Liquid polyfunctional additives for improved fuel lubricity

Abstract: The lubricity (anti-wear properties) of fuels, for example hydrocarbon fuels, oxygenated fuels or mixtures thereof, particularly diesel or aviation fuels having reduced sulphur and/or aromatic content for compliance with regulator requirements, is improved by addition of at least a product which can be obtained by reacting components a), b) and c), where component a) is a compound of the formula I or a mixture of compounds of the formula I, component b) is a compound of the formula II or a mixture of compounds of the formula II and component c) is a compound of the formula III or a mixture of compounds of the formula III, in which the general symbols are as defined in claim 1, the compound of the formula I being, for example, pentaerythritol, thiodiethylene glycol, 1,4-butanediol, 1,4-propanediol, diethylene glycol, triethylene glycol, diethanolamine or glycerol, the compound of the formula II being, for example, sunflower oil or coconut fat, and the compound of the formula III being, for example, methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The abovementioned products also improve corrosion inhibition.

Description: The present invention relates to a process for reduction of wear in a Diesel engine The United States Government has mandated a reduction in the sulfur and aromatic content of commercial diesel fuels. Regulatory agencies in other countries have either introduced such a requirement or are contemplating doing so. This regulatory regime causes a problem insofar as the fuel industry recognises that fuels which comply with the regulation will exhibit reduced lubricity. The refining processes needed to produce these fuels require more severe hydrotreatment which removes polar species from the fuel and reduces its lubricity. Lubricity is a measure of the capacity of the fuel to flow through the engine without causing excessive wear. Even marginal changes in lubricity may be significant in increasing wear of fuel pumps, valves and injector nozzles over an extended period of use. WO 96/16143 discloses that specific phosphorus esters improve the lubricity (anti-wear properties) of hydrocarbon fuels, oxygenate fuels or mixtures thereof, particularly diesel or aviation fuels having reduced sulfur and/or aromatic content. EP-A-0 565 487 which is related to U.S. 5,478,875 discloses liquid antioxidants as stabilizers for polymers and lubricants. Surprisingly, it has now been found that these liquid antioxidants possess also anti-wear, lubricity improving and corrosion inhibiting properties in fuels having lower sulfur and/or aromatic contents. The present invention relates to a process for the reduction of wear in a Diesel engine, which comprises adding to the engine fuel system an antiwear fuel composition comprising α) A Diesel fuel having reduced sulphur content of less than 0.05 % by weight and/or an aromatic content of less than 35% by weight; and β) At least one product obtainable by reacting components a), b) and c), in any desired sequence in the presence of a catalyst and the optional presence of a solvent at a temperature range from 130 to 250°C, wherein component a) is a compound of the formula I or a mixture of compounds of the formula I, component b) is a compound of the formula II or a mixture of compounds of the formula II and component c) is a compound of the formula III or a mixture of compounds of the formula III X(Y) a , in which in the compound of the formula I, a is an integer from 2 to 4, where if a is 2, Y represents hydroxy, and X is -C c H 2c - c is the number 2, 3 or 4; or if a is 3, Y represents hydroxy and X is or, if a is 4, Y represents hydroxy and X is and in the compound of the formula II, the radicals Z are hydrogen or a group of the formula k is the number 1 and R 11 is C 1 -C 20 alkyl or C 8 -C 20 alkenyl, with the proviso that the compound of the formula comprises a group and in the compound of the formula III, R 12 is tert-butyl, R 15 is C 1 -C 4 alkyl and is bonded in the ortho-position relative to the OH group, s is the number 1, Q is -C m H 2m - and is bonded in the para-position relative to the OH group, where m is 2, n is 1 and R 17 is C 1 -C 4 alkyl. Alkyl having not more than 45 C atoms is a branched or unbranched radical such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl or pentacosyl. Cycloalkyl having not more than 12 C atoms is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl. Alkenyl having not more than 30 C atoms is, for example, vinyl, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, oleyl, n-octadec-2-enyl