MXPA98000903A - Liquid polifunctional additives for improved lubrication of combusti - Google Patents

Liquid polifunctional additives for improved lubrication of combusti

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Publication number
MXPA98000903A
MXPA98000903A MXPA/A/1998/000903A MX9800903A MXPA98000903A MX PA98000903 A MXPA98000903 A MX PA98000903A MX 9800903 A MX9800903 A MX 9800903A MX PA98000903 A MXPA98000903 A MX PA98000903A
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Mexico
Prior art keywords
alkyl
formula
hydrogen
compound
phenyl
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Application number
MXPA/A/1998/000903A
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Spanish (es)
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MX9800903A (en
Inventor
Evans Samuel
Dubs Paul
Ribeaud Marc
Michaelrasberger
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Ciba Specialty Chemicals Corporation
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Publication of MX9800903A publication Critical patent/MX9800903A/en
Publication of MXPA98000903A publication Critical patent/MXPA98000903A/en

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Abstract

The present invention relates to: The lubricity (anti-wear properties) of fuels is improved, for example, hydrocarbon oils, oxygenated fuels or mixtures thereof, particularly diesel or aviation fuels, which have a reduced sulfur content and / or aromatics, to comply with the regulatory requirements, by the addition of at least one product, which can be obtained by the reaction of components a), b) and c), wherein component a) is a compound of formula I or a mixture of compounds of the formula I, the component b) is a compound of the formula II or a mixture of compounds of the formula II, and the 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 formula I is, for example, pentaerythritol tiodiethylene glycol, 1,4-butanediol, 1,4-propanediol, diethylene glycol, triethylene glycol , d ietanolamine or glycerol, the compound of formula II is, for example, sunflower oil or coconut fat, and the compound of formula III is, for example, 3- (3 ', 5'-di-tert. -butyl-4'-hydroxyphenyl) -propianat or methyl. The aforementioned products also improve the inhibition of corrosion

Description

LIQUID POLYFUNTIONAL ADDITIVES FOR IMPROVED LUBRICATION OF FUEL The present invention relates to anti-wear fuel compositions, which comprise a fuel, preferably a diesel fuel and other fuels having lower sulfur and / or aromatic contents, a liquid polyfunctional additive, and the use of this liquid polyfunctional additive. as an antiwear agent and an agent that improves lubricity for a motor fuel system. The Government of the United States of America has ordered a reduction in the sulfur and aromatics content of commercial diesel fuels. Regulatory agencies in other countries have already introduced such a requirement or consider doing so. This regulatory regime causes a problem because the fuel industry recognizes that fuels that comply with this regulation will exhibit reduced lubricity. The refining processes necessary to produce these fuels require a more severe hydrotreatment, which removes the polar species from the fuel and reduces its lubricity. Lubricity is a measure of the ability of the fuel to flow through the engine without causing excessive wear. Even marginal changes in lubricity can be significant in increasing wear on fuel pumps, valves and injector nozzles over an extended period of use.
Patent WO 96/16143 discloses that specific phosphorus esters improve the lubricity (anti-wear properties) of hydrocarbon fuels, oxygenated fuels or mixtures thereof, particularly diesel or aviation fuels, which have a reduced sulfur content and / or aromatics.
EP-A-0 565 487, which is related to the U.S. patent. 5,478,875, discloses antioxidants as stabilizers for polymers and lubricants.
Surprisingly, it has been found that these antioxidants also have lubricity against wear, which improves and has corrosion inhibiting properties in fuels having better sulfur and / or aromatic contents.
Accordingly, the present invention relates to a fuel composition against wear, which comprises: a) a fuel and ß) at least one product, which can be obtained by reaction of components a), b) and c) wherein component a) is a compound of formula I or a mixture of compounds of formula I, component b) is a compound of formula II or a mixture of compounds of formula II and component c) is a compound of formula III or a mixture of compounds of formula III, X (Y) a (I) (ni) (ID wherein, in the compound of formula I, the radicals Y, independently of each other, are OH (HOCH2CH2) N- or -HNR; L and the radicals R1 are hydrogen, I rent C3-C6 alkenyl, C7-C9 phenylalkyl, phenyl or phenyl which is substituted by 1 to 3 radicals A] _, these radicals A ^, independently of each other, are C? -C? alkyl? , halogen, hydroxyl, methoxy or ethoxy, where R 2 is hydrogen, C 1 -C 6 alkyl, 0 *, OH, NO, -CH 2 CN, C 1 -C 12 alkoxy C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl, or C 7 -C 9 phenylalkyl, which is mono- di- or tri-substituted on the phenyl ring by C ^ C ^ alkyl or R2 is also acyl C ^ -Cg, or HOCH CH2-, it is already the number 1, 2, 3, 4 or 6, where, If Y is OH and a is 1, X is alkyl ^ -045, C3-C18 alkenyl, -CH2CH2T? (CH2CH20) bR or in which Ro has the above definitions and \ Ti is oxygen, sulfur or .N-R5, / R4 is C ^ ^ alkyl, b is an integer varying from 0 to 10 and R5 is hydrogen, C ^ -Cl-Ci alkyl, or phenyl or If Y is OH and a is 2, X is -CH2CH2T2 (CH2CH20) bCH2CH2-, where b has the above definitions, Rß -CH2CH2- N O O -CH2-CH = CH-CH2- f-CH2CH2-NH-C-C-H-CH? CH2 or wherein \? 7 T2 is oxygen, sulfur t NN - RR55 0o - - SS - CC - SS-- and R5 has the / 1 R « above definitions, Rβ is hydrogen, C?-C18 alkyl, or phenyl, c is an integer ranging from 2 to 10, d is an integer ranging from 2 to 6 and R7 and R8 'independently of each other, are hydrogen, alkyl cl ~ 18 '° phenyl, or R7 and R8 together with the C atom to which they are attached, form a cycloalkyl ring C? ~ C12, or if a is 3, X is C3-C10 alkanethyl, or N (CH2CH2-) 3, or if Y is OH and a is 4, CH? - I 1 X is C4-C10-C3-alkyotetrayl, (-CH2-CH-CH2) 20, -CH2-CH-CH2-0-CH-CH2-, , 0l1Je Rg is C ^ -C4 alkyl, if Y is OH and a is 6, X is -CH or C C-C alca alca alkanohexayl, ° / if Y is HNRi and a is 1, X is alkyl ^ -CIQ, C3-C18 alkenyl, C5-C12 cycloalkyl, C7-C9 phenylalkyl, phenyl, R2 is as defined before or X is or X together with R1 is a group of the formula -CH CH2CH CH2CH2- or -CH2CH2OCH2CH2-, wherein R10 is hydrogen or methyl and e is 2 or 3, or, if Y is -HNR and a is 2, X is -CfH2f-, CH2CH2-, where f is an integer that varies from 2 to 10 and g is an integer that varies from 1 to 6, and in the compound of the formula II, the radicals Z are hydrogen or a group of the formula: O - (ChHhO C-Rn k is an integer ranging from 0 to 6, where h is 2 or 3, i is an integer ranging from 0 to 12 and Rn is alkyl ^^ 30, C8-C30 alkenyl, C4-C2 cycloalkyl, phenyl or C7-C9 phenylalkyl, with the proviso that the O II compound of formula II has a group - (C ^ H ^ O ^ -C-RI,; in the compound of formula III, R12 is C2-C18 alkyl, C5-C2 cycloalkyl, phenyl or C7-C9 phenylalkyl, wherein R ^ 5 is as defined above, m is an integer ranging from 0 to 3, R16 is alkyl Cj ^ -Cg, and n is an integer ranging from 1 to 6, where if n is 1, R-L7 is hydrogen, C1-C45 alkyl, C5-C cycloalkyl? , C 2 -C 8 alkenyl, a monovalent radical of a hexose, a monovalent radical of a hexitol, wherein R2 has the above definitions or furthermore R17 is CH2CH2- T -R 19 where T3 is oxygen, sulfur or N-R 22, / Ri 9 is where R12 and R15 are as defined above, or R? g is also hydrogen, C C24 alkyl, phenyl, C5-C1 cycloalkyl or O -CH2-C-0-R25 'where p is an integer ranging from 2 to 4, q is a whole which varies from 2 to 20, R22 is alkyl ^ -C ^, phenyl or phenyl which is substituted by 1 to 3 radicals A] _, where the radicals A] _, independently of each other, are C1-C12 alkyl, halogen, hydroxyl, methoxy or ethoxy, or R22 is also C5-C8 cycloalkyl, R23 and R24 'independently of one another, are hydrogen or methyl, with the proviso that R23 and R24 are not simultaneously methyl-iote; R 4 is hydrogen or C 4 -C 24 alkyl, or if n is 2, R-L7 is a divalent radical of a hexose, a radical divalen _CrH2r-, was defined before, -CH2CH2-T4-CH2CH2-, -CH2-CH = CH-CH2-, -CH2-C = C-CH2-, wherein R18 and R20 'independently of each other, are hydrogen or C ^ -C ^ alkyl, or together are the radial -CH2CH2CH2CH2CH2-, r is an integer ranging from 2 to 10, T is sulfur, where R7 and R8 have the above definitions and R26 is hydrogen, C alquilo-Cg alkyl / phenyl or phenyl which is substituted by 1 to 3 radicals A] _, where the radicals A ^ are as defined above in Formula I, or R2g is also C5-Cg cycloalkyl, or where R2 has the previous definitions, or if n is 3, R ± -j is a trivalent radical of a hexose, a radical CH2CH -trivalent of a hexitol, I -CH2CH2-N-CH2CH2- ' -CH2 CH2-CH-CH3 I or -CH2-C-R27 5 CH, -CH-CHo-N-CH2-CH-CH3 where 3 2 2! -CH, R27 is hydrogen, CH2OH, C -C ^ alkyl, C? -C? Alkylamido, or where Q, R ^ 2 and R ^ g have the above definitions, or if n is 4, R17 is a tetravalent radical of a hexose, a tetravalent radical of a hexitol, to the if n is 5, R17 is a pentavalent radical of a hexose or a pentavalent radical of a hexitol or if n is 6, R17 is a hexavalent radical of a hexitol or The alkyl, having no more than 45 carbon atoms, is a branched or unbranched radial, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary 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, 1,1,2,2-tetra ethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1, 1,2,2, 5, 5- hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl, docosyl or pentacosyl. One of the preferred meanings of lf R 4 and R 16 is, for example, C 1 -C 4 alkyl, of R 2 is methyl, of R 1L is C1-C alkyl, of R12 and R15 is C1-C4 alkyl, in particular tertiary butyl, and of R17 is C1-C4 alkyl. The cycloalkyl, which has no more than 12 carbon atoms, is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl. One of the preferred meanings of Rlf R11 (R12 and R15 is C5-C7 cycloalkyl) Cyclohexyl is particularly preferred Alkenyl having no more than 30 carbon 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 If Rl 'R2 and x are C3-C6 alkenyl, then the carbon atom with which they bind to the nitrogen is advantageously saturated.Phenylalkyl, which has 7 to 9 carbon atoms. carbon 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 Ai are o-, m- or p- methylphenyl, 2,3-di-ethylphenyl, 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-dimethylphenyl, 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, 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-methylphenol, 3-hydroxy-4-methylphenyl, 2-methoxy -5-methylphenyl, 4-methoxy-2-methylphenyl, 3-chloro-4-methoxyphenyl, 3-chloro-6-ethoxyphenyl, 3-chloro-4,6-dimethoxyphenyl and 4-chloro-2,5-dimethoxyphenyl. Preferred is phenyl which is substituted by 1 or 2, in particular 1, radicals A_, where A ^ is, in particular, alkyl. The alkyl having 1 to 18 carbon atoms is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. One of the preferred meanings of R 2 is C 2 -C 2 alkoxy - Heptoxy and octoxy are particularly preferred. Cycloalkoxy having 5 to 12 carbon atoms is, for example, cyclopentoxy, cyclohexoxi, cycloheptoxy, cyclooctoxy, cyclodecyloxy or cyclododecyloxy. One of the preferred meanings of R2 is C5-C8-cialkoalkoxy. Cyclopentoxy and cyclohexoxi are particularly preferred. Examples of C7-C9 phenylalkyl, which is mono-, di- or tri-substituted on the phenyl ring by C -C4 alkyl, are methylbenzyl, dimethylbenzyl, trimethylbenzyl or tere. -butylbenzyl.
