GB2116583A - Lubricant and fuel additives containing aminophenols - Google Patents

Abstract

Additives for lubricants and fuels comprise an amino phenol of formula <IMAGE> where R is a substantially saturated hydrocarbon-based substituent of at least C8 aliphatic atoms a, b and c are 1 to 3 times the number of aromatic nuclei in Ar and Ar is an aromatic group which may be substituted with 0-3 alkyl, alkoxy, nitro or halo with (I) A carboxylic derivative which may be post-treated and is produced by reacting a succinic acylating agent with an (a) amine, (b) alcohol, and/or (c) reactive metal or reactive metal compounds, where said agent consists of substituent groups derived from a polyalkene, which has a Mn of 1,200 to 5,000 and a Mw/Mn of 1.5 to 6, and succinic groups and has an average of at least 1.3 succinic groups for each equivalent weight of substituent groups, and/or (II) A chlorine-containing compound which is a chloroaliphatic hydrocarbon-based compound and/or a chloroalicyclic hydrocarbon-based compounds; and optionally (III) a sulfurized olefinically unsaturated compound.

Description

SPECIFICATION Additive compositions containing aminophenol combinations useful as lubricant and fuel additives Field of the invention This invention relates to nitrogen-containing organic compositions. These compositions are useful as lubricant and fuel additives. Additionally, this invention relates to concentrates of these compositions and to lubricant and fuel compositions comprising these compositions. This invention also relates to a method for operating an internal combustion engine by lubricating said engine during operation with these lubricating compositions.

Summary of the invention A principal object of the present invention is to provide novel nitrogen-containing organic compositions.

Another principal object of the present invention is to provide novel nitrogen-containing organic compositions which impart to lubricants and fuels one or more of the following properties: detergent, dispersant, antioxidant, anticorrosive, antiwear, friction reducing and fluidity modifying properties.

Another object is to provide novel concentrates comprising these novel nitrogen-containing organic compositions.

Still another object is to provide novel lubricant and fuel compositions containing these novel nitrogen-containing organic compositions.

An additional object is to provide a method for lubricating an internal combustion engine which comprises lubricating said engine during operation with these novel lubricating compositions.

These and other objects of the invention are accomplished by providing a nitrogen-containing organic composition comprising a combination of: (A) at least one amino phenol of the general formula

wherein R is a substantially saturated, hydrocarbon-based substituent of at least 8 aliphatic carbon atoms; a, b and c are each independently an integer of one up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic moiety having 0--3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, halo or combinations of two or more of said substituents; and (B) one or more carboxylic derivative compositions produced by reacting at least one substituted succinic acylating agent with a reactant selected from the group consisting of (a) of amine characterized by the presence within its structure of at least one H-N = group, (b) an alcohol, (c) a reactive metal or reactive metal compound, and (d) a combination of two or more of any of (a) through (c), the components of (d) being reacted with said one or more substituted succinic acylating agents simultaneously or sequentially in any order, wherein said substituted succinic acylating agents consist of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene, said polyalkene being characterized by a Mn value of 1200 to about 5000 and a Mw/Mn value of about 1.5 to about 6, said acylating agents being characterized by the presence within their structure of an average of at least 1.3 succinic groups for each equivalent weight of substitutent groups.

One or more objects of this invention are also accomplished by providing a nitrogen-containing organic composition comprising a combination of (A) and (B) wherein, said (B) is a post-treated carboxylic derivative composition prepared by reacting one or more post-treating reagents with said one or more carboxylic derivative composition.

One or more objects of this invention are also accomplished by providing compositions wherein the nitrogen-containing compositions mentioned hereinabove and described in detail hereinafter are further combined with (C) at least one chlorine-containing compound selected from the group consisting of chloroaliphatic hydrocarbon-based compounds, chloroalicyclic hydrocarbon-based compounds or mixtures thereof.

One ore more objects of this invention are also accomplished by providing a nitrogen-containing organic composition comprising a combination of: (a) at least one amino phenol of the general formula

wherein R is a substantially saturated, hydrocarbon-based substituent of at least 8 aliphatic carbon atoms; a, b and c are each independently an integer of one up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic moiety having 0--3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, halo or combinations of two or more of said substituents; and (C) at least one chlorine-containing compound selected from the group consisting of chloroaliphatic hydrocarbon-based compounds, chloroalicyclic hydrocarbon-based compounds or mixtures thereof.

One ore more objects of this invention can be accomplished by providing compositions wherein the nitrogen-containing composition comprising a combination of (A) and (C) as mentioned hereinabove and described in detail hereinafter are further combined with at least one sulfurized olefinically unsaturated compound.

Detailed description of the invention (A) The amino phenol.

The aromatic moiety Ar The amino phenols useful for the purposes of this invention are of the general formula

The aromatic moiety, Ar, 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; that is, wherein at least one aromatic nucleus is fused at two points to another nucleus such as found in naphthalene, anthracene, the azanaphthalenes, etc. Alternatively, such polynuclear aromatic moieties can be of the linked type wherein at least two nuclei (either mono-or polynuclear) are linked through bridging linkages to each other.Such bridging linkages can be chosen from the group consisting of carbon-to-carbon single bonds, ether linkages, keto linkages, sulfide linkages, polysulfide linkages of 2 to 6 sulfur atoms, sulfinyl linkages, sulfonyl linkages, methylene linkages, alkylene linkages, di-(lower alkyl)methylene linkages, lower alkylene ether linkages, alkylene keto linkages, lower alkylene sulfur linkages, lower alkylene polysulfide linkages of 2 to 6 carbon atoms, amino linkages, polyamino linkages and mixtures of such divalent bridging linkages. In certain instances, more than one bridging linkage can be present in Ar between aromatic nuclei. For example, a fluorene nucleus has two benzene nuclei linked by both a methylene linkage and a covalent bond. Such a nucleus may be considered to have 3 nuclei but only two of them are aromatic.Normally, however, Ar will contain only carbon atoms in the aromatic nuclei per se (plus any lower alkyl or alkoxy substituent present).

The number of aromatic nuclei, fused, linked or both, in Ar can play a role in determining the integer values of a, b and c in Formula I. For example, when Ar contains a single aromatic nucleus, a, b and c are each independently 1 to 3. When Ar contains two aromatic nuclei, a, b and c can each be an integer of 1 to 6, that is, up to three times the number of aromatic nuclei present (in naphthalene, 2).

With a tri-nuclear Ar moieity, a, b and c can each be an integer of 1 to 9. For example, when Ar is a biphenyl or a naphthyl moiety, a, b and c can each independently be an integer of 1 to 6. The values of a, b and c are obviously limited by the fact that their sum cannot exceed the total unsatisifed valences of Ar, that is, the sum of a, b and c cannot exceed the number of carbon atoms in the aromatic moiety (Ar) that would otherwise be bonded to a hydrogen.

The single ring aromatic nucleus which can be the Ar moiety can be represented by the general formula ar(Q)m wherein ar represents a single ring aromatic nucleus (e.g., benzene) of 4 to 10 carbons, each Q independently represents a lower alkyl group, lower alkoxy group, nitro group, or halogen atom, and m is O to 3. As used in this specification and appended claims, "lower" refers to groups having 7 or less carbon atoms such as lower alkyl and lower alkoxyl groups. Halogen atoms include fluorine, chlorine, bromine and iodine atoms; usually, the halogen atoms are fluorine and chlorine atoms.

Specific examples of single ring Ar moieties are the following:

wherein Me is methyl, Et is ethyl, Pr is n-propyl, and Nit is nitro.

When Ar is a polynuclear fused-ring aromatic moiety, it can be represented by the general formula

wherein ar, Q and m are as defined hereinabove, m' is 1 to 4 and 2 represents a pair of fusing bonds fusing two rings so as to make two carbon atoms part of the rings of each of two adjacent rings.

Specific examples of fused ring aromatic moieties Ar are: etc.

