-dimyl-1-6- (1'-methyltr idec-1'-yl) phenol, and mixtures thereof 2. Alkyltiomethyl-enols. for example, 2, 4-dioctylthiomethyl-6-tertiary butyl-f-enol, 2,4-dioctylthiomethyl-6-methyl-1-ene, 2,4-di-oc-i-iomet-il-6 -et i-1-ene, 2,6 -didodecylthiomethyl-4-nonylfolol. 3. Hydroquinones and alkylated hydroquinones, for example, 2,6-tertiary dibutyl-4-methoxyphenol, 2,5-tertiary dibutyl-hydroquinone, 2,5-tertiary diamyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6 -butyl tertiary-hydroquinone, 2, 5-tertiary-dibutyl-4-hydroxyanisole, 3, 5-tertiary-dibutyl-4-hydroxyanisole, tertiary-3,5-dibutyl-4-hydroxyphenyl stearate, bis (3,5-tertiary dibutyl) adipate -4-hydroxyphenyl). 4_j_ Tocopherols, for example, α-tocopherol, β-tocopherol, β-tocopherol, 5-tocopherol, and mixtures thereof (Vitamin E).

. Hydroxylated thiodiphenyl ethers. for example, 2, 2 • thiobis (6-tertiary butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4-thiobis (6-tertiary butyl-3-methylphenol), 4 , 4'-thiobis (6-tertiary butyl-2-methylphenol), 4,4'-thiobis- (3,6-diamyl secondary-phenol), disulfide of 4, '-bis (2,6-dimethyl-4-) hydroxyphenyl). 6. Bisphenols of alkylidene. for example, 2,2'-methylenebis (6-butyl tertiary io-4-methylfol), 2,2'-methylenebis (6-butyl tertiary-4-ethylphenol), 2,2'-methylenebis [4-methyl- 6- (α-me ylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-dibutyl tertiary io-f enol), 2,2 * -ethylidenebis (4,6-dibutyl tertiary-phenol), 2,2'-ethylidebis (6-tertiary butyl-4-isobutylphenol), 2,2 '-methylenebis [6- (a-methylbenzyl) -4-nonylfolol], 2,2'-menenybis [6- (a, a-dimethylbenzyl) -4-nonylfolol], 4,4'-methylenebis (2) , 6-dibutyl tertiary-phenol), 4,4 '-methylenebis (6-tertiary butyl-2-methylphenol), 1, 1-bis (5-tertiary butyl-4-hydroxy-2-methylphenyl) butane, 2,6 bis (3-tertiary butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1, 3-tris (5-tertiary butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis ( 5-butyl tertiary-4-hydroxy-2-methylphenyl) -3-dodecyl normal-mercaptobutane, bis [3, 3-bis (3 '-butyl tertiary-4'-hydroxyphenyl) butyrate] ethylene glycol or, bis (3-butyl-4-butyl-2-oxo-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tertiary butyl-2'-hydroxy-5-methyl) -6-tertiary butyl terephthalate 4-methylphenyl], 1, l-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-dibutyl tertiary-4-hydroxyphenyl) propane, 2,2-bis (5 tertiary butyl-4-hydroxy-2-methylphenyl) -4-dodecyl normal-mercaptobutane, 1, 1, 5,5-tetra- (5-tertiary butyl-4-hydroxy-2-methylphenyl) pentane. 7. Compounds of O-r N-. and S-benzyl. for example, ether 3, 5, 3 ', 5'-tertiary-tert-butyl-4,4'-dihydroxydibenzyl, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris- (3, 5-dibutyl-tertiary-4-amine) -hydroxybenzyl), bis (4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-dibutyl tertiary-4-hydroxybenzyl) sulfide, tertiary isooctyl-3,5-dibutyl mercaptoacetate -4-hydroxybenzyl. 8___ Hydroxybenzylated malonates. for example, dioctadecyl-2,2-bis- (3, 5-tertiary-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tertiary butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl malonate -2,2-bis- (3,5-tertiary dibutyl-4-hydroxybenzyl), di- [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3, 5) malonate -tertiary dibutyl-4-hydroxybenzyl). 9. Aromatic hydroxybenzyl compounds, for example, l, 3,5-tris- (3,5-dibutyl tertiary-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-dibutyl tertiary- 4-hydroxybenzyl) -2, 3, 5, 6-tetramethylbenzene, 2,4,6-tris (3,5-dibutyl-tertiary-4-hydroxybenzyl) phenol.