Acyl having 1 to 8 carbon atoms is, for example, formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, benzoyl, acryloyl or crotonyl, C alca ~ C8 alkanoyl, C3-C8 alkenoyl, or benzoyl, in particular, acetyl is preferred. The alkanetriyl having from 3 to 10 carbon atoms is, for example, | -CH2-CH-C -H 2-,. -CH.2-CHt2 - CH-CH, -.
-CH2-CH2-CH-CH2-CH2-, -CH2-CH2-CH-CH2-CH2-CH2- 0 -CH2-CH "CH2-CH-CH2-CH2-CH2-" Glyceryl is preferred.
The alkylethalyl having from 4 to 10 carbon-CH2 atoms is, for example. \ CH2-C-CH2- f _ ^ H2.¿H.H-CH2-, ~ CH2-CH2 - ¿HH - CHH - CCHH2 - C CHH22 --- CH2 - CH2 - CH - CH - CH2 -CH2-, _CH2-CH2-CH-CH2-? PHH-Cr.Ht-2-Cr.HH2- or > - GC: HH2 - C? HH2 - CGH - C? H - I2 - ^ CHL, 2-.CH? -. CHM --.C Pentaerythrityl is preferred. The alkanohexyl having 6 to 10 carbon atoms 0 is, for example, -CH2-c? -CH-c? -H-CH2-, -CH 2 -H-CH-CH 2 -H-CH-CH 2 - or -CH 2 -CH-CH-CH 2 -CH 2 -CH-CH-CH 2 -.
If R17, with n = 1 to 6 is an n-valent radical of a hexose, then this radical is derived, for example, from allose, altrose, glucose, mannose, gulose, iodine, galactose or talose, i.e. to obtain the corresponding compounds of formula III, one, two, three, four, five or six -OH groups must be replaced by the ester group El, in which R? , R15 s and Q have the above definitions. For example, R- with n = 5, can be a group Yes? is an n-valent radial of a hexitol, then the corresponding compounds of the formula III are obtained by replacing the -OH groups with the ester group E-1, mentioned above. R17, as a hexavalent radial of a hexitol, can be, for example.
This group is derived from D-sorbitol.
The alkylamido having 1 to 18 carbon atoms is, for example, CH3-CO-NH-, CH3CH2-CO-NH-, C6H13-CO-NH- or C18H37-CO-NH-. means that the phenyl ring can be ortho-, meta- or para-substituted. The three components a), b) and c) can react with each other to give the products of the present invention in any desired sequence. Preferably, component a) is reacted first 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 butyl lithium or methyl lithium. An example of a preferred metal arylide is phenyllithium.
Examples of preferred metal hydroxides are lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide or aluminum hydroxide. Examples of preferred metal alcoholates are sodium methanolate, sodium ethanolate, potassium methanolate, ethanoia or potassium, 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 the radicals R30, R31, R32, R33, R34, R35, R36, R37, R38 and R39 are, independently of each other, for example, alkyl or phenyl. Alkyl C] _-C] _g is preferred. A particularly preferred Lewis acid catalyst is dibutyl tin oxide.
The catalyst is added to components a), b) and c), for example, in an amount of 0.05 to 10 per thousand by weight, preferably in an amount of 0.1 to 5 per thousand by weight. An addition of 1 to 2 per thousand by weight of the dibutyltin oxide is particularly preferred. The components a), b) and e) can react in a solvent, for example xylene, or without a solvent. The reaction is preferably carried out without solvent. The reaction temperature is, for example, between 130 and 250SC. The reaction is preferably carried out at a temperature in the range of 130 to 1902C. A preferred process for the preparation of the component (ß) products comprises reacting components a), b) and c) in a molar quantitative ratio of 0.1: 1: 0.1 to 15: 1: 30 and is manifested in the EP-patent. A-0 565 487, which is related to the U.S. patent. 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 formula III can be found, for example, in the following publications: patents 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.
Of interest are compositions comprising as component (ß) products where, in the compound of formula III, s is number 1 or 2. Of specific interest are compositions comprising as component (ß) products in which , in the compound of the formula I, the radicals Y, independently of each other, are OH, (HOCH2CH2) 2N- or -HNR; L and Ri is hydrogen, C ^ -C ^ alkyl »- C5-C7 cycloalkyl, 1 C3-C6 alkenyl, benzyl or phenyl, in where R2 is hydrogen, C1-C4 alkyl, OH, CH2CN, Cg-C12 alkoxy, C5-C8 cycloalkoxy, allyl, benzyl, acetyl or HCOCH2CH2- and a is number 1, 2, 3, 4 or 6, where if Y is OH and a is 1, X is alkyl ^^ 30, C3-C18 alkenyl, -CH2CH2T1 (CH2CH0) ^ 4 or it is how it was defined before, and T e R 4 is C 1 -C 10 alkyl, b is an integer ranging from 0 to 10, and R 5 is hydrogen, alkyl, -CO 3, or phenyl. if Y is OH and a is 2, X is -CH2CH2T2 (CH2CH20) bCH CH2-, wherein b has the above definitions, O O - CH2CH2-NH -C -C - NH-CH2CH2 - or R7 T is oxygen, sulfur, N-R-S-C-S- and R5 is as defined above. / 5 ° R'8 Rg is hydrogen, alkyl CI-C ^ Q, O phenyl, c is an integer ranging from 2 to 10, d is an integer ranging from 2 to 6 and R7 and R8 'independently from each other, they are hydrogen, alkyl c ~ c10 ° phenyl, or R7 and R8 together with the carbon atom to which they are attached, form a C5-C7 cycloalkyl ring, or if Y is -HNRi is already 1, X is C 3 -C 8 alkyl, C 5 -C 7 cycloalkyl, benzyl, phenyl in which R 2 is as ant or X was defined together with ^ is a group of the formula -CH2CH2CH CH2CH2 or CH2CH2? CH CH2-, where R ^ O is hydrogen or methyl and e is 2 or 3 and in the compound of formula II, the radicals Z are hydrogen or a group of the formula O - (ChH2hO) --C-R1, and k is an integer ranging from 0 to 4, where h is 2 or 3, i is an integer ranging from 0 to 6 and Rll is C1-C20 alkyl, C1-C20 alkenyl, C5-C7 cycloalkyl, phenyl or benzyl, with the proviso that the compound of formula II comprises a group - (ChHghO CR ^; in the compound of the formula III R 1 is C 1 C alkyl, C 5 -C 7 cycloalkyl, phenyl or benzyl, s is 1 or 2, where R ^ has the above definitions, m is an integer ranging from 0 to 3, R16 is alkyl C ± -C and n is an integer ranging from 1 to 6, where, if n is 1, R17 is hydrogen, alkyl? -30, C5-C7 cycloalkyl, C2-C18 alkenyl, a monovalent radical of a hexose, a monovalent radical of a hexitol. where R2 has the above definitions, or equally R17 is C in which T3 is ox R 9 is 12 and R15 are as defined above, or R19 is likewise hydrogen, alkyl, O-c18-phenyl, C5-C7-cycloalkyl, or where p is an integer ranging from 2 to 4, q is an integer ranging from 2 to 20, R22 is alkyl-C-Q, phenyl or C5-C8 cycloalkyl, R23 and R24 are not simultaneously methyl; R25 is hydrogen or C ^ -C-alkyl, or if n is 2, R17 is a divalent radical of a hexose, a radical where p and q have the above definitions, -CH2CH2-T4-CH2CH2-, -CH2-CH = CH-CH2-, -CH2-C == C-CH2 wherein R18 and R20 'independently of each other, are hydrogen or C ^ -Cg alkyl, or together they are a radical -CH2CH2CH CH2CH2-, r is an integer ranging from 2 to 10, N-Rj, or -s-c-s-t T4 is sulfur, / ', wherein R7 and R8 have the above definitions and R26 is hydrogen, CI-C ± Q alkyl, C5-Cg cycloalkyl, or where R2 has the above definitions.
