Patent Application
20090105102
The invention relates to novel benzotriazole compositions comprising mixtures of benzotriazoles and N-substituted benzotriazoles, the process for preparing N-substituted benzotriazoles and a method for improving the functional properties of lubricants, hydraulic or metal-working fluids or coating compositions.
Additives, which can be used as metal deactivators display their protective action in functional liquids, such as mineral oil or fuels, by deactivating the metal ions, such as copper or iron, contained therein. These metal ions can have catalytic effects in undesired oxidative decomposition processes of mineral oil or fuels. The protective action is explained by the formation of film-like layers on the surface of metals or by complex formation with metal ions.
EP-A-365 476 discloses benzotriazole compounds:
Wherein R1 represents C1-C12 straight or branched chain alkyl; and
R2 represents C1-C12 straight or branched chain alkyl interrupted by one or more O-atoms or represents C5-C12cycloalkyl;
and lubricant compositions comprising these benzotriazole compounds.
Owing to their volatility at high operating temperatures of machines, metal deactivators of the triazole type are problematic. Because of high temperatures, in particular in internal combustion engines and turbines, which are exposed to oils and fuels, the deactivator concentration can rapidly decrease with a corresponding reduction in the protective action.
It is the object of the invention to prepare, from readily obtainable starting materials, such as tolutriazole (TTA), alkyl aldehydes and cycloalkanols, additive components which can be used in lubricant compositions as metal deactivators, possess improved solubility and, in functional liquids, have lower volatility than tolutriazole itself.
This object is achieved by the present invention, which relates to novel benzotriazole compositions comprising mixtures of benzotriazoles and N-substituted benzotriazoles.
The invention relates to a composition comprising
A more specific embodiment of the invention relates to a composition comprising
The compositions defined above are prepared by conventional mixing procedures and are suitable as metal deactivators in functional liquids.
The expressions and terms used above and below are preferably defined as follows in the description of the present invention:
The compounds (I) present in the compositions according to the invention are defined by the following isomeric structures:
Wherein R1, R2 and R3 are as defined above.
The term isomer includes any structural and positional isomers, tautomeric forms, cis-trans isomers and stereoisomers, e.g. enantiomeric forms and racemic mixtures.
R1 and R1′ defined as C1-C4alkyl represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl. According to a preferred embodiment, R1 represents methyl.
R2 represents a substituent selected from the group consisting of C1-C12alkyl, C5-C7cycloalkyl, (C1-C4alkyl)1-3C5-C7cycloalkyl or C5-C7cycloalkyl-C1-C4alkyl.
R2 defined as C1-C12alkyl represents C1-C4alkyl as defined above with regard to R1 and R1′ and additionally represents straight chain or branched C5-C12alkyl, e.g. pentyl, hexyl, heptyl, octyl, nonyl, undecyl or dodecyl.
R2 defined as C5-C7cycloalkyl is preferably cyclopentyl or cyclohexyl.
R2 defined as (C1-C4alkyl)1-3C5-C7cycloalkyl is preferably cyclopentyl or cyclohexyl substituted with C1-C4alkyl, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
R2 defined as C5-C7cycloalkyl-C1-C4alkyl is e.g. cyclopentylmethyl, cyclohexylmethyl, cyclopentyl-1,1-ethyl, cyclohexyl-1,1-ethyl, cyclopentyl-1,2-ethyl or cyclohexyl-1,2-ethyl.
In the compound (I) the index a represents a numeral from 1 to 10, and the index n represents a numeral from 2 to 8.
According to a preferred embodiment, the index a represents a numeral from 1 to 6, and the index n represents a numeral from 2 to 6.
According to a highly preferred embodiment, the index a represents a numeral from 1 to 4, and the index n represents a numeral from 2 to 4.
R3 represents a substituent a substituent selected from the group consisting of C1-C12alkyl, C5-C7cycloalkyl, (C1-C4alkyl)1-3C5-C7cycloalkyl, C5-C7cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl, (C1-C4alkyl)1-3phenyl and (C1-C4alkyl)1-3phenyl-C1-C4alkyl.