When the aromatic moiety Ar is a linked polynuclear aromatic moiety it can be represented by the general formula ar-(-Lng--ar-)w(Q)mw wherein w is an integer of 1 to about 20, ar is as described above with the proviso that there are at least 3 unsatisfied (i.e., free) valences in the total of ar groups, Q and m are as defined hereinbefore, and each Lng is a bridging linkage individually chosen from the group consisting of carbon-to-carbon single bonds, ether linkages (e.g. -0-), keto linkages

sulfide linkages (e.g., -S-), polysulfide linkages of 2 to 6 sulfur atoms (e.g., --2-8), sulfinyl linkages (e.g., -S(O)-), sulfonyl linkages (e.g., -S(O)2-), lower alkylene linkages (e.g., CH2-,-CH2- CH2-,

di(lower alkyl)methylene linkages (e.g., CR02-), lower alkylene ether linkages (e.g., -CH2O-, -CH2O-CH2-,-CH2-CH2O-,-CH2CH2OCH2CH2-,

etc.), lower alkylene sulfide linkages (e.g, wherein one or more --O--'s in the lower alkylene ether linkages is replaced with an -S- atom), lower alkylene polysulfide linkages (e.g., wherein one or more --OO-'s is replaced with a --S2-6 group), amino linkages (e.g.,

where alk is lower alkylene, etc.), polyamino linkages (e.g.,

where the unsatisifed free N valences are taken up with H atoms or R0 groups), and mixtures of such bridging linkages (each R0 being a lower alkyl group). It is also possible that one or more of the ar groups in the above-linked aromatic moiety can be replaced by fused nuclei such as ar 4 ar Specific examples of linked moieties are:

Usually all these Ar moieties are unsubstituted except for the R, -OH and -NH2 groups (and any bridging groups).

For such reasons as cost, availability, performance, etc., the Ar moiety is normally a benzene nucleus, lower alkylene bridged benzene, nucleus, or a naphthalene nucleus. Thus, a typical Ar moiety is a benzene or naphthalene nucleus having 3 to 5 unsatisfied valences, so that one or two of said valences may be satisfied by a hydroxyl group with the remaining unsatisfied valences being, insofar as possible, either ortho or para to a hydroxyl group. Preferably, Ar is a benzene nucleus having at least 3 unsatisfied valences so that one can be satisfied by a hydroxyl group with the remaining 2 or 3 being either ortho or para to the hydroxyl group.

The substantially saturated hydrocarbon-based group R The amino phenols of the present invention contain, directly bonded to the aromatic moiety Ar, a substantially saturated monovalent hydrocarbon-based group R of at least about 8 aliphatic carbon atoms. This R group can have up to about 750 aliphatic carbon atoms. More than one such group can be present, but usually, no more than 2 or 3 such groups are present for each aromatic nucleus in the aromatic moiety Ar. The total number of R groups present is indicated by the value for "a" in generic formula used to represent the amino phenols useful in the present invention. Usually, the hydrocarbonbased group has at least about 30, more typically, at least about 50 aliphatic carbon atoms and up to about 750, more typically, up to about 400 aliphatic carbon atoms.

Generally, the hydrocarbon-based groups R are made from homo- or interpolymers (e.g., copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1 -hexene, 1 -octene, etc. Typically, these olefins are 1-monoolefins such as homopolymers of ethylene. The R groups can be derived from the halogenated (e.g., chlorinated or brominated) analogs of such homo- or interpolymers.The R groups can, however, be made from other sources, such as monomeric high molecular weight alkenes (e.g., 1tetracontene) and chlorinated analogs and hydrochlorinated analogs thereof, aliphatic petroleum fractions, particlarly paraffin waxes and cracked and chlorinated analogs and hydrochlorinated analogs thereof, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (e.g., poly(ethylene) greases) and other sources known to those skilled in the art. Any unsaturation in the R groups may be reduced or eliminated by hydrogenation according to procedures known in the art before the nitration step described hereafter.

As used herein, the term "hydrocarbon-based" denotes a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character within the context of this invention. Therefore, hydrocarbon-based groups can contain up to one nonhydrocarbon radical for every ten carbon atoms provided this non-hydrocarbon radical does not significantly alter the predominantly hydrocarbon character of the group. Those skilled in the art will be aware of such radicals, which include, for example, hydroxyl, halo (especially chloro and fluoro), alkoxyl, alkyl mercapto, alkyl sulfoxy, etc. Usually, however, the hydrocarbon-based groups R are purely hydrocarbyl and contain no such non-hydrocarbyl radicals.

The hydrocarbon-based groups R are substantially saturated. By substantially saturated it is meant that the group contains no more than one carbon-to-carbon unsaturated bond for every ten carbon-to-carbon single bonds present. Usually, they contain no more than one carbon-to-carbon nonaromatic unsaturated bond for every 50 carbon-to-carbon bonds present.

The hydrocarbon-based groups of the amino phenols of this invention are also substantially aliphatic in nature, that is, they contain no more than one non-aliphatic moiety (cycloalkyl, cycloalkenyl or aromatic) group of six or less carbon atoms for every ten carbon atoms in the R group. Usually, however, the R groups contain no more than one such non-aliphatic group for every fifty carbon atoms, and in many cases, they contain no such non-aliphatic groups at all; that is, the typical R groups are purely aliphatic. Typically, these purely aliphatic R groups are alkyl or alkenyl groups.

Specific examples of the substantially saturated hydrocarbon-based R groups are the following: a tetra(propylene) group a tri(isobutene) group a tetracontanyl group a henpentacontanyl group a mixture of poly(ethylene/propylene) groups of about 35 to about 70 carbon atoms a mixture of the oxidatively or mechanically degraded poly(ethylene/propylene) groups of about 35 to about 70 carbon atoms a mixture of poly(propylene/1 -hexene) groups of about 80 to about 150 carbon atoms a mixture of poly(isobutene) groups having between 20 and 32 carbon atoms a mixture of poly(isobutene) groups having an average of 50 to 75 carbon atoms A preferred source of the group R are poly(isobutene)s obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75 weight percent and isobutene content of 15 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than 50% of total repeating units) isobutene repeating units of the configuration

The attachment of the hydrocarbon-based group R to the aromatic moiety Ar of the amino phenols of this invention can be accomplished by a number of techniques well known to those skilled in the art. One particularly suitable technique is the Friedel-Crafts reaction, wherein an olefin (e.g., a polymer containing an olefinic bond), or halogenated or hydrohalogenated analog thereof, is reacted with a phenol. The reaction occurs in the presence of a Lewis acid catalyst (e.g., 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 those skilled in the art. See, for example, the discussion in the article entitled, "Alkylation of Phenols" in "Kirk Othmer Encyclopedia of Chemical Technology", Second Edition, Vol. 1, pages 894~895, Interscience Publishers, a division of John Wiley and Company, N.Y., 1 963. Other equally appropriate and convenient techniques for attaching the hydrocarbon-based group R to the aromatic moiety Ar will occur readily to those skilled in the art.

The amino phenols of this invention contain at least one of each of the following substituents: a hydroxyl group, an R group as defined above, and a primary amine group, -NH2. Each of the foregoing groups must be attached to a carbon atom which is a part of an aromatic nucleus in the Ar moiety.

They need not, however, each be attached to the same aromatic ring if more than one aromatic nucleus is present in the Ar moiety.

In a preferred embodiment, the amino phenols of this invention contain one each of the foregoing substituents (i.e., a, b and c are each 1) and but a single aromatic ring, most preferably benzene. This preferred class of amino phenols can be represented by the formula

wherein the R' group is a substantially saturated hydrocarbon-based group of about 30 to about 400 aliphatic carbon atoms located ortho or para to the hydroxyl group, R" is a lower alkyl, lower alkoxyl, nitro group or halogen atom and z is O or 1. Usually z is 0 and R' is a substantially saturated, purely hydrocarbyl aliphatic group. Often R' is an alkyl or alkenyl group para to the -OH substituent. Often there is but one amino group, -NH2, in these preferred amino phenols but there can be two.

In a still more preferred embodiment of this invention, the amino phenol is of the formula

wherein R' is derived from homopolymerized or interpolymerized C2#10 1-olefins and has an average of from about 30 to about 400 aliphatic carbon atoms and R" and z are as defined above. Usually R' is derived from ethylene, propylene, butylene and mixtures thereof. Typically, it is derived from polymerized isobutene. Often R' has at least about 50 aliphatic carbon atoms and z is 0.

The amino phenols of the present invention can be prepared by a number of synthetic routes.

These routes can vary in teh type reactions used and the sequence in which they are employed. For example, an aromatic hydrocarbon, such as benzene, can be alkylated with an alkylating agent such as a polymeric olefin to form an alkylated aromatic intermediate. This intermediate can then be nitrated, for example, 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 or the amino groups into a hydroxyl group and provide the desired amino phenol. Alternatively, one of the nitro groups in the polynitro intermediate can be converted to a hydroxyl group through fusion with caustic to provide a hydroxy-nitro alkylated aromatic which can then be reduced to provide the desired amino phenol.

Another useful route to the amino phenols of this invention involves the alkylation of a phenol with an olefinic alkylating agent to form an alkylated phenol. This alkylated phenol can then be nitrated to form an intermediate nitro phenol which can be converted to the desired amino phenols by reducing at least some of the nitro groups to amino groups.

