DE2702805C2 - Additives for liquid lubricants and / or fuels - Google Patents

Description

The invention relates to additives found in liquid lubricants and normally liquid ones Fuels are useful, especially for two-stroke engines.

The book "Lubricant Additives" by M. W. Ranney, published by Noyes Data Corporation of Parkridge, New Jersey (1973) describes a number of metal salts of various types Sulfonic acids and carboxylic acids and of phenols, which are used as detergent dispersants in Lubricating oil products are useful. The book with the same title "Lubricant Additives" by C.V. Smallheer and R.K. Smith, published by Lezius-Hiles Co., Cleveland, Ohio (1967), describes detergent dispersants such as sulfonates, phenolates and carboxylates, alkyl and Alkenyl succinimides and high molecular amides and polyamides.

It is known that additives are commonly used in engine lubricants and fuel compositions added to the formation of deposits on the engine and fuel system surfaces, with which the lubricant or the fuel can come into contact to prevent. Such deposits interfere with the circulation of lubricants in the engine. they can also act as an abrasive, increasing wear on engine parts, and in In extreme cases, such deposits can even prevent the machine parts from moving.  

Deposits of fuel can disrupt the operation of the carburetor and the spark plugs contaminate.

The increasing use of two-stroke engines combined with the increasing hardness of the Conditions under which they have to work and with the need to take advantage of Maximizing petroleum-derived materials led to increasing scarcity a growing need for oils and fuels that suit such engines lubricate.

Problems associated with the lubrication of two-stroke engines include one Piston ring gluing, rusting, lubrication errors on the connecting rod and in main bearings as well especially the formation of varnish-like deposits, which is a particularly troublesome problem as they lose compression due to failure of the piston and cylinder walls Seal can cause. This is particularly bad with two-stroke engines because of that Suction are dependent on a new fuel feed in the emptied cylinder too pull.

Additives for fuels and lubricants are in US Pat. Nos. 30 85 975, 30 04 837 and 37 53 905 described.

According to US Pat. No. 2,197,835, metal salts of certain aromatic amines can be mineral oils add and lower their pour points and increase viscosity index.

In US-PS 25 02 708 and 25 71 092 describes aminocardanol as an antioxidant Add mineral oils, fats and other petroleum products. Cardanol, also called anacardol is known, a mixture of 3-pentadecylphenol, 3- (8'-pentadecenyl) phenol, 3- (8 ': 11- Pentadecenyl) phenol, 3- (8 ′: 11′-pentadecadienyl) phenol and 3- (8: 11: 14′-pentadecatrienyl) - be phenol. Those in the latter two US patents, as well as in the chemical Literature (see Dictionary of Organic Compounds, Volume 1, Oxford University Press, N.Y., 1965, Page 229) shown formulas show that the C₁₅ substituent in cardanol is in meta- Position to the hydroxyl group. The US-PS 23 67 377 describes the addition of Reaction products of alkylated aminophenols, whose nitrogen atoms are substituted, to oils also as an antioxidant. The US-PS 35 22 179 relates to the addition of esters substituted succinic acids and US-PS 35 76 743 the addition of polyesters with primary Amino groups to oils. All of these compounds keep contaminants in liquid Fuels and lubricating oils dispersed less well than those used according to the invention Aminophenols.  

The object underlying the invention was only to provide better additives for liquid To get lubricants and usually liquid fuels.

To achieve this object, the additive according to the invention for liquid lubricants and / or Fuels containing at least one aminophenol of the general formula

wherein R is an aliphatic hydrocarbon radical with 30 to 750 carbon atoms, each of 10 C-C- Single bonds contain at most one unsaturated C-C bond and 10 carbon atoms each to a radical from the group hydroxyl, halogen, alkoxy, alkylmercapto or alkylsulfoxy may contain, a, b and c each independently represent an integer from 1 to 3 and Ar is a mononuclear aromatic radical with 0 to 3 possible substituents from the Group of C₁-C₇ alkyl groups, C₁-C₇ alkoxy groups, nitro groups and / or halogen atoms means, characterized in that it is additionally in the weight ratio 1:10 to 10: 1 contains at least one dispersant which

• 1. at least one neutral or basic metal salt of an organic sulfuric acid, of Phenol or a carboxylic acid,
• 2. at least one hydrocarbon substituted other than the above aminophenols Amine, wherein the hydrocarbon substituent is aliphatic and at least 12 Contains carbon atoms,
• 3. at least one acylated nitrogen-containing compound having a substituent with at least 10 aliphatic carbon atoms, which is obtained by reacting a carboxy acylating agent with at least one amino compound with at least one has been obtained, the acylating agent being bonded to the amino compound via an imido, amido, amidine or acyloxyammonium group, or
• 4. at least one nitrogen-containing condensate of a phenol, an aldehyde and an amino compound with at least one

is.  

A. The aminophenols

The aromatic radical Ar can be, for example, a benzene nucleus, a pyridine nucleus or a thiophene nucleus.

The aromatic nucleus can contain 4 to 10 carbon atoms. Halogen atoms include fluorine, chlorine, Bromine and iodine atoms. The halogen atoms are usually fluorine and chlorine atoms.

Specific examples of such Ar residues are as follows:

Here, Me means methyl, Et ethyl, Pr n-propyl and Nit Nitro.

The rest of Ar is usually a benzene nucleus for reasons of cost, availability, properties, etc. One or two of the valences of the benzene nucleus may be saturated by a hydroxyl group, the remaining unsaturated valences, if possible, either in the ortho or para position to one Hydroxyl group. Ar is preferably a benzene nucleus with at least 3 unsaturated valences, so that one of one hydroxyl group may be saturated, while the remaining two or three are either in ortho or in are para to the hydroxyl group.

The aminophenols according to the present invention contain directly bound to the aromatic radical Ar at least one group R which is an aliphatic hydrocarbon residue. There can also be several Groups are present, but no more than 2 or 3 groups R are present in the aromatic radical Ar. Usually the group R has at least 50 carbon atoms and typically up to 300 carbon atoms.

In general, these groups R consist of homopolymers or interpolymers (such as copolymers or terpolymers) of mono- and diolefins with 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, Butadiene, isoprene, 1-hexene or 1-octene. Typically, these olefins are 1-monoolefins. The groups R  can also differ from the halogenated (such as chlorinated or brominated) analogs of such homo- or Derive interpolymers or come from other sources, such as from monomeric high molecular weight alkenes (such as 1-tetracontene) and chlorinated analogs and hydrochlorinated analogues thereof, aliphatic petroleum fractions, especially paraffin waxes and cracked and chlorinated analogs and hydrochlorinated analogs of these, white oils, synthetic alkenes, such as those obtained by the Ziegler-Natta process (such as polyethylene greases) and other sources known to those skilled in the art. Any unsaturated bond in groups R can be reduced or eliminated by hydrogenation by methods known in the art before the nitriding step described below takes place.

The term "aliphatic hydrocarbon residue" here means a group with one directly attached to the rest of the molecule bound carbon atom and predominantly hydrocarbon in character. Therefore can the radicals R contain up to one non-hydrocarbon radical per 10 carbon atoms, provided that this non-hydrocarbon residue does not significantly affect the group's predominant hydrocarbon character changed. Those skilled in the art are familiar with such residues, such as hydroxyl groups, halogen atoms (especially Chlorine atoms and fluorine atoms), alkoxy groups, alkyl mercapto groups or alkylsulfoxy groups. Usually however, the hydrocarbon-based groups R are pure hydrocarbonyl radicals and contain none such non-hydrocarbon residue.