R3 defined as C1-C12alkyl, C5-C7cycloalkyl, (C1-C4alkyl)1-3C5-C7cycloalkyl and C5-C7cycloalkyl-C1-C4alkyl has the same meanings as defined above with regard to R2.
R3 defined as phenyl, phenyl-C1-C4alkyl, (C1-C4alkyl)1-3phenyl and (C1-C4alkyl)1-3phenyl-C1-C4alkyl is, for example, phenyl, benzyl, 1- or 2-phenylethyl, 4-methyl or 4-ethyl, cumyl or 4-methylbenzyl.
Compounds of the formula (I) are known from the disclosure of EP 0 365 476, or can be pre-pared in a manner analogous to the methods as described therein, e.g. by the acid catalysed reaction of the R1-substituted benzotriazole, e.g. tolutriazole (tolyltriazole), with the aldehyde R3—C(═O)—H and the alcohol R2—OH in a solvent inert to the reactants, while continuously removing an azeotropic mixture of solvent and water formed during the reaction.
Suitable acid catalysts include mineral acids, e.g. sulphuric acid, acid clays, e.g. bentonite, montmorillonite, Bleicherde Tonsil® (Supreme 110 FF, 126 FF) or Fuller's earth, acid ion-exchange resins, e.g. Amberlyst® 15, and sulphonic acids, e.g. p-toluene sulphonic acid.
The inert solvent may be cyclohexane, benzene, toluene, xylene or carbon tetrachloride.
Compounds (I) wherein R2 represents a group of the partial formulae (A) or (B), can be pre-pared in an analogous manner by the acid catalysed reaction of the R1-substituted benzotriazole, e.g. tolutriazole (tolyltriazole), with the diol HO—(CH2)2-3O—(CH2-3O)a—(CH2-3)—OH and 2 equivalents of the aldehyde R3—(C═O)—H, or with the diol HO—(CH2)n—OH and 2 equivalents of the aldehyde R3—(C═O)—H.
In a compound (II) R1 defined as C1-C4alkyl represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl. According to a preferred embodiment, R1 represents methyl.
Compounds (II) are known and are commercially available, e.g. Irgamet® (Ciba Specialty Chemicals) TTA.
The compounds (III) present in the compositions according to the invention are preferably defined by the following isomeric structure:
Wherein R1, R2 and R3 are as defined above.
Compounds (III), according to the optional component c), can be prepared in a manner analogous to EP 0 365 476, e.g. by the acid catalysed reaction of a R1-substituted triazole, e.g. triazole or methyltriazole, with the aldehyde R3—C(═O)—H and the alcohol R2—OH.
Compounds (III), wherein R2 represents a group of the partial formula (A) or (B), can be pre-pared in an analogous manner by the acid catalysed reaction of the R1-substituted triazole, e.g. triazole or methyltriazole, with the diol HO—(CH2)2-3O—(CH2-3O)a—(CH2-3)—OH and 2 equivalents of the aldehyde R3—(C═O)—H, or with the diol HO—(CH2)n—OH and 2 equivalents of the aldehyde R3—(C═O)—H.
The term functional liquid selected from the group consisting of lubricants, hydraulic agents, metal working fluids and coating agents includes non-aqueous, partially aqueous and aqueous liquids which are in contact with metals to be deactivated, in particular copper or iron.
Examples of non-aqueous functional liquids are fuels, e.g. hydrocarbon mixtures comprising mineral oil fractions which are liquid at room temperature and are suitable for use in internal combustion engines, e.g. internal combustion engines with external (petrol engines) or internal ignition (diesel engines), e.g. petrol having different octane contents (regular grade or premium grade petrol) or diesel fuel, and lubricants, hydraulic fluid, metal working fluid, engine coolants, transformer oil and switch gear oil.