Techniques for alkylating phenols are well known to those skilled in the art as the above-noted article in Kirk-Othmer "Encyclopedia of Chemical Technology" demonstrates. Techniques for nitrating phenols are also known. See, for example, in Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. 13, the article entitled "Nitrophenols", page 888 et seq., as well as 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, 1 961; 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. Generally, nitric acid of a concentration of, for example, about 30~90% is a convenient nitrating reagent. Substantially inert liquid diluents and solvents such as acetic or butyric acid can aid in carrying out the reaction by improving reagent contact.

Conditions and concentrations for nitrating hydroxy aromatic compounds are also well known in the art. For example, the reaction can be carried out at temperatures of about -1 50C. to about 1 SOC C.

Usually nitration is conveniently carried out between about 25--750C.

Generally, depending on the particular nitrating agent about 0.5 4 moles of nitrating agent is used for every mole of aromatic nucleus present in the hydroxy aromatic intermediate to be nitrated. If more than one aromatic nucleus is present in the Ar moiety, the amount of nitrating agent can be increased proportionately according to the number of such nuclei present. For example, a mole of naphthalene-based aromatic intermediate has, for purposes of this invention, the equivalent of two single ring" aromatic nuclei so that about 1 4 moles of nitrating agent would generally be used.

When nitric acid is used as a nitrating agent usually about 1.0 to about 3.0 moles per mole of aromatic nucleus is used. Up to about a 5-molar excess of nitrating agent (per "single ring" aromatic nucleus) may be used when it is desired to drive the reaction forward or carry it out rapidly.

Nitration of a hydroxy aromatic intermediate generally takes 0.25 to 24 hours, though it may be convenient to react the nitration mixture for longer periods, such as 96 hours.

Reduction of aromatic nitro compounds to the corresponding amines is also well known. See, for example, the article entitled "Amination by Reduction" in Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. 2, pages 76~99. Generally, such reductions can be carried out with, for example, hydrogen, carbon monoxide or hydrazine, (or mixtures of same) in the presence of metallic catalysts such as palladium, platinum and its oxides, nickel, copper chromite, etc. Co-catalysts such as alkali or alkaline earth metal hydroxides or amines (including amino phenols) can be used in these catalyzed reductions. The reduction of the amino phenols useful for the purposes of this invention can be carried out by hydrazine reduction with or without a catalyst as described in Canadian Pat. No.

1,096,887 which is expressly incorporated herein by reference for its teachings in regard to such processes.

Reduction can also be accomplished through the use of reducing metals in the presence of acids, such as Hydrochloric acid. Typical reducing metals are zinc, iron and tin; salts of these metals can also be used.

Nitro groups can also be reduced in the Zinin reaction, which is discussed in "Organic Reactions", Vol. 20, John Wiley 8 Sons, N.Y., 1973, page 455 et seq. Generally, the Zinin reaction involves reduction of a nitro group with divalent negative sulfur compounds, such as alkali metal sulfides, polysulfides and hydrosulfides.

The nitro groups can be reduced by electrolytic action; see, for example, the "Amination by Reduction" article, referred to above.

Typically the amino phenols of this invention are obtained by reduction of nitro phenols with hydrazine such as discussed above. This reduction is generally carried out in the absence of a catalyst at temperatures of about 500--2500C., typically, about 1000--2000C. The reaction time for reduction usually varies between about 2~24 hours. Substantially inert liquid diluents and solvents, such as ethanol, hexane, cyclohexane, naphtha, mineral oil, etc., can be used to facilitate the reaction.

The amino phenol product is obtained by well-known techniques such as distillation, filtration, extraction, and so forth.

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

The typical route to the amino phenols of this invention just described can be summarized as (I) nitrating with at least one nitrating agent at least one compound of the formula

wherein R is a substantially saturated hydrocarbon-based group of at least 10 aliphatic carbon atoms; a and c are each independent an integer of 1 up to three times the number of aromatic nuclei present in Ar with the proviso that Ar contains at least one carbon atom which is part of the aromatic nucleus and which is bonded directly to a hydrogen atom and the sum of a and c does not exceed the remaining unsatisfied valences of Ar; and Ar is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo, or combinations of two or more optional substituents, with the proviso that when Ar is a benzene having only one hydroxyl and one R substituent, the R substituent is ortho or para to said hydroxyl substituent, to form a first reaction mixture containing a nitro intermediate, and (II) reducing at least about 50% of the nitro groups in said first reaction mixture to amino groups.

Usually this means reducing at least about 50% of the nitro groups to amino groups in a compound or mixture of compounds of the formula

wherein R is a substantially saturated hydrocarbon-based substituent of at least 10 aliphatic carbon atoms; a, b and c are each independently an integer of 1 up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsatisfied valencies of Ar; and Ar is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, halo, or combinations of two or more of said optional substituents; with the proviso that when Ar is a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is ortho or para to said hydroxyl substituent.

The amino phenols useful for the purposes of this invention and processes for their preparation are described in U.S. Patent 4,100,082 which is expressly incorporated herein by reference for its teachings in this regard.

(B) The carboxylic derivative compositions and post-treated carboxylic derivative compositions The substituted succinic acylating agent The substituted succinic acylating agent (hereinafter referred to as the "acylating agent") useful for making composition (B) of this invention are those which can be characterized by the presence within their structure of two groups of moieties. The first group or moiety is referred to herein, for convenience, as the "substituent group(s)" and is derived from a polyalkene. The polyalkene from which the substituted groups are derived is characterized by a Mn (number average molecular weight) value of from 1200 to about 5000 and a Mw/Mn value of about 1.5 to about 6.

The second group or moiety is referred to herein as the "succinic group(s)". The succinic groups are those groups characterized by the structure

wherein X and X' are the same or different provided at least one of X and X' is such that the acylating agent can function as carboxylic acylating agents. That is, at least one of X and X' must be such that the acylating agent can esterify alcohols, form amides or amine salts with ammonia or amines, form metal salts with reactive metals or basically reacting metal compounds, and otherwise function as a conventional carboxylic acid acylating agents. Transesterification and transamidation reactions are considered, for purposes of this invention, as conventional acylating reactions.

Thus, X and/or X' is usually --OH, --OO-hydrocarbyi, --O-M+ where M+ represents one equivalent of a metal, ammonium or amine cation, -NH2 -Cl, -Br, and together, X and X' be~O~ so as to form the anhydride. The specific identity of any X or X' group which is not one of the above is not critical so long as its presence does not prevent the remaining group from entering into acylation reactions. Preferably, however, X and X' are each such that both carboxyl functions of the succinic group (i.e., both and

can enter into acylation reactions.

One of the unsatisfied valences in the grouping -C-C- of the succinic group structure hereinabove forms a carbon-to-carbon bond with a carbon atom in the substituent group. While the other such unsatisfied valence may be satisfied by a similar bond with the same or different substituent group, all but the said one such valence is usually satisfied by hydrogen; i.e., -H.

The substituted succinic acylating agents are characterized by the presence within their structure of at least 1.3 succinic groups for each equivalent weight of substituent groups. For purposes of this invention, the number of equivalent weights of substituent groups is deemed to be the number corresponding to the quotient obtained by dividing the Mn value of the polyalkene from which the substituent is derived into the total weight of the substituent groups present in the acylating agents.

Thus, if an acylating agent is characterized by a total weight of substituent group of 40,000 and the Mn value for the polyalkene from which the substituent groups are derived is 2000, then that acylating agent is characterized by a total of 20 (40,000/2000=20) equivalent weights of substituent groups.

Therefore, that particular acylating agent must also be characterized by the presence within its structure of at least 26 succinic groups to meet one of the requirements of the succinic acylating agents of this invention.

Another requirement for the acylating agents within this invention is that the substituent groups must have been derived from a polyalkene characterized by a Mw/Mn value of about 1.5 to about 6, Mw being the conventional symbol representing weight average molecular weight.

Before proceeding, it should be pointed out that the Mn and Mw values for polyalkene, for purposes of this invention, are determined by gel permeation chromatography (GPC). This separation method involves column chromatography in which the stationary phase is a heteroporous, solventswollen polymer network of a polystyrene gel varying in permeability over many orders of magnitude.

As the liquid phase (tetrahydrofuran) containing the polymer sample passes through the gel, the polymer molecules diffuse into all parts of the gel not mechanically barred to them. The smaller molecules "permeate" more completely and spend more time in the column; the larger molecules "permeate" less and pass through the column more rapidly. The Mn and Mw values of the polyalkenes of this invention can be obtained by one of ordinary skill in the art by the comparison of the distribution data obtained to a series of calibration standards of polymers of known molecular weight distribution.

For purposes of this invention a series of fractionated polymers of isobutene, polyisobutene being the preferred embodiment, is used as the calibration standard.