or n-octadec-4-enyl. Phenylalkyl having 7 to 9 C atoms is, for example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl or phenylethyl. Benzyl is preferred. Examples of phenyl which is substituted by 1 to 3 radicals A 1 are o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 2-methyl-4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2,6-diethyl-4-methylphenyl, 2,6-diisopropylphenyl, 4-tert-butylphenyl, p-nonylphenyl, o-, m- or p-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, o-, m- or p-hydroxyphenyl, o-, m- or p-methoxyphenyl, o- or p-ethoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,5-diethoxyphenyl, o-, m- or p-methoxycarbonyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl, 3-chloro-4-methylphenyl, 4-chloro-2-methylphenyl, 5-chloro-2-methylphenyl, 2,6-dichloro-3-methylphenyl, 2-hydroxy-4-methylphenyl, 3-hydroxy-4-methylphenyl, 2-methoxy-5-methylphenyl, 4-methoxy-2-methylphenyl, 3-chloro-4-methoxyphenyl, 3-chloro-6-methoxyphenyl, 3-chloro-4,6-dimethoxyphenyl and 4-chloro-2,5-dimethoxyphenyl. Alkyl having 1 to 18 C atoms is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Cycloalkoxy having 5 to 12 C atoms is, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy or cyclododecyloxy. Examples of C 7 -C 9 phenylalkyl which is mono-, di- or trisubstituted on the phenyl ring by C 1 -C 4 alkyl are methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl. Acyl having 1 to 8 C atoms is, for example, formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, benzoyl, acryloyl or crotonyl. C 1 -C 8 Alkanoyl, C 3 -C 8 alkenoyl or benzoyl, in particular acetyl, are preferred. means that the phenyl ring can be ortho-, meta- or para-substituted. The three components a), b) and c) can be reacted with each other to give the products of the present invention in any desired sequence. Preferably, component a) is first reacted with component b), and component c) is then added. The reaction is advantageously carried out in the presence of a catalyst. Suitable catalysts are Lewis acids or bases. Examples of suitable basic catalysts are metal hydrides, metal alkylides, metal arylides, metal hydroxides, metal alcoholates, metal phenolates, metal amides or metal carboxylates. Examples of preferred metal hydrides are lithium hydride, sodium hydride or potassium hydride. Examples of preferred metal alkylides are butyllithium or methyllithium. An example of a preferred metal arylide is phenyllithium. Examples of preferred metal hydroxides are lithium hydroxide, sodium hydroxide, potassium hydroxide, caesium hydroxide, rubidium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide or aluminium hydroxide. Examples of preferred metal alcoholates are sodium methanolate, sodium ethanolate, potassium methanolate, potassium ethanolate, sodium isopropylate or potassium tert-butylate. Examples of preferred metal phenolates are sodium phenolate or potassium phenolate. Examples of preferred metal amides are sodium amide or lithium amide. An example of a preferred metal carboxylate is calcium acetate. Examples of suitable Lewis acid catalysts are or the radicals R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 and R 39 being, independently of one another, for example C 1 -C 18 alkyl or phenyl. C 1 -C 8 Alkyl is preferred. A particularly preferred Lewis acid catalyst is dibutyltin oxide. The catalyst is added to components a), b) and c) for example in an amount of from 0.05 to 10 per mil by weight, preferably in an amount of from 0.1 to 5 per mil by weight. An addition of 1 to 2 per mil by weight of dibutyltin oxide is particularly preferred. The components a), b) and c) can be reacted in a solvent, for example xylene, or without solvent. The reaction is preferably carried out without solvent. The reaction temperature is, for example, between 130 and 250°C. The reaction is preferably carried out in a temperature range from 130 to 190°C. A preferred process for the preparation of the products of component (β) comprises reacting the components a), b) and c) in a molar quantitative ratio of 0.1:1:0.1 to 15:1:30 and is disclosed in EP-A-0 565 487 which is related to U.S. 5,478,875. If components a), b) and c) are not commercially available, they can be prepared by known processes or analogously. Possible preparation processes for the compounds of the formula III can be found, for example, in the following publications: GB-A-996 502, U.S. 3,330,859; U.S. 3,944,594; U.S. 4,593,057; EP-A-154 518 or U.S. 3,960,928. Examples of preferred compounds of the formula I are pentaerythritol, 1,4-butanediol, 1,2-propanediol, glycerol,. Glycerol is