Examples of suitable partially aqueous functional liquids are hydraulic fluids based on aqueous polyglycol/polyglycol ether mixtures or glycol systems, water-in-oil or oil-in-water systems and engine cooling systems based on aqueous glycol.
Examples of aqueous functional liquids are industrial cooling water, filling compositions of a water conditioning plant, steam generation systems, sea water evaporation systems, sugar evaporation systems, irrigation systems, hydrostatic boilers and heating systems or cooling systems having a closed circulation.
The compositions according to the invention preferably comprise 0.01 to 5.0% by weight, in particular 0.02 to 1.0% by weight, of a compound (I), based on the weight of the functional liquid.
Non-aqueous functional liquids are preferred, in particular base oils of lubricating viscosity, which can be used for the preparation of greases, metal working fluids, gear fluids and hydraulic fluids.
Suitable greases, metal working fluids, gear fluids and hydraulic fluids are based, for example, on mineral or synthetic oils or mixtures thereof. The lubricants are familiar to a person skilled in the art and are described in the relevant literature, such as, for example, in Chemistry and Technology of Lubricants; Mortier, R. M. and Orszulik, S. T. (Editors); 1992 Blackie and Son Ltd. for GB, VCH-Publishers N.Y. for U.S., ISBN 0-216-92921-0, cf. pages 208 et seq. and 269 et seq.; in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition 1969, J. Wiley & Sons, New York, Vol. 13, page 533 et seq. (Hydraulic Fluids); Performance Testing of Hydraulic Fluids; R. Tourret and E. P. Wrght, Hyden & Son Ltd. GB, on behalf of The Institute of Petroleum London, ISBN 0 85501 317 6; Ullmann's Encyclopedia of Ind. Chem., Fifth Completely Revised Edition, Verlag Chemie, DE-Weinheim, VCH-Publishers for U.S., Vol. A 15, page 423 et seq. (Lubricants), Vol. A 13, page 165 et seq. (Hydraulic Fluids).
The lubricants are in particular oils and greases, for example based on mineral oil or vegetable and animal oils, fats, tallow and wax or mixtures thereof. Vegetable and animal oils, fats, tallow and wax are, for example, palm kernel oil, palm oil, olive oil, colza oil, rapeseed oil, linseed oil, soy bean oil, cotton wool oil, sunflower oil, coconut oil, maize oil, castor oil, walnut oil and mixtures thereof, fish oils, and chemically modified, e.g. epoxidised or sulphoxidised, forms or forms prepared by genetic engineering, for example soy bean oil prepared by genetic engineering.
Examples of synthetic lubricants include lubricants based on aliphatic or aromatic carboxylic esters, polymeric esters, polyalkylene oxides, phosphoric acid esters, poly-α-olefins or silicones of the diester of a dibasic acid with a monohydric alcohol, e.g. dioctyl sebacate or dinonyl adipate, of a triester of trimethylolpropane with a monobasic acid or with a mixture of such acids, e.g. trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, of a tetra ester of pentaerythritol with a monobasic acid or with a mixture of such acids, e.g. pentaerythrityl tetracaprylate, or of a complex ester of monobasic and dibasic acids with polyhydric alcohols, e.g. a complex ester of trimethylolpropane with caprylic and sebacic acid or of a mixture thereof. Particularly suitable in addition to mineral oils are, for example, poly-α-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene glycols and mixtures thereof with water.
Said lubricants or mixtures thereof can also be mixed with an organic or inorganic thickener (base fat). Metal working fluids and hydraulic fluids can be prepared on the basis of the same substances as described above for the lubricants. These are frequently also emulsions of such substances in water or other liquids.
A further embodiment of the invention relates to a composition, which comprises additional additives selected from the group consisting of metal deactivators, antioxidants, rust inhibitors, viscosity index improvers, pour-point depressants, dispersants, surfactants, extreme-pressure additives, and antiwear additives.