For example, the Mw values disclosed herein are obtained using a Waters Associates Model 200 gel permeation chromatograph equipped with a 2.5 ml syphon, a 2 ml sample injection loop and four stainless steel columns 7.8 mm in diameter by 120 centimeters long. Each column was packed with ,u STYROGEL, a commercially available, rigid, porous gel (in particle form) of crosslinked styrene/divinyl benzene copolymers. These gels are also obtained from Waters Associates. The first column contains y STYROGEL having a retention volume of 103A. The second and third columns contain STYROGEL having a retention size of 500 A. The fourth column contains STYROGEL having a retention volume of 60 A. The first column is connected to the sample loop with stainless steel tubing, 83.8 cm long.The first column is connected to the second with a 2.3 cm length of the stainless steel tubing. The second and third columns are each connected by 10.2 cm lengths of tubing. The fourth column is connected to the detector by a 25.4 cm length of tubing. All the connecting tubing is 1.6 cm in diameter.

Calibration standards are prepared by dialyzing a polyisobutylene sample having a specific gravity at 600F. (1 5.50C) of 0.89 and a viscosity at 21 00F (990C.) of 12.50 SUS. A sample of this polymer is fractionated by dialysis using a rubber membrane and a soxhlet extraction apparatus with refluxing petroleum ether as solvents. Eleven fractions are taken; one sample each hour for the first seven hours, then three samples each four hours, and finally the residue which did not permeate the membrane over a four-hour period and the Mn of each was measured using vapor phase osmometry and benzene solvent.

Each calibration sample is then chromatographed. Approximately 7 mg of sample is weighed into a small bottle which is then filled with 4 ml of reagent grade tetrahydrofuran. The sealed bottle is stored overnight before analysis. The afore-described liquid phase chromatograph is degassed at 590 C.

and a flow rate of 2.0 ml per minute of tetrahydrofuran maintained. Sample pressure is 1 80 psi and the reference pressure 1 75 psi. The retention time of each sample is measured. The Mw of each calibration sample is calculated from the Mn assuming the relationship 2 Mn=Mw. The retention times and Mw for each sample, which are shown in the following table, are plotted to provide a standardization curve.

The Mn and Mw for sample polymers is then obtained using this curve and the methods described in "Topics in Chemical Instrumentation, Volume XXIX, Gel Permeation Chromatography" by Jack Cages, published in The Journal of Chemical Education, Volume 43, numbers 7 and 8, (1966).

Polyalkenes having the Mn and Mw values discussed above are known in the art and can be prepared according to conventional procedures. Several such polyalkenes, especially polybutenes, are commercially available.

Table Rt* Mw Rt* Mw Rt* Mw 30 42240 40 638 50 229 31 26400 41 539 51 216 32 16985 42 453 52 202 33 10780 43 400 53 189 34 6710 44 361 54 178 35 4180 45 330 55 167 36 2640 46 304 56 156 37 1756 47 282 38 1200 48 264 39 865 49 246 *Rt=retention time in units of number of times syphon (2.5 ml) empties. The syphon empties every 2.5 minutes.

Again, tuming to the characteristics of the succinic acylating agents of this invention, the succinic groups will normally correspond to the formula

wherein Ra and R2 are each independently selected from the group consisting of --OH, --CI, -O- lower alkyl, and when taken together, R, and R2 are -0-. In the latter case, the succinic group is a succinic anhydride group. All the succinic groups in a particular acylating agent need not be the same, but they can be the same. Preferably, the succinic groups will correspond to

and mixtures thereof.Providing acylating agents wherein the succinic groups are the same or different is within the ordinary skill of the art and can be accomplished through conventional procedures such as treating the acylating agents themselves (for example, hydrolyzing the anhydride to the free acid or converting the free acid to an acid chloride with thionyl chloride) and/or selecting the appropriate maleic or fumaric reactants.

As previously mentioned, the minimum number of succinic groups for each equivalent weight of substituent group is 1.3. Preferably, however, the minimum will be 1.4; usually 1.4 to about 3.5 succinic groups for each equivalent weight of substituent group. An especially preferred minimum is at least 1.5 succinic groups for each equivalent weight of substituent group. A preferred range based on this minimum is at least 1.5 to about 2.5 succinic groups per equivalent weight of substituent groups.

From the foregoing, it is clear that the substituted succinic acylating agents of this invention can be represented by the symbol X1~(X2)y where X1 represents one equivalent weight of substituent group, X2 represents one succinic group, as discussed above, and y is a number equal to or greater than 1.3; i.e., 21.3. The more preferred embodiments of the invention could be similarly represented by, for example, letting X, and X2 represent more preferred substituents groups and succinic groups, respectively, as discussed elsewhere herein and by letting the value of y vary as discussed above; e.g., y is equal to or greater than 1.4 (y21.4); y is equal to or greater than 1.5 (Y21.5); y equals 1.4 to about 3.5 (y=1 .4-3.5); and y equals 1.5 to about 3.5 (y=1 .5-3.5).

In addition to preferred substituted succinic groups where the preference depends on the number and identity of succinic groups for each equivalent weight of substituent groups, still further preferences are based on the identity and characterization of the polyalkenes from which the substituent groups are derived.

With respect to the value of Mn, for example, a minimum of about 1200 is preferred with an Mn value in the range of from about 1200 to about 3200 also being preferred. A more preferred Mn value is one in the range of from about 1 500 to about 2800. A most preferred range of Mn values is from about 1500 to about 2400. With polybutenes, an especially preferred minimum value for Mn is about 1700 and an especially preferred range of Mn values is from about 1700 to about 2400.

As to the values of the ratio Mw/Mn, there are also several preferred values. A minimum Mw/Mn value of about 1.8 is preferred with a range of values of about 1.8 up to about 3.6 also being preferred.

A still more preferred minimum value of Mw/Mn is about 2.0 with a preferred range of values of from about 2.0 to about 3.4 also being a preferred range. An especially preferred minimum value of Mw/Mn is about 2.5 with a range of values of about 2.5 to about 3.2 also being especially preferred.

Before proceeding to a further discussion of the polyalkenes from which the substituent groups are derived, it should be pointed out that these preferred characteristics of the acylating agents are, for lack of better terminology to describe the situation contemplated by this invention, intended to be understood as being both independent and dependent. They are intended to be independent in the sense that, for example, a preference for a minimum of 1.4 or 1.5 succinic groups per equivalent weight of substituent group is not tied to a more preferred value of Mn or Mw/Mn. They are intended to be dependent in the sense that, for example, when a preference for a minimum of 1.4 or 1.5 succinic groups is combined with more preferred values of Mn and/or Mw/Mn, the combination of preferences does in fact describe still further more preferred embodiments of the invention.Thus, the various parameters are intended to stand alone with respect to the particular parameter being discussed but can also be combined with other parameters to identify further preferences. This same concept is intended to apply throughout the specification with respect to the description of preferred values, ranges, ratios, reactants, and the like unless a contrary intent is clearly demonstrated or apparent.

The polyalkenes from which the substituent groups in (B) are derived are homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms. The interpolymers are those in which two or more olefin monomers are interpolymerized according to well-known conventional procedures to form polyalkenes having units within their structure derived from each of said two or more olefin monomers. Thus, "interpolymer(s)" as used herein is inclusive of copolymers, terpolymers, tetrapolymers, and the like. As will be apparent to those of ordinary skill in the art, the polyalkenes from which the substituent groups are derived are often conventionally referred to as "polyolefin(s)".

The olefin monomers from which the polyalkenes are derived are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups (i.e.,

that is, they are monoolefinic monomers such as ethylene, propylene, butene-1, isobutene, and octene1 or polyolefinic monomers (usually diolefinic monomers) such as butadiene-1,3 and isoprene.

These olefin monomers are usually polymerizable terminal olefins; that is, olefins characterized by the presence in their structure of the group C=CH2. However, polymerizable internal olefin monomers (sometimes referred to in the patent literature as medial olefins) characterized by the presence within their structure of the group

can also be used to form the polyalkenes. When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers. For the purposes of this invention, when a particular polymerized olefin monomer can be classified as both a terminal olefin and an internal olefin, it will be deemed to be a terminal olefin. Thus, pentadiene-1,3 (i.e., piperylene) is deemed to be a terminal olefin for purposes of this invention.

