NO161865B - MIXTURE OF ALKYLPHENOL AND AMINOPHENOL AND USE OF IT. - Google Patents

Description

The background of the invention

(1) Field of the invention

This invention relates to additive combinations useful for lubricants containing a substantial portion of an oil of lubricating viscosity and a minor amount of the additive combination. The lubricants are useful in two-stroke internal combustion engines. The invention relates more particularly to additive materials which comprise a mixture of at least Sn alkylphenol and at least one aminophenol, each of which has at least one hydrocarbon-based group with at least 10 aliphatic carbon atoms. Since two-stroke engine oils are often combined with fuels before or during use, this invention also relates to two-stroke fuel-lubricant mixtures.

(2) State of the art

A number of phenolic compounds have been described which are useful as lubricants and fuel additives. Alkylated aminophenols have been described in US patent 4,320,021 as useful as additives for lubricants and fuels. Aminophenol and surfactant/dispersant combinations are i

US Patent 4,200,545 have been described as useful in lubricants, particularly for two-stroke internal combustion engines, and also as additives and lubricant-fuel blends for two-stroke engines. Hydrocarbon-substituted methylolphenols are described in US patent 4 05 3 428 as useful in lubricants and fuels.

(3) The general background

Over the past several decades, the use of two-stroke (two-stroke) internal spark ignition combustion engines, including rotary engines such as those of the Wankel type, has steadily increased. They are currently found in powered lawn mowers and other powered garden equipment, powered chain saws, pumps, electric generators, outboard motors, snowmobiles or motorcycles etc.

The use of two-stroke engines, together with increasing stress conditions where these have been used, has led to an increasing need for oils to adequately lubricate such engines. Among the problems associated with the lubrication of two-stroke engines are piston rings sticking, rust formation, lack of lubrication of tie rods and main bearings and general formation of carbon and other paint deposits on the engine's internal surface. The formation of varnish is a particularly vexing problem because the accumulation of varnish on the piston and cylinder walls is believed to eventually cause the ring to seize, which causes the sealing function of the piston rings to fail. Such seal failure causes loss of cylinder compression, which is particularly detrimental to two-stroke engines because they rely on intake to draw the new fuel charge into the depleted cylinder. Ring jamming can thus lead to a deterioration of the engine's performance and to unnecessary consumption of fuel and/or lubricant. Problems with fouling of the spark plugs and clogging of the engine port also occur in two-stroke engines.

The distinctive problems and methods associated with the lubrication of two-stroke engines have led to the recognition by professionals in the field of lubricants for two-stroke engines that these are a special type of lubricant. See e.g. US Patents 3,085,975, 3,004,837 and 3,753,905.

The invention described here aims to reduce these problems to a minimum by providing effective additives for two-stroke engine oils and oil-fuel combinations, which eliminate or reduce engine varnish deposits and failure of the piston ring seal.

Summary of the invention

The present invention relates to a mixture comprising the combination of

(A) at least one alkylphenol of the formula

and

(B) at least one aminophenol of the formula

wherein each R is independently a substantially saturated hydrocarbon-based group having an average of at least 10 aliphatic carbon atoms, a, b, and c are each independently

an integer of from one up to three times the number of aromatic nuclei present in Ar, provided that the sum of a, b, and c does not exceed the unsatisfied valences of Ar, and where Ar is independently a single ring, a fused or a fused polynuclear ring aromatic moiety with from 0 to 3 optional substituents selected from lower alkyl, lower alkoxyl, carboalkoxymethylol or lower hydrocarbon-based substituted methylol, nitro, nitroso, halogen or combinations of two or more of said optional substituents.

The term "phenol" is used here in the generic sense accepted in the relevant art, in that it refers to hydroxyaromatic compounds with at least one hydroxyl group attached directly to a carbon atom in an aromatic ring.

Lubricants and lubricating oil-fuel mixtures for two-stroke engines and methods of lubricating two-stroke engines, including Wankel engines, are also within the scope of the invention.

Description of the invention

As mentioned above, the invention relates to an additive mixture which comprises

(A) at least one alkylphenol of the formula

and

(B) at least one aminophenol of the formula

wherein the various substituents are as more complete

defined below. The aromatic part, the R groups and the optional groups, if these are present in the alkylphenols and aminophenols, may be the same or different.