. Triazine compounds. for example, 2,4-bisoctylmercapto-6- (3,5-dibutyl tertiary-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-dibutyl-tertiary-4-) hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-dibutyl tertiary-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3 , Tertiary-5-dibutyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3-tris- (3,5-dibutyl-tertiary-4-hydroxybenzyl) isocyanurate, isocyanurate of 1,3,5- tris (tertiary-4-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4,6-trLs (3,5-dibutyl-tertiary-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5 -tris (3, 5-tertiary dibutyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,4-tris (3, 5-dicyclohexyl-4-hydroxybenzyl) isocyanurate. 11. Benzyl phosphonates. for example, 2,5-tertiary dibutyl-4-hydroxybenzylphosphonate dimethyl, 3,5-tertiary dibutyl-4-hydroxybenzylphosphonate diethyl, 3,5-dibutyl tertiary-4-hydroxybenzylphosphonate dioctadecyl, 5-tertiary butyl-4-hydroxy -3-methylbenzylphosphonate dioctadecyl, the calcium salt of tertiary 3,5-dibutyl-4-hydroxybenzylphosphonate monoethyl. 12. Acylaminophenols for example, 4-hydroxylauric, 4-hydroxystearic, N- (3,5-dibutyl-tertiary-4-hydroxyphenyl) carbate octyl anide. 13. Esters of ß- (3,5-dibutyl tertiary-4-hydroxy-nyl) propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, 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, oxalamide N, W-bis (hydroxyethyl), 3-thiaundecanol, 3 -thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane. 14. Esters of β- (5-tertiary butyl-4-hydroxy-3-methyl-phenyl) propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, 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, -bis (hydroxyethyl) oxalamide, -thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6,7-trioxabicyclo [2.2.2] octane.

. Esters of ß- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, glycol ethylene, 1,2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3- tiapentadecanol, trimethylhexane-diol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane. 16. Esters of 3,5-dibutyl tertiary-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, 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) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane- diol, trimethylolpropane, 4-hydroxyethexyl-1, -f osf a-2, 6, 7 -trioxabicyclo [2.2.2] octane. 17. Amides of ß- (3,5-dibutyl tertiary-4-hydroxy-enyl) propionic acid. for example, diamine N, N '-bis (3,5-dibutyl tertiary-4-hydroxyphenylpropionyl) hexamethylene, diamine N, N' -bis (3,5-dibutyl tertiary-4-hydroxyphenylpropionyl) tri ethylene, hydrazine N, N '-bis (3,5-dibutyl tertiary-4-hydroxyphenylpropionyl).

Examples of amine type antioxidants: Diamine N, N'-diisopropyl-p-phenylene, diamine N, N'-dibutyl secondary-p-phenylene, diamine N, N'-bis (1,4-dimethylpentyl) -p-phenylene, diamine N, N'- bis (l-ethyl-3-methylpentyl) -p-phenylene, diamine N, N'-bis (l-methylheptyl) -p-phenylene, diamine N, N'-dicyclohexyl-p-phenylene, diamine N, N * - diphenyl-p-phenylene, diamine N, N'-di (2-naphthyl) -p-phenylene, diamine N-isopropyl-N'-phenyl-p-phenylene, diamine N- (1,3-dimethylbutyl) -N ' phenyl-p-phenylene, diamine N- (l-methylheptyl) -N'-phenyl-p-phenylene, diamine N-cyclohexyl-N'-phenyl-p-phenylene, amine 4- (p-toluenesulfonamido) -diphenyl, N, N'-dimethyl-N, N'-secondary-p-phenylene dimethyl diamine, diphenylamine amine, N-allyldiphenyl amine, 4-isopropoxydiphenyl amine, N-phenyl-1-naphthalene amine, N-phenyl-2-amine naphthyl, octylated diphenyl amine, for example, amine p, p'-dithyroctyldiphenyl, 4-butyl normal-amino-enol, 4-butyrylaminophenol, 4-thio-onanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di- (4-methoxyphenyl) amine, 2,6-dibutyl tertiary-4-dimethyl: minomethylphenol, 2,4'-diaminodifenylmethane, 4,4'-diaminodifenylmethane, N, N, N ', N' -tetramethyl-4,4'-diaminodiphenyl-ethane, 1,2-di [(2-methylphenyl) amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) biguanide, amine di [4- (l ', 3'-dimethylbutyl) phenyl], N-phenyl-1-naphthalethyl-tertiary amine, a mixture of tertiary butyl- / tertiary-octyl-diphenyl amines - and di-alkylated, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenyl amines, a mixture of mono- and di-alkylated tertiary-diphenyl amines, 2,3-dihydro-3,3-dimethyl-4H-1 , 4-benzothiazine, phenothiazine, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-l, 4-diaminobut-2-ene, diamine N, N-bis (2,2,6,6-tetramethylpiperid- 4-yl-hexamethylene, r -sebacate of bis (2, 2,6,6-tetramethylpiperid-4-yl), 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6 -tetramethylpiperidin-4-ol.