While the polyalkenes from which the substituent groups of the acylating agents are derived generally are hydrocarbon polyalkenes, they can contain non-hydrocarbon groups such as lower alkoxy, lower alkyl mercapto, hydroxy, mercapto, oxo (i.e.,

as in keto and aldehydo groups; e.g.,

nitro, halo, cyano, carboalkoxy (i.e.,

where "alkyl" is usually lower alkyl) alkanoyloxy (i.e., alkyl

where alkyl is usually lower alkyl) and the like provided the non-hydrocarbon substituents do not substantially interfere with formation of the acylating agents of this invention. When present, such nonhydrocarbon groups normally will not contribute more than about 10% by weight of the total weight of the polyalkenes.Since the polyalkene can contain such non-hydrocarbon substituent, it is apparent that the olefin monomers from which the polyalkenes are made can also contain such substituents.

Normally, however, as a matter of practicality and expense, the olefin monomers and the polyalkenes will be free from non-hydrocarbon groups, except chloro groups which usually facilitate the formation of the substituted succinic acylating agents of this invention. (As used herein, the term "lower" when used with a chemical group such as in "lower alkyl" or "lower alkoxy" is intended to describe groups having up to and including seven carbon atoms.) Although the polyalkenes may include aromatic groups (especially phenyl groups and lower alkyland/or lower alkoxy-substituted phenyl groups such as para-(tertbutyl)-phenyl) and cycloaliphatic groups such as would be obtained from polymerizable cyclic olefins or cycloaliphatic substitutedpolymerizable acyclic olefins, the polyalkenes usually will be free from such groups.Nevertheless, polyalkenes derived from interpolymers of both 1,3-dienes and styrenes such as butadiene-1,3 and styrene or para-(tertbutyl)-styrene are exceptions to this generalization. Again, because aromatic and cycloaliphatic groups can be present, the olefin monomers from which the polyalkenes are prepared can contain aromatic and cycloaliphatic groups.

From what has been described hereinabove in regard to the polyalkene, it is clear that there is a general preference for aliphatic, hydrocarbon polyalkenes free from aromatic and cycloaliphatic groups (other than the dienestyrene interpolymer exception already noted). Within this general preference, there is a further preference for polyalkenes which are derived from the group consisting of homopolymers and interpolymers of terminal hydrocarbon olefins of 2 to about 16 carbon atoms. This further preference is qualified by the proviso that, while interpolymers of terminal olefins are usually preferred, interpolymers optionally containing up to about 40% of polymer units derived from internal olefins of up to about 16 carbon atoms are also within a preferred group.A more preferred class of polyalkenes are those selected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to about 6 carbon atoms, more preferably 2 to 4 carbon atoms. However, another preferred class of polyalkenes are the latter more preferred polyalkenes optionally containing up to about 25% of polymer units derived from internal olefins of up to about 6 carbon atoms.

Specific examples of terminal and internal olefin monomers which can be used to prepare the polyalkenes according to conventional, well-known polymerization techniques include ethylene; propylene; butene-1; butene-2; isobutene; pentene-1; hexene-1; heptene-1 ; octene-1; nonene-1; decene-1; pentene-2; propylene-tetramer; diisobutylene; isobutylene trimer; butadiene-1,2; butadiene1,3; pentadiene-1,2; pentadiene-1,3; pentadiene-1,4; isoprene; hexadiene-1,5; 2-chloro-butadiene-1 ,3; 2-methyl-heptene-1; 3-cyclohexyl-butene-1; 2-methyl-5-propyl-hexene-1; octene-4; 3,3-dimethylpentene-1; styrene; 2,4-dichloro styrene; divinylbenzene; vinyl acetate; allyl alcohol; 1-methyi-vinyl acetate; acrylonitrile; ethyl acrylate; methyl methacrylate; ethyl vinyl ether; and methyl vinyl ketone.Of these, the hydrocarbon polymerizable monomers are preferred and of these hydrocarbon monomers, the terminal olefin monomers are particularly preferred.

Specific examples of polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, styrene-isobutene compolymers, isobutene-butadiene-1 ,3 copolymers, propene-isoprene copolymers, isobutene-chloroprene copolymers, isobutene-(para-methyl)styrene copolymers, copolymers of hexene-1 with hexadiene-1,3, copolymers of octene-1 with hexene-1, copolymers of heptene-1 with pentene-1, copolymers of 3-methyl-butene-1 with octene-1, copolymers of 3,3dimethyl-pentene-1 with hexene-1, and terpolymers of isobutene, styrene and piperylene.More specific examples of such interpolymers include copolymer of 95% (by weight) of isobutene with 5% (by weight) of styrene; terpolymer of 98% of isobutene with 1% of piperylene and 1% of chloroprene; terpolymer of 95% of isobutene with 2% of butene-1 and 3% of hexene-1 ; terpolymer of 60% of isobutene with 20% of pentene-1 and 20% of octene-1; copolymer of 80% of hexene-1 and 20% of heptene-1; terpolymer of 90% of isobutene with 2% of cyclohexene and 8% of propylene; and copolymer of 80% of ethylene and 20% of propylene.A preferred source of polyalkenes are the poly(isobutene)s obtained by polymerization of C4 refinery stream having a butene content of about 35 to about 75 percent by weight and an isobutene content of about 30 to about 60 percent by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than at least about 50% of the total repeating units) of isobutene repeating units of the configuration

Obviously, preparing polyalkenes as described above which meet the various criteria for Mn and Mw/Mn is within the skill of the art and does not comprise part of the present invention.Techniques readily apparent to those in the art include controlling polymerization temperatures, regulating the amount and type of polymerization initiator and/or catalyst, employing chain terminating groups in the polymerization procedure, and the like. Other conventional techniques such as stripping (including vacuum stripping) a very light end and/or oxidatively or mechanically degrading high molecular weight polyalkene to produce lower molecular weight polyalkenes can also be used.

In preparing the acylating agents of this invention, one or more of the above-described polyalkenes is reacted with one or more acidic reactants selected from the group consisting of maleic or fumaric reactants of the general formula

wherein X and X' are as defined hereinbefore. Preferably the maleic and fumaric reactants will be one or more compounds corresponding to the formula

wherein R, and R2 are as previously defined herein. Ordinarily the maleic or fumaric reactants will be maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more of these. The maleic reactants are usually preferred over the fumaric reactants because the former are more readily available and are, in general, more readily reacted with the polyalkenes (or derivatives thereof) to prepare the substituted succinic acylating agents of the present invention.The especially preferred reactants are maleic acid, maleic anhydride, and mixtures of these. Due to availability and ease of reaction, maleic anhydride will usually be employed.

The one or more polyalkenes and one or more maleic or fumaric reactants can be reacted according to any of several known procedures in order to produce the acylating agents useful in the present invention. Basically, the procedures are analogous to procedures used to prepare the high molecular weight succinic anhydrides and other equivalent succinic acylating analogs thereof except that the polyalkenes (or polyolefins) of the prior art are replaced with the particular polyalkenes described above and the amount of maleic or fumaric reactant used must be such that there is at least 1.3 succinic groups for each equivalent weight of the substituent group in the final substituted succinic acylating agent produced.

The process presently deemed to be best for preparing the substituted succinic acylating agents of this invention from the standpoint of efficiency, overall economy, and the performance of the acylating agents thus produced, as well as the performance of the derivatives thereof, is the so-called "one-step" process. This process is described in U.S. Patents 3,215,707 and 3,231,587. Both are expressly incorporated herein by reference for their teachings in regard to that process.

Basically, the one-step process involves preparing a mixture of the polyalkene and the maleic reactant (i.e., the maleic and fumaric reactants of the formula and

wherein X, X' R, and R2 are as previously defined) containing the necessary amounts of both to provide the desired acylating agents of this invention. This means that there must be at least 1.3 moles of maleic reactant for each mole of polyalkene in order that there can be at least 1.3 succinic groups for each equivalent weight of substituent groups. Chlorine is then introduced into the mixture, usually by passing chlorine gas through the mixture with agitation, while maintaining a temperature of at least about 1400C.

A variation on this process involves adding additional maleic reactant during or subsequent to the chlorine introduction but, for reasons explained in 3,215,707 and 3,231,587, this variation is presently not as preferred as the situation where all the polyalkene and all the maleic reactant are first mixed before the introduction of chlorine.

Usually, where the polyalkene is sufficiently fluid at 1400C., and above, there is no need to utilize an additional substantially inert, normally liquid solvent/diluent in the one-step process. However, if a solvent/diluent is employed, it is preferably one that resists chlorination. Again, the poly- and perchlorinated and/or -fluorinated alkanes, cycloalkanes, and benzenes can be used for this purpose.

Chlorine may be introduced continuously or intermittently during the one-step process. The rate of introduction of the chlorine is not critical although for maximum utilization of the chlorine, the rate should be about the same as the rate of consumption of chlorine in the course of the reaction. When the introduction rate of chlorine exceeds the rate of consumption, chlorine is evolved from the reaction mixture. It is often advantageous to use a closed system, including superatmospheric pressure, in order to prevent loss of chlorine so as to maximize chlorine utilization.