The aromatic part, Ar

The aromatic part, Ar, of the alkylphenol and the aminophenol can be a single aromatic nucleus, such as a benzene nucleus, a pyridine nucleus, a thiophene nucleus, a 1,2,3,4-tetrahydronaphthalene nucleus, etc., or a polynuclear aromatic moiety. Such polynuclear moieties can be of the fused type, i.e. in which at least two aromatic nuclei are fused at two points to another nucleus, as found in the naphtha, anthracene, azanaphthalenes, etc. Such aromatic polynuclear moieties can also be of the bonded type,, in which at least two cores (either monocore or multicore.)> are. connected to each other via. bridge ties. Such bridging bonds* can be selected from the group: consisting of ca^rbom—till-carbon single bonds. ether bindings, ke two bindings,. s.ulfidMm— things, poly-Lysulfide bonds with 2 — 6. s-vojvel'a<(tom, sulfinyl.-bondpr,, sulfonyl bonds:,, methylene bonds, alkyl/lene-binfdinger„ di— ('lower: ad'kyl ,);-metSiylene bonds, lower» alkylenetheaebiiiixJiniger-,, alkyleneketo bonds, lower alkylene-s.vove bonds, lower alkylene lead sulphide bonds with 2-6 carbon atoms, amino bonds, polyamino bonds and mixtures of such divalent bridging bonds. In some cases, more than one bridging bond can be present in Ar between aromatic nuclei. For example, a fluorene nucleus has two benzene nuclei linked via both a methylene bond and one covalent bond. Such a nucleus can be thought of as having 3 nuclei, but only two of these are aromatic. Normally, Ar contain only carbon atoms in the aromatic nuclei as such. ;The number of aromatic nuclei, fused, bonded, or both, in Ar may play a role in determining the values of a and b in formula I. When, for example, Ar contains ^ a single, aromatic core-,, are a and b both independent of each other? 1st tiil. 3. Nåirr Aar contains: 2<> >aromatic cores, each of; ai and; b) be? e.t. heltJ tail.ll from 1 to 6, i.e. from 1 up to 3S times: airttadeÆ:. of aromatic nuclei present (e.g. i. naÆthalem 2?. kqj;emer)j.. When Ar is a three-iron part, again" a and b can both be © a-, whole number from 1 tii 9 Thus, when, for example, Ar en: em b^phenyl part, a and b can both independently of each other be an integer from 1 to 6. The values for a and b are of course limited by the fact that their sum cannot exceed the total unsatisfied valences for Ar. ;The one-ring aromatic core that can be the Ar moiety can be represented by the general formula ;ar(Q)m ;where ar denotes a one-ring aromatic core (e.g. benzene) with 4-10 carbon atoms, each Q independently of the others denotes a lower alkyl group, lower alkoxyl group, methylol or lower hydrocarbon-based substituted methylol, or a halogen atom, and m is 0 - 3. As used herein, "lower" denotes groups with 7 and fewer carbon atoms , such as lower alkyl and lower alkoxy groups. Halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The halogen atoms are usually fluorine - and chlorine atoms. ;Specific examples of such single-ring Ar moieties are the following: ;where Me denotes methyl, Et denotes ethyl, and Pr denotes n-propyl. When Ar is a polynuclear aromatic portion of the fused ring tvpen, it can be represented by the general formula in which ar, Q and m are as defined above, ra' is 1 - 4, and ^p represents a pair of fused bonds that fuse two rings so that two carbon atoms are made part of the rings for each of two adjacent rings. Specific examples of fused ring aromatic moieties Ar include: ;When the aromatic moiety Ar is a bonded polynuclear aromatic moiety, it can be represented by the general formula ;wherein w is an integer from 1 to 20, ar is as described above, with with the caveat that there are at least 3 unsatisfied (i.e. free) valences in the total number of ar groups, Q and m are as defined above, and each Lng is a bridging bond individually selected from the group consisting of carbon-to- carbon single bonds, ether bonds (e.g. -CH2-0-CH2-) 1 keto bonds (e.g. sulfide bonds (e.g. -S-), polysulfide bonds with 2-6 sulfur bonds (e.g. "S2- 6~^' sulrinyl bonds (e.g. (-S(O)-), sulfonyl bonds (e.g. -S(0)2~), lower alkylene bonds (e.g. ~CH2-, -C<H> 2<->CH2-, -CH-0(R°)H-, etc. di-(lower alkyl)-methylene bonds (e.g. -CR°), lower alkylene ether bonds (e.g. -CH20-, - CH20-CH2-r etc), lower alkylene keto bonds (e.g. lower alkylene sulphide bonds (f .ex. in which one or more of the -0- in the lower alkylene ether bonds is replaced by an -S-atora), lower alkylene polysulfide bonds (e.g. in which one or more -O- is replaced by a -S2_g group), amino bonds (e.g. e.g. ;-CH2N-, -CH2NCH2-, -alk-N-, in which alk is lower alkylene etc), polyamino bonds (e.g. -N(alkN), in which the unsatisfied free N-valences are taken up by H- atoms or R° groups), or mixtures of such bridging bonds (each R° is a lower alkyl group). ;Specific examples of Ar when this is a linked polynuclear aromatic moiety include: ;As a rule, all of these Ar moieties are unsubstituted, except for the R and -OH groups (and any bridging groups). ;For reasons such as price, availability and performance etc., the Ar part is normally a benzene core, a benzene core provided with a lower alkylene bridge, or a naphthalene core. A typical Ar part is thus a benzene or naphthalene nucleus with 3-5 unsatisfied valences, so that one or two of these valences can be satisfied by a hydroxyl group, the other unsatisfied valences being as far as possible either in the ortho position or in the para position to a hydroxyl group. Preferably, Ar is a benzene nucleus with 3-4 unsatisfied valences, so that one can be satisfied by a hydroxyl group, while the other 2 or 3 are in the ortho or para position to the hydroxyl group. The essentially saturated hydrocarbon-based group R The phenolic compounds and amino compounds used in the combination according to the present invention contain directly bound to the aromatic part Ar an essentially saturated, monovalent hydrocarbon-based group R with at least 10 aliphatic carbon atoms. This group R preferably contains at least 20 and up to 400 aliphatic carbon atoms. More than one such group may be present, but as a rule no more than 2 or 3 such groups are present for each aromatic nucleus in the aromatic part Ar. The total number of R groups present is indicated by the value of "a" in Formula I. As a rule, the hydrocarbon-based group has at least 30, and more typically at least 50, aliphatic carbon atoms and up to 400, more typically up to 300, aliphatic carbon atoms. Illustrative of hydrocarbon-based groups containing at least 10 carbon atoms are n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chlorooctadecyl, triiconta-nyl etc. The hydrocarbon-based groups R are generally made from homo- or copolymers (e.g. eg copolymers, terpolymers) of mono- and diolefins with 2-10 carbon atoms, such as ethylene, propylene, butene-1-, isobutene, butadiene, isoprene, 1-hexene, 1-octene etc. These olefins are typically 1-monoolefins. The groups R may also be derived from the halogenated (e.g. chlorinated or brominated) analogues of such homo- or copolymerized When the group R is a low molecular weight polymer of an olefin, the group R may comprise a mixture of groups of more varying chain length, and the average number of carbon atoms must be at least 10, preferably at least 30 carbon atoms. However, the groups R can be made from other starting materials, such as high molecular weight monomeric alkenes (e.g. 1-tetracontene) and chlorinated analogues and hydrochlorinated analogues thereof, aliphatic petroleum fractions, especially paraffin wax and cracked and chlorinated analogues and hydrochlorinated analogues thereof, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (eg polyethylene consistency grease), and other starting materials known to those skilled in the art. Any unsaturation in the groups R can be reduced or eliminated by hydrogenation using well known methods. As used here, "hydrocarbon-based" denotes a group with a carbon atom directly bonded to the rest of the molecule and with a dominant hydrocarbon character in the sense in which this term is used. Hydrocarbon-based groups can therefore contain up to one non-hydrocarbon radical for every 10 carbon atoms, provided that this non-hydrocarbon radical does not significantly change the dominant hydrocarbon character of the group. Professionals will be aware of what kind of radicals these are, and they include e.g. hydroxyl, halogen (especially chlorine and fluorine), axoxyl, alkyl mercapto, alkyl-sulfoxy etc. However, the hydrogen-based groups R are as a rule pure hydrocarbyl groups and contain no such non-hydrocarbyl radicals. ;The hydrocarbon-based groups R are essentially saturated, i.e. they contain no more than one unsaturated carbon-to-carbon bond for every ten carbon-to-carbon single bonds present. They usually contain no more than one non-aromatic unsaturated carbon-to-carbon bond for every 50 carbon-to-carbon bonds present. ;The hydrocarbon-based groups in the alkyl and aminophenols used according to the invention are also essentially aliphatic in nature, i.e. they do not contain more than one non-aliphatic part (cycloalkyl, cycloalkenyl or aromatic) group with 6 or fewer carbon atoms for every 10 carbon atoms in the R group. As a rule, however, the R groups contain no more than one such non-aliphatic group for every 50 carbon atoms, and in a number of cases they contain no such non-aliphatic groups at all, i.e. the typical R groups are purely aliphatic . These purely aliphatic R groups are typically alkyl or alkenyl groups. Specific examples of the essentially saturated hydrocarbon-based R groups containing on average more than 30 carbon atoms are the following: a mixture of poly(ethylene/propylene) groups with 35 - 70 carbon atoms a mixture of the oxidizing or mechanically degraded poly( ethylene/propylene) groups with 35-70 carbon atoms a mixture of poly(propylene/1-hexene) groups with 80 - 150 carbon atoms a mixture of poly(isobutene) groups with an average of 50 - 75 carbon atoms. A preferred starting material for the group R is the polyiso-butenes obtained by polymerization of a C^ refinery stream with a butene content of 35 - 75% by weight and an isobutene content of 30 - 60% by weight in the presence of a Lewis acid as a catalyst, such as aluminum trichloride or boron trifluoride. These polybutenes mainly contain (more than 80% of the total repeating units) repeating isobutene units with the structure; The binding of the hydrocarbon-based group R to the aromatic part Ar in the amino and alkylphenols used according to the invention can be achieved by a number of methods which are well known to those skilled in the art. A particularly suitable method is the Friedel-Crafts reaction, in which an olefin (eg a polymer containing an olefinic bond) or a halogenated or hydrohalogenated analogue thereof is reacted with a phenol. The reaction takes place in the presence of the Lewls acid catalyst (eg boron trifluoride and its complexes with ethers, phenols, hydrogen fluoride etc, aluminum chloride, aluminum bromide, zinc dichloride etc). Methods and conditions for carrying out such reactions are well known to the person skilled in the art, see e.g. the discussion in the article entitled "Alkylation of Phenols" in Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. 1, pp. 894 - 895, Interscience Publishers, a division of John Wiley and Company, N.Y., 1963. Other similar well-known suitable and convenient methods for attaching the hydrocarbon-based group R to the aromatic moiety Ar will be apparent to those skilled in the art. It will appear from an examination of Formula I that the alkylphenols used according to the present invention contain at least one of each of the following substituents: A hydroxyl group and an R group as defined above, and that the aminophenols with Formula II contain at least one amino group and at least one R group as defined above. Each of the above groups must be attached to a carbon atom that is part of an aromatic nucleus in the Ar part. However, each of these need not be bound to the same aromatic ring if more than one aromatic nucleus is present in the Ar part. ;The optional substituents ( R") ;As mentioned, the aromatic part Ar can contain up to 3 optional substituents which are lower alkyl, lower alkoxyl, carboalkoxymethylol or lower hydrocarbon-based substituted methylol, nitro, nitroso, halogen or combinations of two or more of these optional substituents. These substituents may be attached to a carbon atom that forms part of the aromatic core of Ar. However, they need not be attached to the same aromatic ring if more than one ring is present in Ar. ;A preferred substituent for the alkylphenols are a methylol or substituted methylol as defined above The lower hydrocarbon based substituents have up to 7 carbon atoms and can be alkyl (eg methyl, ethyl etc), alkenyl (propenyl etc), aryl (eg phenyl, tolyl), or alkaryl (e.g. benzyl). They can be represented by "hyd", and the methylol substituents can thus be represented by -CH2OH-(methylol)., ;As a rule, the substituent is methylol as such nt or an alkyl-substituted methylol or a phenyl-substituted methylol substituent, e.g. Methylol or the substituted methylol group can be introduced by reacting the phenol or the alkylated phenol with a hydrocarbon-based aldehyde or a functional equivalent thereof. Suitable aldehydes include formaldehyde, benzaldehyde, acetaldehyde, butyraldehyde, hydroxybutyraldehyde, hexanals etc. "Functional equivalents" are materials (eg solutions, polymers, hydrates etc) which react like aldehydes under the reaction conditions, and they include such materials as paraformaldehyde, hexamethylene tetramine, paraldehyde, formalin and methylol. If substituted methylol groups are desired, the aldehyde is replaced with a suitable ketone, such as acetone, methylethyl ketone, acetophenone, benzophenone and the like. Mixtures of aldehydes and/or ketones can also be used to form compounds with mixtures of methylol groups. Formaldehyde and functional equivalents are generally preferred because these provide the preferred methylol groups. Introduction of the methylol groups usually takes place by reacting phenolic compounds with an aldehyde, ketone or a functional equivalent of these in the presence or absence of an acidic or alkaline reactant. When the reaction takes place in the absence of such a reactant, as a rule, part of the mixture will become acidic or alkaline due to in situ decomposition of the aldehyde or ketone. An excess of phenol can also fulfill this function. However, the reaction of the aldehyde, ketone or functional equivalent thereof generally takes place in the presence of an alkaline reagent, such as an alkali metal or alkaline earth metal oxide, hydroxide or lower alkoxide, at a temperature up to 160° C. Other alkaline reagents such as may be used include sodium carbonate, sodium bicarbonate, sodium acetate, sodium propionate, pyridine or hydrocarbon-based amines such as methylamine or aniline. Of course, mixtures of two or more bases can be used. The reaction preferably takes place within the temperature range 30 - 125° C, and more commonly it is carried out between 70 and 100° C. The relative amounts of alkylphenolic compound and aldehyde, ketone or a functional equivalent thereof are not of critical importance. It is generally satisfactory to use 0.1 - 5 equivalents of aldehyde and 0.05 - 10.0 equivalents of alkaline reagent per equivalent phenolic compound. As used here, the term "equivalent" when referring to a phenolic compound shall indicate the weight of such a compound equal to its molecular weight divided by the number of unsubstituted aromatic carbon atoms having hydrogen atoms. As used in connection with the aldehyde, ketone or functional equivalent thereof, an "equivalent" is the weight required to form one molecule of monomeric aldehyde. An equivalent of alkaline reagent is the weight of the reagent which, when dissolved in one liter of solvent (eg water), will give one normal solution. An equivalent of alkaline reagent will therefore neutralize, i.e. bring to a pH of 7, a one normal solution of e.g. hydrochloric or sulfuric acid. It is usually convenient to carry out the reaction for the phenol in the presence of an essentially inert, organic, liquid diluent which may be volatile or non-volatile. This diluent may or may not dissolve all the reactants, but in any case it will not significantly affect the course of the reaction under the prevailing conditions, although in some cases it may promote the reaction rate by increasing the contact between the reactants. Suitable diluents include hydrocarbons such as naphtha, ethyl alcohol, benzene, toluene, xylene, mineral oils (which are among the preferred), synthetic oils (as described below), alcohols such as isopropanol, butanol, isobutanol, amyl alcohol, ethylhexanols and the like, ethers such as triethylene or diethylene glycol mono- or di-ethyl ether and the like, as well as mixtures of two or more of these. ;The reaction between the phenolic compound and the aldehyde or ketone generally takes place within 0.5 to 8 hours depending on such variables as the reaction temperature and the amount and nature of the alkaline catalyst used etc. The regulation of such variables is well within the skill of the skilled person , and the effect of these variables is clear. After the reaction has been completed to the desired extent, it can essentially be stopped by neutralization of the reaction mixture when an alkaline reagent is present. This neutralization can be carried out with any suitable acidic material, typically a mineral acid or an organic acid or anhydride. An acidic gas, such as carbon dioxide, hydrogen sulphide, sulfur dioxide or the like, can also be used. In general, the neutralization is carried out with a carboxylic acid, especially a lower alkane carboxylic acid, such as formic acid, acetic acid or propionic acid. Of course, mixtures of two or more acids can be used for the neutralization. This is carried out at a temperature of 30 - 150° C. An amount of neutralizing agent which is sufficient to essentially neutralize the reaction mixture is used. An essentially neutralization means that the reaction mixture is brought to a pH of 4.5 - 8.0. As a rule, the reaction mixture is brought to a minimum pH of 6 or a maximum pH of 7.5. ;The reaction product, i.e. the phenolic compound, can be recovered from the reaction mixture by such methods as filtration (e.g. to remove the product formed by neutralization of the alkaline reagent), followed by distillation, evaporation, etc. Such methods are well known to professionals. ;These materials contain at least one compound which can be represented by the general formula ;where x, z and g are all at least one, y' is 0 or at least one, the sum of x, y', z and g does not exceed the available valences for Ar, each R' is a hydrogen atom or a "hyd" substituent as described above, and R is as described above. However, it is often not necessary to isolate the phenolic compound formed from the reaction solvent, especially if it is to be mixed in a fuel mist or lubricant. When the reaction temperature is within the higher range, i.e. above 100° C, significant amounts of ether condensation products can be formed. It is assumed that these condensates have the general formula in which q is a number from 2 to 10. These condensates thus contain alkylene ether bonds, i.e. -CR'20 bonds. Thus, e.g. by the reaction between an alkylphenol and formaldehyde ether condensates formed with the general formula ;wherein g is a number from 2 to 10, and R" is an alkyl group of at least 30 carbon atoms. It is possible that small amounts of such ether condensates accompany the predominant larger uncondensed hydroxyaromatic compounds formed at lower temperatures. ;If a strong acid, such as a mineral acid, is used for the neutralization, it is important to regulate the amount of this present so that the reaction mixture is not brought to a lower pH than specified above. For example, overcondensation takes place at lower pH values during the formation of methylene-bridged phenols However, by using carboxylic acids this problem is avoided because these have a sufficiently low acidity that they will not promote over-condensation, and it is not necessary to regulate the amount used so precisely of carboxylic acid. ;The typical phenol or naphthol/formaldehyde-based compounds have the general e formula; in which Ar' is a benzene, naphthalene, X-substituted benzene or X-substituted naphthalene ring, when 1 or 2, and R is a hydrocarbon-based substituent with at least 30 aliphatic carbon atoms, and X is selected from the group consisting of of lower alkyl groups, lower alkoxy groups, lower mercapto groups, fluorine atoms and chlorine atoms. A particularly preferred group are those which have the general formula: ; in which R° is an alkyl substituent with 30 - 300 carbon atoms which results from the polymerization or copolymerization of at least one monoolefin with 2-10 carbon atoms, and in which m is 1 or 0. ; The polynuclear rings for Ar can also be connected to each other by means of alkylene bonds, such as -C^-. Such methylol-substituted phenolic compounds can be represented by the formula wherein each R is a substantially saturated hydrocarbon-based group with an average of over 10 aliphatic carbon atoms, preferably over 30 carbon atoms and up to 450 carbon atoms, R' is a lower alkylene group of from 1 to 7 carbon atoms, and n is an integer from 0 to 20, preferably 0 to 5. These linked phenolic compounds can be prepared by reacting the alkylphenols with a small excess of aldehydes under alkaline conditions in the presence of a hydrocarbon solvent at reflux temperature. Examples of suitable aldehydes include formaldehyde (formalin or another formaldehyde-forming compound), acetaldehyde, propionaldehyde, butyraldehyde, etc. Formaldehyde is preferred. When the reaction is finished, the alkali can be washed away from the hydrocarbon solution of the product, and the product can be recovered by evaporation or distillation of the solvent. Unreacted aldehyde is also removed in this step. The alkylated phenols may be any of the alkylated phenolic compounds described previously. The production of alkylene-linked methylol-substituted phenols is described in the prior art, such as e.g. in US patent 3,737,465. According to another preferred embodiment, the alkylphenols used according to the invention contain one each of the above substituents and only a single aromatic ring, preferably benzene. This preferred group of phenols can be represented by the formula ;; in which the group R' is a hydrocarbon-based group with ; at least 30 and up to 400, aliphatic carbon atoms in the ortho- or para-position in relation to the hydroxy group, R<1>' is a lower alkyl, lower alkoxyl, carboalkoxymethylol or lower hydrocarbon-based substituted methylol, nitro, nitroso or halogen atom, and z is 0 or 1. As a rule, z is 0-2, and R' is a substantially saturated, purely aliphatic group. R' is often an alkyl or alkenyl group in the para position in relation to the -OH substituent. According to an even more preferred embodiment of the invention, the phenol has the formula: in which R' is derived from homopolymerized or copolymerized C2_^Q-olefins and on average has 30 - 300 aliphatic carbon atoms, and R<11> and z are as defined above . ;As a rule, R<1> is derived from ethylene, propylene, butylene and mixtures thereof. It is typically derived from polymerized isobutene. Often R' has at least 50 aliphatic carbon atoms, and z is 0. According to another preferred embodiment, the aminophenols used according to the invention contain one each of the above substituents (ie that a, b and c are all one), and only one single aromatic ring, preferably benzene. This preferred group of aminophenols can be represented by the formula: wherein R<1> is a substantially saturated hydrocarbon-based substituent having an average of 30-400 aliphatic carbon atoms, R" is a monomer selected from the group consisting of lower alkyl, lower alkoxyl, carboalkoxynitro , nitroso and halogen, and z is 0 or 1. The R' group is generally in the ortho or para position relative to the hydroxyl group, and z is usually 0. Most often only one amino group is found in the aminophenol used according to According to an even more preferred embodiment of the invention, the aminophenol has the formula: in which R' is derived from homopolymerized or copolymerized C2-10~^~ °^- erines 0l3 on average have 30-400 aliphatic carbon atoms, and R" and z are as defined above for formula IV. As a rule, R' is derived from ethylene, propylene, butylene and mixtures thereof. R' is typically derived from polymerized isobutene and has at least 50 aliphatic carbon atoms. The aminophenol according to the invention can be produced using a number of synthetic methods. These methods can vary in terms of the type of reactions used and the order in which they are used. For example, an aromatic hydrocarbon, such as benzene, can be alkylated with an alkylating agent, such as a polyolefin, forming an alkylated aromatic intermediate. This intermediate can then be nitrated, e.g. to form a polynitro intermediate. The polynitro intermediate can in turn be reduced to a diamine which can then be diazotized and reacted with water to convert one of the amino groups to a hydroxyl group and to provide the desired aminophenol. Alternatively, one of the nitro groups in the polynitro intermediate can be converted to a hydroxyl group by melting with alkali hydroxide to obtain a hydroxy-nitroalkylated aromatic compound which can then be reduced to the desired aminophenol. Another useful method for obtaining the aminophenols of the invention involves alkylating a phenol with an olefinic alkylating agent to form an alkylated phenol. This alkylated phenol can then be nitrated to form a nitrophenol intermediate which can then be converted to the desired aminophenols by reducing at least a portion of the nitro groups to amino groups. Methods for the nitration of phenols are known, see e.g. in Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. 