Examples of other antioxidants: Aliphatic or aromatic phosphites, thiodipropionic acid or thiodiacetic acid esters, or salts of dithiocarbamic acid 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.

Examples of metal deactivators, for example for copper, are: a) Benzotriazoles and their derivatives, for example, benzotriazoles 4- or 5-alkyls (for example, tolutriazole), and their derivatives, 4, 5, 6, 7-tetrahydrobenzotriazole, 5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole or tolutriazole such as tolutriazole l- [di (2-ethylhexyl) aminometic] and benzotriazole l- [di (2-ethylhexyl) aminomethyl]; benzotriazoles alkoxyalkyl, such as benzotriazole (1-nonyloxymethyl), benzotriazole 1- (1-butoxyethyl), and tolutriazole l- (1-cyclohexyloxybutyl). b) 1,2,4-triazoles and their derivatives, for example, 1,2,4-triazoles 3-alkylanes (or aries), Mannich bases of 1,2,4-triazoles, such as 1,2 , 4-triazoles l- [di (2-ethylhexyl) aminometyl]; 1,2,4-triazoles alkoxyalkyl, such as 1,2,4-triazoles l- (1-butoxyethyl); 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 ester. d) Heterocyclic sulfur-containing compounds, for example, 2-mercaptobenzotriazole, 2,5-dimercapto-l, 3,4-thiadiazole and their derivatives; 3, 5-bis [di (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one. e) Amino compounds, for example, diamine salicylidene propylene, salicylic aminoguanidine, and salts thereof.

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 acids -scipients, 4-nanylphepoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids, such as dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid, and the amine salts thereof, and also N-oleoilic sarcosine, sorbitol mopoleoleate, naphthenate lead, alkenyl succinic anhydrides. for example, dodecenylsuccinic anhydride, 2-carbaxymethyl-1-dodecyl-3-methyl glycerol and amine salts thereof. b) Nitrogen-containing compounds, for example: I. Primary, secondary, or tertiary aliphatic or cycloaliphatic amines, and amipic salts of organic and inorganic acids, for example, oil soluble alkoxide carboxylates, and also 1- [N. N-bis (2-hydroxyethyl) amylo] -3- (4-nopilphenoxy) propan-2-ol.

II. Heterocyclic compounds, for example: imidazolines and substituted oxazalipas, imidazolines 2-heptadecenil-l- (2-hydroxyethyl). c) Phosphorus-containing compounds, for example: amipic salts of partial phosphoric esters or partial fasphopic esters, dialkyl zinc dithiophosphates. d) Sulfur-containing compounds, for example: dinucleic barium naphthalenesulfonates, calcium petroleum sulfonates, aliphatic carboxylic acids substituted by thioalkyl, esters of aliphatic 2-sulfocarboxylic acids and salts thereof. e) Glycerol derivatives, for example: glycerol ono-oleate, glycerol 1- (alkylphepoxy) -3- (2-hydroxyethyl), glycerol 1- (alkylphenoxy) -3- (2,3-dihydroxypropyl) , glycerol 2-carboxyalkyl 1- 1, 3-dialkine.

The examples of the viscosity index improvers are: Pol i acri 1 atos. pol imetaer i] atoe .. copel. pyrrolidone vinyl lica-metacri lato. pyrrol idonas pol iviní 1 icas. polybutenes olefin copolymers. styrene-acrylate copolymers, polyethers, Examples of the pour point depressants are: polymethacrylate, alkylated naphthalene derivatives, Examples of the dispersants / surfactants are: succinicides or polybutenyl succinimides, polybutenylphosphonic acid derivatives, basic magnesium, sulfonates and calcium and barium fepolates.