The residues are essentially saturated, i.e. that is, they contain no more than one unsaturated one Carbon-carbon bond each 10 carbon-carbon single bonds. They usually contain no more than one non-aromatic unsaturated carbon-carbon bond per 50 carbon-carbon Single bonds.

The radicals R are essentially aliphatic in nature, i. that is, they contain no more than one non-aliphatic Radical (cycloalkyl group, cycloalkenyl group or aromatic group) having 6 or less carbon atoms 10 carbon atoms each in the radical R. Usually, however, the groups R contain no more than one such non-aliphatic group of 50 carbon atoms each, and in many cases they contain none at all such non-aliphatic groups, i. that is, the typical R groups are purely aliphatic. Typically are these purely aliphatic groups R alkyl groups or alkenyl groups.

Specific examples of the substantially saturated hydrocarbon-based R are as follows: Tetra (propylene) group, a tri (isobutene) group, a tetracontanyl group, a henpentacontanyl group, a mixture of poly (ethylene / propylene) - Groups with 35 to 70 carbon atoms, a mixture of oxidatively or mechanically degraded poly (ethylene / propylene) groups with 35 to 70 carbon atoms, a mixture of poly (propylene / 1-hexene) groups with 80 to 150 carbon atoms, a mixture of poly (isobutene) groups with 20 to 32 carbon atoms, a mixture of poly (isobutene) groups with an average of 50 to 75 carbon atoms.

A preferred source for the group R are poly (isobutenes), which are obtained by polymerizing a C₄ refinery stream with a butene content of 35 to 75% by weight and an isobutene content of 15 to 60, typically 30 to 60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (more than 80% of the total repeating ones Units) repeating isobutene units of the formula

The introduction of the radical R into the aromatic radical Ar of the aminophenols can be done in a number of ways Methods are carried out which are known to the person skilled in the art. A particularly suitable method is the Friedel-Crafts Reaction in which an olefin (such as a polymer with an olefinic bond) or a halogenated or hydrohalogenated analogue thereof is reacted with a phenol. The implementation takes place in the presence a Lewis acid catalyst (such as boron trifluoride or its complexes with ethers, phenols, hydrofluoric acid etc., aluminum chloride, aluminum bromide, zinc dichloride etc.) (see "Alkylation of Phenols" in Kirk-Othmer, "Encyclopedia of Chemical Technology", 2nd edition, volume 1, pages 894 to 895, Interscience Publishers, John Wiley and Company, N.Y., 1963).

The aminophenols according to the invention thus each contain at least one hydroxyl group, one radical R, one primary amino group -NH₂. Each of these groups must be attached to a carbon atom, which part of the aromatic nucleus in the remainder is Ar.

A preferred class of aminophenols can be represented by the following formula:  

wherein the group R is an aliphatic hydrocarbon radical having 30 to 400 carbon atoms in ortho- or Para position to the hydroxyl group means R 'is a C₁-C Alkyl alkyl group, C₁-C₇ alkoxy group, nitro group or represents a halogen atom and z represents 0 or 1. Usually z 0 and R are essentially one saturated, purely aliphatic group. It is often an alkyl or alkenyl group para to that OH substituents. One or two amino groups can be present.

In another embodiment of the invention, the aminophenols have the general formula

wherein R is derived from homopolymerized or interpolymerized C _2-10 -1 olefins and has on average 30 to 400 aliphatic carbon atoms and R 'and z are as defined above. Usually R is derived from ethylene, propylene, butylene or mixtures thereof. Typically, it comes from polymerized isobutene. Often R has at least about 50 aliphatic carbon atoms and is z 0.

The aminophenols according to the present invention can be prepared in various synthetic ways become. These ways can be in terms of the type of reaction used in the reaction sequence used, in which they are used vary. For example, an aromatic hydrocarbon such as Benzene, with an alkylating agent such as a polymeric olefin to form an alkylated aromatic Intermediate be alkylated. This intermediate can then, for example, form a Polynitro intermediate are nitrided. The polynitro intermediate can then in turn become one Diamine are reduced, which can then be diazotized and reacted with water to one of the Convert amino groups to a hydroxyl group and get the desired aminophenol. Instead of  one of which can be one of the nitro groups in the polynitro intermediate by fusing with caustic alkali into one Hydroxyl group can be converted to get an alkylated hydroxy-nitroaromatic, which in turn can then be reduced to get the desired aminophenol.

Another useful route to the aminophenols of the invention is to alkylate one Phenol with an olefinic alkylating agent to form an alkylated phenol. This alkylated Phenol can then be nitrided to form a nitrophenol intermediate, which is among those desired Aminophenols converted into amino groups by reduction of at least one of the nitro groups can be.

Methods for the alkylation of phenols are known to the person skilled in the art, for example from the above article in Kirk-Othmer, "Encyclopedia of Chemical Technology" known. Methods for nitrating phenols are also known see for example in Kirk-Othmer, "Encyclopedia of Chemical Technology", 2nd edition, volume 13, the Article "Nitrophenols", page 888 ff., As well as the work "Aromatic Substitution, Nitration and Halogenation" by P. B. D. de la Mare and J.H. Ridd, N.Y., Academic Press, 1959, "Nitration and Aromatic Reactivity" by J.G. Hogget, London, Cambridge University Press, 1961, and "The Chemistry of the Nitro and Nitroso Groups", Henry Feuer, Interscience Publishers, N.Y., 1969.

Aromatic hydroxyl compounds can be mixed with nitric acid, mixtures of nitric acids and others Acids such as sulfuric acid or boron trifluoride, nitrogen tetraoxide, nitronium tetrafluoroborates and acyl nitrates be nitrided. Generally, nitric acid is at a concentration of, for example, about 30 to 90 a convenient nitrating agent. Essentially inert liquid diluents and solvents, such as acetic acid or butyric acid, can carry out the reaction by improved contact of the Support reaction partners.

The conditions and concentrations for nitrating the aromatic hydroxy compounds are also known in the art. For example, the reaction can be carried out at a temperature of about -15 to about 150 ° C are carried out. Usually, nitriding is conveniently between about 25 and 75 ° C.

In general, depending on the specific nitrating agent, about 0.5 to 4 moles of nitrating agent per mole become more aromatic Core used in the aromatic hydroxy intermediate to be nitrided. If nitric acid than Nitrating agent is used, usually about 1.0 to about 3.0 moles per mole of aromatic core. Up to about a 5 molar excess of nitrating agent can be used if desired to rapidly advance or carry out the reaction.

Nitration of an aromatic hydroxy intermediate generally takes 0.25 to 24 hours, although it can also be convenient to implement the nitration mixture for a long time, at 96 hours.

Reduction of aromatic nitro compounds to the corresponding amines is also known, see for example the article "Amination by Reduction" in Kirk-Othmer, "Encyclopedia of Chemical Technology", 2. Edition, volume 2, pages 76 to 99. In general, such reductions can be carried out, for example, with hydrogen, carbon monoxide or hydrazine (or mixtures thereof) in the presence of metallic catalysts, such as palladium, Platinum and its oxides, nickel, copper chromite, etc. are carried out. Cocatalysts, such as alkali or alkaline earth metal hydroxides or amines (such as aminophenols) can be used in these catalyzed reductions become.

The reduction can also be accomplished by using reducing metals in the presence of acids such as Hydrochloric acid. Typical reducing metals are zinc, iron and tin. Salts of these metals can also be used.