particularly preferred. Preferred compounds of the formula II are naturally occurring vegetable oils, fats and waxes, animal oils and fats as well as artificial polyol derivatives. Preferred vegetable oils, fats and waxes are, for example, sunflower oil, coconut fat, rapeseed oil, soya oil, maize germ oil, safflower oil, olive oil, groundnut oil, cottonseed oil, sesame seed oil, castor oil, tallow oil, pumpkin seed oil or linseed oil. Preferred animal oils and fats are, for example, butter fat, lard, fish oil, sperm oil, neat's foot oil or train oils. Examples of preferred artificial polyol derivatives are Radiamuls (glycerol tri C 8 /C 10 ) or sorbitan derivatives. The sorbitan derivatives are commercially available, for example, under the names Span®20, Span®40, Span®60, Span®65, Span®80, Span®85, Tween 20®, Tween 40®, Tween 60®, Tween 65®, Tween 80® or Tween 85®. Sunflower oil, coconut fat or rapeseed oil are particularly preferred. Particularly preferred compounds of the formula III are methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate and methyl 3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate. Of particular preference is a process according to claim 1 using compositions, wherein the compound of the formula I is pentaerythritol, 1,4-butanediol, 1,2-propanediol, glycerol, or a mixture of these, component b) is a compound of the formula II, in particular sunflower oil, coconut oil, rapeseed oil, maize germ oil, safflower oil, olive oil, groundnut oil or Radiamuls or a mixture of these, and component c) is a compound of the formula III, in particular methyl 3-(3',5'-ditert-butyl-4'-hydroxyphenyl)propionate or methyl 3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate. The present invention furthermore relates to a process according to claim 1 using compositions comprising as component (β) products which can be obtained by reacting components a), b) and c) in a molar quantitative ratio of 0.1:1:0.1 to 15:1:30. A molar quantitative ratio of 1:1:1 to 10:1:20 is preferred. A molar quantitative ratio of 4:1:5 to 10:1:20 is particularly preferred. A molar quantitative ratio of 5:1:10 is especially preferred. Of special interest are compositions comprising as component (β) products in which the amount by weight of active group E-2 in component (β) is 30 to 80 % by weight, preferably 35 to 80% by weight, in particular 50 to 80% by weight. As already mentioned, the present products of component (β) possess anti-wear and corrosion inhibiting properties in fuels. Particular mention is made of their outstanding improvement of the lubricity (anti-wear properties) of fuels with lower sulfur and/or aromatic contents. The present invention therefore also relates to the use of the products of component (β) as anti-wear agent for a diesel engine fuel system. As a rule, the products of component (β) are added to the diesed fuel in amounts from 0.0001 to 10.0 %, preferably 0.001 to 0.2 %, in particular 0.005 to 0.1 %, based on the weight of component (α). The products of component (β) may also be blended with liquid carriers, compatible with the end product fuels, to form concentrates for subsequent addition to fuel basestocks or formulated fuels. Such concentrates may facilitate mixing, blending, pouring or transferring (bulk or line) of the products of component (β). Typically, the carriers are organic solvents for the products of component (β), such as hydrocarbons like for example xylene or toluene, ethers, alcohols or mixtures thereof, or they may be portions of the fuel basestocks or formulated fuels intended as the end products. Addition of the concentrates to basestocks of formulated fuels to form end product fuels may be batchwise, for example from unit containers of concentrates sold at retail or other outlets, or may be added by metering at refineries or fuel distribution sites. Other modes of addition will be evident. The amount of the products of component (β) in the concentrate may vary, depending on desired concentrate properties such as viscosity. Generally, about 10 to 90 % by weight of the products of component (β) in the carrier medium is suitable, more usually about 20 to 50 % by weight. The composition of these diesel fuels varies widely with the nature of the crude oil, the refining process, the components with which the raw fuel is blended, and the climate in which the fuel is to be marketed. As noted above, this invention finds particular application in diesel fuels having a reduced sulfur and/or aromatic content which are now being produced in order to comply with regulatory requirements. These fuels typically have sulfur