13, the article entitled "Nitrophe-nols", from page 888, and also the treatises "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, Editor, Interscience Publishers, N.Y., 1969. ;Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid with acids, such as sulfuric acid, or boron trifluoride, nitrogen tetraoxide, nitronium tetrafluoroborates and acyl nitrates. Nitric acid with a concentration of e.g. 30 - 90% is generally a convenient nitrating agent. Essentially inert liquid diluents and solvents, such as acetic acid or butyric acid, can aid in the performance of the reaction by improving contact between the reactants. Conditions and concentrations for nitration of hydroxyaromatic compounds are also well known in the state of the art. For example, the reaction can be carried out at temperatures from -15° C to 150° C. As a rule, the nitration is conveniently carried out between 25 and 75° C. ;Depending on the particular nitrating agent, generally 0.5 - 4 molecules of nitrating agent are used per molecule aromatic nuclei present in the hydroxyaromatic intermediate to be nitrated. If more than one aromatic core is present in the Ar part, the amount of nitrating agent can be increased proportionally in accordance with the number of such cores present. For example, a molecule of naphthalene-based aromatic intermediate, according to the invention, has an equivalent of two "single ring" aromatic nuclei so that 1-4 molecules of nitrating agent will generally be used. When nitric acid is used as a nitrating agent, as a rule 1-3 molecules are used per molecule aromatic nucleus. Up to a 5 molar excess of the nitrating agent (per "single ring" aromatic core) can be used when it is desired to drive the reaction forward or to carry it out quickly. Nitration of a hydroxyaromatic intermediate generally takes 0.25 - 24 hours, although it may be convenient to react the nitration mixture for a longer time, as e.g. 96 hours. Reduction of aromatic nitro compounds to the corresponding amines is also well known, see e.g. the article entitled "Amination by Reduction" in Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. ;2, pp. 76 - 99. Such reductions can generally be carried out with e.g. 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. Cocatalysts, such as alkali or alkaline earth metal hydroxides or amines (including aminophenols), can be used for these catalyzed reductions. ;Reduction can also be achieved 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 by the Zinin reaction discussed in "Organic Reactions", Vo. 20, John Wiley & Sons, N.Y., 1973, from p. 455. The zinin reaction generally involves the reduction of a nitro group with divalent negative sulfur compounds, such as alkali metal sulfides, polysulfides, and hydrosulfides. ;The nitro groups can be reduced electrolytically, see e.g. the article "Amination by Reduction" referred to above. The aminophenols used according to the invention are typically formed by the reduction of nitrophenols with hydrogen in the presence of a metallic catalyst as mentioned above. This reduction is generally carried out at a temperature of 15 - 250° C, typically 50 - 15° C, and a hydrogen pressure of 0 - 140.6, typically 3.5 - 17.6, kg/cm o manometer pressure. The reaction time for reduction usually varies between 0.5 and 50 hours. Essentially inert liquid diluents and solvents, such as ethanol, cyclohexane, etc., can be used to facilitate the reaction. The aminophenol product is obtained using well-known methods, such as distillation, filtration or extraction, etc. The reduction is carried out to at least 50%, as a rule; approx. 80% of the nitro groups present in the nitro intermediate mixture have been converted to amino groups. The typical route to the aminophenols according to the invention and as just described can be summarized as (I) nitration using at least one nitrating agent of at least one compound of the formula ;; in which R and Ar are as defined above for Formula IV, and Ar has from 0 to 3 optional substituents as defined above for Formula IV, and (II) reduction of at least 50% of the nitro groups in the first reaction mixture to amino groups. The following examples (A series) describe examples of the preparation of typical alkylphenols for use according to the invention. A person skilled in the art will readily understand that alkylphenols produced using other methods can also be used. All parts and percentages are based on weight, and all temperatures are in degrees Celsius in these examples and elsewhere in the description unless the contrary is expressly stated. ;Example A- I ;An alkylated phenol is produced by reacting phenol with polyisobutene with a number average molecular weight of approx. 1000 (vapor phase osmometry) in the presence of a boron trifluoride phenol complex catalyst. Removal of the thus formed product first to 2 30° C/76 0 torr (steam temperature) and then to 205° C steam temperature/50 torr gives purified alkylated pheno1. ;Example A-2 ;The method according to Example A-I is repeated, except that the polyisobutene has a number average molecular weight of approx. 1400. ;Example A- 3 ;Polyisobutenyl chloride (4,885 parts) having a viscosity at 99° C of 1306 SUS and containing 4.7% chlorine is added to a mixture of 1,700 parts of phenol, 118 parts of a sulfuric acid treated clay and 141 parts of zinc chloride at 110 - 155° C over a period of 4 hours. The mixture was then held at 155-185°C for 3 hours before being filtered through diatomaceous earth. The filtrate is driven off under vacuum to 165° C/0.5 torr. The rest is again filtered through diatomaceous earth. The filtrate is a substituted phenol with an OH content of 1.88%. ;Example A-4 ;Sodium hydroxide (42 parts of a 20% aqueous sodium hydroxide solution) is added to a mixture of 453 parts of the substituted phenol described in Example A-3 and 450 parts of isopropanol at 30° C. during 0.5 hour. Tek-style alcohol (60 parts) and 112 parts of a 37.7% formalin solution are added at 20°C over a period of 0.8 hour, and the reaction mixture is held at 4-25°C for 92 hours. Additional textile spirits (50 parts), 50 parts isopropanol and acetic acid (58 parts of a 50% aqueous acetic acid solution) are added. The pH of the mixture is 5.5 (determined using ASM method D-974). The mixture is dried over 20 parts magnesium sulphate and then filtered through diatomaceous earth. The filtrate is vacuum driven to 25° C/10 torr. The remainder is the desired methylol-substituted product with an OH content of 3.29%. ;Example A- 5 ;Aluminum chloride (76 parts) is slowly added to a mixture of 4220 parts polyisobutylene chloride having a number average molecular weight, Mn, of 1000 (VPO) and containing 4.2% chlorine, 1516 parts phenol and 2500 parts toluene at 60° C. The reaction mixture is maintained at 95° C. under a subsurface nitrogen gas purge for 1.5 hours. Hydrochloric acid (50 parts of a 37.5% aqueous hydrochloric acid solution) is added at room temperature, and the mixture is stored for 1.5 hours. The mixture is washed five times with a total of 2500 parts of water and is then vacuum driven to 215° C./1 torr. The residue is filtered at 150°C through diatomaceous earth to improve its clarity. The filtrate is a substituted phenol with an OH content of 1.39%, a Cl content of 0.46% and a Mn of 898 (VPO). ;Example A-6 ;Paraformaldehyde (38 parts) is added to a mixture of 1399 parts of the substituted phenol described in example A-5, 200 parts of toluene, 50 parts of water and 2 parts of a 37.5% aqueous hydrochloric acid solution at 50 ° C and kept for 1 hour. The mixture is then vacuum driven to 150° C/ 15 torr, and the residue is filtered through diatomaceous earth. The filtrate is the desired product with an OH content of 1.60%, a Mn of 1688 (GPC) and a weight number average molecular weight, Mw, of 2934 (GPC). ;Example A- 7 ;168 g (0.19 mol) p-polypropylphenol with 894 Mn (polypropyl group with about 800 Mn), 31 g formalin (37% CH2o) to give 0.38 mol formaldehyde, 100 ml hexane and 130 ml of aqueous 1.5 N sodium hydroxide are brought together and stirred in a reactor with a reflux condenser. The resulting stirred mixture is heated under reflux (approx. 70° c) for approx. 16 hours. The resulting mixture is then washed carefully with water to remove the sodium hydroxide, and the hexane is evaporated by heating the water-washed solution to approx. 100° C. The residue, which is a viscous liquid at ambient temperature, contains the bis-methylol compound with a Mn of approx. 4588 and with the structure indicated above where x is 4 and each R is polypropyl with a Mn of approx. 800. ;Example A-8 ;To a reactor with a stirrer and reflux condenser, 1070 g of 0.5 gram molecule of p-polypropylphenol with a Mn of 900 (polypropyl group with a Mn of approx. 80 3) is added dissolved ( 42%) in a mixture of 10% by weight polypropylene (Mn 80 3) and 90% by weight light mineral oil, 40 g NaOH and 200 ml isooctane. The resulting solution is stirred and heated while 170 g of formalin (37% CH 2 O) is added slowly to give 2.08 mol of formaldehyde. The reaction mixture is stirred and heated to 121°C at which point nitrogen is injected to facilitate the removal of isooctane. The stirred residue is kept for 2 hours at 14 9° C. The liquid residue is filtered to remove solid NaOH. The filtrate is an oil solution of the desired product. ;Other examples of alkylated phenols which can be used according to the invention are reproduced in Table A. ;The following specific illustrative examples (B series) describe the preparation of the aminophenols which are applicable for the materials according to the invention. ;Example B-1 ;A mixture of 4578 parts of a polyisobutene-substituted phenol prepared by boron trifluoride-phenol-catalyzed alkylation of phenol with a polyisobutene having a number average molecular weight of approx. 1000 (vapor phase osmometry), 3052 parts of diluting mineral oil and 725 parts of textile spirit are heated to 60° C to achieve homogeneity. After cooling to 30° C, 319.5 parts of 16 molar nitric acid in 600 parts of water are added to the mixture. Cooling is necessary to keep the temperature of the mixture below 40° C. After the reaction mixture has been stirred for an additional 2 hours, a portion of 3710 parts is transferred to another reaction vessel. This second portion is treated with a further 127.8 parts of 16 molar nitric acid in 130 parts of water at 25 - 30° C. The reaction mixture is stirred for 1.5 hours and then evaporated to 220° C/30 torr. An oil solution of the desired intermediate product is obtained by filtration. A mixture of 810 parts of the oil solution of the intermediate product prepared above, 405 parts of isopropyl alcohol and 405 parts of toluene is filled into an autoclave of a suitable size. A platinum oxide catalyst (0.81 part) is added, and the autoclave is evacuated and flushed with nitrogen four times to remove any residual air. Hydrogen is introduced into the autoclave at a pressure of 2.0 - 3.9 kg/cm 2 manometer pressure while the contents are stirred and heated to 27 - 92° C for a total time of 13 hours. Excess hydrogen is removed from the reaction mixture by evacuation and purging with nitrogen four times. The reaction mixture is then filtered through diatomaceous earth, and the filtrate is driven off so that an oil solution with the desired aminophenol is obtained. This solution contains 0.5 78% nitrogen. ;Example B- 2 ;To a mixture of 361.2 parts of a deca (propylene)-substituted phenol and 270.9 parts of glacial acetic acid at 7 - 13° C is added a mixture of 90.3 parts of nitric acid (70 - 71%- ig HNO^) and 90.3 parts glacial acetic acid. The addition is carried out over 1.5 hours while the reaction mixture is cooled externally to keep it at 7 - 17° C. The cooling bath is removed, and the reaction mixture is stirred for 2 hours at room temperature. The reaction mixture is then evaporated at 134°C/35 torr and filtered to give the desired nitrated intermediate as a filtrate with a nitrogen content of 4.65%. A mixture of 150 parts of the intermediate product described above and 50 parts of ethanol is added to an autoclave. This mixture is degassed by flushing with nitrogen, and 0.75 part palladium-on-charcoal catalyst is added. The autoclave is evacuated and pressurized with nitrogen several times and then placed under a hydrogen pressure of 7.0 kg/cm<2 >manometer pressure. The reaction mixture is held at 95 - 100°C for 2.5 hours while the hydrogen pressure varies from 7.0 to 14.1 kg/cm o gauge pressure. As the hydrogen pressure drops below 2.1 kg/cm 2 gauge pressure, it is regulated back to 7.0 kg/cm<2> gauge pressure. The reaction is continued for 20.5 hours, at which time the autoclave is opened again and a further 0.5 part palladium-on-charcoal catalyst is added. After repeated flushing with nitrogen (3 times), the autoclave is again pressurized to 7.0 kg/cm 2 with hydrogen and the reaction continues for a further 6.5 hours. A total amount of 2.0 molecules of hydrogen is introduced into the autoclave. The reaction mixture was filtered and stripped to 130°C/16 torr. Another filtration gives the aminophenol product in the form of a filtrate which is mainly a monoamine product with the amino group in the ortho position in relation to the hydroxyl group and the decapropylene substituent in the para position in relation to the hydroxyl group. ;Example B-3 ;To a mixture of 3685 parts of a polybutene-substituted phenol (in which, the polybutene substituent contains 40 - 45 carbon atoms) and 1400 parts of textile spirit, 790 parts of nitric acid (70%) are added. The reaction temperature is kept below 50° C. After stirring for approx. After 0.7 hours, the reaction mixture is poured into 5000 parts of ice and stored for 16 hours. The separated organic layer is washed twice with water and then combined with 1000 parts of benzene. The solution is stripped to 170° C, and the residue is filtered to give the desired intermediate in the form of a filtrate. A mixture of 130 parts of the above-mentioned intermediate, 130 parts of ethanol and 0.2 part of platinum oxide (86.4% PtO 2 ) is charged into a hydrogenation bomb. The bomb is flushed several times with hydrogen and then filled with hydrogen up to a pressure of 3.8 kg/cm 2 manometer pressure. The bomb is rocked for 24 hours and is again filled with hydrogen up to a pressure of 4.92 kg/cm<2 >manometer pressure. The rocking is continued for another 4-8 hours. Evaporation of the obtained reaction mixture to 14 5° C/76 0 torr gives the desired aminophenol product in the form of a semi-solid residue. ;Example B-4 ;A mixture of 420 parts of the intermediate according to Example B-3, 326 parts of ethanol and 12 parts of commercially available nickel-on-silica catalyst is charged into a hydrogenation bomb of suitable size. The bomb is placed under a pressure of 104 kg/cm 2 manometer pressure with hydrogen and stirred for 5.25 hours. The resulting reaction mixture is evaporated to 65° C/30 torr and gives the aminophenol product in the form of a semi-solid residue. ;Example B-5 ;A mixture of 105 parts of the intermediate according to Example B-3, 303 parts of cyclohexane and 4 parts of commercially available Raney nickel catalyst is charged into a hydrogenation bomb of suitable size. The bomb is pressurized to 70.3 kg/cm 2 manometer pressure with hydrogen and stirred for 16 hours at approx. 50° C. The bomb is again put under a pressure of 77.3 kg/cm 2 gauge pressure and stirred for 24 hours. The bomb is then opened and the reaction mixture filtered and refilled into the bomb along with a fresh portion of 4 parts Raney nickel catalyst. The bomb is put under a pressure of 77.3 kg/cm 2 gauge pressure and stirred for 24 hours. The resulting reaction mixture is evaporated to 95° C/28 torr to give the aminophenol product in the form of a semi-solid residue. ;Example B- 6 ;An alkylated phenol is produced by reacting phenol with polybutene with a number average molecular weight of approx. 1000 (vapor phase osmometry) in the presence of a boron trifluoride-phenol complex catalyst. Evaporation of the thus formed product first to 230° C/760 torr and then to 205° C/50 torr (steam temperatures) gives the desired alkylated phenol. ;To a mixture of 265 parts of the alkylated phenol, 176 parts of mixed oil and 42 parts of a petroleum naphtha-with a boiling point of approx. At 20° C, a mixture of 18.4 parts concentrated nitric acid (6 9 - 70%) and 35 parts water is added slowly. The reaction mixture is stirred for 3 hours at 30 - 45° C, evaporated to 120° C/20 torr and filtered to give as filtrate an oil solution of the desired nitrophenol intermediate. A mixture of 1500 parts of the above intermediate, 642 parts of isopropanol and 7.5 parts of nickel-on-silica catalyst is charged into an autoclave under a nitrogen atmosphere. After flushing and evacuating with nitrogen three times, the autoclave is pressurized to 7.03 kg/cm^ gauge pressure with hydrogen, and stirring is started. The reaction mixture is kept at 96° C for a total time of 14.5 hours while a total of 1.66 molecules of hydrogen are introduced into it. After flushing with nitrogen three times, the reaction mixture is filtered, and the filtrate is driven off until 120° C/18 torr. By filtration, the desired aminophenol product is obtained in the form of an oil solution. ;Example B- 7 ;To a mixture of 400 parts of polybutene-substituted phenol (in which the polybutene substituent contains approx. 100 carbon atoms), 125 parts of textile spirit and 266 parts of a dilution mineral oil at 28° C, 22.8 parts of nitric acid (70%) in 50 divides water slowly over a period of ;0.33 hours. The mixture is stirred at 28 - 34° C for 2 hours and evaporated to 158° C/30 torr. Filtration gives an oil solution (40%) of the desired nitrophenol intermediate with a nitrogen content of 0.88%. A mixture of 93 parts of the above intermediate and 93 parts of a mixture of toluene and isopropanol (50/50 based on weight) is charged into a hydrogenation vessel of suitable size. The mixture is degassed and flushed with nitrogen. 0.31 part of a commercially available platinum oxide catalyst (86.4% PtO 9 ) is added. The reaction vessel z 2 is pressurized up to 4.0 kg/cm gauge pressure and kept at 50 - 60° C. for 21 hours. A total amount of 0.6 molecules of hydrogen is introduced into the reaction vessel. The reaction mixture is then filtered and the filtrate evaporated to give the desired aminophenol product in the form of an oil solution containing 0.44% nitrogen. ;Example B-8 ;To a mixture of 654 parts of the polybutene-substituted phenol according to Example B-6 and 654 parts of isobutyric acid at 27 - 31° C, 90 parts of 16 molar nitric acid are added over a period of 0.5 hour. The reaction mixture is kept at 50° C. for 3 hours and then stored at room temperature for 63 hours. Evaporation to 160°C/26 torr and filtration through filter aid gives the desired dinitro intermediate. A mixture of 600 parts of the above intermediate, 257 parts of isopropanol and 3.0 parts of nickel-on-silica catalyst is charged into an autoclave under a nitrogen atmosphere. After flushing and evacuating with nitrogen three times, the autoclave is pressurized to 7.03 kg/cm 2 gauge pressure with hydrogen, and stirring is started. The reaction mixture is kept at 96° C. for a total time of 14.5 hours while a total amount of 1.66 molecules of hydrogen is introduced into it. After flushing with nitrogen three times, the reaction mixture is filtered and the filtrate evaporated to 120°C/18 torr. Filtration gives the desired product as efr oil solution. ;The nitrations in the following examples B-9 to B-12 are carried out in essentially the same manner as described in Example B-1 using the hydroxyaromatic compounds and quantities of nitric acid as indicated in Table B. Reduction of the nitro intermediates in these examples is carried out by using by essentially the same method as described in Example B-4. ;The cleaning agent/dispersing agents (C) ;Generally, the cleaning agents/dispersing agents (C) that can be used according to the invention are materials that are known to those skilled in the art, and they have been described in several books, articles and patents. A number of patents are indicated below in connection with specific types of cleaning agents/dispersants, and where this has been done, it will be understood that these have been included because of the description in them which applies to the subject of the application in question at the place in the specification tion in which they are identified. Preferred groups of cleaning agent/dispersants are as follows: (C)(i) The neutral or basic metal salts of organic sulfuric acids, carboxylic acids or phenols; The choice of metal used to make these salts; is usually not of critical importance, and therefore practically any metal can be used. Due to availability, price and maximum efficiency, certain metals are more commonly used. These include the metals in groups I, II and III, especially the alkali and alkaline earth metals, i.e. the metals from Group IA and IIA, not including francium and radium). The metals from Group IIB as well as polyvalent metals, such as aluminium, animon, arsenic, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel and copper, can also be used. Salts containing a mixture of ions of two or more of these metals are often used. ;These salts can be neutral or basic. The former contain an amount of metal cations that is just sufficient to neutralize the acidic groups present in the salt anion. The latter contains an excess of metal cations and is often referred to as overbased, hyperbased or superbased salts. ;These basic and neutral salts can be of oil-soluble, organic sulfuric acids, such as sulfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, partially esterified sulfuric, sulfuric acid and thiosulfuric acids. They are generally salts of carbocyclic or aliphatic sulphonic acids. The carbocyclic sulfonic acids include the mono- or polynuclear aromatic or cycloaliphatic compounds. The oil-soluble sulfonates can mostly be represented by the following formulas: In the above formulas, M is a metal cation as described above or hydrogen, T is a cyclic nucleus, such as e.g. benzene, naphthaene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxin, diphenylene sulfide, phenothiazine, diphenyloxide, diphenylsulfide, diphenylamine, cyclohexane, petroleum naphthenes, decahydronaphthaene, cyclopentane, etc. R in Formula V is an aliphatic group, such as alkyl, alkenyl . R' in Formula VI is an aliphatic group containing at least 15 carbon atoms, and M is either a metal cation or hydrogen. Examples of types of the group R' are alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R<1> are groups derived from vaseline, saturated and unsaturated paraffin waxes and poly-olefins, including polymerized C2, C-^, C^, C^, Cg etc, olefins containing 15 - 7000 carbon atoms or more. The groups T, R and R' in the above formulas may also contain other inorganic or organic substituents besides those summarized above, such as e.g. hydroxyl, mercapto, halogen, nitro, amino, nitroso, sulphide, disulphide etc. In Formula V, x, y, z and b are at least 1, and likewise in Formula Via, a, b and d are at least 1. ;The following are specific examples of oil-soluble sulphonic acids which come within the scope of the above Formulas V and VI, and it will be understood that such examples also serve to illustrate the salts of such sulphonic acids which can be used according to the invention. In other words, for each summarized sulphonic acid it is intended that the corresponding neutral and basic metal salts of this should also be considered to be described. Such sulphonic acids are mahogany sulphonic acids, "bright stock" sulphonic acids, sulphonic acids derived from lubricating oils* fractions with Saybolt viscosity from 100 seconds at 37.8°C to 200 seconds at 98.9°C, vaseline sulfonic acids, mono- and polywax-substituted' sulfonic and polysulfonic acids of e.g. benzene, naphthalene, phenol, diphenyl ether, naphthalene disulfide, diphenylamine, thiophene, ct-chloronaphthalene, etc., other substituted sulfonic acids, such as alkylbenzenesulfonic acids (in which the alkyl group has at least 8 carbon atoms), cetylphenol monosulfide sulfonic acids, dicetylthianthrindisulfonic acids, dilauryl-3-naphthyl- sulfonic acids, dicaprylnitronaphthalene sulfonic acids and alkaryl sulfonic acids, such as dodecylbenzene "bottom fraction" sulfonic acids.