The minimum temperature at which the reaction in the one-step process takes place at a reasonable rate is about 1400 C. Thus, the minimum temperature at which the process is normally carried out is in the neighborhood of 1400C. The preferred temperature range is usually between about 1 600C. and about 2200 C. Higher temperatures such as 2500C or even higher may be used but usually with little advantage. In fact, temperatures in excess of 2200C are often disadvantageous with respect to preparing the particular acylating agents useful for this invention because they tend to "crack" the polyalkenes (that is, reduce their molecular weight by thermal degradation) and/or decompose the maleic reactant.For this reasons, maximum temperatures of about 2000 to about 21 O0C. are normally not exceeded. The upper limit of the useful temperature in the one-step process is determined primarily by the decomposition point of the components in the reaction mixture including the reactants and the desired products. The decomposition point is that temperature at which there is sufficient decomposition of any reactant or product such as to interfere with the production of the desired products.

In the one-step process, the molar ratio of maleic reactant to chlorine is such that there is at least about one mole of chlorine for each mole of maleic reactant to be incorporated into the product.

Moreover, for practical reasons, a slight excess, usually in the neighborhood of about 5% to about 30% by weight of chlorine, is utilized in order to offset any loss of chlorine from the reaction mixture. Larger amounts of excess chlorine may be used but do not appear to produce any beneficial results.

As mentioned previously, the molar ratio of polyalkene to maleic reactant is such that there is at least about 1.3 moles of maleic reactant for each mole of polyalkene. This is necessary in order that there can be at least 1.3 succinic groups per equivalent weight of substituent group in the product.

Preferably, however, an excess of maleic reactant is used. Thus, ordinarily about a 5% to about 25% excess of maleic reactant will be used relative to that amount necessary to provide the desired number of succinic groups in the product.

The carboxylic derivative compositions useful for the purposes of this invention are prepared by the process comprising reacting one or more substituted succinic acylating agents with a reactant selected from the group consisting of (a) an amine characterized by the presence within its structure of at least one

group, (b) an alcohol, (c) a reactive metal or reactive metal compound, and (d) a combination of two or more of (a) through (c), the components of (d) being reacted with said acylating reagents simultaneously or sequentially in any order.

The amine, (a), useful for reacting with the acylating agents useful for this invention are those characterized by the presence within their structure of at least one

group can be a monoamine or polyamine compound. For purposes of this invention, hydrazine and substituted hydrazines containing up to three substituents are included as amines suitable for preparing carboxylic derivative compositions. Mixtures of two or more amines can be used in the reaction with one or more acylating agents useful for this invention. Preferably, the amine contains at least one primary amino group (i.e., -NH2) and more preferably the amine is a polyamine, especially a polyamine containing at least two

groups, either or both of which are primary or secondary amines.The polyamines result in carboxylic derivative compositions which are usually more effective as dispersant/detergent additives, relative to derivative compositions derived from monoamines. Suitable monoamines and polyamines are described in greater detail hereinafter.

Alcohol, (b), which can be reacted with the acylating agents useful for this invention include the monohydric and polyhydric alcohols. Again, the polyhydric alcohols are preferred since they usually result in carboxylic derivative compositions which are more effective dispersant/detergents relative to carboxylic derivative compositions derived from monohydric alcohols. Alcohols suitable for use in this invention are described in greater detail hereinafter.

Reactive metals and reactive metal compounds useful as (c) are those which are known to form salts and complexes when reacted with carboxylic acid and carboxylic acid acylating agents. These metals and metal compounds are described further hereinafter.

The amine (a) The monoamines and polyamines useful in this invention must be characterized by the presence within their structure of at least one H-N group. Therefore, they have at least one primary (i.e., H2N-) or secondary amino (i.e., H~N=) group.The amines can be aliphatic, cycloaliphatic, aromatic, or heterocyclic, including aliphatic-substituted aromatic, aliphatic-substituted cycloaliphatic, aliphaticsubstituted aromatic, aliphatic-substituted heterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphatic-substituted aromatic, cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic, heterocyclic-substituted aliphatic, heterocyclic-substituted cycloaliphatic, and heterocyclic-substituted aromatic amines and may be saturated or unsaturated.If unsaturated, the amine will be free from acetylenic unsaturation (i.e., -C=C-). The amines may also contain non-hydrocarbon substituents or groups as long as these groups do not significantly interfere with the reaction of the amines with the acylating reagents of this invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl mercapto, nitro, interrupting groups such as -0- and -S- (e.g., as in such groups as -CH2CH2-X- CH2CH2- where X is -0-or-S-).

With the exception of the branched polyalkylene polyamine, the polyoxyalkylene polyamines, and the high molecular weight hydrocarbyl-substituted amines described more fully hereafter, the amines used in this invention ordinarily contain less than about 40 carbon atoms in total and usually not more than about 20 carbon atoms in total.

Aliphatic monoamines include mono-aliphatic and di-aliphatic substituted amines wherein the aliphatic groups can be saturated or unsaturated and straight or branched chain. Thus, they are primary or secondary aliphatic amines. Such amines include, for example, mono- and di-alkyl-substituted amines, mono- and di-alkenyl-substituted amines, and amines having one N-alkenyl substituent and one N-alkyl substituent and the like. The total number of carbon atoms in these aliphatic monoamines will, as mentioned before, normally not exceed about 40 and usually not exceed about 20 carbon atoms.

Specific examples of such monoamines include ethylamine, diethylamine, n-butylamine, di-nbutylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, octadecylamine, and the like. Examples of cycloaliphaticsubstituted aliphatic amines, aromatic-substituted aliphatic amines, and heterocyclic-substituted aliphatic amines, include 2-(cyclohexyl)-ethylamine, benzylamine, phenylethylamine, and 3-(furylpropyl)amine.

Cycloaliphatic monoamines are those monoamines wherein there is one cycloaliphatic substituent attached directly to the amino nitrogen through a carbon atom in the cyclic ring structure.

Examples of cycloaliphatic monoamines include cyclohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamine, dicyclohexylamines, and the like. Examples of aliphatic-substituted, aromatic-substituted, and heterocyclic-substituted cycloaliphatic monoamines include propyl-substituted cyclohexyalm ines, phenyl-substituted cyclopentylamines, and pyranylsubstituted cyclohexylamine.

Suitable aromatic amines include those monoamines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The aromatic ring will usually be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthylene. Examples of aromatic monoamines include aniline, di(para-methylphenyl)amine, naphthylamine, N-(n-butyl)aniline, and the like. Examples of aliphatic-substituted, cycloaliphatic-substituted, and heterocyclic-substituted aromatic monoamines are para-ethoxyaniline, para-dodecylaniline, cyclohexyl-substituted naphthylamine, and thienyl-substituted aniline.

Suitable polyamines are aliphatic, cycloaliphatic and aromatic polyamines analogous to the above-described monoamines except for the presence within their structure of another amino nitrogen.

The other amino nitrogen can be a primary, secondary or tertiary amino nitrogen. Examples of such polyamines include N-aminopropyl-cyclohexylamines, N-N'-di-n-butyl-para-phenylene diamine, bis (para-aminophenyl)methane, 1 ,4-diaminocyclohexane, and the like.

Heterocyclic mono- and polyamines can also be used in making the substituted carboxylic acid acylating agent derivative compositions of this invention. As used herein, the terminology "heterocyclic mono- and polyamine(s)" is intended to describe those heterocyclic amines containing at least one primary or secondary amino group and at least one nitrogen as a heteroatom in the heterocyclic ring.

However, as long as there is present in the heterocyclic mono- and polyamines at least one primary or secondary amino group, the hetero-N atom in the ring can be a tertiary amino nitrogen; that is, one that does not have hydrogen attached directly to the ring nitrogen. Heterocyclic amines can be saturated or unsaturated and can contain various substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the total number of carbon atoms in the substituents will not exceed about 20. Heterocyclic amines can contain heteroatoms other than nitrogen, especially oxygen and sulfur. Obviously they can contain more than one nitrogen heteroatom. The five- and sixmembered heterocyclic rings are preferred.

Among the suitable heterocyclics are aziridines, azetidines, azolidines, tetra- and di-hydro pyridines, pyrroles, indoles, piperidines, imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N,N'-di-aminoalkylpipernzines, azepines, azocines, azonines, azecinds and tetra-, di- and perhydro-derivatives of each of the above and mixtures of two or more of these heterocyclic amines. Preferred heterocyclic amines are the saturated 5-and 6-membered heterocyclic amines containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like.Piperidine, aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substituted piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especially preferred. Usually the aminoalkyl substituents are substituted on a nitrogen atom forming part of the hetero ring. Specific examples of such heterocyclic amines include N-aminopropyimorpholine, Naminoethylpiperazine, and N,N'-di-aminoethylpiperazine.