Nitro groups can also be reduced in the tin reaction described in "Organic Reactions", Volume 20, John Wiley & Sons, N.Y., 1973, page 455 ff. In general, the tin reaction is the reduction of one Nitro group with negative divalent sulfur compounds, such as alkali sulfides, polysulfides and hydrogen sulfides.

The nitro groups can be reduced by electrolysis, such as according to the above Article "Amination by Reduction".

Typically, the aminophenols according to the invention are obtained by reducing nitrophenols Hydrogen in the presence of a metallic catalyst, as discussed above. This reduction takes place generally at temperatures from about 15 to 250 ° C, typically at about 50 to 150 ° C, and at hydrogen pressures from about 1 to 134 bar, typically from about 4.3 to 17.6 bar. The response time for the reduction usually varies between about 0.5 to 50 hours. They can be essentially inert liquid diluents and solvents such as ethanol, cyclohexane, etc. can be used to facilitate the reaction. The aminophenol product is produced by known methods, such as by distillation, filtration or extraction receive.

The reduction is carried out until at least about 50%, usually about 80%, of the nitro groups present in the nitro intermediate mixture are converted to amino groups.  

B) The dispersants 1. The neutral or basic metal salts of organic Sulfuric acids, carboxylic acids or phenols

The choice of the metal used to make these salts is usually not critical, so virtually any metal can be used. For reasons of availability, costs and maximum effectiveness, certain metals become more common used. These are the alkali and alkaline earth salts (exclusively Francium and Radium). Group IIB metals and polyvalent ones Metals, such as aluminum, chromium, molybdenum, tungsten, manganese, Iron, cobalt, nickel and copper can also be used become. Often salts are also used, which are a mixture of ions contain two or more of these metals used.

These salts can be neutral or basic. The former included a lot of metal ions just enough, the acidic  Neutralize groups in the salt anion. The latter contain an excess of metal cations and are often referred to as overbased, hyperbased or superbased salts.

These basic and neutral salts can be those of oil-soluble organic sulfuric acids, such as sulfonic acid, sulfamic acid, Thiosulfonic acid, sulfinic acid, sulfenic acid, partial ester sulfuric acid, Sulfuric acid or thiosulfuric acid. General they are salts of carbocyclic or aliphatic sulfonic acids.

The carbocyclic sulfonic acids are, for example, the mononuclear or polynuclear aromatic or cycloaliphatic Links. The oil-soluble sulfonates can mostly through the following formulas are given:

[R _x -T- (SO₃) _y ] _z M _b

[R ′ - (SO₃) _a ] _d M _b

In the above formulas, M is either a metal cation as described above or a hydrogen atom. T is a cyclic nucleus, such as, for example, the benzene radical, naphthalene radical, anthracene radical, phenanthrene radical, diphenylene oxide radical, thianthrene radical, phenothioxin radical, diphenylene sulfide radical, phenothiazine radical, diphenyl oxide radical, diphenyl sulfide radical, diphenylamine radical, cyclohexane radical, petroleum naphthenrene radical radical, petroleum naphthane radical radical. R is an aliphatic group such as an alkyl, alkenyl, alkoxy, alkoxyalkyl or carboalkoxyalkyl group, x is at least 1 and R _x + T contains at least about 15 carbon atoms in total. R 'is an aliphatic radical containing at least about 15 carbon atoms. Examples of types of the radical R 'are alkyl, alkenyl, alkoxyalkyl or carboalkoxyalkyl groups. Specific examples of R 'are groups derived from paraffin oil, saturated and unsaturated paraffin wax and polyolefins including polymerized C₂-, C₃-, C₄-, C₅-, C₆- and other polymerized olefins with about 15 to 7000 or more carbon atoms. The groups T, R and R 'in the above formulas can also contain other inorganic or organic substituents in addition to those listed above, such as hydroxyl, mercapto, halogen, nitro, amino, nitroso, sulfide or Disulfide substituents. In the above formulas, x, y, z, a, b and d are at least 1.

Below are specific examples of oil-soluble sulfonic acids according to the formulas above, but these serve Examples merely illustrating the after the invention usable salts of such sulfonic acids. Of the enumerated sulfonic acids can be their corresponding neutral and basic metal salts can be used. Such sulfonic acids are mahogany sulfonic acids, Sulfonic acids from lubricating oil fractions with a Saybolt Viscosity from about 100 seconds at 38 ° C to about 200 seconds at 99 ° C, paraffin oil sulfonic acids or Vaseline sulfonic acids, mono- and poly wax-substituted sulfonic acids and polysulfonic acids, such as benzene, naphthalene, phenol,  Diphenyl ether, naphthalene disulfide, diphenylamine, thiophene, α-chloronaphthalenesulfonic acids, other substituted sulfonic acids, such as alkylbenzenesulfonic acids (wherein the alkyl group has at least 8 carbon atoms), cetylphenol monosulfide sulfonic acids, Dicetylthianthrene disulfonic acids, dilauryl-β-naphthyl sulfonic acids, Dicaprylnitronaphthalenesulfonic acids and alkarylsulfonic acids. The latter are acids derived from benzene, which alkylated with propylene tetramers or isobutene trimers was in order to 1, 2, 3 or more two-chain C₁₂ substituents in insert the benzene ring. Mainly Mixtures of mono- and didodecylbenzenes are considered By-products from the manufacture of household cleaning products available. Similar products that are used in alkylation of soil products that are linear during manufacture Alkyl sulfonates formed are also used in the manufacture of sulfonates used in the invention.

The production of sulfonates from by-products of detergent production by implementation, for example, with SO₃ Known to those skilled in the art, see for example the article "Sulfonates" in Kirk-Othmer, "Encyclopedia of Chemical Technology", 2nd edition, Volume 19, page 291 ff., John Wiley & Sons, N.Y. (1969).

Other neutral and basic sulfonate salts and methods too their manufacture can be found in the following US-PS: 21 74 110, 21 74 506, 21 74 508, 21 93 824, 21 97 800, 22 02 781, 22 12 786, 22 13 360, 22 28 598, 22 33 676, 22 39 974, 22 63 312, 22 76 090, 22 76 097, 23 15 514, 23 19 121,  23 21 022, 23 33 568, 23 33 788, 23 35 259, 23 37 552, 23 46 568, 23 66 027, 23 74 193, 23 83 319, 33 12 618, 34 71 403, 34 88 284, 35 95 790 and 37 98 012.

Aliphatic sulfonic acids, such as paraffin wax sulfonic acids, can also be used. unsaturated paraffin wax sulfonic acids, hydroxyl-substituted paraffin wax sulfonic acids, hexapropylene sulfonic acids, Tetraamylene sulfonic acids, polyisobutene sulfonic acids, wherein the polyisobutene residue has 20 to 7000 or more carbon atoms contains, chlorine-substituted paraffin wax sulfonic acids, Nitroparaffin wax sulfonic acids, cycloaliphatic Sulfonic acids, such as petroleum naphthenesulfonic acids, cetylcyclopentylsulfonic acids, Laurylcyclohexylsulfonic acids, bis (diisobutyl) - cyclohexylsulfonic acids, mono- or polywax-substituted cyclohexylsulfonic acids.

Regarding the sulfonic acids or salts thereof described here the term "petroleum sulfonic acids" or "petroleum sulfonates" include any sulfonic acids or salts thereof that derived from petroleum products. A particularly valuable one Group of petroleum sulfonic acids is that of mahogany sulfonic acids, which one as By-product in the manufacture of petroleum oils after a Sulfuric acid process.