Preferred are compositions comprising as component (ß) products in which, in the compound of formula I, the radicals Y, independently of each other, are OH, (OH-CH2CH2) 2N- or -HNRi and Rl is hydrogen, C-C4 alkyl, or where R2 is hydrogen, C -C4 alkyl, OH, allyl, benzyl, acetyl or HOCH2CH2- and a is a number of 1,2,3,4 or 6, where if Y is OH and a is 1, X is C -C 8 alkyl, C 3 -C 8 alkenyl, -CH2CH2T, (CH2CH2O) bR4 wherein R2 is as defined above, and is oxygen, R4 is C1-C4 alkyl, and b is an integer ranging from 0 to 10, or if Y is OH and a is 2, X is -CH2CH2T2 (CH2CH20) bCH2CH2-, where b has the above definitions or equally X is where R5 is hydrogen, b is the number 0 or 1 and c is an integer that varies from 2 to 8, or if a is 3 X is -CH? -CH-CH2- or N (CH2CH2-) 3, if Y is OH and a is 4, CH2 'CH2- -CH2-C-CH2- (-CH2-CH-CH2) or -CH2-CH-CH2-0-CH-CH2-X is -V. , n2- > - -'- 'i > 2, v- \ _t '2"" CH2-if Y is OH is already 6 -CH2 CH2 X is ii -CH2-C-CH-0-CH2-C-CH2- -CH, -C 1H-C'H -CiH-CJlH-CH, - I -CH2 CH2-if Y is -HNRi is already 1, X is C 1 -C 6 alkyl, C 3 -C 8 alkenyl,. C5-C7 cycloalkyl, or where R2 has the above definitions, if Y is -HNRi and a is 2, X is CfH2f-, in which f is an integer that varies from 2 to 10 and in the compound of formula II, Or the radicals Z are hydrogen or a group of the formula. ^ U J] - (° H2h °) fC-R11 and k is l, 2 Ó 3, h is 2 or 3, i is an integer that varies from 0 to 4 and Rll is C? -C20 alkyl, or C8-C20 alkenyl, with the proviso that the compound of formula II comprises an O group p ChH2hO) tCR; in the compound of formula III, l2 is C alquilo-Cg alkyl or C5-C7 cycloalkyl, s is 1 -o 2, Q is -CmH2m- or -CH2-CH- > R 16 m is an integer ranging from 0 to 3, Rlg is C 1 -C 4 alkyl, and n is an integer ranging from 1 to 6, where, if n is 1, R 7 is hydrogen, C 1 -C 8 alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl, a monovalent radical of a hexose, a monovalent radical of a hexitol -CH 2, wherein R2 has the above definitions, or likewise R17 is -f- (CH2) p04- (CH2) pOR19 in? to which R? g is hydrogen, C? -C 8 alkyl, or C5-C7 cycloalkyl, wherein p? is an integer that varies from 2 to 4, q is an integer that varies from 2 to 10, or if n is 2, Rl7 is a divalent radical of a hexose, a radical -CH, divalent of a hexitol, -CH2-C-CH2OH -CrH2r- "(CH2) pO-" (CH2) CH2OH in which p and q have the definitions previous CHCH-T4-CH2CH2-, c - wherein r is a tr.tero ranging from 2 to 10, 4 is sulfur or NR 10 26 / R2g is hydrogen, C? -C? 0 alkyl, or C5? C8 cycloalkyl, or if n is 3, Rl7 is a trivalent radical of a hexose or a radical Trivalent of a hexitol CHCH2- -CH2CH2-N-CH2CH2-CH2-CH-CH, CH3-CH-CH2-N-CH2-CH-CH, if n is 4, Rl is a tetravalent radial of a hexose, a radical Preference is also given to compositions comprising as component (ß) products in which, in the compound of formula I, the radicals Y, independently of one another, are hydroxyl or -NH2 is already an integer ranging from 1 to 4, where, R is hydrogen, methyl or HOCH2CH -, or if Y is OH and a is 2, X is -CH2CH2T2 (CH2CH2O) bCH2CH2-, where -I »2 is oxygen, sulfur or N_R / 5 ' R5 is hydrogen, b is the number 0 or 1 and c is the number 2, 3 or 4 or if Y is OH and a is 3, X is -C? 2 - ^? - H2- if Y is OH and a is 4, in the compound of the formula II, OR the radicals Z are hydrogen or a group of the formula II -C-? rk is the number 1 and Rn is C -C20 alkyl, or C8-C2Q alkenyl, with the condition O that the The compound of the formula II comprises a group ¡-CR r ry in the compound of the formula III, Ri2 is tertiary butyl, R15 is C1-C4 alkyl, and is bonded in the ortho position with respect to the OH group, s is number 1, Q is -CItlH2m- and binds in the para position with respect to the OH group, where m is the number 2, n is 1 and Rl is C -C4 alkyl.
Examples of preferred compounds of formula I are pentaerythritol tiodiethylene glycol, 1,4-butanediol, 1,2-propanediol, diethylene glycol, triethylene glycol, diethanolamine, glycerol. Particular preference is given to glycerol or tiodiethylene glycol. Preferred compounds of formula II are vegetable oils, which occur naturally, 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, turnip oil, soybean oil, corn germ oil, safflower oil, olive oil, peanut oil, seed oil. of cotton, sesame oil, castor oil, tallow oil, pumpkin seed oil or flaxseed oil. Preferred animal oils and fats are, for example, butter fat, lard, fish oil, sperm oil, "cow paw" oil or whale oils. Examples of preferred artificial polyol derivatives are those of Radiamuls (glycerol tri C8 C? 0) or sorbitan derivatives. 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 oil or turnip oil are particularly preferred. Of particular interest are compositions comprising as component (ß) products in which, in the compound of formula III, Ri2 is C1-C4 alkyl, or cyclohexyl, R5 is C1-C4 alkyl, or cyclohexyl and is attached to the ortho position in relation to the OH group, s is the number 1, Q is -CmH2ltl-, and joins in the para position in relation to the OH group, where m is an integer that varies from 0 to 3 and n is an integer that varies from 1 to 4, where, if n is 1, R17 is hydrogen, C? -C? 0 alkyl, cyclohexyl, alkenyl CH2OH if n is 2, R17 is 0 -CH2CH2-T4-CH2CH2- wherein p is an integer ranging from 2 to 4, q is an integer ranging from 2 to 10, r is an integer ranging from 2 to 6, -4 is sulfur or "? | -% c and Y2g is hydrogen or C1-C4 alkyl, or if n is 3, I CH2CH2- CH2-CH-CH3 Rl7 is I -CH2CH2-N-CH2CH2- ~ CH3-CH-CH2-N-CH2-CH-CH3 if n is 4, Of particular interest are compositions comprising as component (ß) products in which, in the compound of formula III, Rl2 is tertiary butyl, Rl5 is C1-C4 alkyl, and is bonded in the ortho position with respect to the OH group, s is number 1, is -CmH2? ,, -, and binds in the para position relative to the group OH, where m is the number 2 and n is an integer, 1, 2, or, where, if n is 1, R is C -C4 alkyl, or if n is 2, R17 is - (CH2) p0 - where p is number 2, q is number 2 and T4 is sulfur or if n is 4 Other preferred compounds of formula III are Particularly preferred compounds of formula III are methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, 3- (3'-tere. -butyl-4'-hydroxy) Methyl 5'-methylphenyl) -propionate. Particular preference is also given to compositions comprising, as component (ß), products which can be obtained by reacting components a), b) and e), component a) being a compound of formula I, in particular pentaerythritol, thiodiethylene glycol, 1,4-butanediol, 1,2-propanediol, diethylene glycol, triethylene glycol, diethanolamine, glycerol, or a mixture thereof, component b) is a compound of formula II, in particular sunflower oil, coconut oil, turnip seed oil, corn germ oil, safflower oil, olive oil, oil of peanut or Radiamul or a mixture thereof, and component c) is a compound of formula III, in particular methyl 3- (3 ', 5'-diterc.-butyl-4 * -hydroxyphenyl) propionate or 3- (3'-tere. Methyl-4'-hydroxy-5'-methylphenyl) propionate. The present invention also relates to compositions comprising, as the component (ß), products that can be obtained by the reaction of components a), b) and c) in a quantitative molar ratio of 0.1: 1.0: 0.1 to 15: 1:30 A quantitative molar ratio of 1: 1: 1 to 10: 1: 20 is preferred. A quantitative molar ratio of 4: 1: 5 to 10: 1: 20 is particularly preferred. A quantitative molar ratio of 5: 1: 10 is especially preferred.
Of special interest are the compositions comprising, as the component (ß), products in which the amount by weight of the active group E-2 in the component (ß) it is from 30 to 80% by weight, preferably from 35 to 80% by weight, in particular from 50 to 80% by weight.