Hydroxyamines both mono- and polyamines, analogous to those described above are also useful in this invention provided they contain at least one primary or secondary amino group. Hydroxysubstituted amines having only tertiary amino nitrogen such as in tri-hydroxyethyl amine, are thus excluded as an amine, but can be used as an alcohol as disclosed hereafter. The hydroxy-substituted amines contemplated are those having hydroxy substituents bonded directly to a carbon atom other than a carbonyl carbon atom; that is, they have hydroxy groups capable of functioning as alcohols.

Examples of such hydroxy-substituted amines include ethanolamine, di-(3-hydroxypropyl)-amine, 3- hydroxybutyl-amine, 4-hydroxybutyl-amine, diethanolamine, di-(2-hydroxypropyl)-amine, N-(hydroxypropyl)propylamine, N-(2-hydroxyethyl)-cyclohexylamine, 3-hydroxycyclopentylamine, parahydroxyaniline, N-hydroxyethyl piperazine, and the like.

The terms hydroxyamine and aminoalcohol describe the same class of compounds and, therefore, can be used interchangeably. Hereinafter, in the specification and appended claims, the term hydroxyamine will be understood to include aminoalcohols as well as hydroxyamines.

Also suitable as amines are the aminosulfonic acids and derivatives thereof corresponding to the general formula:

wherein R3 is -OH, -NH2, ONH4, etc., Ra is a polyvalent organic radical having a valence equal to x+y; Rb and Rc are each independently hydrogen, hydrocarbyl, and substituted hydrocarbyl with the proviso that at least one of Rb or Rc is hydrogen per aminosulfonic acid molecule; x and y are each integers equal to or greater than one. From the formula, it is apparent that each aminosulfonic reactant is characterized by at least one

or H2N- group and at least one

group. These sulfonic acids can be aliphatic, cycloaliphatic, or aromatic aminosulfonic acids and the corresponding functional derivatives of the sulfo group.Specifically, the aminosulfonic acids can be aromatic aminosulfonic acids, that is, where Ra is a polyvalent aromatic radical such as phenylene where at least one

group is attached directly to a nuclear carbon atom of the aromatic radical. The aminosulfonic acid may also be a mono-amino aliphatic sulfonic acid; that is, an acid where x is one and Ra is a polyvalent aliphatic radical such as ethylene, propylene, trimethylene, and 2-methylene propylene. Other suitable aminosulfonic acids and derivatives thereof useful as amines in this invention are disclosed in U.S.

Patents 3,926,820; 3,029,250; and 3,367,864; which are expressly incorporated herein by reference for such disclosure.

Hydrazine and substituted-hydrazine can also be used as amines in this invention. At least one of the nitrogens in the hydrazine must contain a hydrogen directly bonded thereto. Preferably there are at least two hydrogens bonded directly to hydrazine nitrogen and, more preferably, both hydrogens are on the same nitrogen. The substituents which may be present on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the substituents are alkyl, specially lower alkyl, phenyl, and substituted phenyl such as lower alkoxy-substituted phenyl or lower alkyl-substituted phenyl.Specific examples of substituted hydrazines are methylhydrazine, N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenyl hydrazine, N-phenyl-N'-ethylhydrazine, N-(para-tolyl)-N'-(n-butyl)-hydrazine, N-(paranitrophenyl)-hydrazine, N-(para-nitrophenyl)-N-methyl-hydrazine, N,N'-di-(para-chlorophenol)hydrazine, N-phenyl-N'-cyclohexylhydrazine, and the like.

The high molecular weight hydrocarbyl amines, both monoamines and polyamines, which can be used as amines in this invention are generally prepared by reacting a chlorinated polyolefin having a molecular weight of at least about 400 with ammonia or amine. Such amines are known in the art and described, for example, in U.S. Patents 3,275,554 and 3,438,757, both of which are expressly incorporated herein by reference for their disclosure in regard to how to prepare these amines. All that is required for use of these amines is that they possess at least one primary or secondary amino group.

Another group of amines suitable for use in this invention are branched polyalkylene polyamines.

The branched polyalkene polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylehe

group per nine amino units present on the main chain, for example,1~4 of such branched chains per nine units on the main chain, but preferably one side chain unit per nine main primary amino grou4Em and at least one tertiary amino group.

These reagents may be expressed by the formula:

wherein R is an alkylene group such as ethylene, propylene, butylene and other homologs (both straight chained and branched), etc., but preferably ethylene; and x, y and z are integers, x being, for example, from 4 to 24 or more but preferably 6 to 18, y being, for example, 1 to 6 or more but preferably 1 to 3, and z being, for example, 0--6 but preferably 0--1. The x and y units may be sequential, alternative, orderly or randomly distributed.

The preferred class of such polyamines includes those of the formula:

wherein n is an integer, for example,1~20 or more but preferably 1-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched).

The preferred embodiments are presented by the following formula:

(n=1 -3).

The radicals in the brackets may be joined in a head-to-head or a head-to-tail fashion.

Compounds described by this formula wherein n=1-3 are manufactured and sold as Polyamines N400, N--800, N~1200, etc. Polyamine N 400 has the above formula wherein n=1.

U.S. patents 3,200,106 and 3,259,578 are expressly incorporated herein by reference for their disclosure of how to make such polyamines and processes for reacting them with carboxylic acid acylating agents since analogous processes can be used with the acylating reagents of this invention.

Suitable amines also include polyoxyalkylene polyamines, e.g., polyoxyalkylene diamines and polyoxyalkylene triamines, having average molecular weights ranging from about 200 to 4000 and preferably from about 400 to 2000. Illustrative examples of these polyoxyalkylene polyamines may be characterized by the formulae: NH2-alkylen#O-Alkylene#jNH2 where m has a value of about 3 to 70 and preferably about 1.0 to 35; R+AIkylene+O-AlkYleneAnNH2 ] 3- wherein n is such that the total value is from about 1 to 40 with the proviso that the sum of all of the n's is from about 3 to about 70 and generally from about 6 to about 35 and R is a polyvalent saturated hydrocarbyl radical of up to ten carbon atoms having a valence of 3 to 6.The alkylene groups may be straight or branched chains and contain from 1 to 7 carbon atoms, and usually from 1 to 4 carbon atoms. The various alkylene groups present within the above formulae may be the same or different.

More specific examples of these polyamines include:

wherein x has a value of from about 3 to 70 and preferably from about 10 to 35 and:

wherein x+y+z have a total value ranging from about 3 to 30 and preferably from about 5 to 10.

The preferred polyoxyalkylene polyamines for purposes of this invention include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2000. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under the trade name "Jeffamines D--230, D 400, D-1 000, D~2000, T~403, etc.".

U.S. patents 3,804,763 and 3,948,800 are expressly incorporated herein by reference for their disclosure of such polyoxyalkylene polyamines and process for acylating them with carboxylic acid acylating agents which processes can be applied to their reaction with the acylating reagents of this invention.

The most preferred amines for use in this invention are the alkylene polyamines, including the polyalkylene polyamines, as described in more detail hereafter. The alkylene polyamines include those conforming to the formula:

wherein n is from 1 to about 10; each R" is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having up to about 30 atoms, and the "Alkylene" group has from about 1 to about 10 carbon atoms but the preferred alkylene is ethylene or propylene. Especially preferred are the alkylene polyamines where each R" is hydrogen with the ethylene polyamines and mixtures of ethylene polyamines being the most preferred. Usually n will have an average value of from about 2 to about 7.Such alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, etc. The higher homologs of such amines and related aminoalkyl-substituted piperazines are also included.

Alkylene polyamines useful in preparing the carboxylic derivative compositions include ethylene diamine, triethylene tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine, N (2-aminoethyl)piperazine, 1 ,4-bis(2-aminoethyl)piperazine, and the like. Higher homologs as are obtained by condensing two or more of the above-illustrated alkylene amines are useful as amines in this invention as are mixtures of two or more of any of the afore-described polyamines.