contents below 500 ppm (0.05 %) and/or an aromatic content of less than 35 % by weight. The composition of the diesel fuel and hence its inherent lubricity may vary according to the severity of the local regulatory regime. In addition to the products of component (β), the compositions according to the invention can also contain conventional additives which are added to improve the basic properties of fuel even further as disclosed in the Handbook "Lubricant and Fuel Additives" published by Kline & Company, Inc. International Business Consultants, Fairfield, NJ, USA, pages 309-320 (1990); these include: antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour-point depressants, dispersants, detergents, high-pressure additives, antifriction additives, antiwear additives, demulsifying agents, cloud point depressants, waxy anti-settling additives, anti-static additives, anti-foams, dehazer additives, biocides, odor masks, dyes, cetane improvers, antiicings, antiknock additives, conductivity improvers, PFI/IVD cleanliness additives and other lubricity additives. Examples of such conventional additives are the following: 1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof. 1.2. Hydroquinones and alkylated hydroquinones , for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate. 1.3. Alkylidenebisphenols , for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane. 1.4. O- and N-benzyl compounds , for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether or tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine. 1.5. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis-[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate. 1.6. 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-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol. 1.7. Triazine Compounds, for example 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine , 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahy dro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate. 1.8. Benzylphosphonates , for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.9. Acylaminophenols , for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate. 1.10. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.11. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.12. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.13. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.14. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine. Examples of aminic antioxidants: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis-(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol. Examples of other antioxidants : Aliphatic or aromatic phosphites, esters of thiodipropionic acid or of thiodiacetic acid, or salts of dithiocarbamic 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 derivatives thereof, for example 4- or 5-alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole or tolutriazole, e.g. 1-[bis(2-ethylhexyl)aminomethyl)tolutriazole and 1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)-benzotriazole, 1-(1-butoxyethyl)benzotriazole and 1-(1-cyclohexyloxybutyl) tolutriazole. b) 1,2,4-Triazoles and derivatives thereof, for example 3-alkyl(or aryl)-1,2,4-triazoles, and Mannich bases of 1,2,4-triazoles, such as 1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole; and acylated 3-amino-1,2,4-triazoles. c) Imidazole derivatives, for example 4,4'-methylenebis(2-undecyl-5-methylimidazole) and 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 and derivatives thereof; and 3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin- 2-one. e) Amino compounds, for example salicylidenepropylenediamine, salicylaminoguanidine and salts thereof. 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 alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids such as dodecyloxyacetic acid, dodecyloxy(ethoxy)acetic acid and the amine salts thereof, and also N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydrides, for example dodecenylsuccinic anhydride, 2-carboxymethyl-1-dodecyl-3-methylglycerol and the amine salts thereof. b) Nitrogen-containing compounds, for example: I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates, and also 1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol. II. Heterocyclic compounds, for example: substituted imidazolines and oxazolines, and 2-heptadecenyl-1-(2-hydroxyethyl)imidazoline. c) Phosphorus-containing compounds, for example: Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, and zinc dialkyldithiophosphates. d) Sulfur-containing compounds, for example: barium dinonylnaphthalenesulfonates, calcium petroleum sulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and salts thereof. e) Glycerol derivatives, for example: glycerol monooleate, 1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols, 1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols and 2-carboxyalkyl-1,3-dialkylglycerols. Examples of viscosity index improvers are: Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinyl-pyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers and polyethers. Examples of pour-point depressants are: Polymethacrylate and alkylated naphthalene derivatives. Examples of dispersants/surfactants are: Polybutenylsuccinic amides or -imides, polybutenylphosphonic acid derivatives and basic magnesium, calcium and barium sulfonates and phenolates. Examples of antiwear additives are : Sulfur- and/or phosphorus- and/or halogen-containing compounds, e.g. sulfurised olefins and vegetable oils, zinc dialkyldithiophosphates, alkylated triphenyl phosphates, tritolyl phosphate, tricresyl phosphate, chlorinated paraffins, alkyl and aryl di- and trisulfides, amine salts of mono- and dialkyl phosphates, amine salts of methylphosphonic acid, di-ethanolaminomethyltolyltriazole, bis(2-ethylhexyl)aminomethyltolyltriazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, ethyl 3-[(diisopropoxyphosphinothioyl)thio]propionate, triphenyl thiophosphate (triphenylphosphorothioate), tris(alkylphenyl) phosphorothioate and mixtures thereof (for example tris(isononylphenyl) phosphorothioate), diphenyl monononylphenyl phosphorothioate, isobutylphenyl diphenyl phosphorothioate, the dodecylamine salt of 3-hydroxy-1,3-thiaphosphetane 3-oxide, trithiophosphoric acid 5,5,5-tris[isooctyl 2-acetate], derivatives of 2-mercaptobenzothiazole such as 1-[N,N-bis (2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiazole, and ethoxycarbonyl-5-octyldithiocarbamate. The conventional additives are added for example at concentrations of 0.01 to 10% based on the total weight of the fuel. The products of component (β) of this invention may be combined with any of these additives provided the components of such mixtures are mutually compatible. The products of component (β) of this invention may be added separately to the fuel or they may be combined with one or more of the additives described to produce an additive formulation which is suitable for addition to a base fuel. The examples which follow illustrate the invention in greater detail. Parts and percentages are by weight, unless otherwise indicated. Example 1 : Preparation of the sunflower oil derivatives using pentaerythritol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. In a sulfonation flask equipped with reflux condenser and mechanical stirrer, a mixture of 30 g (~34 mmol) sunflower oil, 4.64 g (34 mmol) of pentaerythritol and 37 mg (0.15 mmol) of dibutyltin oxide is kept under nitrogen for 7 hours at 180-190°C. 9.94 g (34 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate and another 37 mg (0.15 mmol) of dibutyltin oxide are subsequently added. Stirring of the reaction mixture is continued for 15 hours at 180-190°C. When cold, 40.64 g (91%) of product are obtained as a yellow oil having a refractive index n 20 D of 1.4882. Example 2 : Preparation of the coconut oil derivatives using pentaerythritol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 1 is repeated, except that 403 g (~0.616 mol) of coconut fat, 83.1 g (0.610 mol) of pentaerythritol, 1.0 g (4 mmol) of dibutyltin oxide and 178.4 g (0.610 mol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 653 g (98%) of product as a brown oil having a refractive index n 20 D of 1.4781. Example 3 : Preparation of the sunflower oil derivatives using 1,4-butanediol and methyl 3-(3' ,5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 1 is repeated, except that 30 g (~34 mmol) sunflower oil, 14 g (155 mmol) of 1,4-butanediol, 199 mg (0.80 mmol) of dibutyltin oxide and 87.7 g (300 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 124 g (94%) of product as a reddish oil having a refractive index n 20 D of 1.5070. Example 4 : Preparation of the coconut oil derivatives using 1,4-butanediol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 1 is repeated, except that 30 g (~46 mmol) of coconut fat, 14 g (155 mmol) of 1,4-butanediol, 199 mg (0.80 mmol) of dibutyltin oxide and 87.7 g (300 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 123 g (93%) of product as a reddish oil with a refractive index n 20 D of 1.5025. Example 5 : Preparation of the sunflower oil derivatives using 1,2-propanediol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 1 is repeated, except that 30 