The carboxylic acids that make up suitable neutral and basic Salts for use according to the invention can be prepared  can be, for example, aliphatic, cycloaliphatic and aromatic monovalent and polyvalent carboxylic acids such as the naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl or alkenyl-substituted cyclohexanoic acids or alkyl or alkenyl substituted aromatic carboxylic acids. The aliphatic acids generally contain at least 8 carbon atoms and preferably at least 12 carbon atoms. They usually have no more than about 400 carbon atoms. When the aliphatic carbon chain branches in general, the acids are more oil soluble in any one certain carbon atom content. The cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated his. Specific examples are 2-ethylhexanoic acid, α-linolenic acid, propylene tetramer-substituted maleic acid, behenic acid, Isostearic acid, pelargonic acid, capric acid, palmitoleic acid, Linoleic acid, lauric acid, oleic acid, ricinoleic acid, Undecylic acid, dioctylcyclopentane carboxylic acid, myristic acid, Dilauryldecahydronaphthalene carboxylic acid, stearyl octahydroindenecarboxylic acid, Palmitic acid, commercial mixtures of two or several carboxylic acids, such as tall oil acids, rosin acids.

A preferred group of oil-soluble carboxylic acids that are used in the Preparation of the salts used according to the invention is useful are the oil-soluble aromatic carboxylic acids. This Acids have the general formula

wherein R⁺ is an aliphatic hydrocarbon group  with at least 4 carbon atoms and not means more than 400 aliphatic carbon atoms, a is an integer from 1 to 4, Ar⁺ is a multiple bond aromatic hydrocarbon core with up to 14 carbon atoms means each X independently means a sulfur or oxygen atom from the others and m is an integer from 1 to 4, where R⁺ and a are each are such that an average of at least 8 aliphatic carbon atoms by the groups R⁺ per acid molecule of the above Formula. Examples of aromatic Cores represented by the variable Ar⁺ are the polyvalent or polyvalent aromatic residues that from benzene, naphthalene, anthracene, phenanthrene, indene, Derive fluorene or biphenyl. Are general the residues represented by Ar⁺ multi-bonded Cores derived from benzene or naphthalene such as phenylene radicals, or derived from naphthylene, such as Methylphenylene, ethoxyphenylene, nitrophenylene, isopropylphenylene, Hydroxyphenylene, mercaptophenylene, N, N-diethylaminophenylene, Chlorophenylene, dipropoxynaphthylene, triethylnaphthylene and similar tri, tetra and pentavalent nuclei thereof.

The groups R⁺ are usually pure Hydrocarbon groups, preferably alkyl or alkenyl groups. However, the groups R⁺ can have a small number of substituents, such as phenyl radicals, cycloalkyl groups (e.g. cyclohexyl or cyclopentyl groups) or non-hydrocarbon groups, such as nitro groups, amino groups, halogen atoms (e.g. chlorine atoms  or bromine atoms), low molecular weight alkoxy groups, low molecular weight Alkyl mercapto groups, oxo substituents (i.e. = O), thio groups (i.e. = S), disrupting groups such as -NH-, -O-, -S-, included, provided that the essentially obtained hydrocarbon-like character of the group R⁺ remains. The hydrocarbon character is used for the present Get invention as long as any in the groups R⁺ existing non-carbon atoms no more than about Make up 10% of the total weight of groups R⁺.

Examples of groups R⁺ are butyl, isobutyl, pentyl, octyl, Nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyloctyl, 4- (p-chlorophenyl) octyl, 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl and substituents, which are derived from polymerized olefins, such as from Polychloroprenes, polyethylenes, polypropylenes, polyisobutylenes, Ethylene-propylene copolymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers and the like. The Ar⁺ group may also have non-hydrocarbon substituents or contain heteroatoms, such as C₁-C₇ alkoxy groups, C₁-C₇- Alkyl mercapto groups, nitro groups, halogen atoms, alkyl groups or alkenyl groups with less than 4 carbon atoms, hydroxyl groups or mercapto groups.

A group of particularly useful carboxylic acids consists of those the general formula

wherein R⁺, X, Ar⁺, m and a are as defined above and p represents an integer from 1 to 4, usually 1 or 2. There is a particularly preferred class within this group oil-soluble carboxylic acids from those of the general formula

wherein R ⁺⁺ in formula X denotes an aliphatic hydrocarbon group with at least 4 to 400 carbon atoms, a denotes an integer from 1 to 3, b denotes 1 or 2, c denotes 0, 1 or 2 and preferably 1, where R ⁺⁺ and a are such that the acid molecules contain on average at least 12 aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule. In this latter group of oil-soluble carboxylic acids are found the salicylic acids substituted by aliphatic hydrocarbon groups, in which each aliphatic hydrocarbon substituent contains on average at least 16 carbon atoms per substituent and 1 to 3 substituents per molecule, and these are particularly useful. Salts prepared from such salicylic acids are particularly useful if the aliphatic hydrocarbon substituents are derived from polymerized olefins, especially polymerized low molecular weight 1-monoolefins such as polyethylene, polypropylene, polyisobutylene or ethylene / propylene copolymers and have an average carbon content of 30 to 400 carbon atoms.

Carboxylic acids of the type illustrated by the formulas above and processes for producing neutral and basic metal salts the same are known, for example from US Pat 21 97 832, 21 97 835, 22 52 662, 22 52 664, 27 14 092, 34 10 798 and 35 95 791.

Another type of neutral and basic carboxylic acid salts, the useful according to the invention is that which differs from alkenyl succinates the general formula

derives in which R⁺ has the same meaning as above owns. Such salts and means of making the same are in U.S. Patents 32 71 130, 35 67 637 and 36 32 510.

Other patents that have special manufacturing methods basic salts of the sulfonic acids, carboxylic acids described above and describe mixtures of two or more of them, are US-PS 25 01 731, 26 16 904, 26 16 905, 26 16 906, 26 16 911, 26 16 924, 26 16 925, 26 17 049, 27 77 874, 30 27 325, 32 56 186, 32 82 835, 33 84 585, 33 73 108, 33 65 396, 33 42 733, 33 20 162, 33 12 618, 33 18 809, 34 71 403, 34 88 284, 35 95 790 and 36 29 109.

Neutral and basic salts of phenols (commonly called phenolates known) are also in the additives according to the invention  useful. The Phenols from which these phenolates are made are the the general formula

wherein R⁺, n, Ar⁺, X and m are the above general and preferred Have meaning.

A commonly available class of phenolates consists of those of the phenols of the general formula

wherein a is an integer from 1 to 3, b is 1 or 2 and z is 0 or 1 means, and R 'one essentially saturated hydrocarbon substituents with an average of 30 to 400 aliphatic carbon atoms and R⁴ is a C₁-C₇ alkyl group, C₁-C₇ alkoxy group, Nitro group or a halogen atom means.

A special class of phenolates for use after the invention consists of the basic Group IIA sulfurized metal phenolates obtained by sulfurization or sulfurization of a phenol as described above, with a sulfurizing or sulfurizing agent, such as sulfur, a sulfur halide or sulfide or hydrogen sulfide salt. Methods of making these sulfurized or sulfurized Phenolates are described in US Pat. Nos. 2,680,096, 30,36,971 and 37 75 321.  

Other useful phenates (also called phenates) are those obtained from phenols by alkylene bridges (like methylene groups). This gets by reacting phenols with one or more rings Wrestling with aldehydes or ketones, typically in the presence an acidic or basic catalyst. Such networked Phenolates as well as sulfurized or sulfurized phenolates in particular in US Pat. No. 3,350,038, especially in the columns 6 to 8 of the same.