The latter are acids derived from benzene which has been alkylated with propylene tetramers or with iso-butene trimers to introduce 1, 2, 3 or more branched ~substituents on the benzene ring. Dodecylbenzene bottom fractions, which mainly consist of mixtures of mono- and di-dodecylbenzenes, are available as by-products from the manufacture of household cleaning agents. Similar products obtained from alkylation bottom fractions formed during the production of linear alkyl sulfonates (LAS) can also be used for the production of the sulfonates used according to the invention.

The production of sulphonates from detergent production by-products by reaction with e.g. SO^ are well known to those skilled in the art, see e.g. the article "Sulfonates" in the Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley & Sons, N.Y. (1969) .

Other descriptions of neutral and basic sulfonate salts and methods for their production can be found in the following US patents: 2,174,110, 2,174,506, 2,174,508, 2,193,824, 2,197,800, 2,202,781, 2,212,786 . 335,259, 2,337,552, 2,347,568, 2,366,027, 2,374,193, 2,383,319, 3,312,618, 3,471,403, 3,488,284, 3,595,790 and 3,798,012.

Also included are aliphatic sulfonic acids, such as paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, hexapropylene sulfonic acids, tetraamylene sulfonic acids, polyisobutene sulfonic acids in which the polyisobutene contains 20 - 7000 carbon atoms or more, chlorine-substituted paraffin wax sulfonic acids, nitroparaffin/ox-sulfonic acids, etc., cycloaliphatic sulfonic acids, such as petroleum-naphthene sulfonic acids, cetylcyclopentanesulfonic acids, laurylcyclohexanesulfonic acids, bis-(diisobutyl)cyclohexanesulfonic acids, mono- or poly-wax substituted cyclohexanesulfonic acids etc

As regards the sulphonic acids or their salts which are described here and in the appended patent claims, it is intended here to use the term "petroleum sulphonic acid" or "petroleum sulphonates" to cover all sulphonic acids or their salts which are derived from petroleum products. A particularly valuable group of petroleum sulphonic acids are the mahogany sulphonic acids (named so because of their reddish-brown colour) obtained as a by-product in the production of petroleum white oils using a sulfuric acid process.

In general, neutral and basic salts of the above-described synthetic and petroleum sulphonic acids, metals from Groups IA, HA and IIB are usable in the implementation of the present invention.

The carboxylic acids from which suitable neutral and basic salts for use according to the invention can be prepared include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids, such as the naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, alkyl- or alkenyl-substituted aromatic carboxylic acids. The aliphatic acids generally contain at least 8 carbon atoms, preferably at least 12 carbon atoms. They usually have no more than 400 carbon atoms. If the aliphatic carbon chain is branched, the acids will generally be more oil-soluble for any given carbon atom content. The cycloaliphatic and aliphatic carboxylic acids may be saturated or unsaturated. Specific examples include 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, castor oleic acid, undecyl acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthaenecarboxylic acid, stearyloctahydroinden- carboxylic acid, palmitic acid, commercially available mixtures of two or more carboxylic acids, such as tall oil acids, rosin acids and the like.

A preferred group for oil-soluble carboxylic acids which can be used for the preparation of the salts used according to the present invention are the oil-soluble aromatic carboxylic acids. These acids can be represented by the general formula:

wherein RX is an aliphatic hydrocarbon-based group of at least 4 carbon atoms and no more than 400 aliphatic carbon atoms, a is an integer from 1 to 4, Ar<x> is a polyvalent aromatic hydrocarbon nucleus of up to 14 carbon atoms, each X is independent of the others a sulfur or oxygen atom, and m is an integer from 1 to 4, with the proviso that Rx and a are such that an average of at least 8 aliphatic carbon atoms of the groups R are provided for each acid molecule represented by Formula VII. Examples of aromatic nuclei represented by the variable Ar<x> are the polyvalent aromatic radicals derived from benzene, naphthaene, anthracene, phenanthrene, indene, fluorine, biphenyl and the like. The radical represented by Ar toe will generally be a polyvalent nucleus derived from benzene or naphtha, such as phenylenes and naphthylene, e.g. methylphenylenes, ethoxyphenylenes, nitrophenylenes, isopropylphenylenes, hydroxyphenylenes, mercaptophenylenes, N,N-diethylaminophenylenes, chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes and similar tri-, tetra-, pentavalent nuclei of these etc.

The groups Rx are usually pure hydrocarbyl groups, preferably such groups as alkyl or alkenyl radicals. The groups Rx may, however, contain a smaller number of substituents, such as phenyl, cycloalkyl (e.g. cyclohexyl, cyclopentyl etc.) and non-hydrocarbon groups, such as nitro, amino, halogen (e.g. chlorine, bromine etc.) . retained. The hydrocarbon character is retained for the purposes of the invention as long as any non-carbon atoms present in the groups R do not account for more than 10% of the total weight of the groups Rx.