Examples of wear additives are: compounds comprising sulfur and / or phosphorus and / or halogen, such as sulfurized olefins and vegetable oils, dialkyl zinc dithiophosphates. alkylated triphenyl phosphates, tritolylic phosphate, tricresolic phosphate. chlorinated paraffins, di- and tri-sulphides of alkyl and aryl. amine salts of mono- and di-alkylated phosphates, amino salts of methylphosphoic acid, tolyltriazole diethanolamiprometic, tolyltriazole di (2-ethylhexyl) aminomethyl, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, 3- [(bis -isopropyloxy-phosphinothioyl) thio] ethyl propionate, triphenyl thiophosphate (triphenyl phosphorothioate), tris (alkylphenyl) phosphorothioates, and mixtures thereof (for example). *), diphenylmonononi phosphothioate lphenyl, isobutyl phosphorothioate lfeni ldifeni lo, the salt dodeci la inica 3-oyida 3-hydroxy-l, 3-thiafosfetano, 5, 5, 5-tris [2-isooctyl acetate] of trithiophosphoric acid, 2-mercaptobenzothiazole derivatives, such as 2-mercapto-lH-1, 3-benzo-iazol 1- [N, N-bis (2-ethylhexyl) aminomethyl], dithiocarbamic acid 5-ethoxycarbonyloctyl.

The compounds according to the invention are particularly effective together with antioxidants of the phenolic and / or amine type. The coating compositions generally consist of binders and additives with or without coloring components. Suitable binders are mainly all those that are customary in the art, for example, those described in Ullmann's Encyclopaedia of Industrial Chemistry, 5th edition, Volume A18, pages 368-426, VCH, Weinhei 1991. The binder is in general a binder for forming of film based on a thermoplastic or thermosetting resin, predominantly a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy, and polyurethane resins, and mixtures thereof. The binder can be a cold-curable or hot-curable binder, the addition of a curing catalyst possibly being convenient. Examples of suitable catalysts that accelerate the curing of the binder are described in Ullmann's Epcyclopaedia of Industrial Chemistry, Volume A18. page 469, VCH Verlagsgesellschaft, Weipheim 1991. Preferred coating compositions are those in which the film-forming binder comprises episodic resins. resins of paliuretano, resins of palester. acrylic resins, and copolymer resins thereof, polyvinyl resins, phenolic resins, alkyd resins, or mixtures of these resins. The compounds of the formula I can be present in the coating compositions in proportions of 0.001 to 10 percent, preferably 0.1 to 5 percent. When the compositions according to the invention are coating compositions, or paints or varnishes, then these in the same manner may comprise other components customary from the groups, for example. which consist of dyes, pigments, fillers, flow control agents, adhesion promoters, curing catalysts, light stabilizers. and antioxidants. The preferred compounds according to the invention. as described above, they lead to preferred compositions. The present invention also provides the use of dt. compounds or mixtures of compounds of the formula I as additives in lubricants, hydraulic fluids;, and fluids for metal work, to coating compositions, and a method for improving the service properties of lubricants, fluids for metal work, or fluids Hydraulic, or coating compositions, which comprises adding compounds or mixtures of compounds of the formula I to these lubricants, fluids, or compositions. The following examples illustrate the invention in greater detail but without limiting it. Unless it is specified from another t? way, the parts and the percentages are by weight. All operations are carried out under nitrogen. If the products already begin to crystallize while the reaction solution is cooling, they are isolated by filtration, and are not subjected to further purification.

Examples Preparation Examples (In the tables and in the rest of the description, Me is methyl, and the group «: II is cyclohexyle).

Method 1 0.2 moles of (benzo) triazole, 0.2 moles of aldehyde, 0.1 moles of diol (cf Table 1), and 0.2 grams of p-toluenesulfonic acid in 200 milliliters of cyclohexane, are charged to a four-neck sulfonation flask ( flat bottom reaction vessel) with mechanical stirrer, Dean-Stark water separator, thermometer, and nitrogen inlet. The reaction solution is heated to reflux until the theoretical amount of 0.2 moles of water has been separated. The reaction solution is cooled to room temperature, and washed three times with 100 milliliters of a 5 percent aqueous solution of Na 2 CO 3, and twice with 100 milliliters of water, and dried over MgSO 4, and the solvent is stir by distillation on a rotary evaporator. Finally, the residue is dried at 60 ° C under a high vacuum for 2 hours. abla lt (Examples according to method 1 abla 1 Examples according to method 1 Method 2 0.2 moles of triazole, 0.1 moles of divinyl ether, and 0.2 grams of p-toluenesulfonic acid in 100 milliliters of solvent (Comp Table 2) are charged to a four-necked sulfonation flask with mechanical stirrer, reflux condenser, thermometer, and nitrogen inlet. The reaction solution is refluxed until the precursors have disappeared (it is verified by thin layer chromatography). The reaction solution is cooled to room temperature, washed three times with 100 milliliters of a 5 percent aqueous solution of a2C03, and twice with 100 milliliters of water, and dried over gSO2, and the solvent is added. stir by distillation on a rotary evaporator. Finally, the residue is dried at 60 ° C under a high vacuum for 2 hours.