Mixtures of two or more neutral can of course or basic salts of the organic sulfuric acids described above, Carboxylic acids and phenols in the additives after of the invention can be used. Usually the basic ones Salts sodium, lithium, magnesium, calcium and / or barium salts.

2. The hydrocarbon-substituted amines

The manufacture of the additives according to the invention hydrocarbon-substituted amines used are known to the person skilled in the art known and described in a number of patents, such as in US-PS 32 75 554, 34 38 757, 34 54 555, 35 65 804, 37 55 433 and 38 22 209.

A typical hydrocarbon substituted amine has the general formula

wherein A is a hydrogen atom, a hydrocarbon group with 1 to 10 carbon atoms or a hydroxy hydrocarbon group with 1 up to 10 carbon atoms, X is a hydrogen atom, a A hydrocarbon group having 1 to 10 carbon atoms or a hydroxy hydrocarbon group with 1 to 10 carbon atoms or together with A a ring of 5 to 6 ring members and can have up to 12 carbon atoms, U is an alkylene group having 2 to 10 carbon atoms, R² is an aliphatic Hydrocarbon group of about 30 to 400 carbon atoms means a is an integer from 0 to 10, b is an integer from 0 to 1, a + 2b an integer from 1 to 10 and c is an integer from 1 to 5 and on average in the range from 1 to 4 and equal to or less than the number of Nitrogen atoms in the molecule, x is an integer from 0 to 1, y is an integer from 0 to 1 and x + y is 1.

When interpreting this formula it should be noted that R² and H atoms on the unsaturated nitrogen bonds in the Parentheses of the formula are bound. For example, the formula closes Sub-formulas in which the R² has terminal nitrogen atoms and isomeric sub-formulas, wherein it is bound to non-permanent nitrogen atoms. Not on a R² bonded nitrogen atom can be a hydrogen atom or carry an AXN substituent.

The hydrocarbon substituted amines of the above useful in the invention Examples of formulas are monoamines of the general formula

AXNR²

Examples of such monoamines are as follows:  

Poly (propylene) amine
N, N-dimethyl-N-poly- (ethylene / propylene) amine (molar ratio of the monomers 50:50)
Poly (isobutene) amine
N, N-di- (hydroxyethyl) -N-poly- (isobutene) amine
Poly (isobutene / 1-butene / 2-butene) amine (molar ratio of the monomers 50:25:25)
N- (2-hydroxypropyl) -N-poly- (isobutene) amine
N-poly- (1-butene) aniline
N-poly (isobutene) morpholine

Among the hydrocarbon-substituted amines of the general formula above there are polyamines of the general formula

Examples of such polyamines are as follows:

N-poly (isobutene) ethylenediamine
N-poly (propylene) trimethylene diamine
N-poly (1-butene) diethylenetriamine
N ', N'-poly (isobutene) tetraethylene pentamine
N, N-dimethyl-N'-poly- (propylene) -1,3-propylenediamine

The hydrocarbon substituted amines used to make the Additives useful in the invention include certain N-amino hydrocarbon morpholines that are not listed below the general formula above fall. This have the general formula

wherein R² is an aliphatic hydrocarbon group 30 to 400 carbon atoms, A is a hydrogen atom, a hydrocarbon radical having 1 to 10 carbon atoms or a hydroxy hydrocarbon group having 1 to 10 carbon atoms and U represents an alkylene group having 2 to 10 carbon atoms.

3. The acylated nitrogenous compounds

A series of acylated nitrogen containing compounds a substituent of at least 10 aliphatic carbon atoms, by reacting a carboxy acylating agent with an amino compound are in the art known. In such compositions the acylating agent to the amino compound via an imido, amido, amidine or acyloxyammonium group. The substituent with 10 aliphatic Carbon atoms can either be in the part of the molecule present, which is different from the carboxy acylating agent derives, or it can be present in the part of the molecule that derives from the amino compound. Preferably located however, it is in the part of the acylating agent. The acylating agent can of formic acid and its acylating derivatives up to acylating agents with aliphatic substituents high molecular weight with up to 5000, 10,000 or 20,000 Carbon atoms vary. The amino compounds can be from Ammonia itself up to amines with aliphatic substituents vary with up to 30 carbon atoms.  

Typically the acylating agent is one Monocarboxylic acid or polycarboxylic acid (or a reactive equivalent thereof), such as a substituted succinic acid or propionic acid, and the amino compound is a polyamine or a Polyamine blend, most typically a blend of ethylene polyamines. The aliphatic substituent in such acylating agents often has at least 50 and up to 400 carbon atoms. Usually it belongs to the same general Class like the group R 'of the aminophenols (A), and thus meet the preferred compounds, examples and definitions that were discussed above for R ', in the same way for this one aliphatic substituents. Examples of amino compounds, those for the preparation of these acylated compounds are the following:

• 1. Polyalkylene polyamines of the general formula wherein each group R '''independently of the others is a hydrogen atom or a C₁-C₇-alkyl group or a C₁-C₇-hydroxyalkyl group, wherein at least one group R''' is a hydrogen atom, n is an integer from 1 to 10 and U represents a C _2-10 alkylene group;
• 2. heterocyclically substituted polyamines of the general formula wherein R '''and U are as defined above, m is 0 or an integer from 1 to 10, m' is an integer from 1 to 10 and Y is an oxygen atom or a double-bonded sulfur atom or the group NR '''; or
• 3. aromatic polyamines of the general formula Ar (NR '''₂) _y wherein Ar is an aromatic nucleus having 6 to 20 carbon atoms, each of the groups R''' is as defined above and y is 2 to 8. Specific examples of the polyalkylene polyamines (1) are ethylene diamine, tetra (ethylene) pentamine, tri (trimethylene) tetramine and 1,2-propylene diamine. Specific examples of the heterocyclically substituted polyamines (2) are N-2-aminoethylpiperazine, N-2- and N-3-aminopropylmorpholine and N-3- (dimethylamino) propylpiperazine. Specific examples of the aromatic polyamines (3) are the various isomeric phenylenediamines and the various isomeric naphthylenediamines.

There are numerous patents that can be acylated Nitrogen compounds describe how the US-PS 31 72 892, 32 19 666, 32 72 746, 33 10 492, 33 41 542, 34 44 170, 34 55 831, 34 55 832, 35 76 743, 36 30 904, 36 32 511 and 38 04 763. One typical acylated nitrogen-containing compound of this class is the one you get by implementing a poly (isobutene) substituted  Succinic anhydride acylating agent (such as the anhydride, acid or ester), in which the poly (isobutene) - Has a substituent of 50 to 400 carbon atoms, with a Mixture of ethylene polyamines with 3 to 7 amino nitrogen atoms per ethylene polyamine and 1 to 6 ethylene units obtained from the condensation of ammonia with ethylene chloride. With regard to the detailed description of this type Acylated amino compounds is another discussion of theirs here Nature and the method of their preparation is not required. Instead, reference is made to the above-mentioned US patents pointed out.