Examples of groups Rx include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 2-hexenyl, e-cyclohexyloctyl, 4-(p-chlorophenyl)-octyl, 2 ,3,5-trimethylheptyl, 2-ethyl-5-methyl-octyl and substituents derived from polymerized olefins, such as polychloroprenes, polyethylenes, polypropylenes, polyisobutylenes, ethylene-propylene copolymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers and the like. Likewise, the group Ar can contain non-hydrocarbon substituents, e.g. such various substituents as lower alkoxy, lower alkyl mercapto, nitro, halogen, alkyl or alkenyl groups with less than 4 carbon atoms, hydroxy, mercapto and the like.

A group of particularly useful carboxylic acids are those having the formula: in which Rx, X, Ar<x>, m and a are as defined for Formula XIV, and p is an integer from 1 to 4, usually 1 or 2. Within this group is a particularly preferred group of oil-soluble carboxylic acids of the formula:

wherein R in formula IX is an aliphatic hydrocarbon group containing at least from 4 to 400 carbon atoms, a is an integer from 1 to 3, b is 1 or 2, c is zero, 1 or 2, and preferably 1, with the proviso that R xx and a are such that the acid molecules contain at least an average of 12 aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule. And within this latter group of oil-soluble carboxylic acids are the aliphatic-hydrocarbon substituted hydrochloric acids, in which each aliphatic hydrocarbon substi-

tuent contains on average at least 16 carbon atoms per substituent and one to three substituents per molecule, particularly applicable. Salts prepared from such salicylic acids in which the aliphatic hydrocarbon substituents are derived from polymerized olefins, especially polymerized lower 1-monoolefins, such as polyethylene, polypropylene, polyisobutylene, ethylene/propylene copolymers and the like and with an average carbon content of 30 - 400 carbon atoms.

The carboxylic acids corresponding to the above formulas VII and VIII are well known or they can be prepared using well-known methods. Carboxylic acids of the type shown by means of the above formulas, and methods for the preparation of their neutral and basic metal salts are well known and are described e.g. in such US patents as 2,197,832, 2,197,835, 2,252,662, 2,252,664, 2,714,092,

3,410,798 and 3,595,791. Another type of neutral and basic carboxylate salt used according to the invention are those derived from alkenyl succinates with the general formula wherein R is as defined above in Formula VII. Such salts and methods for their production are described in US patents 3,271,130, 3,567,637 and 3,632,610.

Other patents that specifically describe methods for preparing basic salts of the above-described sulfonic acids, carboxylic acids, and mixtures of any two or more of these include US patents 2,501,731, 2,616,904, 2,616,905, 2,616,906, 2,616,911, 2,616,924, 2,616,925, 2,617,049, 2,777,874, 3,027,325, 3,256,186, 3,282,835, 3,384,585, 3,373,108, 3,368,392, 3,333,334 162, 3,312,618, 3,318,809, 3,471,403, 3,488,284, 3,595,790 and 3,629,109. In addition to describing such methods, these patents also describe particularly suitable vbasic metal salts.

Neutral and basic salts of phenols (commonly known as phenates) are also useful in the compositions of the invention and are well known to those skilled in the art. The phenols from which these phenates are formed have the general formula:

wherein Rx, n, Ar<x>, X and m have the same meaning and preference as described above with reference to Formula VII. The same examples described in connection with Formula VII also apply.

The commonly available group of phenates are those prepared from phenols of the general formula:

wherein a is an integer of 1 - 3, b is 1 or 2, z is 0 or 1, R' in Formula XII is a substantially saturated hydrocarbon-based substituent having an average of 30 - 400 aliphatic carbon atoms, and R consists of lower alkyl, lower alkoxyl, nitro or halogen groups.

A particular group of phenates for use in accordance with the invention are the basic (ie overbased etc.) sulphurised metal phenates of Group IIA prepared by sulphurisation of a phenol, as described above, with a sulphurising agent, such as sulphur, a sulfur halide or sulfide or hydrosulfide salt. Methods for the production of these sulphurized phenates are described in US patents 2,680,096, 3,036,971 and 3,775,321.

Other phenates which can be used are those made from phenols which have been linked via alkylene (eg methylene) bridges. These are prepared by reacting phenols with a single ring or multiple rings with aldehydes or ketones, typically in the presence of an acid catalyst or a basic catalyst. Such linked phenates as well as sulfurized phenates are described in detail in US patent 3,350,038, especially in columns 6-8 thereof.

Of course, mixtures of two or more neutral and basic salts of the above-described organic sulfuric acids, carboxylic acids and phenols can be used in the mixtures according to the invention. As a rule, the neutral basic salts will be sodium, lithium, magnesium, calcium, or barium salts, including mixtures of two or more of any of these.

(C)(ii) The hydrocarbyl substituted amine

The hydrocarbyl-substituted amines used for

the production of the materials according to the invention are well known to those skilled in the art, and they are described in a number of patents. Among these are US patents 3,275,554, 3,438,757, 3,454,555, 3,565,804, 3,755,433 and 3,822,209. These patents describe suitable hydrocarbylamines for use according to the invention, including the production methods for these.

A typical hydrocarbylamine has the general form:

in which A is hydrogen, a hydrocarbyl group with 1-10 carbon atoms, or a hydroxyhydrocarbyl group with 1-10 carbon atoms, X is hydrogen, a hydrocarbyl group with 1-10 carbon atoms or a hydroxyhydrocarbyl group with 1-10 carbon atoms and together with A and N can form a ring with 5-6 ring members and up to 12 carbon atoms, U is an alkylene group with 2-10 carbon atoms, R 2 is an aliphatic hydrocarbon with 30 - 400 carbon atoms, a is an integer from 0 to 10, b is an integer number from 0 to 1, a+2b is a whole number from 1 to 10,

c is an integer from 1 to 5 and lies on average within the range from 1 to 4 and is 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 equals 1.

When interpreting this formula, it will be understood that R 2 and H atoms are connected with the unsatisfied nitrogen valences indicated within brackets in the formula. Thus, the formula includes subgeneric formulas in which R 2 is attached to terminal nitrogen atoms, and isomer subgeneric formulas in which it is attached to nitrogen atoms that are not terminal. Nitrogen atoms which are not bound to R 2 can have a hydrogen or an AXN substituent.

The hydrocarbylamines which can be used according to the invention and which are covered by the above formula include monoamines with the general formula:

Illustrative of such monoamines are the following: polypropyleneamine, N,N-dimethyl-N-polyethylene/propyleneamine (50:50 molar ratio between monomers) polyisobutenamine, N,N-dihydroxyethyl)-N-polyisobutenamine, polyisobutene/l-butene/2- butenamine (50:25:25 molar ratio between monomers), N-2-hydroxypropy1-N-polyisobutenamine, N-poly-1-butene-aniline, N-polyisobutene-morpholine. Among the hydrocarbylamines which are encompassed by the general Formula XIII stated above, the polyamines of the general formula

Illustrative of such polyamines are the following: N-polysibuteneethylenediamine, N,polypropylenetrimethylenediamine, N-poly-l-butenediethylenetriamine, N<1>,N'-polyisobutenetetraethylenepentamine, N,N-dimethyl-N<1->polypropylene- 1,3-propylenediamine.

The hydrocarbyl-substituted amines which can be used for the production of the materials according to the invention include certain N-aminohydrocarbyl morpholines which are not covered by the above general Formula XIII. These hydrocarbyl-substituted aminohydrocarbyl morpholines have the general formula:

wherein R 2 is an aliphatic hydrocarbon group of 30-400 carbon atoms, A is hydrogen, hydrocarbyl of 1-10 carbon atoms or a hydroxycarbyl group of 1-10 carbon atoms, and U is an alkylene group of 2-10 carbon atoms. These hydrocarbyl substituted aminohydrocarbyl morpholines as well as the polyamines described by Formula XIV are among them

typical hydrocarbyl-substituted amines used for the production of materials according to the invention.

(C) (iii) The acylated nitrogenous compounds

A number of acylated, nitrogen-containing compounds with

a substituent with at least 10 aliphatic carbon atoms and prepared by reacting a carboxylic acid acylating agent with an amino compound are known to those skilled in the art. In such materials, the acylating agent is bound to the amino compound via an imide, amide, amidine or acyloxy-ammonium bond. The substituent with 10 aliphatic carbon atoms can be present in the part of the molecule which is derived from the carboxylic acid acylating agent, or in the part of the molecule which is derived from the amino compound. However, it is preferably present in the acylating agent part. The acylating agent can vary from formic acid and its acylating derivatives to acylating agents with high molecular weight aliphatic substituents and up to 5000, 10,000 or 20,000 carbon atoms. The amino compounds can vary from ammonia as such to amines with aliphatic substituents of up to 30 carbon atoms.

A typical group of acylated amino compounds which are useful for the production of the materials according to the invention are those which are formed by reacting an acylating agent with an aliphatic substituent with at least 10 carbon atoms and a nitrogen compound which is characterized by the presence of at least one -NH group. The acylating agent will typically be a mono- or polycarboxylic acid (or a reactive equivalent thereof), such as a substituted succinic or propionic acid, and the amino compound will be a polyamine or a mixture of polyamines, most typically a mixture of ethylene polyamines. The aliphatic substituent in such acylating agents often has at least 50 and up to 400 carbon atoms. As a rule, it belongs to the same generic group as the group R<1> in the phenols (A), and the preference, examples and limitation discussed above regarding R' therefore apply equally to this aliphatic substituent. Examples of amino compounds which can be used for the preparation of these acylated compounds are the following: (1) polyalkylene polyamines of the general formula: in which each R"' is independent of the other hydrogen atoms or a C^_^2-hydrocarbon-based group, provided that at least one R is a hydrogen atom, n is an integer from 1 to 10, and U is a C2_-LQ alkylene group, (2) heterocyclic substituted polyamines of the formula: wherein R"' and U are as defined above, m is 0 or an integer from 1 to 10, m<1> is an integer from 1 to 10, and Y is oxygen or a divalent sulfur atom or a group N-R"', and (3) aromatic polyamines of the general formula: wherein Ar is an aromatic ring of 6-20 carbon atoms, each R"' is as defined above, and y is from 2 to about 8. Specific examples of the polyalkylene polyamines (1) are ethylenediamine, tetraethylenepentamine, tritrimethylenetetramine, 1,2-propylenediamine etc. Specific examples of the heterocyclic substituted polyamines (2) are N-2-aminoethylpiperazine, N-2- and N -3-aminopropylmorpholine, N-3-dimethylaminopropylpiperazine etc. Specific examples of the aromatic polyamines (3) are the different isomeric phenylenediamines, the different isomeric naphthalene diamines etc.

In a number of patents useful acylated nitrogen compounds are described, including US Patents 3,172,892, 3,219,666, 3,272,746, 3,310,492, 3,341,542, 3,444,170, 3,455,831, 3,455,832, 3,576,743, 3 630 904, 3 632 511 and 3 804 76 3. A typical acylated nitrogenous compound within this group is that produced by reacting a polyisobutene-substituted succinic anhydride acylating agent (e.g. anhydride, acid, ester, etc.) in which the polyisobutene substituent has 50 - 400 carbon atoms, with a mixture of ethylene polyamines with 3-7 amino nitrogen atoms per ethylene polyamine and 1 - 6 ethylene units formed by condensation of ammonia with ethylene chloride. Because of the extensive description of this type of acylated amine compound, no further discussion regarding their nature and method of preparation is necessary here. It appears instead of the above-mentioned US patents.

Another type of acylated nitrogen compounds belonging to this group is that produced by reaction

of the above-described alkylene amines with the above-described substituted succinic acids or anhydrides and aliphatic monocarboxylic acids with 2-22 carbon atoms. In these types of acylated nitrogen compounds, the molar ratio between succinic acid and monocarboxylic acid varies from 1:0.1 to 1:1. Typical of the mono-carboxylic acids are formic acid, acetic acid, dodecanoic acid, butanoic acid, oleic acid, stearic acid, the commercially available mixture of stearic acid isomers known as isostearic acid, toluene acid, etc. Such materials are more fully described in US patents

3,216,936 and 3,250,715.

A further type of acylated nitrogen compounds that can be used for the production of the materials according to the invention is the product of the reaction between a fatty monocarboxylic acid with 12-30 carbon atoms and the above-described alkylene amines, typically ethylene, propylene or trimethylene polyamines containing 2-8 amino groups or mixtures thereof. The fatty monocarboxylic acids are generally mixtures of straight-chain and branched fatty carboxylic acids with 12 - 30 carbon atoms. A widely used type of acylated nitrogen compound is prepared by reacting the above-described alkylene polyamines with a mixture of fatty acids with 5-30 mol% straight-chain acid and 70-95 mol% branched-chain fatty acids. Among the commercially available mixtures are those which are well known in the male section as isostearic acid. These mixtures are produced as a by-product by dimerization of unsaturated fatty acids, as described in US patents 2,812,342 and 3,260,671.

The branched-chain fatty acids may also include those in which the branching is not of the alkyl type, as in phenyl- and cyclohexylstearic acid and the chlorostearic acids. Fatty carboxyl branched chain/alkyl polyamine products have been extensively described in the prior art, see e.g. US Patents 3,251,853, 3,326,801, 3,337,459, 3,405,064, 3,429,674, 3,468,639, 3,857,791. These patents are referred to because of their description of fatty acid/polyamine condensates for use in lubricating oil blends.