As already mentioned, the present products of the component (ß) have properties against wear and that inhibit corrosion in fuels. Particular mention is made of its outstanding improvement of lubricity (property against wear) of fuels with lower sulfur and / or aromatic contents. Therefore, the present invention also relates to the use of the component (ß) products as an anti-wear agent for a motor fuel system. As a rule, the component (ß) products are added to the fuel in amounts from 0.0001 to 10.0%, preferably from 0.001 to 0.2%, in particular from 0.005 to 0.1%, based on the weight of component (a). Component products (ß) can be mixed with liquid carriers, compatible with the fuels of the final product, to form concentrates for subsequent addition to fuel-based materials or formulated fuels. Such concentrates can facilitate the mixing, composition, emptying or transfer (in volume or in line) of the component products (ß). Typically, the carriers are organic solvents for the component (ß) products, such as hydrocarbons, such as, for example, xylene or toluene, ethers, alcohols or mixtures thereof, or they may be portions of materials a, fuel base or formulated fuels that are intended as the final products. The addition of the concentrates to the base materials of the formulated fuels, to form the fuels of the final product can be in batches, for example of single containers of concentrates, sold at retail or other products, or they can be added by dosage in the refineries or fuel distribution sites. Other modes of addition will be evident. The amount of the products of the component (ß) in the concentrate may vary, depending on the desired properties of the concentrate, such as the viscosity. Generally, about 10 to 90% by weight of the products of the component (ß) in the carrier medium is suitable, more usually around 20 to 50% by weight. The fuels of the final product can be hydrocarbon fuels, oxygenates or mixtures of the two. The hydrocarbon fractions that can be used for the fuel compositions include the distillate fuels having a boiling point in the range of kerosene and diesel (165 to 565ac). Typical middle distillate fuels of this class include diesel fuels for road and other diesel fuels, with boiling ranges ranging from 200 to 370ac, and jet fuel, kerosene, gas oil, and cycle oils. Such middle distillate fuels may comprise straight-run distillate oils, thermally decomposed distillate fuel oils, or mixtures of straight-run distillate fuel oils, naphthas, and the like with distilled thermal decomposition oils. These fuels are normally derived from petroleum, but they can be derived, at least in part, from other sources, such as shales, tar sands, coal, lignite, biomass and similar sources. The fuels may contain a proportion of oxygenated mixture components, such as alcohols or ethers, which include methyl ether and tertiary butyl ether (MTBE). The fuels may also fully comprise oxygenated products, such as methanol and / or ethanol. The fuels can also be those that have been subjected to conventional treatment processes, such as treatment with an acid or a base, hydrogenation, solvent refining or clay treatment. Of particular interest are the compositions comprising as component (a) a diesel fuel. The fuels can be used, for example, in the operation of a jet engine, a vehicle engine, a gas turbine engine or a diesel engine. In a preferred embodiment of this invention, the fuel is one which is suitable for use in a diesel engine.
The composition of these diesel fuels varies widely with the nature of the crude oil, the refining process, the components with which the untreated fuel is mixed, and the climate in which the fuel is sold. As noted above, this invention finds particular application in diesel fuels having a reduced content of sulfur and / or aromatics, which are now produced in order to comply with the requirements of the regulations. These fuels typically have sulfur contents below 500 ppm (0.05%) and / or an aromatic content less than 35% by weight. Of particular interest are, therefore, compositions comprising as component (a) a fuel, which contains less than 0.10%, preferably less than 0.05%, in particular less than 0.01% by weight of sulfur. The composition of the fuel and thus its inherent lubricity may vary according to the severity of the local regimen of regulations. The invention also finds application in aviation fuels, such as those commonly used in gas turbine engines. Such fuels have a narrow composition to that of diesel fuels that have a low aromatic and sulfur content. The addition of the products of the component (ß) of this invention to these fuels can reduce engine wear.
The invention may also find application in lead-free or reformulated automotive fuels, as is now commonly used in piston engines in aircraft and engine vehicles. The addition of the component (ß) products to these fuels can improve the performance of the engine and make it possible for the fuel to be replaced by unleaded fuel in uses such as in piston-engine aircraft, where fuel is currently used. unleaded. Therefore, the invention also relates to a process for the reduction of wear in a motor fuel system, which comprises adding a product of the component (ß) to the fuel. In addition to the component (ß) products, the compositions, according to the invention, may also contain conventional additives, which are added to improve the basic properties of the fuel even more, as discussed in the Lubricant and Fuel Auditives manual, published by Kline & Company, Inc., International Business Consultant, Fairfield, NJ, E.U.A., pages 309-320 (1990); they include: antioxidants, metal passivators, rust inhibitors, agents that improve the viscosity index, people that decrease the pour point, dispersants, detergents, high pressure additives, antifriction additives, antiwear additives, de-emulsifying agents, agents that reduce the point of darkness, anti-sedimentation waxy additives, anti-static additives, anti-foaming agents, anti-fog additives, biocides, odor-hiding agents, dyes, cetane-improving agents, antifreezes, anti-tapping additives, agents that improve conductivity, PFI / IVD cleaning additives and other lubricity additives. Examples of such conventional additives are the following: l. 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-buylphenol, 2,6-di-tert. -butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-phenylcyclohexyl) -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-di-methyl-6- (1-ethyltridec-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. -hydrohydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tere. -butyl-4-hydroxyanisole, 3, 5-di-tert. -butyl-4-hydroxy-anisole, 3, 5-di-tert. -butyl-4-hydroxyphenyl-stearate, bis (3, 5-di-tert.-butyl-4-hydroxyphenyl) -adipate. l3-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- (a-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'- methylenebis (4,6-di-tere-butylphenol), 2,2-ethylidebisbis (4,6-di-tert.-butylphenol), 2,2'-ethylidebis (6-tert-butyl-4-isobutylphenol) ), 2,2'-ethylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-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) -methyl-nyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1,3-tris (5-tert -butyl-4-) hydroxy-2-methylpheneyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol-bis [3, 3 bis (3'-tere .- 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-hydroxy-2-methylphenyl) -4-n-dodecylmercapto-butane, 1, 1,5, 5-tetra- (5-tert.-butyl- 4-hydroxy-2-methyl-phenyl) pentane. 1. 4. Compounds of O- v N-benzyl. for example 3, 5,3 ', 5'-tetra-tert, -butyl-4,4 * -dihydroxydibenzyl ether or tris- (3, 5-di-tert-butyl-4-hydrobenzyl) 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, didodecylmercaptoethyl-2, 2-bis- (3, 5-di-tert-butyl-4-hydroxy-benzyl) -malonate, bis- [4- (1,1,3,3-tetramethylbutyl) phenyl] -2, 2-bis (3, 5-di-tert.-butyl-4-hydroxybenzyl) -malonate. 1. 6. Hydroxybenzyl aromatic compounds. for example, 1, 3, 5- (3,5-di-tert.-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-hydroxy-benzyl) 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-hydroxyphenyl-propionyl) -hexahydro-1, 3,5-triazine, 1,3,5-tris (3,5-di-cyclohexyl-4-hydroxybenzyl) isocyanurate. 1. 8. Benzophosphonates. for example dimethyl-2,5-di-tert. -butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert. -butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert. -butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert. -butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the 3,5-di-tert. -butyl-4-hydroxybenzylphosphonic acid. 1. 9. Acylaminophenols. for example, 4-hydroxylauranylide, 4-hydroxystearanilide, N- (3,5-di-tert.-butyl-4-hydroxy-phenyl) -carbamic acid octyl ester. 1. 10. steres of ß- (3,5-di-tert.-butyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols, for example 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- tiapentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl-l-phospha-2, 6-7-trioxabicyclo [2.2.2] -octane. 1. 11. Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphene) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, tisdiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, -thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl-l-phospha-2, 6-7-trioxabicyclo [2.2.2] -octane. 1. 12 Esters of ß- (3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonane-diol, 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, trimethylpropane, 4-hydroxymethyl-l-phospha-2, 6-7-trioxabicyclo [2.2.2] -octane. 1. 13. Esters of 3,5-di-tert. -butyl-4-hydroxyphenyl-acetic with monohydric or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodieti-len-glycol, diethylene glycol, triethylene glycol, penta-erythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl -l-phospha-2, 6-7-trioxabicyclo [2.2.2] -octane. 1. 14. Amides of ß- (3,5-di-tert.-butyl-4-hydroxyphenyl) -propionic acid, for example N, N'-bis (3,5-di-tert.-butyl-4-hydroxyphenylpropionyl) hexamethyleneamine, 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 amine antioxidants: N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine , N, N'-bis (l-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- (l-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N * -phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, -butyl- p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p * -diter, -octyldiphenylamine, 4-n-butylaminophenol , 4-butyryl-aminophenol, 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- (I ', 3'-dimethylbutyl) phenyl] amine, N-phenyl-1-naphthylamine tere . -octilated, a mixture of tere. -butil / tere. mono- and dialkylated octyl diphenyl amines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, tere mixtures. -butyldiphenylamine mono- and dialkylated, 2,3-dihydro-3/3-dimethyl-4H-l, 4-benzothiazine, phenothiazine, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut -2-one, N, N • bis (2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6 , 6-tetra-methylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol.