Another type of acylated nitrogen compounds that lead to This class belongs to those you get by implementing the above described alkylene amines with the succinic acids described above or with anhydrides and aliphatic monocarboxylic acids Gets 2 to 22 carbon atoms. In these types of The molar ratio of acylated nitrogen compounds is Succinic acid to monocarboxylic acid in the range of about 1: 0.1 to about 1: 1. Typical monocarboxylic acids Formic acid, acetic acid, dodecanoic acid, butanoic acid, oleic acid, Stearic acid, the commercially available mixtures of stearic isomers, known as isostearic acid or tolylic acid. Such materials are described in detail in U.S. Patents 32 16 936 and 32 50 715 described. Yet another type of useful acylated nitrogen compound  is the product of the implementation of a fatty monocarboxylic acid having 12 to 30 carbon atoms and that described above Alkylene amines, typically of ethylene, propylene or trimethylene polyamines with 2 to 8 amino groups and mixtures of this. The fatty monocarboxylic acids are generally mixtures of straight-chain or branched-chain fatty carboxylic acids 12 to 30 carbon atoms. A common type of Acylated nitrogen compounds are obtained by reaction of the alkylene polyamines described above with a mixture of Fatty acids with 5 to 30 mol% straight-chain acid and 70 to 95 mol% of branched chain fatty acids. Among the Commercial mixtures are those that are widely available in the trade are known as isostearic acid. These mixtures are called one By-product in the dimerization of unsaturated fatty acids obtained according to the US-PS 28 12 342 and 32 60 671.

The branched chain fatty acids can also include those wherein the chain has no alkyl nature, as in phenyl and cyclohexylstearic acid as well as in the chlorostearic acids. Products branched chain fatty carboxylic acids and alkylene polyamine are in the technology described on a large scale, see for example US-PS 31 10 673, 32 51 853, 33 26 801, 33 37 459, 34 05 064, 34 29 674, 34 68 639 and 38 57 791.

4. The nitrogen-containing condensates of phenols, aldehydes and amino compounds

The for the additives according to the invention usable condensates of phenol, aldehyde and amino compound  are, for example, those called Mannich condensates designated. Generally they are made in the way that you have at least one active at the same time or in succession Hydrogen compound, such as a hydrocarbon-substituted one Phenol (e.g. an alkylphenol, wherein the alkyl group Has 30 to 400 carbon atoms) with at least a hydrogen atom on an aromatic carbon with at least one aldehyde or aldehyde producing material (typically formaldehyde or a formaldehyde precursor) and at least one amino or polyamino compound with implements at least one NH group. Close the amino compounds primary or secondary monoamines with hydrocarbon substituents with 1 to 30 carbon atoms or hydroxyl-substituted Hydrocarbon substituents of 1 to about 30 carbon atoms a. Another type of typical amino compound are the polyamines that are acylated during the discussion nitrogen-containing compounds have been described.

Examples of monoamines are methyl ethylamine, methyl octadecylamine, Aniline, diethylamine, diethanolamine and dipropylamine. The following US-PS contain a comprehensive description of Mannich condensates that can be used: 24 59 112, 34 13 347, 35 58 743, 29 62 442, 34 42 808, 35 86 629, 29 84 550, 34 48 047, 35 91 598, 30 36 003, 34 54 497, 36 00 372, 31 66 516, 34 59 661, 36 34 515, 32 36 770, 34 61 172, 36 49 229, 33 55 270, 34 93 520, 36 97 574, 33 68 972, 35 39 633.  

Condensates from sulfur-containing reactants can also be used in the additives according to the invention. Such sulfur-containing condensates are described in US Pat. Nos. 3,368, 36,429,229, 3,600,372, 3,649,659 and 37,41996. Generally, the condensates used are made from a phenol bearing an alkyl substituent of 6 to 400 carbon atoms, typically one having 30 to 250 carbon atoms. These condensates are obtained from formaldehyde or aliphatic C _2-7 aldehyde and an amino compound, such as one described for the preparation of the acylated nitrogen-containing compounds described under 3.

These preferred condensates are made by reacting about one mole of phenol compound with about 1 to 2 moles Aldehyde and about 1 to 5 equivalents Amino compound produced (one equivalent of amino compound is their molecular weight divided by the number of them = NH groups).  

A particularly preferred class of condensation products for use in the present invention consists of those obtained by a two-step process. Briefly, these nitrogen-containing condensates are prepared by 1. at least one hydroxyl aromatic compound having an aliphatic or cycloaliphatic substituent having at least 30 carbon atoms and up to 400 carbon atoms, with an aliphatic C _1-7 aldehyde or a polymer thereof in the presence an alkaline reagent, such as an alkali hydroxide, at a temperature up to about 150 ° C., 2. the reaction intermediate mixture thus formed is essentially neutralized and 3. the neutralized intermediate is reacted with at least one compound which has an amino group with at least one

contains.

These two-stage condensates are more preferred a) Phenols that have a hydrocarbon substituent Bear 30 to 250 carbon atoms, this substituent differs from a polymer of propylene, 1-butene, 2-butene or Derives isobutene, and b) formaldehyde or a Polymer of the same (such as trioxane or paraformaldehyde) or one functional equivalent thereof (such as methylal) and c) one Alkylene polyamines, such as ethylene polyamines with 2 to 20 nitrogen atoms, produced.  

The following specific examples describe how the aminophenols and dispersants containing the additives make up according to the invention, are to be produced. In these Examples and the description and claims are all Percentages, parts and ratios Weight percentages, parts by weight and weight ratios, unless expressly stated otherwise is specified. The temperatures are in degrees Celsius unless otherwise expressly stated.

Example 1

A mixture of 4578 parts of a polyisobutene substituted Phenol, which is catalyzed by alkylation with boron trifluoride phenol of phenol with a polyisobutene with a medium Molecular weight (number average) of about 1000 (vapor phase osmometry) was made, 3052 parts mineral oil as a diluent and 725 parts of textile alcohol was heated to 60 ° C, to achieve homogeneity. After cooling to 30 ° C became 319.5 parts of a 16 molar nitric acid in 600 parts Water was added to the mixture. Cooling was required to to keep the temperature of the mixture below 40 ° C. After this the reaction mixture was stirred for a further 2 hours a share of 3710 parts in a second reaction vessel transferred. This second portion was made up with another 127.8 parts a 16 molar nitric acid in 130 parts of water at 25 to 30 ° C treated. The reaction mixture was stirred for 1.5 hours and then stripped at 220 ° C / 40 mbar. Filtration gave one Oil solution of the desired intermediate (1A).  

A mixture of 810 parts of the oil solution of the intermediate (1A) described in Example 1A, 405 parts isopropyl alcohol and 405 parts of toluene was made into a sufficiently large one Given autoclaves. Platinum oxide catalyst (0.81 parts) was added and the autoclave was evacuated and 4 times with nitrogen purged to remove residual air. Became hydrogen in the autoclave with a pressure of 2.9 to 4.6 bar fed while the contents of the autoclave as a whole Was stirred for 13 hours and heated to 27 to 92 ° C. Residual excess hydrogen was removed from the reaction mixture by four evacuations and flushing with nitrogen away. The reaction mixture was then quenched with diatomaceous earth filtered, and the filtrate was stripped to an oil solution of the desired aminophenol. This solution contained 0.578% nitrogen.

Example 2

A mixture of 906 parts of an oil solution of an alkylphenyl sulfonic acid (with an average molecular weight of 450, vapor phase osmometry), 564 parts mineral oil, 600 parts toluene, 98.7 parts of magnesium oxide and 120 parts of water were used to carbon dioxide at a temperature of 78 to 85 ° C for 7 hours at a speed of about 0.085 m³ Blow in carbon dioxide per hour. The reaction mixture was Stir constantly during the carbon dioxide treatment. After this Carbon dioxide treatment, the reaction mixture was at 165 ° C / Stripped out 26.7 mbar and the residue filtered. The filtrate  was an oil solution of the desired overbased magnesium sulfonate with a metal ratio of about 3.