(C)(iv) The nitrogenous condensates of phenols, aldehydes and amino compounds

The phenol/aldehyde/amino compound condensates which can be used for the production of the cleaning agent/dispersants according to the invention include those which are generically designated as Mannich condensates. These are generally produced by reacting simultaneously or in sequence at least one of the hydrogen compounds, such as a hydrocarbon-substituted phenol (e.g. an alkylphenol in which the alkyl group has at least 30 and up to 400 carbon atoms) which has at least one hydrogen atom bonded to an aromatic carbon atom, with at least one aldehyde or an aldehyde-giving material (typically formaldehyde or formaldehyde starting material) and at least one amino or polyamino compound with at least one NH group. The amino compounds include primary or secondary monoamines with hydrocarbon substituents of 1-30 carbon atoms or hydroxyl-substituted hydrocarbon substituents of 1-30 carbon atoms. Another type of typical amino compound is the polyamides described under the discussion of the acylated nitrogenous compounds.

Examples of monoamines include methylethylamine, methyloctadecylamine, aniline, diethylamine, diethanolamine, dipropylamine, etc. The following US patents contain extensive descriptions of Mannich condensates which are used for the production of the materials according to the invention:

These patents are referred to here because of the disclosure therein regarding the preparation and use of Mannich condensate products in lubricants.

Condensates produced from sulfur-containing reactants can also be used in the materials according to the invention. Such sulfur-containing condensates are described in US Patents 3,368,972, 3,539,229, 3,600,372, 3,649,659 and 3,741,896. These patents are also referred to because of the description therein of sulfur-containing Mannich condensates. The condensates used for the production of the materials according to the invention are generally made from a phenol with an alkyl substituent of 6 - 400 carbon atoms, with typically 30 - 250 carbon atoms. These typical condensates are prepared from formaldehyde or an aliphatic C 2 aldehyde and an amino compound, such as those used for the preparation of the acylated nitrogen-containing compounds described under (C) (iii).

These preferred condensates are produced by reacting approx. a molar portion of a phenolic compound with 1-2 molar portions of aldehyde and 1-5 equivalent portions of amino compound (an equivalent of amino compound is its molecular weight divided by the number of NH= groups present). The conditions in which condensate reactions are carried out are well known to those skilled in the art, as can be seen from the above-mentioned patents. These patents are therefore also referred to because of the description therein regarding reaction conditions.

A particularly preferred group of condensation products for use in accordance with the invention are those produced by means of a "2-step process" as described in commonly assigned US Patent Application No. 4,51,644 filed March 15, 1974 and now abandoned. Briefly, these nitrogenous condensates (1) are prepared by reacting at least one hydroxyaromatic compound containing an aliphatic-based or cycloaliphatic-based substituent of at least 30 carbon atoms and up to 400 carbon atoms, with a lower aliphatic C^_^-aldehyde or a reversible polymer thereof in the presence of an alkaline reagent, such as an alkali metal hydroxide, at a temperature up to 150° C., (2) by substantially neutralizing the intermediate reaction mixture thus formed, and (3) by reacting the neutralized intermediate with at least one compound which contains an amino group with at least one NH group.

More preferably, these 2-stage condensates are prepared from (a) phenols with a hydrocarbon-based substituent of 30-250 carbon atoms, the substituent being derived from a polymer of propylene, 1-butene, 2-butene or isobutene, and (b) formaldehyde or a reversible polymer thereof (eg trioxane, paraformaldehyde) or a functional equivalent thereof (eg methylol) and (c) an alkylene polyamine, such as ethylene polyamines having 2-10 nitrogen atoms. Additional details regarding this preferred group of condensates are found in the above-mentioned US Patent Application No. 451,644 to which reference is made due to its description of 2-stage condensates.

(C)(v) The esters of substituted polycarboxylic acids

The esters which can be used as cleaning agents/dispersants according to the invention are derivatives of substituted carboxylic acids in which the substituent is an essentially aliphatic, essentially saturated hydrocarbon-based group containing at least 30 (preferably 50 - 750) aliphatic carbon atoms. As used here, the term "hydrocarbon-based group" shall denote a group with a carbon atom directly bonded to the rest of the molecule and with dominant hydrocarbon character in the sense that this term is used here. Such groups include the following:

(1) Hydrocarbon groups, i.e. aliphatic groups, aromatic- and alycylic-substituted aliphatic groups and the like, of the type known to those skilled in the art.

(2) Substituted hydrocarbon groups, i.e. groups containing non-hydrocarbon substituents which, in the textual context according to the invention, do not change the dominant hydrocarbon character of the group. Those skilled in the art will be aware of suitable substituents, examples of which are halogen, nitro, hydroxyl, alkoxy, carboxy and alkylthio.

(3) Heterogroups, i.e. groups which, although they are predominantly of a hydrocarbon nature in the textual context according to the invention, contain atoms other than carbon atoms which are present in a chain or ring which is otherwise made up of carbon atoms. Suitable heteroatoms will be self-evident to those skilled in the art and include e.g. nitrogen, oxygen and sulphur.

In general, no more than approx. three substituents or heteroatoms, and preferably no more than one, be present for every 10 carbon atoms in the hydrocarbon-based group.

The substituted carboxylic acids (and derivatives thereof, including esters, amides and imides) are normally prepared by alkylating an unsaturated acid or a derivative thereof, such as an anhydride, an ester, an amide or an imide, with a starting material for the desired hydrocarbon-based group. Suitable unsaturated acids and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid and 2 -pentene-1,3,5-tricarboxylic acid. Particularly preferred are the unsaturated dicarboxylic acids and their derivatives, especially maleic acid, fumaric acid and maleic anhydride.

Suitable alkylating agents include homopolymers and copolymers of polymerizable olefin monomers containing 2-10 and as a rule 2-6 carbon atoms, and polar substituent-containing derivatives thereof. Such polymers are substantially saturated (i.e. they contain no more than 5% olefinic linkages) and substantially aliphatic (i.e. they contain at least 80% by weight, preferably at least 95% by weight, units derived from aliphatic monoolefins) . Examples of monomers that can be used for the production of such polymers are ethylene, propylene, 1-butene, 2-butene, isobutene, 1-octene and 1-decene. Any unsaturated units may be derived from conjugated dienes, such as 1,3-butadiene and isoprene, non-conjugated dienes such as 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene and 1,6- octadiene, and trienes such as 1-isopropylidene-3a,4,7,7a-tetrahydroindene, 1-isopropylidene-dicyclopentadiene and 2-(2-methylene-4-methyl-3-penteny1)-[2,2,1]-bicyclo -5-heptene.

A first preferred group of polymers includes those of endolefins, such as propylene, 1-butene, isobutene and 1-hexene. Particularly preferred within this group are polybutenes which mainly comprise isobutene units. Another preferred group comprises terpolymers of ethylene, a C-, D-

J —o α-monoolefin and a polyene selected from the group consisting of non-conjugated dienes (which are particularly preferred) and trienes. Examples of these terpolymers are "Ortholeum 2052" which is a terpolymer containing approx. 4 8 mol% ethylene groups, 4 8 mol% propylene groups and 4 mol% 1,4-hexadiene groups and with an intrinsic viscosity of 1.35 (8.2 g polymer in 100 ml carbon tetrachloride at 30° C).

Methods for preparing the substituted carboxylic acids and derivatives thereof are well known in the relevant art and do not need to be described in detail. Reference is made e.g. to US patents 3,272,746, 3,522,179 and 4,234,435. The molar ratio between the polymer and the unsaturated acid or derivative thereof may be equal, greater than or less than 1 depending on the desired product type.

When the unsaturated acid or derivative thereof is maleic acid, fumaric acid or maleic anhydride, the alkylation product is a substituted succinic acid or a derivative thereof. These substituted succinic acids and derivatives are particularly preferred for the production of the materials according to the invention.

The esters are those of the above-described succinic acids with hydroxy compounds which can be aliphatic compounds, such as monohydric and polyhydric alcohols, or aromatic compounds, such as phenols and naphthols. The aromatic hydroxy compounds from which the esters according to the invention can be derived can be illustrated with the help of the following specific examples: phenol, 3-naphthol, α-naphthol, cresol, resorcinol, catechol, p,p'-dihydroxybiphenyl, 2- chlorophenol, 2,4-dibutylphenol, propenetetramer-substituted phenol, didodecylphenol, 4, 4'-methylene-bis-phenol, α-decyl-fj-naphthol, polyisobutene (molecular weight 1000)-substituted phenol, the condensation product of heptylphenol with 0.5 mol formaldehyde, the condensation product of octylphenol with acetone, dihydroxyphenyloxide, dihydroxyphenylsulfide, dihydroxyphenyldisulfide and 4-cyciohexylphenol. Phenol and alkylated phenols with up to three alkyl substituents are preferred. Each of the alkyl substituents may contain 100 carbon atoms or more.

The alcohols from which the esters may be derived preferably contain up to 40 aliphatic carbon atoms. They can be monohydric alcohols, such as methanols, ethanol, iso-octanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, 3-phenylethyl alcohol, 2-methylcyclohexanol, $-chloroethanol, monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, mono-dodecyl ether of triethylene glycol, monooleate of ethylene glycol, monostearate of diethylene glycol, sec. pentyl alcohol, tert. butyl alcohol, 5-bromo-dodecanol, nitro-octadecanol and dioleate of glycerol. The polyhydric alcohols preferably contain 2-10 hydroxyl groups. They can be illustrated e.g. by ethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol and other alkylene glycols in which the alkylene group contains 2-8 carbon atoms. Other useful polyhydric alcohols include glycerol, glycerol monooleate, glycerol monostearate, glycerol monomethyl ether, pentaerythritol, 9,10-dihydroxystearic acid, 9,10-dihydroxystearic acid methyl ester, 1,2-butanediol, 2,3-hexanediol, 2,4 -hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2-cyclohexanediol and xylene glycol. Carbohydrates, such as sugars, starches, cellulose etc., can likewise give the esters according to the invention. The carbohydrates can be exemplified by a glucose, fructose, sucrose, rharanose, mannose, glyceraldehyde and galactose.

A particularly preferred group of polyhydric alcohols are those which have at least three hydroxyl groups, some of which have been esterified with a monocarboxylic acid with 8-30 carbon atoms, such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid or tallow oleic acid. Examples of such partially esterified polyhydric alcohols are the monooleate of sorbitol, the distearate of sorbitol, the monooleate of glycerol, the monostearate of glycerol, the didodecanoate of erythritol.

The esters may also be derived from unsaturated alcohols, such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexen-3-ol and oleyl alcohol. Further other groups of the alcohols which are able to give the esters according to the invention include the ether alcohols and the amino alcohols, including e.g. the oxyalkylene-, oxyarylene-, aminoalkylene- and aminoarylene-substituted alcohols with one or more oxyalkylene-, aminoalkylene- or aminoaryleneoxyarylene radicals. These can be exemplified by Cellosolve^, carbitol, phenoxy-ethanol, heptylphenyl-(oxypropylene)g-H, octyl-(ocyethylene)^q-H, phenyl-(oxyoctylene)2-H, mono (heptylphenyloxypropylene)-substituted glycerol, polystyrene oxide, aminoethanol, 3 -amino-ethylpentanol, dihydroxyethylamine, p-aminophenol, trihydroxy-propylamine, N-hydroxyethylethylenediamine, N,N,N<1>,N<1->tetra-hydroxytrimethylenediamine and the like. For the most part, the ether alcohols with up to 150 oxyalkylene radicals in which the alkylene radical contains 1-8 carbon atoms are preferred.

The esters can be diesters of succinic acids or acid esters, i.e. partially esterified succinic acids, as well as partially esterified polyhydric alcohols or phenols, i.e. esters with free alcoholic or phenolic hydroxyl radicals. Mixtures of the above-described esters are also intended within the scope of the invention.

The esters can be prepared using one of several methods. The method preferred for convenience and superior properties of the esters it yields involves the reaction of a suitable alcohol or phenol with a substantially hydrocarbon-substituted succinic anhydride. The esterification is usually carried out at a temperature above 100°C, preferably between 150 and 300°C.

The water formed as a by-product is removed by distillation as the esterification takes place. A solvent can be used for the esterification to facilitate the mixing and regulation of the temperature. This also facilitates the removal of water from the reaction mixture. Useful solvents include xylene, toluene, diphenyl ether, chlorobenzene and mineral oil.

A modification of the method described above involves replacing the substituted succinic anhydride with the corresponding succinic acid. However, succinic acids are easily subjected to dehydration at temperatures above 100° C. and are thus converted into their anhydrides which are then esterified by the reaction with the alcohol reactant. In this respect, succinic acids appear to be substantially equivalent to their anhydrides by the method.

The relative proportions of the succinic acid reactant and the hydroxy reactant to be used are largely dependent on the desired product type and on the number of hydroxyl groups present in the hydroxy reactant's molecule. For example, the formation of a half-ester of a succinic acid, i.e. an ester in which only the two acid radicals are esterified, involves the use of 1 mole of a monohydric alcohol per moles of the substituted succinic acid reactant, while the formation of a diester of succinic acid involves the use of two moles of the alcohol for each mole of the acid. On the other hand, 1 mole of a hexavalent alcohol can combine with as many as six moles of a succinic acid to form an ester in which each of the six hydroxyl radicals in the alcohol is esterified with one of the two acid radicals of the succinic acid. The maximum proportion of the succinic acid to be used together with a polyhydric alcohol is thus determined by the number of hydroxyl groups present in the molecule of the hydroxy reactant. For the purposes of the invention, it has been shown that esters obtained by reacting equimolecular amounts of the succinic acid reactant and the hydroxy reactant have superior properties and are therefore preferred.

In some cases, it is advantageous to carry out the esterification in the presence of a catalyst, such as sulfuric acid, pyridine hydrochloride, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, phosphoric acid or any other known esterification catalyst. The amount of catalyst during the reaction can be as little as 0.01% (based on the weight of the reaction mixture), and it is more often 0.1 - 5%.