Examples of other antioxidants: aliphatic or aromatic phosphites, thiodi-propionic acid or thiodiacetic acid esters or salts of dithiocarbamic acid or dithiophosphoric acid, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7, -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 the 4- or 5-alkylbenzotriazoles (for example tolutriazole) and their derivatives, 4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole; Mannich or benzotriazole or tolutriazole bases, for example l- [bis (2-ethylhexyl) aminomethyl) tolutriazole and l- [bis (2-ethylhexyl) -aminomethyl) benzotriazole; and alkoxyalkylbenzotriazoles, such as l- (nonyloxymethyl) -benzotriazole, 1- (1-butoethyl) benzotriazole and l- (1-cyclohexyloxybutyl) -tolutriazole. b) 1,2,4-triazoles and their derivatives, for example the 3-alkyl (or aryl) -1,2,4-triazoles, and the Mannich bases of the 1,2,4-triazoles, such as l- [bis (2-ethylhexyl) aminomethyl-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles such as l (l-butoxyethyl) -1,2,4-triazole; and the acylated 3-amino-l, 2,4-triazoles. c) Imidazole derivatives, for example 4,4'-methylenebis (2-undecyl-5-methylimidazole) and bis [(N-methyl) imidazol-2-y1] carbinol-octy1-ether. d) Heterocyclic sulfur-containing compounds, for example 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and their derivatives; and 3, 5-bis [di (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one. e) Amino compounds, for example salicylimidepropyl diamine, salicylaminoguanidine and their salts.
Examples of oxide 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 acids and alkenyl succinic acids, 4- nonylphenoxyacetic acid, alkoxy and alkoxyethoxycarboxylic acids, such as dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid and their amine salts, and also N-oleylsarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydrides, for example, dodecenylsuccinic anhydride, 2-carboxymethyl-1-dodecyl-3-methylglycerol and their amine salts. b) Nitrogen-containing compounds, for example: I. Primary, secondary or tertiary amines, aliphatic or cycloaliphatic, and salts of amines of organic and inorganic acids, for example the oil-soluble alkylammonium carboxylates, and also the l- [N, N-bis (2-hydroxyethyl ) amino] -3- (4-n-nylphenoxy) propan-2-ol.
II. Heterocyclic compounds, for example substituted i-idazolines and oxazolines and 2-heptadecenyl-1- (2-hydroxyethyl) imidazoline. c) Phosphorus-containing compounds, for example the partial amine salts of phosphoric acid, or partial phosphonic acid esters, and zinc dialkyldithiophosphates. d) Sulfur-containing compounds, for example, barium dinonylnaphthalenesulfonates, calcium and petroleum sulfonates, aliphatic carboxylic acids substituted by alkylthio, esters of aliphatic 2-sulfocarboxylic acids and their salts. 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 agents that improve the viscosity index are: Polyacrylates, polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinyl pyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers and polyethers.
Examples of agenets that decrease the pour point are: polymethacrylate and alkylated naphthalene derivatives.
Examples of dispersants / surfactants are: Polybutenyl-succinic amines or imides, polybutenyl-phosphonic acid derivatives and basic sulfonates and phenolates of magnesium, calcium and barium.
Examples of anti-skid additives are; Compounds containing sulfur and / or phosphorus and / or halogen, for example sulfurized olefins, and vegetable oils, zinc dialkyldithiophosphates, alkylated triphenyl phosphates, tritolyl phosphate, triarylsyl phosphate, chlorinated pafins, alkyl di- and trisulfides and aryl, amine salts of mono- and dialkyl phosphates, amine salts of methylosphonic acid, diethanolaminomethyloltriazole, bis (2-ethylhexyl) aminomethylol thiazole, derivatives of 2,5-dimercapto, 1,3,4-thiadiazole, 3- [(diisopropoxyphosphintiosyl) thio] -ethyl propionate, triphenyl triphosphate (triphenylphosphorothionate), tris- (alkylphenyl) phosphorothionate and their mixtures (for example tris (isononylphenyl) phosphorothioate), diphenyl-monononylphenyl-phosphorothioate, isobutylphenyl-diphenyl-phosphorothioate, the dodecylamine salt of 3-hydroxy-3-oxide, 3-thiaphosphetane, trithiophosphoric acid, 5,5,5-tris [2-acetate isooctyl], 2-mercaptobenzothiazole derivatives, such as lNN-bis- (2-ethylhexyl) aminomethyl [-2-mercapto-lH- 1, 3-benzothiazole and ethoxy-carbonyl-5-octyldithiocarbamate. Conventional additives are added, for example, at concentrations of 0.01 to 10%, based on the total weight of the fuel. The (ß) component products of this invention can be combined with any of these additives, provided that the components of these mixtures are mutually compatible. The (ß) component products of this invention can be separately added to the fuel or they can be combined with one or more of the described additives to produce an aid formulation, which is suitable for addition to a base fuel. The following examples illustrate the invention in more detail. The parts and percentages are by weight, unless otherwise indicated.
Example 1: Preparation of sunflower oil derivatives with the use of pentaerythritol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) ropionate.
In a sulfonation flask, equipped with reflux condenser and mechanical stirrer, a mixture of 30 g (~ 34 mmol) of sunflower oil, 4.64 g (34 mmol) of pentaerythritol and 37 mf (0.15 mmol) of dibutyl ether tin were kept under nitrogen for 7 hours at 180-1902C. 9.94 g (34 mmol) of methyl 3- (3 ', 5 * -di-tert.-butyl-4'-hydroxyphenyl) propionate and another 37 mg (0.15 mmol) of dibutyl tin oxide were added. The stirring of the reaction mixture was continued for 15 hours at 180-1902C. When cooled, 40.64 g (91%) of the product was obtained as a yellow oil, having a n20D refractive index of 1.4882.
Example 2; Preparation of coconut oil derivatives, which use pentaerythritol and methyl 3- (3 ', 5'-di-tert.-butyl-4 • -hydroxyphenyl) propionate. The procedure described in Example 1 was 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 were used. (0.610 mol) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 653 g (98%) of the product as a brown oil, having a refractive index n20rj of 1.4781.
Example 3; Preparation of sunflower oil derivatives, which use thiodiethylene glycol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 50 g (~ 57 mol) of sunflower oil, 41.8 g (343 mmol) of thiodiethylene glycol, 448 mg (1.8 mmol of dibutyltin oxide and 200 mmol) were used. g (684 mmol) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 279.1 g (96%) of the product as a yellow oil, which has a refractive index n20D of 1.5170.
Example 4: Preparation of coconut oil derivatives, which use thiodiethylene glycol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 49.9 g (~ 76 mmol) of coconut fat, 85.1 g (688 moles) of thiodiethylene glycol, 797 mg (3.2 mmol) of dibutyl tin oxide were used and 402.6 g (1.38 mol) of methyl 3- (3 *, 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 500.7 g (93%) of the product as an orange-brown oil, which has a refractive index n20D of 1.5210.
Example 5: Preparation of sunflower oil derivatives, which use 1,4-butanediol and methyl 3- (3 ', 5 • di-tert.-butyl-4 * -hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 30 g (~ 34 mmol) of sunflower oil, 14 g (155 mmol) of 1,4-butanediol, 199 mg (0.80 mmol) of dibutyl ether were used. tin and 87.7 g (300 mmoles) of methyl 3- (3 •, 5 * -di-tert.-butyl-4'-hydroxyphenyl) propionate, to supply 124 g (94%) of the product as a reddish oil, which it has a n20o refractive index of 1.5070.
Example 6: Preparation of coconut oil derivatives, which use 1,4-butanediol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example was repeated 1, except that 30 g (~ 46 mmoles) of coconut fat, 14 g (155 mmoles) of 1,4-butanediol, 199 mg (0.80 mmol) of dibutyl tin oxide and 87.7 g (300 mmoles) were used. of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 123 g (93%) of the product as a reddish oil, having a refractive index n 0rj of 1.5025.
Example 7: Preparation of sunflower oil derivatives, using 1,2-propanediol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate.
The procedure described in Example 1 was 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 dibutyl ether were used. tin and 87.7 g (300 mmol) of methyl 3- (3 ', 5' -di-tert.-butyl-4 • -hydroxyphenyl) propionate, to provide 121.7 g (93.7%) of the product as a yellow oil, which it has a refractive index n20rj of 1.5047.
Example 8: Preparation of sunflower oil derivatives, which use diethylene glycol and methyl 3- (3 ', 5' -di-tert.-butyl-4 • -hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 30 g (~ 34 mmol) of sunflower oil, 16.7 g (157 mmol) of diethylene glycol, 199 mg (0.80 mmol) of dibutyltin oxide were used and 89.5 g (306 mmol) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 137.3 g (99%) of the product as a yellow oil, having a refractive index n20D of 1.5065.
Example 9: Preparation of coconut oil derivatives, using diethylene glycol and methyl 3- (3 •, 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 30 g (-46 mmol) of coconut fat, 22.3 g (210 mmol) of diethylene glycol, 249 mg (1.00 mmol) of dibutyltin oxide were used and 121.1 g (414 mmol) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 158.1 g (91%) of the product as a yellow oil, which it has a refractive index n 0D of 1.5068.
Example 10: Preparation of sunflower oil derivatives, and use triethylene glycol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example was repeated 1, except that 30 g (~ 34 mmol) of sunflower oil, 15 g (100 mmol) of triethylene glycol, 199 mg (0.80 mmol) of dibutyl tin oxide and 90.65 g (310 mmol) of 3 were used. - (3 ', 5'-di-tert.-butyl-4' -hydroxyphenyl) propionate, methyl. to provide 129 g (95%) of the product as a pale yellow oil, which has a refractive index n20 of 1.5050.
Example 11: Preparation of coconut oil derivatives, which use triethylene glycol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example was repeated 1, except that 30 g (~ 46 mmol) of coconut fat was used, . 2 g (100 mmol) of triethylene glycol, 199 mg (0.80 mmol) of dibutyltin oxide and 90.65 g (310 min) of 3- (3", 5 '-di-tert.-butyl-4' - hydroxyphenyl) methyl propionate, to give 129.5 g (95%) of the product as a pale yellow oil, having a n20D refractive index of 1.4992.