Example 3

A polyisobutenyl succinic anhydride was reacted a chlorinated poly (isobutene) (with an average chlorine content of 4.3% and on average 82 carbon atoms) with maleic anhydride made at about 200 ° C. The resulting Polyisobutenyl succinic anhydride had a saponification number of 90. To a mixture of 1246 parts of this succinic anhydride and 1000 parts of toluene became 76.6 parts at 25 ° C Barium oxide added. The mixture was heated to 115 ° C, and 125 parts of water were added dropwise over 1 hour. The mixture was allowed to reflux at 150 ° C until entire barium oxide was implemented. Stripping and filtration gave a filtrate with a barium content of 4.71%.

Example 4

A mixture of 1500 parts of chlorinated poly (isobutene) (molecular weight of about 950 and with a chlorine content of 5.6%), 285 parts of an alkylene polyamine with a medium composition, which corresponded stoichiometrically to tetraethylene pentamine, and 1200 parts of benzene was heated to reflux conditions. The temperature of the mixture was then slow for 4 hours increased to 170 ° C while benzene was removed. The cooled mixture was mixed with an equal volume of a mixture diluted with hexanes and absolute ethanol (1: 1). This Mixture was heated to reflux conditions and 1/3 volume a 10% aqueous sodium carbonate solution was added to it.  After stirring, the mixture was allowed to cool and the Phases separate. The organic phase was washed with water and stripped to give the desired polyisobutenyl polyamine with a nitrogen content of 4.5%.

Example 5

A mixture of 140 parts of toluene and 400 parts of a polyisobutenyl succinic anhydride (made from the poly (isobutene) with a molecular weight of about 850, vapor phase osmometry) with a saponification number of 109 and 63.6 parts of one Ethylene amine mixture with a medium composition, the corresponded stoichiometrically to tetraethylene pentamine, was at 150 ° C. heated while the aceotrope is removed from water and toluene has been. The reaction mixture was then under reduced pressure heated to 150 ° C until toluene stopped distilling. The remaining acylated polyamine had a nitrogen content 4.7%.

Example 6

To 1133 parts of a commercially available diethylene triamine that Was heated to 110 to 150 ° C, slowly 6820 parts of isostearic acid added over 2 hours. The mixture was 1 hour kept at 150 ° C and then at 180 ° C for another hour heated. Finally the mixture was left on for 0.5 hours Heated at 205 ° C and during this heating was added to the mixture Blown in nitrogen to remove volatiles. The mixture was brought to 205 to 11.5 hours in total Held at 230 ° C and then stripped at 230 ° C / 26.7 mbar to the Desired acylated polyamine residue containing To give 6.2% nitrogen.  

Example 7

To a mixture of 50 parts of a polypropyl substituted Phenol (with a molecular weight of about 900, vapor phase osmometry), 500 parts mineral oil (a solvent-refined Paraffin oil with a viscosity of 100 SUS at 38 ° C) and 130 parts of a 9.5% aqueous dimethylamine solution (equivalent to 12 parts of amine) were added dropwise over 1 hour 22 parts of a 37% aqueous formaldehyde solution (corresponding 8 parts of aldehyde) are added. During the addition, the Reaction temperature slowly increased to 100 ° C and 3 hours kept at this point while in the mixture nitrogen was blown in. To the cooled reaction mixture 100 parts of toluene and 50 parts of mixed butyl alcohols were added. The organic phase was washed 3 times with water until it was neutral to litmus paper and the organic phase became filtered and stripped at 200 ° C / 6.7 mbar to 13.4 mbar. Of the Residue was an oil solution of the final product containing of 0.45% nitrogen.

Example 8

A mixture of 140 parts of a mineral oil, 174 parts of a poly (isobutene) (molecular weight 1000), the with succinic anhydride with a saponification number of 105 was substituted, and 23 parts of isostearic acid was at 90 ° C produced. 17.6 parts of a mixture were added to this mixture of polyalkylene amines with a total composition accordingly that of tetraethylene pentamine at 80 to 100 ° C added over a period of 1.3 hours. The reaction was exothermic. Nitrogen was added to the mixture at 225 ° C. with a  Speed of 3.27 kg per hour for 3 hours blown in, after which 47 parts of an aqueous distillate were obtained. The mixture was dried at 225 ° C. for 1 hour, Chilled to 110 ° C and filtered to give the desired end product to result in oil solution.

The lubricating oils in which the nitrogen-containing additive combinations useful according to the invention, synthetic, animal, vegetable or mineral (such as Petroleum). Are general the lubricating oils used flowable oils with a viscosity in the range of 40 SUS (Saybolt Universal Seconds) at 37.5 ° C to 200 SUS at 99 ° C. The additives according to the invention are normally in an amount from 0.5 to 30 parts by weight of the combination 100 parts by weight of the oil used.

According to the invention, other additives can also be used in the lubricating oil compositions can be used according to the invention. This other additives are such conventional types of additives as Antioxidants, extreme pressure agents, corrosion inhibitors, pour point depressants, color stabilizers,  Anti-foaming agents and other such additive materials which the specialist are generally known.

The additives according to the invention are particularly useful for new ones Lubricating oils for two-stroke engines. In general contain the lubricating oil compositions for two-stroke engines 98 to 50% oil or oil mixture with lubricating viscosity. Typical compositions contain 90 to about 60% oil. The currently preferred oils are mineral oils and mixtures of mineral oil and synthetic polymer and / or synthetic Ester oil. Polybutenes with molecular weights of 250 up to 1000 (measured by vapor phase osmometry) and fatty acid ester oils of polyols, such as pentaerythritol and trimethylolpropane, are typical synthetic oils used in the manufacture of these two-stroke oils can be used.

These oil compositions suitably contain 2 to 30%, typically 5 to 20% of at least one aminophenol, and 1 to 30, typically 2 to 20% of at least one Dispersant. The weight ratio of aminophenol to Dispersant in these oils varies between 1:10 and 10: 1. Other additives, such as viscosity index improvers, Lubricants, antioxidants, coupling agents, pour point depressant, agent for extreme Printing, color stabilizers and anti-foaming agents can are also available.  

Polymer viscosity index improvers used to the lubricant film strength and improve lubrication and / or engine cleanliness to improve. Dye can be used for identification purposes used and to indicate whether a two-stroke oil Contains lubricants. Coupling agents such as organic surfactants are incorporated into some products, for better component solubility and improved water compatibility of the mixture of fuel and lubricant to surrender.

Means of preventing wear and improving lubrication, especially sulfurized sperm oil substitutes and others Fatty acid and vegetable oils, such as castor oil, are used in special Applications used, such as in races and at very high ones Fuel-lubricant ratios. Detergent or combustion chamber deposit modifier are sometimes used to promote better spark plug life and remove carbon deposits. Halogenated compounds and / or phosphorus-containing materials can be used for this Purpose.

All types of rust and corrosion inhibiting agents are incorporated and can be incorporated into two-stroke oil compositions become. Odors or deodorants are sometimes made used for aesthetic reasons.

Slipperiness enhancers such as synthetic polymers (e.g. polyisobutene) with a number average molecular weight in the range of about 750 to about 15,000 as measured by Vapor phase osmometry or gel penetration chromatography,  Polyol ethers (such as poly (oxyethylene oxypropylene) ether) and ester oils (like the ester oils described above) can also be found in the interactions according to the invention are used. Neutral Oil fractions can also be used for this purpose become. They are usually in an amount of two-stroke oil about 3 to 20% of the total oil composition is present.

Thinners, such as petroleum naphthas, are in the range of about Boil 38 to 90 ° C (such as Stoddard solvent), can also be incorporated into the oil compositions of the invention typically in an amount of 5 to 25%.