g (~34 mmol) of sunflower oil, 12.2 g (160 mmol) of 1,2-propanediol, 199 mg (0.80 mmol) of dibutyltin oxide and 87.7 g (300 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 121.7 g (93.7%) of product as a yellow oil having a refractive index n 20 D of 1.5047. Example 6 : Preparation of the sunflower oil derivatives using glycerol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 1 is repeated, except that 30 g (~34 mmol) of sunflower oil, 14.22 g (154 mmol) of glycerol, 199 mg (0.80 mmol) of dibutyltin oxide and 87.73 g (300 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 126.5 g (96%) of product as a pale yellow, viscous oil having a refractive index n 20 D of 1.5128. Example 7 : Preparation of the coconut oil derivatives using glycerol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 1 is repeated, except that 30 g (about 46 mmol) of coconut fat, 19.4 g (211 mmol) of glycerol, 249 mg (1.0 mmol) of dibutyltin oxide and 118 g (404 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 154 g (92%) of product as a pale yellow, viscous oil having a refractive index n 20 D of 1.5123. Example 8 : Preparation of the sunflower oil derivatives using glycerol and methyl 3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate. The procedure described in Example 1 is repeated, except that 30 g (~34 mmol) of sunflower oil, 14.5 g (157 mmol) of glycerol, 180 mg (0.72 mmol) of dibutyltin oxide and 75.20 g (300 mmol) of methyl 3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate are used, affording 105.0 g (96%) of product as an orange oil having a refractive index n 20 D of 1.5165. The procedure described in Example 1 is repeated, except that 31.0 g (~47 mmol) of coconut fat, 10.1 g (50 mmol) of N-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 50 mg (0.20 mmol) of dibutyltin oxide and 14.60 g (50 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 52.4 g (98%) of product as a yellow oil having a refractive index n 20 D of 1.4811. Example 9 : Preparation of the rapeseed oil derivatives using glycerol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. In a sulfonation flask equipped with reflux condenser and mechanical stirrer, a mixture of 116.3 g (~134 mmol) of rapeseed oil, 86.1 g (935 mmol) of 85% aqueous glycerol and 2.64 g (15.0 mmol) of calcium acetate is kept for 7 hours under a nitrogen atmosphere at 180-190°C. 357.5 g (1.22 mol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are subsequently added. Stirring of the reaction mixture is continued for 15 hours at 180-190°C. After cooling, 505 g (99%) of product are obtained as a yellow oil having a refractive index n 20 D of 1.5122. Example 10 : Preparation of the maize germ oil derivatives using glycerol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 9 is repeated, except that 100 g (~113 mmol) of maize germ oil, 57.5 g (624 mmol) of 85% aqueous glycerol, 2.32 g (13.0 mmol) of calcium acetate and 282.4 g (966 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 399.0 g (99%) of product as a yellow oil having a refractive index n 20 D of 1.5127. Examples 11 : Preparation of the safflower oil derivatives using glycerol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 9 is repeated, except that 100 g (~113 mmol) of safflower oil, 57.6 g (625 mmol) of 85% aqueous glycerol, 2.11 g (12.0 mmol) of calcium acetate and 286.5 g (980 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 403.2 g (99%) of product as a yellow oil having a refractive index n 20 D of 1.5140. Example 12 : Preparation of the olive oil derivatives using glycerol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 9 is repeated, except that 100 g (~114 mmol) of olive oil, 58.0 g (630 mmol) of 85% aqueous glycerol, 2.11 g (12.0 mmol) of calcium acetate and 290.4 g (993 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 408.6 g (99%) of product as a yellow oil having a refractive index n 20 D of 1.5110. Example 13 : Preparation of the groundnut oil derivatives using glycerol and methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. The procedure described in Example 9 is repeated, except that 100 g (~114 mmol) of groundnut oil, 58.0 g (630 mmol) of 85% aqueous glycerol, 2.11 g (12.0 mmol) of calcium acetate and 291.4 g (997 mmol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate are used, affording 413.5 g (99%) of product as a yellow oil having a refractive index n 20 D of 1.5100. Example 14 : HFRR (High Frequency Reciprocating Rig) test for low sulfur diesel fuel. The anti-wear properties of the products of component (β) in low sulfur diesel fuel (available from EMPA, Switzerland) has