Method 3 0.2 moles of (benzo) triazole, 0.1 moles of divipyl ether, and 0.2 grams of p-toluenesulfonic acid in 100 milliliters of solvent (Comp Table 3) are charged to a four-necked sulfonation flask with mechanical stirrer, condenser reflux, thermometer, and nitrogen inlet. The reaction solution is refluxed until the precursors have disappeared (it is verified by thin layer chromatography). The reaction solution is cooled to room temperature, 5 grams of CaO powder and a little MgSO4 are added, stirring is carried out for 10 minutes, and the suspension is filtered. The filtrate is concentrated on a rotary evaporator, and the product is dried at 60 ° C under a high vacuum for 2 hours.

Solv. (solvent): A = Carbon tetrachloride B = Toluene Method 4 0.2 moles of (benzo) triazole, 0.2 moles of butyric aldehyde, 0.1 moles of l, 4-bis (hydroxymethyl) cyclohexane, and 0.2 grams of p-toluenesulfonic acid in a mixture of 100 milliliters of cyclohexane and 100 milliliters of toluene, is heated to reflux in a four-necked sulfonation flask with mechanical stirrer, Dean-Stark water separator, thermometer, and nitrogen inlet. After the theoretical amount of 0.2 moles of water has been separated, the mixture is cooled to room temperature. 5 grams of CaO and a little MgSO4 are added, stirring is carried out for 10 minutes, and the suspension is filtered. The filtrate is concentrated on a rotary evaporator, and the product is dried at 60 ° C under a high vacuum for 2 hours.

Examples of use Example Al; Copper corrosion test (modified from ASTM D-130) 0.05 weight percent of the compound to be tested is dissolved in a viscosity turbine oil of 29.7 mm2s-1 at 40 ° C and 5.05 mm2s-1 a 100 ° C (sulfur content of 0.22 percent). In addition, 50 ppm of elemental sulfur is added. A copper plate (60 x 10 x 1 millimeters) polished with silicon carbide is completely immersed in the oil solution and left there at 100 ° C for 3 hours. The copper plate is then removed from the oil and rinsed with petroleum ether. Subsequently, it is evaluated in accordance with the Standard Copper Strip Corrosion Diagram of ASTM D 130 (see Table 5). There are four evaluation levels: 1 - without tarnishing 2 - moderate tarnishing 3 - severe tarnishing 4 - corrosion; Within the numerical groups 1 to 4, an additional precision subdivision is made based on the nebulosity of the samples. In this qualitative evaluation, A to E, the evaluation A is before B, B is before C, and so on. The table shows in each case the values for two panels (parallel determination). Table 5; Copper Corrosion Test Compound of Example No. Evaluation 3B / 4A 10 1A / 1A 13 1A / 1A 1 1A / 1B 14 1A / 1A 15 1A / 1A 16 1A / 1A Example A2: Rotating Pump Oxidation Test (RBOT) . ASTM D 2272 0.05 percent by weight of the compound to be tested in a turbine oil is dissolved (viscosity 29.7 mitV1 at 10 ° C and 5.05 mnrs 1 at 100 ° C. Sulfur content of 0.22 percent Other components are 0.15 percent of a phenolic antioxidant, 0.05 percent of an amine-type antioxidant, and 0.07 percent of a corrosion inhibitor (See following Table) .50 milliliters of the mixture Thus obtained are added together with 5 milliliters of water to the test vessel, which contains a copper coil as a catalyst.The vessel is charged with oxygen to a pressure of 620 kPa, and then sealed and turned in a hot bath to 150 ° C. A measurement is made of the time during which the oxygen pressure decreases by 172 kPa.