The table describes several explanatory two-stroke engine oil Lubricant compositions according to the invention.

table

Two-stroke engine oil mixtures

Lubricant- Fuel mixtures generally contain around 15 per part of oil up to 250 parts of fuel, typically they contain 1 part about 50 to 100 parts of fuel each.

The fuels used in two-stroke engines are known to the person skilled in the art known and usually contain a larger part a normally liquid fuel, such as a hydrocarbon Petroleum distillate fuel (e.g. petrol according to ASTM D-439-73). Such fuels can also include non-hydrocarbon materials, such as alcohols, ethers, organic nitro compounds (like methanol, ethanol, diethyl ether, Contain methylethyl ether, nitromethane), and also liquid Fuels that come from vegetable or mineral sources  derive from cereals, alfalfa, slate and coal, are within the spirit of the invention. Examples of such Fuel mixtures are combinations of gasoline and ethanol, Diesel fuel and ether, gasoline and nitromethane. Especially gasoline is preferred, i. H. a mixture of hydrocarbons with an ASTM boiling point of 60 ° C at a 10% distillation point up to about 205 ° C and 90% distillation point.

Two-stroke fuels can also contain other additives that are known to the expert. These can be anti-knock agents, such as Tetraalkyl lead compounds, lead detergents, such as haloalkanes (such as ethylene dichloride and ethylene dibromide), dyes, cetane number improvers, Antioxidants such as 2,6-ditertiary butyl 4-methylphenol, rust inhibitors, such as alkylated succinic acids and anhydrides thereof, bacteriostatic agents, gum inhibitors, Metal deactivators, demulsifiers, Upper cylinder lubricant, anti-icing agent lock in.

The additives can also be used in concentrates of the invention included. These concentrates usually range from 20 to 80% of one or more of the oils described above and approximately 20 to about 80% of one or more nitrogenous compositions.

Claims (17)

1. Additive for liquid lubricants and / or fuels containing at least one aminophenol of the general formula wherein R is an aliphatic hydrocarbon radical having 30 to 750 carbon atoms, which contains 10 CC single bonds at most one unsaturated CC bond and each 10 carbon atoms up to a radical from the group hydroxyl, halogen, alkoxy, alkyl mercapto or alkyl sulfoxy, a , b and c each independently represent an integer from 1 to 3 and Ar is a mononuclear aromatic radical with 0 to 3 possible substituents from the group of C₁-C₇ alkyl groups, C₁-C₇ alkoxy groups, nitro groups and / or halogen atoms, thereby characterized in that it additionally contains at least one dispersant in a weight ratio of 1:10 to 10: 1

• 1. at least one neutral or basic metal salt of an organic sulfuric acid, phenol or a carboxylic acid,
• 2. at least one hydrocarbon-substituted amine different from the above aminophenols, wherein the hydrocarbon substituent is aliphatic and contains at least 12 carbon atoms,
• 3. at least one acylated nitrogen-containing compound having a substituent with at least 10 aliphatic carbon atoms, which is obtained by reacting a carboxy acylating agent with at least one amino compound with at least one has been obtained, the acylating agent being bonded to the amino compound via an imido, amido, amidine or acyloxyammonium group, or
• 4. at least one nitrogen-containing condensate of a phenol, an aldehyde and an amino compound with at least one

is. 2. Additive according to claim 1, characterized in that R is a homo- or Interpolymer derived from C₂-C₁₀ olefins. 3. Additive according to claim 2, characterized in that R is ethylene, propylene and / or butylene. 4. Additive according to one of claims 1 to 3, characterized in that a, b and c each represent 1 and Ar is a benzene ring without further substituents. 5. Additive according to one of claims 1 to 4, characterized in that the aminophenol has the general formula has, in which R 'is a substantially saturated hydrocarbon radical having an average of 30 to 400 carbon atoms, R''is a C _1-7 alkyl group, a C _1-7 alkoxy group, a nitro group or a halogen atom and z is 0 or 1 . 6. Additive according to one of claims 1 to 5, characterized in that the Dispersant is at least one alkaline earth metal sulfonate.   7. Additive according to one of claims 1 to 5, characterized in that it is a hydrocarbon-substituted amine (2) of the general formula contains, wherein A represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a hydroxy hydrocarbon group having 1 to 10 carbon atoms, X represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a hydroxy hydrocarbon group having 1 to 10 carbon atoms or taken together with A a ring with 5 to 6 ring members and with up to 12 carbon atoms, U is an alkylene group with 2 to 10 carbon atoms, R² is an aliphatic hydrocarbon radical with 30 to 400 carbon atoms, a is an integer from 0 to 10, b is 0 or 1, a + 2b is an integer from 1 to 10, c is an integer from 1 to 5 and is on the average from 1 to 4 and is equal to or less than the number of nitrogen atoms in the molecule, x is 0 or 1 , y means 0 or 1 and x + y is 1. 8. Additive according to claim 7, characterized in that the hydrocarbon-substituted amine (2) is a polyamine of the general formula where U, R², a, b, c and y are as defined above. 9. Additive according to claim 7, characterized in that the hydrocarbon-substituted Amine one of the general formula AXNR² where A, X and R² are as defined above. 10. Additive according to one of claims 1 to 5, characterized in that the hydrocarbon-substituted amine (2) is a hydrocarbon-substituted aminohydrocarbon morpholine of the general formula where R², A and U are as defined above. 11. Additive according to one of claims 1 to 5, characterized in that the acylated nitrogen-containing compound (3) by reacting an alkylene polyamine of the general formula wherein U represents an alkylene group having 2 to 10 carbon atoms, each group R ′ ′ ′ independently of the others represents a hydrogen atom, a C _1-7 alkyl group or a C _1-7 hydroxylalkyl group, at least one of the groups R ′ ′ ′ is a hydrogen atom and n is 1 to 10 with which acylating agent has been obtained. 12. Additive according to claim 11, characterized in that the acylated nitrogen-containing compound ( 3 ) by reacting the alkylene polyamine with a mono- or polycarboxylic acid or a reactive equivalent thereof, which has an aliphatic hydrocarbon substituent with at least 30 carbon atoms, preferably one of a homo- or interpolymer of a C _2-10 -1 monoolefin or of mixtures of such monoolefins, in particular of ethylene, propylene, 1-butene, 2-butene and / or isobutene-containing substituents. 13. Additive according to claim 11, characterized in that the acylated nitrogen-containing Compound (3) by reacting the alkylene polyamine with at least one monocarboxylic acid or a reactive equivalent thereof having 12 to 30 carbon atoms, preferably a mixture of fatty monocarboxylic acids or reactive equivalents of which has been obtained with straight or branched carbon chains. 14. Additive according to claim 13, characterized in that the amino compound Ethylene, propylene or trimethylene polyamine with 2 to 8 amino groups or is a mixture of such polyamines.   15. Additive according to one of claims 1 to 5, characterized in that it as nitrogen-containing condensate of a phenol, an aldehyde and an amino compound (4) contains one wherein the phenol is an alkyl substituted phenol, the Alkyl group has at least 30 carbon atoms and its aldehyde is preferred Formaldehyde or a reactive equivalent thereof. 16. Additive according to claim 15, characterized in that the nitrogen-containing condensate (4) by reacting the phenol with the aldehyde in the presence of an alkaline catalyst at a temperature of up to 150 ° C, then neutralizing the intermediate product mixture thus formed and finally reacting the neutralized Intermediate mixture with at least one amino compound with at least one has been obtained.