Example 12: Preparation of the Radiamul derivatives, which use diethylene glycol and methyl 3- (3 *, 5'-di-tert.-butyl-4 • -hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 30 g (~ 59 mmol) of Radiamuls (glycerol tri Cg / C o), 16.3 g (154 mmol) of diethylene glycol, 224 g (0.90 mmol) of sodium oxide were used. dibutyltin and 95.6 g (327 mmoles) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 132.6 g (99%) of the product as an pale yellow color, which has a refractive index n20j) of 1.5022.
Example 13: Preparation of sunflower oil derivatives, using diethanolamine and methyl 3- (3 •, 5'-di-tert.-butyl-4 • -hydroxyphenyl) propionate. The procedure described in Example 1 was repeated except that 60 g (-68 mmol) of sunflower oil, 14.3 g (136 mmol) of diethanolamine, 149 mg (0.60 mmol) of dibutyltin oxide and 19.9 were used. g (68 mmol) of methyl 3- (3 ', 5' -di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 88.4 g (95%) of the product as a reddish-brown oil, which it has a refractive index n20D of 1.4940.
Example 14: Preparation of coconut oil derivatives, which use diethanolamine and methyl 3- (3 ', 5 * -di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 60 g (-92 mmol) of coconut fat, 19.1 g (182 mmol) of diethanolamine, 174 mg (0.70 mmol) of dibutyltin oxide and 34.2 were used. g (117 mmol) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 104.9 g (93%) of the product as a brown oil, which has a refractive index n20D of 1.4905.
Example 15: Preparation of sunflower oil derivatives, which use glycerol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example was repeated 1, except that 30 g (-34 mmoles) of sunflower oil, 14.22 g (154 mmoles) of glycerol, 199 mg (0.80 mmol) of dibutyl tin oxide and 87.73 g (300 mmoles) of 3- ( 3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate methyl, to give 126.5 g (96%) of the product as a pale yellow viscous oil, having a refractive index n20rj of 1.5128 .
Example 16: Preparation of coconut oil derivatives, which use glycerol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 30 g (-46 mmol) of coconut fat, 19.4 g (211 mmol) of glycerol, 249 mg (1.0 mmol) of dibutyltin oxide and 118 g were used. (404 mmol) 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate methyl, to give 154 g (92%) of the product as a pale yellow viscous oil, which has a refractive index n20 £) of 1.5123 ..
Example 17: Preparation of sunflower oil derivatives, using glycerol and methyl 3- (3 ', 5' -di-tert.-butyl-4 • -hydroxyphenyl) propionate. The procedure described in Example 1 was 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 were used. (300 mmoles) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 105.0 g (94%) of the product as an orange oil, having an refractive index n20?) of 1.5165.
Example 18: Preparation of coconut oil derivatives, which use diethylene glycol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 1 was repeated, except that 30 g (~ 46 mmol) of coconut fat, 22.6 g (213 mmol) of diethylene glycol, 184 mg (0.70 mmol) of dibutyltin oxide were used and 94.3 g (390 mmol) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 131.9 g (98%) of the product as a yellow oil, which has a refractive index n 0D of 1.5118.
Example 19: Preparation of sunflower oil derivatives, using 4-hydroxy-2,2,6,6-methylpiperidine and 3- (3 ', 5'-di-tert.-butyl-4 • -hydroxyphenyl) Methyl propionate. The procedure described in Example 1 was repeated, except that 41.5 gg (-47 mmoles) of sunflower oil, 7.90 g (50 mmoles) of the 4-hydroxy-2,2,6,6-tetra-methylpiperidine were used, 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, to give 59.4 g ( 95%) of the product as a brown oil, which has a refractive index n20D of 1.4848.
Example 20: Preparation of sunflower oil derivatives, which use 4-amino-2,2,6,6-methylpiperidine and 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) Methyl propionate. The procedure described in Example was repeated 1, except that 41.5 g (-47 mmoles) of sunflower oil, 7.80 g (50 mmoles) of 4-amino-2, 2, 6,6-tetramethyl-piperidine, 50 mg (0.20 mmol) of oxide were used of dibutyl tin and 14.60 g (50 mmol) of methyl 3- (3 ', 5' -di-tert.-butyl-4 • -hydroxyphenyl) propionate, to give 61.8 g (99%) of the product as an oil of chestnut color, which has a refractive index n20D of 1.4887.
Example 21; Preparation of coconut oil derivatives, which use N- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl-piperidine and 3- (3 *, 5'-di-tert. methyl butyl-4'-hydroxyphenyl) -propionate. The procedure described in Example 1 was repeated, except that 31.0 g (-47 mmoles) of coconut fat, 10.1 g (50 mmoles) of N- (2-hydroxyethyl) -4-hydroxy-2,2 were used, 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 , to supply 52.4 g (98%) of the product as a yellow oil, which has a n20o refractive index of 1.4811.
Example 22: Preparation of turnip seed oil derivatives, which use 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 mmoles) of turnip seed oil, 86.1 g (935 mmoles) of 85% aqueous glycerol and 2.63 g (15.0 mmoles) ) of calcium acetate, was maintained for 7 hours under a nitrogen atmosphere at 180-190SC. Then 357.5 g (1.22 moles) of methyl 3- (3 •, 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate were added. The reaction mixture was continued to stir for 15 hours at 180-190ac. After cooling, 505 g (99%) of the product was obtained as a yellow oil having a nD refractive index of 1.5122.
Example 23: Preparation of corn germ oil derivatives, which use glycerol and methyl 3- (3 ', 5' -di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example was repeated 22, except that s used 100 g (~ 113 mmoles) of corn germ oil, 57.3 g (624 mmoles) of 85% aqueous glycerol, 2.32 g (13.0 mmoles) of calcium acetate and 282.4 g (966 mmoles) 3- (3 •, 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate methyl, to give 399.0 g (99%) of the product as a yellow oil, having a refractive index n20D of 1.5127.
Example 24; Preparation of sunflower oil derivatives, which use glycerol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 22 was repeated, except that 100 g (~ 113 mmol) of sunflower oil was used. 57.6 g (625 mmoles) of 85% aqueous glycerol, 2.11 g (12.0 mmoles) of calcium acetate and 286.5 g (980 mmoles) of 3- (3 ', 5' -di-tert.-butyl-4 '- hydroxyphenyl) methyl propionate, to provide 403.2 g (99%) of the product as a yellow oil, having a n20D refractive index of 1.5140.
Example 25; Preparation of olive oil derivatives, which use glycerol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 22 was repeated, except that 100g (~114mmol) of olive oil, 58g (630mmol) of 85% aqueous glycerol, 2.11g 12.0mmol) of calcium acetate and 290.4 were used. g (963 mmoles) of methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 408.6 g (99%) of the product as a yellow oil, which has a refractive index n 0n of 1.5110.
Example 26; Preparation of peanut oil derivatives, which use glycerol and methyl 3- (3 ', 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate. The procedure described in Example 22 was repeated, except that 100 g (~114 mmol) of peanut oil were used 58.0 g (630 mmol) of 85% aqueous glycerol, 2.11 g (12.0 mmol) of calcium acetate and 291.4 g (967 mmoles) of methyl 3- (3 •, 5'-di-tert.-butyl-4'-hydroxyphenyl) propionate, to give 413.5 g (99%) of the product as a yellow oil, which has a refractive index n20D of 1.5100.