Table 6: Rotating Pump Oxidation Test (RBOT) Compound of Example No. Time (minutes) 278 10 830 13 1048 1 751 l ~ '1039 15 1084 16 1155 i) Mixture of butylated phenols with tertiary butyl, which can be obtained as Irganox ™ 140. 2) Mixture of diphenyl amine compounds, commercially available as Irganox - ^ - d ?, cf. U.S. Patent Number 5,073,278, column 2, line 50. 3) Hitec ™ 536, H23C12-CH (COOH) -CH2-CO-NH-CH2-CH2-NH-CH2-CH2- ^ N

Claims (18)

1. . A compound of the formula I: where: Y and Z, independently of each other, are a radical of the formula: R and Rx, independently of one another, are hydrogen, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms substituted by alkyl of 1 to 4 carbon atoms, phenyl , or phenyl substituted by alkyl of 1 to 4 carbon atoms, R 2 is alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, a radical of the formula: or (CnH2nO) mCnH2n, wherein n is 2, 3, or 4, and m is from 1 to 20, R3 is hydrogen or alkyl of 1 to 4 carbon atoms, and R4 is hydrogen or methyl, or a mixture of these compounds .

2. A compound or mixture according to claim 1, wherein R and R- ^ are identical.

3. A compound or mixture according to claim 1, wherein: R and Rx are hydrogen, alkyl of 1 to 9 carbon atoms, or phenyl, R2 is alkylene of 2 to 15 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, a radical of the formula: or (CnH2 nO) mCnH2n, where n is 2, 3, 0 4, and is from 1 to 10, and R3 is hydrogen or methyl.

4. A compound or mixture according to claim 1, wherein R and R? they are hydrogen or alkyl of 1 to 6 carbon atoms, R2 is alkylene of 2 to 12 carbon atoms, cyclohexylene, or a radical of the formula: or (CnH2nO) mCnH2n, wherein n is 2, 3, 6 4, and m is from 1 to 10, and R3 is hydrogen or methyl.

5. A compound or mixture according to claim 4, wherein: R 2 is alkylene of 2 to 8 carbon atoms, or cyclohexylene, or a radical of the formula:

6. A mixture of compounds of the formula I according to claim 1, wherein the radicals Y and Z are different, with compounds of the formula I wherein the radicals Y and Z are identical.

7. A process for the preparation of compounds of the formula I defined in claim 1, and mixtures thereof, which comprises reacting the compound of the formula:, ---- - \ NH (IV) / or a benzotriazole of the formula: or mixtures thereof, (i) with RjCHO or RCHO aldehydes or mixtures of these aldehydes and HO-R2-OH diols, wherein the radicals R, R2, R2, and R3 are as defined in claim 1, or ( ii) if Rj and R are methyl, and R2 and R3 are as defined in claim 1, with divinyl ethers of the formula H2C = CH-0-R2-0-CH = CH2.

8. A process according to the claim 7, wherein mixtures of compounds of formulas IV and V are employed.

9. A process according to claim 8, wherein the molar ratio of IV: V is in the range of 1: 9 to 9: 1.

10. A process according to claim 8, wherein the molar ratio of IU: V is in the range of 1: 4 to 4: 1.

11. A product or mixture of products obtainable by the process of claim 7.

12. A composition comprising: A) a lubricant, a hydraulic fluid, a metal working fluid, or a coating composition, and B) at least one compound or mixture of compounds or a product according to claim 1 or 11.

13. A composition according to claim 12, wherein component A) is a lubricant.

14. A composition according to the claim 13, where the lubricant is an engine oil.

15. A composition according to the claim 14, which additionally comprises other stabilizers such as aptioxidants, other metal deactivators, oxidation inhibitors, viscosity index improvers, pour point depressants, dispersants / surfactants, and / or additives for extreme pressure and wear.

16. A composition according to claim 15, which comprises, as other antioxidants, phenolic and / or amine type antioxidants.

17. The use of a compound or mixture of compounds according to claim 1 or 11 as an additive in lubricants, hydraulic fluids, fluids for metal work. or coating compositions.

18. A method for improving the surface properties of lubricants, fluids for metalworking, hydraulic fluids, or coating compositions, which comprises adding compounds or mixtures of compounds according to claim 1 or 11 to these lubricants, fluids, or compositions. SUMMARY A description is given of compounds of formula I, and mixtures thereof: where: Y and Z, independently of each other, are a radical of the formula: R 1 and R 1 (independently of one another) are hydrogen, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms substituted by alkyl of 1 to 4 carbon atoms, phenyl, or phenyl substituted by alkyl of 1 to 4 carbon atoms, R 2 is alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, a radical of the formula: or (CnH2nO) mCnH2n, wherein n is 2, 3, or 4, and m is from 1 to 20, R3 is hydrogen or alkyl of 1 to 4 carbon atoms, R is hydrogen or methyl. The compounds / mixtures are particularly suitable as metal deactivators for use in lubricants. * * * * *