been tested using the HFFR fuel lubricity tester under the conditions prescribed by the CEC F-06-A-96 test method which is available from CEC Secretariat, Place Madou 1, B-1030 Brussells, Belgium; or SAE Order Department 782, 400 Commonwealth Drive, Warrendale, PA 15096, USA. Details of the test method are disclosed for example in Wei Dan Ping and H.A. Spikes, Wear, 111 , 217-235 (1986) or Wei Dan Ping, S. Korcek and H.A. Spikes, SAE 962010. With the HFFR tester the lubricity of a fuel sample is assessed through the measurement of the wear occurring after 75 minutes of an oscillating displacement of a steel ball against a flat disk. The ball diameter is 6.00 mm, the frequency of the displacement is 50 Hertz, its stroke length is 1 mm and the load applied on the ball is 200 g. The ball and the flat disk are immersed in the fuel to be tested. Other conditions like relative humidity do influence the results and must be hold within the prescribed limits. At the end of the test duration, the diameter of the wear scar on the ball is measured and a correction is applied which normalises all results to a standard water vapour pressure of 14 mbar. The results are reported in micometer (µm). A high lubricity and a low lubricity reference fuel are available for the calibration. The high lubricity fuel gives a wear scar in the range of 380 to 437 µm. The low lubricity fuel gives a wear scar in the range of 600 to 760 µm. Both fuels are available via the CEC working group. The lower the wear scar the better are the anti-wear properties of the products of component (β) in the low sulfur diesel fuel. The results are summarized in Table 1. HFFR test for low sulfur diesel fuel Example Additive Amount Wear Scar (µm) 27a _ _ 650 27b Product of example 7 0.03 % 0.04% 260 220

Claims: A process for the reduction of wear in a Diesel engine, which comprises adding to the engine fuel system an antiwear fuel composition comprising α) A Diesel fuel having reduced sulphur content of less than 0.05% by weight and/or an aromatic content of less than 35% by weight; and β) At least one product obtainable by reacting components a), b) and c), in any desired sequence in the presence of a catalyst and the optional presence of a solvent at a temperature range from 130 to 250°C, wherein component a) is a compound of the formula I or a mixture of compounds of the formula I, component b) is a compound of the formula II or a mixture of compounds of the formula II, and component c) is a compound of the formula III or a mixture of compounds of the formula III: X(Y) a , in which in the compound of the formula I, a is an integer from 2 to 4, where if a is 2, Y represents hydroxy, and X is -C c H 2c - c is the number 2, 3 or 4; or if a is 3, Y represents hydroxy and X is or, if a is 4, Y represents hydroxy and X is and in the compound of the formula II, the radicals Z are hydrogen or a group of the formula k is the number 1 and R 11 is C 1 -C 20 alkyl or C 8 -C 20 alkenyl, with the proviso that the compound of the formula comprises a group and in the compound of the formula III, R 12 is tert-butyl, R 15 is C 1 -C 4 alkyl and is bonded in the ortho-position relative to the OH group, s is the number 1, Q is -C m H 2m - and is bonded in the para-position relative to the OH group, where m is 2, n is 1 and R 17 is C 1 -C 4 alkyl. A process according to claim 1, in which the compound of the formula I is pentaerythritol, 1,4-butanediol, 1,2-propanediol, glycerol, the compound of the formula II is sunflower oil, coconut fat, rapeseed oil, maize germ oil, safflower oil, olive oil, groundnut oil or Radiamuls, and the compound of the formula III is methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate or methyl 3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate. A process according to claim 1, in which the molar quantitative ratio of components a), b) and c) is 0.1:1:0.1 to 15:1:30. A process according to claim 1, in which the amount by weight of active group E-2 in component (β) is 30 to 80% by weight. A process according to claim 1, in which first components a) and b) are reacted with each other and the resulting intermediate is subsequently reacted with component c). A process according to claim 1, wherein the composition contains component (β) in an amount of 0.0001 to 10 %, based on the weight of component (α).

Inventors: DUBS PAUL, EVANS SAMUEL, RASBERGER MICHAEL, RIBEAUD MARC, DUBS, PAUL, EVANS, SAMUEL, RASBERGER, MICHAEL, RIBEAUD, MARC
Applicants: CIBA SC HOLDING AG, CIBA SPECIALTY CHEMICALS HOLDING INC.
Application year: 1998
Main classification: C10L1
IPC codes: C10L1, C10L10