Example 27: HFRR (High Frequency Reciprocal Equipment) test for low sulfur diesel fuel. The anti-wear properties of the component (ß) products in a low sulfur diesel fuel (available from EMPA, Switzerland) have been tested with the use of the fuel lubricity tester, the HFRR, under the prescribed conditions by the CEC test method F-06-A-96, which is available from CEC Secetariat, Place Madow 1, B-1030 Brussels, Belgium; or SAE Order Department 782, 400 Commonwealth Drive, Arrendale, PA 15096, USA, The details of the test method are described, for example, in Wei Dan Ping and HA Spikes, Wear, 111, 217-235 (1986) or ei Dan Ping, S. Korcek and HA Spikes, SAE 962010. With the HFFR tester, the lubricity of a fuel sample was evaluated through the wear measurement that occurred after 75 minutes of an oscillatory displacement of a steel ball against a flat disk. The diameter of the ball is 6.00 mm, the displacement frequency is 50 Hertz, its stroke length is 1 mm and the load applied to the ball is 200 g. The ball and the flat disk were immersed in the fuel to be tested. Other conditions, such as relative humidity, have an influence on the results and must be kept within the prescribed limits. At the end of the test duration of the wear signal on the ball a correction was measured and applied which normalizes all the results of a standard water vapor pressure of 14 mbar. The results are supplied in microns (μm). A reference of high lubricity and low lubricity are available for calibration. The high lubricity fuel gives a wear mark in the range of 380 to 437 μm. The low lubricity fuel gives a wear mark in the range of 600 to 760 μm. Both fuels are available through the CEC working group. The lower the wear mark, the better the anti-wear properties of the component (ß) products in the low sulfur diesel fuel. The results are summarized in Table 1. Table 1: HFFR test for low sulfur diesel fuel

Claims (17)

  1. CLAIMS 1. A fuel composition against wear, which comprises: a) a fuel and ß) at least one product, which can be obtained by reaction of components a), b) and c), where component a) is a compound of formula I or a mixture of compounds of formula I, component b) is a compound of formula II or a mixture of compounds of formula II and component c) is a compound of formula III or a mixture of compounds of the formula III, (I) (ni) (II) wherein, in the compound of formula I, the radicals Y, independently of each other, are OH (HOCH2CH2) N- or -HNRi And the radicals Ri are hydrogen, C -C 8 alkyl, C -C cycloalkyl? , C al-C alkenyl, C 7 -C 9 phenylalkyl, phenyl or phenyl which is substituted by 1 to 3 radicals A, these radicals Ai, independently of each other, are C 1 -C 12 alkyl, halogen, hydroxyl, methoxy or ethoxy, wherein R 2 is hydrogen, C?-C8 alkyl, 0o, OH, NO, -CH2CN, l-18 alkoxy, C5-C?-cycloalkoxy, C C-alkenyl, C fen-C9 phenylalkyl, or C7-C9 phenylalkyl, which is mono - di- or tri-substituted on the phenyl ring by C1-C alkyl, or R2 is also C? -C8 acyl, or HOCH2CH2-, is already the number 1, 2, 3, 4 or 6, where, If Y is OH and a is 1, X is C1-C45 alkyl, C3-C8 alkenyl, -CH2CH2T (CH2CH20)), R4 in which R2 has the definitions previous and Ti is oxygen, sulfur or N-. / 5 'R4 is alkyl CI-C Q, b is an integer varying from 0 to 10 and R5 is hydrogen, C? -C? 8 alkyl, or phenyl or If Y is OH and a is 2, it is -CH2CH2T2 (CH2CH20) bCH2CH2-, where b has the above definitions, c O O - CH2 - CH = CH - CH2 - f - CH2CH2 - NH - C - NH - CH? CH _ or CH3 CH2CH20 - - C < ~ ° CH2CH2- CH, where T2 is oxygen, sulfur, N-R50 -SCS and R5 has the I R8 definitions above, Rg is hydrogen, C -C 8 alkyl, or phenyl, c is an integer ranging from 2 to 10, d is an integer that it varies from 2 to 6 and Ry and R, independently of each other, are hydrogen, alkyl l ~ 18 '° phenyl, or Ry and R8 together with the C atom to which they bind, form a cycloalkyl ring C? -C? 2, or if a is 3, X is C3-C10 alkanetriyl, or N (CH2CH2-) 3, or if Y is OH and a is 4, X is C4-C10, C3-Coteotetrayl, (-CH2-CH-CH2) 20, -CH2-CH-CH2-0-CH-CH. where Rg is C1-C4 alkyl, if Y is OH and a is 6, X is CH or alkanohexayl C -C Q, or, if Y is HNRi Y a is 1, X is C 1 -C 8 alkyl, C 3 -C 18 alkenyl, C 5 -C 12 cycloalkyl, phenylalkyl Cy-C 9, phenyl, where R2 is as defined before or X is also or X together with Rj_, is a group of the formula -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-, where R O is hydrogen or methyl and e is 2 or 3, or, if Y is -HNRi and a is 2, X is -CfH2f- _cffHll2f 'CH2CH2-, where f is an integer that varies from 2 to 10 and g is an integer that varies from 1 to 6, and in the compound of the formula II, the radicals Z are hydrogen or a group of the formula: O ll and ChH2h0) rC-R k is an integer that varies from 0 to 6, where h is 2 or 3, i is an integer that varies from 0 to 12 and Rn is. alkyl-030, C8-C30 alkenyl, C4-C2 cycloalkyl, phenyl or phenyl-C7-C9 alkyl, with the proviso that the compound or formula II has a group - (chH2ho; rc-R1 ?; in the compound of the formula III, R 2 is C 1 -C 8 alkyl, C 5 C 2 cycloalkyl, phenyl or phenylalkyl Cy-C 9, s is 0, 1 or 2, wherein R 5 is as defined above, m is an integer ranging from 0 to 3, i6 is C C-C8 alkyl, and n is an integer ranging from 1 to 6, where if n is 1, Ri7 is hydrogen, C-C45 alkyl, C5-C2 cycloalkyl, C2-C8 alkenyl, a monovalent radical of a hexose, a monovalent radical of a hexitol, -CH 'where R2 has the above definitions or likewise Riy is CH2CH2-T3-R? 9 or where \ T3 is oxygen, sulfur or N R22 R19 is where R? and R15 are as defined above, or R19 is also hydrogen, C ~ C4 alkyl, phenyl, C5-C2 cycloalkyl or O 11, where -CHg-C-O-Rjjs, p is an integer ranging from 2 to 4, q is an integer ranging from 2 to 20, R22 is alkyl C? -C? 8, phenyl or phenyl which is substituted by 1 to 3 radicals Aif wherein the radicals A , independently of one another, are C 1 -C 2 alkyl, halogen, hydroxyl, methoxy or ethoxy, or R 22 is also C 5 -C 8 cycloalkyl, R 23 and 24 f independently of each other, are hydrogen or methyl, with the proviso that 23 and R 24 do not they are simultaneously methyl; R24 is hydrogen or C-24 alkyl, or if n is 2, R17 is a divalent radical of a hexose, a divalent radical of a hexitol, -CH -) - (CH2) pO- | - (CH2) p- § C.H 2r ~ in which p and q are as defined above, -CH2CH -T4-CH2CH-, -CH2-CH = CH-CH2-, -CH2-C = C-CH2-, wherein R18 and R20 'independently of each other, are hydrogen or C? -C? 2 alkyl, or together are the radial -CH2CH2CH2CH2CH2-, r is an integer ranging from 2 to 10, ? T4 is sulfur, N-RI or -SCS- where R7 and R8 / IR «have the above definitions and R g is hydrogen, C? -C? 8 alkyl, phenyl or phenyl which is substituted by 1 to 3 radicals A? , where the radicals Ai are as defined above in formula I, or R2g is also C5-C8 cycloalkyl, or where R2 has the above definitions, if n is 3, Rl7 is a trivalent radical of a hexose, a trivalent radical of a hexitol, CCHH22CCHH-I -CH2CH2-N-CH2CH2- ' where R 27 is hydrogen, CH 2 H, C 1 -C alkyl, C 1 -C 8 alkylamido, or where Q, Ri2 and R? 6 have the above definitions, or if n is 4, Rl7 is a tetravalent radical of a hexose, a tetravalent radical of a hexitol, alcanotetrail if h is 5, Rl7 is a pentavalent radical of a hexose or a radial Rl7 is a hexavalent radical of a hexitol or
  2. 2. A composition, according to claim 1, wherein, in the compound of the formula III, s is the number 1 or 23. A composition, according to claim 1, wherein, in the compound of the formula I, the radicals Y, independently of each other, are: OH, (HOCH2CH2) 2N- or -HN i and Ri is hydrogen, alkyl cl ~ c10"C5-C7 cycloalkyl, C3-C6 alkenyl, benzyl or phenyl, wherein R2 is hydrogen, C1-C4 alkyl, OH, CH2CN, C6-C alkoxy? , C5 ~ C8 cycloalkoxy, allyl, benzyl, acetyl or HCOCH CH2- and a is number 1, 2, 3, 4 or 6, where, if Y is OH and a is 1, X is C? -C30 alkyl, C3-C18 alkenyl, -CH2CH2T? (CH2CH20) bR4 T is oxygen, sulfur or N_R / R4 is C 1 -C 6 alkyl, b is an integer ranging from 0 to 10 and R 5 is hydrogen, alkyl CI-CIQ or phenyl or if Y is OH and a is 2, X is -CH2CH2T2 (CH2CH20) bCH2CH2-, in which b has the above definitions, O O - CH2CH2 - NH - C - C - NH - CH2CH2 - or wherein? R? 77 T is oxygen, sulfur, N-R 50 -S-C-S and R 5 is as defined previously. R « R6 is hydrogen, alkyl CI-CIQ, O phenyl, c is an integer ranging from 2 to 10, d is an integer ranging from 2 to 6 and R7 and R8 'independently of each other, are hydrogen, alkyl l ~ c10 ° phenyl, or R7 and R8 together with the carbon atom to which they are attached, form a C5-C7 cycloalkyl ring, or if Y is -HNRi and a is 1, X is alkyl C? -C? 0, C3-C? alkenyl? 8, C5-C7 cycloalkyl, benzyl, phenyl, to R2 is like it was defined before or or X together with Ri cs a group of the formula -CH2CH2CH CH2CH2 or CH2CH20CH2CH2-, where R or is hydrogen or methyl and e is 2 or 3 and in the compound of formula II, the radicals Z are hydrogen or a group of the formula O and k- is an integer ranging from 0 to 4, where h is 2 or 3, i is an integer ranging from 0 to 6 and Rn is alkyl C? -C20 C, -C20 alkenyl, C5-C7 cycloalkyl, phenyl or benzyl, with the proviso that the compound of formula II comprises a group; in the compound of the formula III Ri2 is C ^ C alkyl, C5-C7 cycloalkyl, phenyl or benzyl, s is 1 or 2, Q is CmmH112m "'-CH, wherein R15 has the above definitions, is an integer ranging from 0 to
  3. 3, Rlg cs C1-C4 alkyl and n is an integer ranging from 1 to 6, where, if n is 1, R 7 is hydrogen, C 1 -C 30 alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl, a monovalent radical of a hexose, a monovalent radical of a hexitol. where R has the above definitions, or equally Ri7 is CH2CH2-T3-R? 9 or | ~ (CH2) p ° -MCH2) pOR19, in which T3 is oxygen, sulfur or N - R 22 / R19 is where Ri2 and i5 are as defined above, or R19 is likewise hydrogen, alkyl, O-c18-phenyl, C5-C7-cycloalkyl or 11-H- -rc- where p is an integer ranging from 2 to 4, q is an integer that varies from 2 to 20, R22 is C 1 -C 8 alkyl, phenyl or C 5 -C 8 cycloalkyl, R 23 and R 24 are not simultaneously methyl; R25 is hydrogen or C -C 8 alkyl, or if n is 2, Rl7 is a divalent radical of a hexose, a radical where p and q have the above definitions, -CH2CH2-T4-CH2CH2-, -CH2-CH = CH-CH2-, -CH2-C = C-CH2- wherein R18 and R20 'independently of each other, are hydrogen or C? -Cg alkyl, or together are a radical -CH2CH2CH2CH2CH2-, r is an integer ranging from 2 to 10, T 4 is sulfur, S, wherein R 7 and R 8 have the above definitions and R g is hydrogen, C 1 -C 6 alkyl, C 5 cycloalkyl, or where R2 has the above definitions.