The esters used according to the invention can also be obtained by reacting a substituted succinic acid or succinic anhydride with an epoxide or a mixture of an epoxide and water. Such a reaction is similar to the reaction involving the acid or anhydride with a glycol. The product can e.g. is produced by the reaction of a substituted succinic acid with one mole of ethylene oxide. In a similar way, the product can be obtained by reacting a substituted succinic acid with two moles of ethylene oxide. Other epoxides commonly available for use in such a reaction include e.g. propylene oxide, styrene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, cyclohexenoxyd, 1,2-octylene oxide, epoxidized soybean oil, methyl ester of 9,10-epoxystearic acid, and butadiene mono-epoxyd. For the most part, the epoxides are made up of the alkylene oxides in which the ethylene radical has 2-8 carbon atoms, or of the epoxidized fatty tree esters in which the fatty acid radical has up to 30 carbon atoms and the ester radical is derived from a lower alcohol with up to 8 carbon atoms.

Instead of the succinic acid or the anhydride, a substituted succinic acid halide can be used in the method described above for producing the esters according to the invention. Such acid halides can be acid dibromides, acid dichlorides, acid monochlorides and acid monobromides. The substituted succinic anhydrides and acids can be prepared, e.g. by reacting maleic anhydride with a high molecular weight olefin or a halogenated hydrocarbon, such as a hydrocarbon formed by chlorination of an olefin polymer as described above. The reaction simply involves heating the reactants to a temperature of preferably 100 - 250° C. The product of such a reaction is alkenyl succinic anhydride. The alkenyl group can be hydrogenated to an alkyl group. The anhydride can be hydrolysed by treatment with water or steam to the corresponding acid. Another method which is applicable for the preparation of the succinic acids or anhydrides involves reacting itaconic anhydride with an olefin or a chlorinated hydrocarbon at a temperature generally in the range of 100 - 250° C. The succinic acid halides can be prepared by reacting the acids or anhydrides thereof with a halogenating agent, such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride. These and other methods for producing the succinic acid compounds are well known in the art and do not need to be further described.

Further other methods for producing the esters according to the invention are available. For example, the esters can be obtained by reacting maleic acid or

anhydride with eh alcohol, as illustrated above, forming a mono- or diester of maleic acid, then reacting this ester with an olefin or a chlorinated hydrocarbon, as illustrated above. They can also be obtained by first esterifying itaconic anhydride or itacic acid and then reacting the ester intermediate with an olefin or a chlorinated hydrocarbon under conditions similar to those described above.

The following specific illustrative examples describe the production of examples of cleaning agent/dispersant that can be used in the materials according to the invention.

Example C-l

A mixture of 906 parts of an oil solution of an alkylphenol sulfonic acid (with an average molecular weight of 450, a vapor phase osmometry), 564 parts of mineral oil, 600 parts of toluene, 98.7 parts of magnesium oxide and 120 parts of water is flushed with carbon dioxide at a temperature of 78 - 85 ° C for 7 hours in a quantity of 84.9 dm carbon dioxide per hour. The reaction mixture is constantly stirred during the carbonation. After the carbonation, the reaction mixture is evaporated to 165° C/20 torr, and the residue is filtered. The filtrate is an oil solution of the desired overbasic magnesium sulphonate with a metal ratio of approx. 3.

Example C- 2

A mixture of 1140 parts mineral oil, 8.3 parts water, 1.3 parts calcium chloride, 136 parts lime and 221 parts methyl alcohol is prepared and heated to a temperature of approx. 50° C. 1000 parts of an alkylbenzenesulphonic acid with an average molecular weight (vapor phase osmometry) of 500 are added to this mixture while stirring. The mixture is then flushed with carbon dioxide at a temperature of 45 - 50° C in a quantity of 2.05 kg per hour for approx. 5 hours. After the carbonation, the mixture is freed of volatile materials at a temperature of 150 - 155° C at a pressure of 50 mm. The residue is filtered, and the filtrate is the desired oil solution of the overbasic calcium sulphonate with a calcium content of approx. 3.05%.

Example C- 3

A polyisobutenyl succinic anhydride is prepared by reacting a chlorinated polyisobutene (with an average chlorine content of 4.3% and an average of 82 carbon atoms) with maleic anhydride at approx. 200° C. The obtained polyisobutenyl succinic anhydride has a saponification number of 90. To a mixture of 1246 parts of this succinic anhydride and 100 parts of toluene, 76.7 parts of barium oxide are added at 25° C. The mixture is heated to 115° C, and 125 parts of water are added drop by drop over the course of 1 hour. The mixture is then heated under reflux at 150° C until all the barium oxide has been reacted. Stripping and filtration gives a filtrate with a barium content of 4.71%.

Example C- 4

A mixture of 1,500 parts of chlorinated polyisobutene (with a molecular weight of approximately 950 and a chlorine content of 5.6%), 285 parts of an alkylene polyamine with an average composition corresponding stoichiometrically to tetraethylenepentamine, and 1,200 parts of benzene is heated to reflux. The temperature of the mixture is then slowly increased over a period of 4 hours to 170°C while the benzene is removed. The cooled mixture is diluted with an equal volume of mixed hexanes and absolute ethanol (1:1). This mixture is heated to reflux, and a 1/3 volume of 10% aqueous sodium carbonate is added to this. After stirring, the mixture is allowed to cool, and the phases are separated. The organic phase is washed with water and stripped to give the desired polyisobutenyl polyamine with a nitrogen content of 4.5%.

Example C- 5

A mixture of 140 parts of toluene and 400 parts of a polyisobutenyl succinic anhydride (prepared from the polyisobutene with a molecular weight of about 850, vapor phase osmometry. with a saponification number of 109 and 63.6 parts of an ethyleneamine mixture with an average composition corresponding stoichiometrically to tetraethylenepentamine is heated to 150° C. while the water/toluene azeotrope is removed. The reaction mixture is then heated to 150° C. under reduced pressure until toluene ceases to distill off. The acylated polyamine obtained has a nitrogen content of 4.7%.

Example C- 6

To 1133 parts of commercially available diethylenetriamine heated to 110 - 150° C, 6820 parts of isostearic acid are added slowly over the course of 2 hours. The mixture is held at 150° C. for 1 hour and then heated to 180° C. for a further 1 hour. Finally, the mixture is heated to 205° C. for 0.5 hour. Throughout this heating, the mixture is flushed with nitrogen to remove volatile constituents. The mixture is held at 205-230°C for a total time of 11.5 hours and then stripped at 230°C/20 torr to give the desired acylated polyamine as a residue containing 6.2% nitrogen.

Example C- 7

To a mixture of 50 parts of a polypropyl-substituted phenol (with a molecular weight of about 900, vapor phase osmometry), 500 parts of mineral oil (a solvent-refined paraffinic oil with a viscosity of 100 SUS at 37.8°C) and 130 parts 9.5% aqueous dimethylamine solution (equivalent to 12 parts amine) is added dropwise over the course of 1 hour 2 2 parts of a 37% aqueous solution of formaldehyde (equivalent to 8 parts aldehyde). During the addition, the reaction temperature is slowly increased to 100° C. and held at this temperature for 3 hours while the mixture is flushed with nitrogen. 100 parts of toluene and 50 parts of mixed butyl alcohols are added to the cooled reaction mixture. The organic phase is washed three times with water until it is neutral to litmus paper, and the organic phase is filtered and stripped at 200° C/5 - 10 torr. The rest is an oil solution of the final product containing 0.45% nitrogen.

Example C- 8

A mixture of 140 parts of a mineral oil, 174 parts of a polyisotuene (molecular weight 1000)-substituted succinic anhydride with a saponification number of 105 and 23 parts of isostearic acid is prepared at 90° C. To this mixture is added 17.6 parts of a mixture of polyalkylene amines with an overall composition corresponding to the composition for tetraethylenepentamine, at 80 - 100° C during a period of 1.3 hours. The reaction is exothermic. The mixture is flushed at 22 5° C with nitrogen in a quantity of 2.25 kg per hour for 3 hours, after which 47 parts of an aqueous distillate are obtained. The mixture is dried for 1 hour at 225° C., cooled to 100° C. and filtered to give the desired end product in an oil solution.

Example C-9

An essentially hydrocarbon-substituted succinic anhydride is produced by chlorinating a polyisobutene with a molecular weight of 1000 to a chlorine content of 4.5%, after which the chlorinated polyisobutene is heated with 1.2 molar portions of maleic anhydride at a temperature of 150 - 220°C.

The succinic anhydride thus obtained has an acid number of 130. A mixture of 874 g (1 mol) of the succinic anhydride and 104 g

(1 mol) neopentyl glycol is mixed for 12 hours at 240 - 250° C/ 30 mm. The rest is a mixture of the esters which have been formed by the esterification of one or both of the glycol's hydroxyl radicals. It has a saponification number of 101 and an alcoholic hydroxyl content of 0.2%.

Example C- 10

The dimethyl ester of the substantially hydrocarbon-substituted succinic anhydride according to Example 1 is prepared by heating a mixture of 2185 g of the anhydride, 4 80 g of methanol and 1000 cm^ of toluene at 50 - 65° C while hydrogen chloride is bubbled through the reaction mixture for 3 hours. The mixture is then heated for 2 hours at 50-65°C, dissolved in benzene, washed with water, dried and filtered. The filtrate is heated at 150° C/60 mm to free it of volatile components. The remainder is the defined dimethyl ester.

Example C-ll

A carboxylic acid ester is prepared by slowly adding 3240 parts of a high molecular weight carboxylic acid (prepared by reacting chlorinated polyisobutylene and acrylic acid in an equivalent ratio of 1:1 and having an average molecular weight of 982) to a mixture of 200 parts sorbitol and 1000 parts diluent oil over a period of 1.5 hours while maintaining a temperature of 115 - 125°C. Then 400 parts of additional diluent oil are added, and the mixture is held at 195 - 205° C. for 16 hours while the mixture is flushed with nitrogen. A further 755 parts of oil are then added and the mixture cooled to 140°C and filtered. The filtrate is an oil solution of the desired ester.

Example C- 12

An ester is prepared by heating 658 parts of a carboxylic acid with an average molecular weight of 1018 (prepared by reacting chlorinated polyisobutene with acrylic acid) with 22 parts of pentaerythritol while a temperature of 180 - 205°C is maintained for approx. 18 hours during which time nitrogen is blown through the mixture. The mixture is then filtered, and the filtrate is the desired ester.

Example C- 13

To a mixture comprising 408 parts of pentaerythritol and 1100 parts of oil heated to 120° C, 2946 parts of the acid according to Example B-9 which has been preheated to 120° C, 225 parts of xylene and 95 parts of diethylene glycol dimethyl ether are slowly added. The resulting mixture is heated at 195-205° C. under a nitrogen atmosphere and under reflux conditions for 11 hours, stripped to 140° C. at a pressure of 22 mm (Hg) and filtered. The filtrate comprises the desired ester. It is diluted to a total oil content of 40%.

Example C- 14

To 205 parts commercially available tetraethylenepentamine heated to approx. 75° C, 1000 parts of isostearic acid are added while flushing with nitrogen, and the mixture's temperature is maintained at 75 - 110° C. The mixture is then heated to 220° C and held at this temperature until the mixture's acid number is less than 10. After cooling to approx. 150° C, the mixture is filtered, and the filtrate is the desired acylated polyamine with a nitrogen content of approx. 5.9%.

As mentioned above, the present invention relates to materials comprising (a) at least one alkylphenol and (b) at least one aminophenol as defined above. According to a preferred embodiment, the weight ratio between (a) and (b) is 9:1 - 1:9. According to another preferred embodiment, the materials according to the invention also contain at least one cleaning agent/dispersant of the type described above. When incorporated into the material, the amount of cleaning agent/dispersant present can vary within a wide range,

and the weight ratio between the combination of alkylphenol and aminophenol and the total amount of cleaning agent/dispersant is generally within the range of 1:10 - 10:1.

The present invention also relates to lubricants and lubricating fuels for two-stroke engines and containing the above-defined alkylphenol compounds (a) and aminophenol compounds (b) and possibly the cleaning agents/dispersants, (c). The lubricants used for two-stroke engines will comprise a substantial amount by weight of at least one oil of lubricating viscosity and a minor amount, sufficient to control piston ring attachment and to promote general engine cleanliness, of at least one alkylphenol and at least one aminophenol as defined above . The lubricants will optionally and preferably also contain a cleaning agent/dispersant (c) as defined above.

Oil with lubricating viscosity

The lubricants according to the invention comprise a main quantity of oil with lubricating viscosity and which can be based on natural or synthetic oils or mixtures thereof. This viscosity is typically within the range 2.0 - 150 cSt at 19.9°C, more typically within the range 5.0 - 130 cSt at 98.9°C.

These lubricants include crankcase lubricating oils for internal spark ignition and compression ignition combustion engines, such as car and truck engines and marine diesel engines and railway diesel engines, etc. Automatic transmission fluids, transmission shaft lubricants, gear lubricants, metalworking lubricants, hydraulic fluids and other lubricating oils and fat mixtures can also benefit from the incorporation in these of the alkylphenol-aminophenol materials according to the invention. A preferred application of the materials according to the invention is in oil mixtures for two-stroke engines.

Natural oils include mineral lubricating oils, such as liquid petroleum oils and solution treated or acid treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils with lubricating viscosity that are derived from coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils and halogen-substituted hydrocarbon oils, such as polymerized and copolymerized olefins (eg polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes etc), poly-l-hexenes, poly-l-octenes, poly-1- decenes etc and mixtures thereof, alkylbenzenes (eg dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexylbenzenes etc), polyphenyls (eg biphenyls, terphenyls, alkylated polyphenyls etc), alkylated diphenyl ethers and alkylated diphenyl sulphides and derivatives, the analogues and homologues thereof and the like.