Such additives are added in the amounts customary in each case for the purpose, each in the range from 0.01 to 10.0% by weight. Examples of further additives are listed below:
Said components can be mixed with the lubricants in a manner known per se. It is also possible to prepare a concentrate or a so-called additive packet, which can be diluted to the concentrations of use for the corresponding lubricant according to consumption.
A preferred embodiment of the invention relates to a composition comprising
A highly preferred embodiment of the invention relates to a composition comprising
The invention particularly refers to a composition comprising
Another highly preferred embodiment of the invention relates to composition comprising
A further embodiment of the invention relates to a mixture comprising
The mixtures defined above is particularly useful in method for improving the functional properties of lubricants, hydraulic or metal-working fluids or coating compositions, which comprises adding to a functional fluid the mixture defined above and, optionally, further additives.
The following examples illustrate the invention:
99.9 g (0.75 mol) tolutriazole (IRGAMET TTA, 2:3 mixture of 4(5)-methyl-1H-benzotriazole (2:3)), 75.15 g (0.75 mol) cyclohexanol (Riedel 24217) and 18.8 g (7% per weight based on the weight of all reactants) Montmorillonite K5 (Fluka 69908) are added to 147.0 g cyclohexane. The suspension is stirred and heated under reflux conditions. The water from the earth clay is removed for 30 min. in the gas phase and separated. 90.06 g (0.789 mol) heptanal are added within a time period of 30 min. The mixture is stirred and heated for 4 h under reflux conditions and, when the separation of water ceases, cooled to room temperature and filtered. The solvent is removed from the yellowish filtrate in the vacuum and a yellowish oil is obtained, which contains less than 1% TTA (HPLC). In the gas chromatogram 0.7% TTA, 1.1% heptanal and 0.8% cyclohexanol are found.
According to an alternative embodiment of the process, Montmorillonit is replaced with Bleicherde Tonsil® Supreme 110FF.
Mixtures comprising different amounts of tolutriazole (I) with regard to the condensation product (II) are prepared in a manner analogous to Example 1 by adding excess amounts of (I) to the reaction mixture:
A 0.05% solution of the test composition in a mineral oil of turbine quality is prepared, which oil has a viscosity of 26.2 mm2/sec (40° C.) and 4.8 mm2/sec (100° C.) and a sulphur content of 0.54%. The solution can also contain a phenolic or amine antioxidant. The time required at a temperature of 150° C. for a minimum pressure drop of 1.75 bar starting from the maximum pressure of 6.2 bar is measured.
A 0.04% solution of the test composition in a poly-alpha-olefin (PAO), which has a viscosity of 7.7-8.0 cSt (100° C.) and a content of 50 ppm of elemental sulphur, is prepared. A copper strip (50×10×1 mm) is polished with grade 150 silicon carbide, which was absorbed with a wool pad wet with high-boiling petroleum ether. The polished strip is then completely immersed in the prepared solution, which is kept at 100° C. for two hours. The strip is then removed, washed with isooctane and dried and its colour is compared with the standardized colour samples of the tarnish chart, which is applicable for the corrosion test of copper strips according to ASTM D130.
1)Group II, ISO 46 (blend of Jurong 150 and 500)
2)IRGALUBE AF 1
3)Base Formulation
1)RPVOT: Average of duplicates, minutes; ASTM D 2272
2)Copper corrosion per ASTM D 130, 3 h at 125° C. with 50 ppm elemental sulphur present
The findings in the RPVOT show outstanding antioxidative properties exerted by representative compositions in a non-aqueous functional fluid in the presence of phenolic and aminic antioxidants.
The findings in the copper corrosion test show outstanding deactivation of copper, which is achieved in a non-aqueous functional fluid in the presence of representative blends.
| Number | Date | Country | Kind |
|---|---|---|---|
| 04105973.4 | Nov 2004 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP05/55934 | 11/14/2005 | WO | 00 | 5/15/2007 |