  4. 4. A composition, according to claim 1, wherein, in the compound of formula I, the radicals Y, independently of each other, are OH, (OH-CH2CH2) 2N- or -HNRi and Rl is hydrogen, C? -C4 alkyl, or where R2 is hydrogen, C?-C4 alkyl, OH, allyl, benzyl, acetyl or HOCH2CH2- and a is a number of 1,2,3,4 or 6, where if Y is OH and a is 1, X is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, wherein R2 is as defined above, and Ti is oxygen, R4 is C -C4 alkyl, and b is an integer ranging from 0 to 10, or if Y is OH and a is 2, X is -CH2CH2T2 (CH2CH20) bCH2CH2-, where b has the above definitions or equally X is - C c-Hp2, c ~ - CH2-CH = CH-CH2 - wherein T2 is oxygen, sulfur or N-R / 5 ' R5 is hydrogen, b is the number 0 or 1 and c is an integer that varies from 2 to 8, or if a is 3 X is -CH2-CH-CH2- or N (CH2CH2-) 3, if Y is OH it is already 4, CH2- C 2- II "H" X is -CH2-C-CH2- ^ (-CH2-CH-CH2) 20 0 -CH2-CH-CH2-0-CH-CH CH, if Y is OH it is already 6, X is -C 0 -CH 2 -CH-CH-c? -H-CH 2 -, if Y is -HNR and a is 1, X is C 1 -C 0 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl, or where R2 has the above definitions, or if Y is -HNRi and a is 2, X is CfH2f-, in which f is an integer ranging from 2 to 10 and in the compound of formula II, the radicals Z are hydrogen or a group of the formula O - (ChH2hO) rC-Rr (Y is 1, 2 or 3, h is 2 or 3, i is an integer ranging from 0 to 4 and ll is alkyl CI- C2Q, or C8-C2Q alkenyl, with the proviso that the compound of formula II comprises an O group || - (ChH2hO) rC-R1 ?; in the compound of formula III, R 2 is C 1 -Cg alkyl or C 5 -C 7 cycloalkyl, s is 1 or 2, Q is -CmH 2m- or "CH 2 -CH- § R 16 m is an integer ranging from 0 to 3, Rig is C 1 -C 4 alkyl, and n is an integer that varies from 1 to 6, where, if n is 1, Ri7 is hydrogen,? -C? 8 alkyl, C5-C7 cycloalkyl, C2-C? 8 alkenyl, a monovalent radical of a hexose, a monovalent radical of a hexitol, CH? , where R2 has the above definitions, or equally i is -I- (CH2) pO - (CH2) pOR19 in which Rig is hydrogen, C -C 8 alkyl, or C 5 -C cycloalkyl, wherein p is an integer ranging from 2 to 4, q is an integer ranging from 2 to 10, or if n is 2, Rl7 is a divalent radical of a hexose, a divalent radical of a hexitol, -CH, where p and q have the above definitions -CH2CH2-T4-CH2CH2-, or. -CH2CH2-N where CH CH, r is an integer that varies from 2 to 10, \ T4 is sulfur or N - Roe and R26 is hydrogen, C? -C? 0 alkyl, or C5-C8 cycloalkyl, or if n is 3, Ri7 is a trivalent radical of a hexose or c.,. trivalent radical of a hexitol CCHH2CCHH22-- CH2CH2-N-CH2CH2- CH2-CH-CH CH3-CH-CH2-N-CH2-CH-CH3 if n is 4, Rl7 is a tetravalent radial of a hexose, a tetravalent radical of a hexitol, CH3-CH-CH2 CH-j-CH-CHa NN-CH2CH2-N CH3-CH-CH N CH2-CH-CH3 i I
  5. 5. A composition, according to claim 1, wherein, in the compound of formula I, the radicals Y, independently of each other, are hydroxyl or -NH2 is already an integer varying from 4, where, if a is 1 R2 is hydrogen, methyl or HOCH2CH2-, or if Y is OH and a is 2, where \ T2 is oxygen, sulfur or N _ s, / R5 is hydrogen, b is the number 0 or 1 and c is the number 2, 3 or 4 or if Y is OH and a is 3, X is -CH2-CH-CH2-, if Y is OH and a is 4, CH2- I X is -CH2-C-CH9- and I CH2- in the compound of formula II, Or the radicals Z are hydrogen or a group of the formula j1k is the number 1 and Rll is alkyl CI-C2Q, or C8-C2Q alkenyl, with the proviso that the compound of the formula II comprises a group -C-R1t and in the compound of the formula III, Ri2 is tertiary butyl, R15 is C alquilo-C4 alkyl, and is bonded in the ortho position with respect to the OH group, s is number 1, Q is -CroH2lll- and is attached in the position for relative to the OH group, where m is the number 2, n is 1 and Rl7 is C1-C4 alkyl.
  6. 6. A composition, according to claim 1, wherein, in the compound of the formula III, R 2 is C -C 4 alkyl, or cyclohexyl, R 5 is C 1 -C 4 alkyl, or cyclohexyl and is attached at the ortho position in relation to the OH group, s is the number 1, Q is -CmH2? n-, and joins in the para position in relation to the OH group, where m is an integer that varies from 0 to 3 and n is an integer that varies from 1 to 4, where, if n is 1, Rl7 is hydrogen, C-CQ alkyl, cyclohexyl, alkenyl CH20H c2 ~ c18 '° -CH2-C-CH2OH * CH2OH if n is 2, Ri7 is -CH2CH2-T4-CH2CH2- wherein p is an integer ranging from 2 to 4, q is an integer ranging from 2 to 10, r is an integer ranging from 2 to 6, \ T4 is sulfur or N -R26 / R26 is hydrogen or C1-C4 alkyl, or if n is 3, if n is 4,
  7. 7. A composition, according to claim 1, wherein, in the compound of the formula III, R 2 is tertiary butyl, l 5 is C 1 -C 4 alkyl, and is bonded in the ortho position with respect to the OH group, s is the number 1, Q is -CmH 2m-, and is bonded in the para position with respect to to group OH, where is number 2 and n is an integer, 1, 2, or 4, where, if n is 1, R1 is C1-C4 alkyl, or if n is 2, Rl7 is -f- (CH2) pOj- (CH2) p- 0 CH2CH2-T4-CH2CH2- where p is number 2, q is number 2 and 4 is sulfur or if n is 4
  8. 8. A composition, according to claim 1, wherein the compound of the formula I is pentaerythritol, thiodiethylene glycol, 1,4-butanediol, 1,2-propanediol, diethylene glycol, triethylene glycol, diethanolamine, glycerol, OH the compound of formula II, is sunflower oil, coconut oil, turnip seed oil, corn germ oil, safflower oil, olive oil, peanut oil or Radiamuls, and the compound of the Formula III, in methyl 3- (3 ', 5'-diterc. -butyl-4 * -hydroxyphenyl) propionate or 3- (3'-tere. -butyl-4'-hydroxy-5 • -methylphenyl) -Methyl propionate.
  9. 9. A composition, according to claim 1, wherein the molar quantitative ratio of components a), b) and e) is from 0.1: 1: 0.1 to 15: 1: 30.
  10. 10. A composition, according to claim 1, wherein the amount by weight of the active group E-2: in the component (ß) is from 30 to 80% by weight.
  11. 11. A composition, according to claim 1, wherein the first components a) and b) are reacted with each other and the resulting intermediate product is reacted with the component c).
  12. 12. A composition, according to claim 1, wherein the component (a) is a hydrocarbon fuel, an oxygenated fuel or a mixture thereof.
  13. 13. A composition, according to claim 1, wherein the component (a) is a diesel fuel.
  14. 14. A composition, according to claim 1, wherein the component (a) is a fuel containing less than 0.10% by weight of sulfur.
  15. 15. A composition, according to claim 1, which contains the component (ß) in an amount of 0.0001 to 10%, based on the weight of the component (a).
  16. 16. A method for reducing the wear of an engine fuel system, which comprises adding a component (ß), according to claim 1, to the fuel.
  17. 17. The use of the component (ß), according to claim 1, as an anti-wear agent for a motor fuel system. SUMMARY OF THE INVENTION Lubricity (anti-wear properties) of fuels is improved, for example, hydrocarbon oils, oxygenated fuels or mixtures thereof, particularly diesel or aviation fuels, which have a reduced content of sulfur and / or aromatics, to comply with the regulatory requirements, by the addition of at least one product, which can be obtained by the reaction of components a), b) and e), where component a) is a compound of formula I or a mixture of compounds of formula I, component b) is a compound of formula II or a mixture of compounds of formula II and component c) is a compound of formula III or a mixture of compounds of formula III: (III) (0 (ID in which the general symbols are as defined in claim 1, the compound of formula I is, for example, pentaerythritol tiodiethylene glycol, 1,4-butanediol, 1,4-propanediol, diethylene glycol, triethylene glycol, glycol, diethanolamine or glycerol, the compound of formula II is, for example, sunflower oil or coconut fat, and the compound of formula III is, for example, 3- (3 ', 5' -di methyl-4-methyl-4 '-hydroxyphenyl) -propionate. The aforementioned products also improve the corrosion inhibition.
MXPA/A/1998/000903A 1997-02-03 1998-02-02 Liquid polifunctional additives for improved lubrication of combusti MXPA98000903A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP97810052.7 1997-02-03
EP97810052 1997-02-03

Publications (2)

Publication Number Publication Date
MX9800903A MX9800903A (en) 1998-08-30
MXPA98000903A true MXPA98000903A (en) 1998-11-12

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