Oils produced by polymerizing olefins with less than 5 carbon atoms, such as ethylene, propylene, butylenes, isobutene, pentene and mixtures thereof, are typical synthetic polymeric oils. Manufacturing methods for such polymer oils are well known to those skilled in the art, as shown in US patents 2,278,445, 2,301,052, 2,318,719, 2,329,714, 2,345,574 and

2,422,443-

Alkylene oxide polymers (i.e. homopolymers, copolymers and derivatives thereof in which the end hydroxyl groups have been modified by esterification, etherification, etc.) form a preferred group of known synthetic lubricating oils for the purpose according to the invention, especially for use with alkanol fuels. They can be exemplified by the oils produced by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkyl. a polymer (e.g. methyl polypropylene glycol ether with an average molecular weight of 1000, diphenyl ether of polyethylene glycol with a molecular weight of 500 - 1000, diethyl ether of polypropylene glycol with a molecular weight of 1000 - 1500 etc.) or mono-

and piDlycarboxylates thereof, e.g. the acetic acid esters, mixed C^-Cg fatty acid esters or the C-^-oxo acid diester of tetraethylene glycol.

Another suitable group of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkylsuccinic acids, alkenylsuccinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenylmalonic acids, etc.) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di-2-ethylhexyl sebacate, di-n-hexyl fumarate, dioctyl sebacate, diiso-octyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reaction of one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.

Esters which can be used as synthetic oils also include those made from C-2 monocarboxylic acids and polyols and polyol ethers, such as neopentylglycol, trimethylol-propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

Silicone-based oils, such as polyalkyl, polyaryl, polyalkyloxy, or polyaryloxysiloxane oils, and silica oils comprise another useful group of synthetic lubricants (eg, tetraethylsilicate, tetraisopropylsilicate, tetra-2-ethylhexylsilicate, tetra-4-methylhexylsilicate, tetra-p- tert.butylphenylsilicate, hexyl-4-methyl-2-pentoxydisiloxane, polymethylsiloxanes, polymethylphenylsiloxanes etc). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid etc), polymeric tetrahydrofurans and the like.

Unrefined, refined and re-refined oils, either natural or synthetic (as well as mixtures of two or more or any of these), of the type described above, can be used in the lubricants according to the invention. Unrefined oils are those obtained directly from a natural or synthetic raw material without further purification treatment. For example, a shale oil obtained directly from retort processing, a petroleum oil obtained directly from primary distillation or an ester oil obtained directly from an esterification process and used without further processing will be a crude oil. Refined oils are similar to unrefined oils except that they have been further processed in one or more purification steps to improve one or more properties. A number of such purification methods are known to those skilled in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Newly refined oils are obtained by similar processes to those used to obtain refined oils, and used for refined oils that have already been used. Such newly refined oils are also known as regenerated oils or reprocess oils and are often further processed using methods that involve removing used additives and products from the breakdown of the oils.

The amount of materials according to the invention incorporated into the two-stroke engine oil will be a sufficient amount to control piston ring seizing and promote general engine cleanliness. The mixtures according to the invention contain from 1 to 30%, typically 5-20%, of a mixture of at least one alkylphenol compound (A) as described above, and 1-30%, typically 2-20%, of at least one cleaning agent/dispersant (C). The weight ratio between the combined alkyl and aminophenols and cleaning agent/dispersant in these oils varies between 1:10 and 10:1. Other additive media, such as viscosity index (VI) improvers, lubricity agents, antioxidants, coupling agents, pour point depressants, extreme pressure agents, color stabilizers, and antifoams, may also be present.

Polymeric improvers VI have been and are used as "bright stock" substitutes to improve lubricating film strength and lubricity and/or to improve engine cleanliness. Dye can be used for identification purposes and to indicate whether a two-stroke fuel contains a lubricant. Coupling agents, such as organic surface-active agents, are incorporated into some products to provide better solubility for the components and improved tolerance to water in the fuel/lubricant.

Anti-wear and lubricity improvers, especially sulphurised sperm oil substitutes and other fatty acid and vegetable oils, such as castor oil, are used for special purposes, such as for racing and for very high fuel/lubricant ratios. Scraping agents or agents to modify deposits in the combustion chamber are sometimes used to provide improved spark plug life and to remove carbon deposits. Halogenated compounds and/or phosphorus-containing materials can be used for this purpose.

Rust and corrosion inhibitors of all types are and can be incorporated into two-stroke oil mixtures. Fragrances or deodorants are sometimes used for aesthetic reasons.

Lubricants, such as synthetic polymers (e.g. polyisobutene with a number average molecular weight of 750 - 15,000 (as measured by vapor phase osmometry or gel permeation chromatography), polyol ethers (e.g. polyoxyethylene-oxypropylene ether) and ester oils (e.g. those ester oils described above) can also be used in the oil mixtures according to the invention. Natural oil fractions, such as "bright stocks"

(the relatively viscous products that are formed during the normal production of lubricating oils from petroleum) can also be used for this purpose. They are usually present in the two-stroke oil in an amount of 3 - 20% of the total mixture.

Diluents, such as petroleum naphthas which boil within the range 30 - 90° C (e.g. Stoddard solvent), can also be incorporated into the oil mixtures according to the invention, typically in an amount of 5 - 25%.

In Table C, several examples of oil lubricants according to the invention for two-stroke engines are described.

In some two-stroke engines, the lubricating oil can be injected directly into the combustion chamber together with the fuel or into the fuel just before the time the fuel enters the combustion chamber. The two-stroke lubricants according to the invention can be used in this type of engine.

It is well known to those skilled in the art that lubricating oils for two-stroke engines are often added directly to the fuel to form a mixture of oil and fuel which is then introduced into the engine cylinder. Such lubricant/fuel oil mixtures are within the scope of the invention. Such lubricant/fuel mixtures generally contain 15 - 250 parts of fuel per part oil, typically 25 - 100 fuel per part oil.

The fuels used in two-stroke engines are well known to those skilled in the art and usually contain a substantial portion of a normal liquid fuel, such as a hydrocarbon-like petroleum distillate fuel (eg, motor gasoline as defined in ASTM Specification D-439-73). Such fuels can also contain non-hydrocarbon-like materials, such as alcohols, ethers, organonitro compounds and the like (e.g. methanol, ethanol, diethylether, methylethylether, nitromethane) and are also within the scope of the invention in the same way as liquid fuels which are derived from vegetable or mineral raw materials, such as corn, alfalfa, shale and coal. Examples of such fuel mixtures are combinations of petrol and ethanol, diesel fuel and ether, petrol and nitromethane etc. Petrol is particularly preferred, i.e. a mixture of hydrocarbons with a boiling point according to ASTM of 60° C at 10% the distillation point to 205° C at 90% distillation point.

Two-stroke fuels also contain other additives well known to those skilled in the art. These may include anti-knock agents, such as tetraalkyl lead compounds, lead cleaning agents, such as haloalkanes (e.g. ethylene dichloro and ethylene dibromide), dyes, cetane improvers, antioxidants such as 2,6-di-tert.butyl-4-methylphenol, rust inhibitors, such as alkylated succinic acids and succinic anhydrides, bacteriostatic agents, rubber inhibiting agents, metal deactivators, demulsifiers, lubricants for the upper cylinder part, anti-icing agents and the like. The invention is applicable in connection with both lead-free and lead-containing fuels.

An example of a lubricant fuel mixture covered by the invention is a mixture of motor petrol and the lubricant mixture described above in Example 2, in a ratio (based on weight) of 50 parts petrol to 1 part lubricant.

Concentrates containing the materials according to the invention are also within the scope of the invention. These concentrates usually comprise 20 - 80% of one or more of the oils described above and 20 - 80% of a mixture of one or more alkylphenols and one or more aminophenols with and without the cleaning agent/dispersants. The person skilled in the art will easily understand that such concentrates can also contain one or more of the various types of auxiliary additives described above. Representative of these concentrates according to the invention are the following:

Example 6 (concentrate)

A concentrate for treating two-stroke engine oils is prepared by mixing at room temperature 35 parts of the oil solution described in Example A-I with 65 parts of the oil solution described in Example B-i.

Example 7- (concentrate)

A concentrate for treating two-stroke engine oils is prepared by mixing at room temperature 25 parts of the oil solution according to Example A-I with 50 parts of the oil solution according to Example B-1 and 25 parts of Example C-14.

Claims (17)

1. A mixture, characterized in that it comprises the combination of (A) at least one alkylphenol with the formula: (B) at least one aminophenol with the formula: wherein each R is independently a substantially saturated (hydrocarbon-based group having an average of at least 10 aliphatic carbon atoms, a, b and c are each independently an integer of from one and up to three times the number of aromatic nuclei present in Ar, below the provided that the sum of a, b and c does not exceed the unsatisfied valences of Ar, and each Ar is independently a single ring, a fused or a fused polynuclear ring aromatic moiety having from 0 to 3 optional substituents selected from lower alkyl, lower alkoxyl, carboalkoxymethylol or lower hydrocarbon-based substituted methylol, nitro, nitroso, halogen and combinations of two or more of the aforementioned optional substituents. 2. A mixture according to claim 1, characterized in that each R is a hydrocarbyl substituent. 3. A mixture according to claim 2, characterized in that R is alkyl or alkenyl. 4. A mixture according to claims 1-3, characterized in that a and bi (A) are each 1. 5. A mixture according to claims 1-4, characterized in that the weight ratio between (A) and (B) is 9:1 - 1:9. 6. A mixture according to claim 1, characterized in that the alkylphenol compound (A) is an alkylated phenol with the formula wherein R" is a substantially saturated hydrocarbon-based substituent of 30-400 aliphatic carbon atoms, R" is a member selected from lower alkyl, lower alkoxyl, carboxy-alkoxy methylol or lower hydrocarbon-based substituted methylol, nitro, nitroso and halogen, and z is from 0 to 2. 7. A mixture according to claim 6, characterized in that R' is a purely aliphatic hydrocarbyl group with at least 50 carbon atoms and derived from a polymer or copolymer of an olefin selected from C2-C4Q-1 monoolefins and mixtures thereof. 8. A mixture according to claim 1 or 6, characterized in that the aminophenol (B) has the formula wherein R' is a substantially saturated hydrocarbon-based substituent having an average of 30-400 aliphatic carbon atoms, R" is selected from lower alkyl, lower alkoxyl, carboalkyloxynitro, nitroso and halogen, and z is 0 or 1. 9. A mixture according to claim 8, characterized in that R' is a purely aliphatic hydrocarbyl group with at least 50 carbon atoms and is made from a polymer or copolymer of an olefin selected from C2_10-1-monoolefins and mixtures thereof. 10. A mixture, characterized in that it comprises the combination of (A) at least one alkylphenol with the formula (B) at least one aminophenol with the formula wherein each R is independently a substantially saturated hydrocarbon-based group averaging at least 10 aliphatic carbon atoms, a, b and c are each independently an integer of from one up to three times the number of aromatic nuclei present in Ar, provided that the sum of a, b and c does not exceed the unsatisfied valences of Ar, and each Ar is independently a single ring, a fused or a fused polynuclear ring aromatic moiety with from 0 to 3 optional substituents selected from lower alkyl, lower alkoxyl, nitro, nitroso , halogen and combinations of two or more of the optional substituents. 11. A mixture, characterized in that it comprises the combination of (A) at least one alkylated phenol of the formula wherein R' is an essentially saturated hydrocarbon-based substituent with an average of from 10 to 400 aliphatic carbon atoms, R" is selected from lower alkyl, lower alkoxyl, nitro, nitroso and halogen, and z is from 0 to 2, and (B)at least one aminophenol of the formula wherein R' is a substantially saturated hydrocarbon-based substituent having an average of from 30 to 400 aliphatic carbon atoms, R" is a member selected from the group consisting of lower alkyl, lower alkoxyl, nitro, nitroso and halogen, and z is 0 or 1. 12. A mixture according to claims 1-11, characterized in that it also contains (C) at least one cleaning agent/dispersant selected from i, at least one neutral or basic metal salt of a organic sulfuric acid, phenol or carboxylic acid, ii. at least one hydrocarbyl substituted amine wherein the hydrocarbyl substituent is essentially aliphatic and contains at least 12 carbon atoms, lii. at least one acylated, nitrogenous compound with a substituent of at least 10 aliphatic carbon atoms prepared by reacting a carboxylic agent with at least one amino compound containing at least one -NH group, the acylating agent being attached to the amino compound via an imido, amido, amidine or acyloxyammonium bond, iv. at least one nitrogenous condensate of a phenol, aldehyde and amino compound with at least one -NH group, and v. at least one ester of a substituted polycarboxylic acid. 13. A mixture according to claim 12, characterized in that the cleaning agent/dispersant is (iii) at least one acylated nitrogenous compound which has a substituent with at least 10 aliphatic carbon atoms and is produced by reacting a carboxylic acylating agent with at least one amino compound containing at least one -NH group, the acylating agent being bound to the amino compound via an imido, amido, amidine or acyloxy-ammonium bond. 14. Additive concentrate for use in normally liquid fuels or lubricating oils with lubricating viscosity, characterized in that it comprises an essentially inert solvent/diluent and 30-90% by weight of a mixture according to claims 1-13. 15. A lubricating mixture for two-stroke engines, characterized in that it comprises an essentially weight amount of at least one oil of lubricating viscosity and a smaller amount, sufficient to control piston-ring attachment and to promote general engine cleanliness, of a mixture according to claim 1 -13. 16. Procedure for lubricating a two-stroke internal combustion engine, characterized in that it comprises the use of a lubricant mixture according to claim 15. 17. A lubricant-fuel mixture for use in two-stroke internal combustion engines, characterized in that the lubricant is the mixture according to claim 15.