Ethylene polyamines, such as those mentioned above, are especially useful for reasons of cost and effectiveness. Such polyamines are described in detail under the heading "Diamines and Higher Amines" in The Encyclopedia of Chemical Technology, Second Edition, Kirk and Othmer, Volume 7, pages 27~39, Interscience Publishers, Division of John Wiley and Sons, 1965, which is hereby incorporated by reference for their disclosure of useful polyamines. Such compounds are prepared most conveniently by the reaction of an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia, etc. These reactions result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in preparing compositions of the present invention. Preferred hydroxyalkylsubstituted alkylene polyamines are those in which the hydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less than eight carbon atoms. Examples of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylene diamine, N,N-bis(2-hydroxyethyl)ethylene diamine, 1-(2hydroxyethyl)piperazine, monohydroxypropyl-substituted diethylene triamine, dihydroxypropyl-substituted tetraethylene pentamine, N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as are obtained by condensation of the above-illustrated hydroxy alkylene polyamines through amino radicals or through hydroxy radicals are likewise useful as amines in this invention.Condensation through amino radicals results in a higher amine accompanied by removal of ammonia and condensation through the hydroxy radicals results in products containing ether linkages accompanied by removal of water.

The substituted carboxylic derivative compositions produced from the reaction of the acylating agents and the amines described hereinbefore yield acylated amines which include amine salts, amides, imides and imidazolines as well as mixtures thereof. To prepare carboxylic derivative compositions from the acylating agents and the amines, one or more acylating agents and one or more amines are heated, optionally in the presence of a normally liquid, substantially inert organic liquid solvent/diluent, at temperatures in the range of about 800 C. up to the decomposition point (the decomposition point is the temperature at which there is sufficient decomposition of any reactant or product such as to interfere with the production of the desired product) but normally at temperatures in the range of about 1 O00C. up to about 3000 C. provided 3000 C. does not exceed the decomposition point. Temperatures of about 1 25 C. to about 2500 C. are normally used. The acylating agent and the amine are reacted in amounts sufficient to provide from about one-half equivalent to about 2 moles of amine per equivalent of acylating reagent.For purposes of this invention an equivalent of amine is that amount of the amine corresponding to the total weight of amine divided by the total number of nitrogens present. Thus, octylamine has an equivalent weight equal to its molecular weight; ethylene diamine has an equivalent weight equal to one-half its molecular weight; and aminoethylpiperazine has an equivalent weight to one-third its molecular weight. Also, for example, the equivalent weight of a commercially available mixture of polyalkylene polyamine can be determined by dividing the atomic weight of nitrogen (14) by the %N contained in the polyamine. Therefore, a polyamine mixture having a %N of 34 would have an equivalent weight of 41.2.The number of equivalents of acylating agent depends on the number of carboxylic functions (e.g., carboxylic acid groups or functional derivatives thereof) present in the acylating reagent. Thus, the number of equivalents of acylating agents will vary with the number of carboxy groups present therein. In determining the number of equivalents of acylating agents, those carboxyl functions which are not capable of reacting as an acylating agent are excluded. In general, however, there is one equivalent of acylating agent for each carboxy group in the acylating agents. For example, there would be two equivalents in the acylating agents derived from the reaction of one mole of olefin polymer and one mole of maleic anhydride.Conventional techniques are readily available for determining the number of carboxyl functions (e.g., acid number, saponification number) and thus, the number of equivalents of acylating agent available to react with amine.

U.S. Patents 3,172,892; 3,219,666; and 3,272,746 describe the preparation of acylated amine from high molecular acylating agents and, therefore, are expressly incorporated herein by reference for their disclosure with respect to the procedures applicable to reacting the substituted succinic acylating agents of this invention with the amines as described above. In applying the disclosures of these patents to the substituted acylating agents of this invention, the latter can be substituted for the high molecular weight carboxylic acid acylating agents disclosed in these patents on an equivalent basis.

That is, where one equivalent of the high molecular weight carboxylic acylating agent disclosed in these incorporated patents is utilized, one equivalent of the acylating agent of this invention can be used.

The alcohols (b) Alcohols (b) useful in preparing carboxylic derivative compositions of this invention from the acylating agents previously described include those compounds of the general formula: R3~(OH)m wherein R3 is a monovalent or polyvalent organic radical joined to the -OH groups through carbon-to oxygen bonds (that is,~COH wherein the carbon is not part of a carbonyl group) and m" is an integer of from 1 to about 10, usually 2 to about 6.As with the amine reactants, the alcohols can be aliphatic, cycloaliphatic, aromatic, and heterocyclic, including aliphatic-substituted cycloaliphatic alcohols, aliphatic-substituted aromatic alcohols, aliphatic-substituted heterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols, cycloaliphatic-substituted aromatic alcohols, cycloaliphatic-substituted heterocyclic alcohols, heterocyclic-substituted aliphatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols. Except for the polyoxyalkylene alcohols, the mono- and polyhydric alcohols corresponding to the formula R3~(OH)mlS will usually contain not more than about 40 carbon atoms and generally not more than about 20 carbon atoms.

The alcohols may contain non-hydrocarbon substituents of the same type mentioned with respect to the amines above, that is, non-hydrocarbon substituents which do not interfere with the reaction of the alcohols with the acylating agents of this invention. In general, polyhydric alcohols are preferred.

Among the polyoxyalkylene alcohols suitable for use in the preparation of the carboxylic derivative compositions of this invention are the polyoxyalkylene alcohol demulsifiers for aqueous emulsions. The terminology "demulsifier for aqueous emulsions" as used in the present specification and claims is intended to describe those polyoxyalkylene alcohols which are capable of preventing or retarding the formation of aqueous emulsions or "breaking" aqueous emulsions. The terminology "aqueous emulsion" is generic to oil-in-water and water-in-oil emulsions.

Many commercially available polyoxyalkylene alcohol demulsifiers can be used. Useful demulsifiers are the reaction products of various organic amines, carboxylic acid amides, and quaternary ammonium salts with ethylene-oxide. Such poiyoxyethylated amines, amides, and quaternary salts are available from Armour Industrial Chemical Co. under the names ETHODOUMEEN T, an ethyleneoxide condensation product of an N-alkyl alkylenediamine under the name DUOMEEN T; ETHOMEENS, tertiary amines which are ethyleneoxide condensation products of primary fatty amines; ETHOMIDS, ethyleneoxide condensates of fatty acid amides; and ETHOQUADS, polyoxyethylated quaternary ammonium salts such as quaternary ammonium chlorides.

The preferred demulsifiers are liquid polyoxyalkylene alcohols and derivatives thereof. The derivatives contemplated are the hydrocarbyl ethers and the carboxylic acid esters obtained by reacting the alcohols with various carboxylic acids. Illustrative hydrocarbyl groups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc., containing up to about forty carbon atoms. Specific hydrocarbyl groups are methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenyl ethyl, cyclohexyl, and the like. Carboxylic acids useful in preparing the ester derivatives are mono- or polycarboxylic acids such as acetic acid, valeric acid, lauric acid, stearic acid, succinic acid, and alkyl or alkenyl-substituted succinic acids wherein the alkyl or alkenyl group contains up to about twenty carbon atoms.Members of this class of alcohols are commercially available from various sources; e.g. PLURONIC polyols from Wyandotte Chemicals Corporation; POLYGLYCOL 112~2, a liquid triol derived from ethyleneoxide and propyleneoxide available from Dow Chemical Co.; and TERGITOLS, dodecylphenyl or nonylphenyl polyethylene glycol ethers, and UCONS, polyalkylene glycols and various derivatives thereof, both available from Union Carbide Corporation. However, the demulsifiers used must have an average of at least one free alcoholic hydroxyl group per molecule of polyoxyalkylene alcohol. For purposes of describing these polyoxyalkylene alcohols which are demulsifiers, an alcoholic hydroxyl group is one attached to a carbon atom that does not form part of an aromatic nucleus.

In this class of preferred polyoxyalkylene alcohols are those polyols prepared as "block" copolymers. Thus, a hydroxy-substituted compound, R4~(OH)q (where q is 1 to 6, preferably 2 to 3, and R4 is the residue of a mono- or polyhydric alcohol or mono- or polyhydroxy phenol, naphthol, etc.) is reacted with an alkylene oxide,

to form a hydrophobic base, R5 being a lower alkyl group of up to four carbon atoms, R6 being H or the same as R5 with the proviso that the alkylene oxide does not contain in excess of ten carbon atoms.

This base is then reacted with ethylene oxide to provide a hydrophilic portion resulting in a molecule having both hydrophobic and hydrophilic portions. The relative sizes of these portions can be adjusted by regulating the ratio of reactants, time of reaction, etc., as is obvious to those skilled in the art. It is within the skill of the art to prepare such polyols whose molecules are characterized by hydrophobic and hydrophilic moieties present in a ratio rendering them suitable as demulsifiers for aqueous emulsions in various lubricant compositions and thus suitable as alcohols in this invention. Thus, if more oil-solubility is needed in a given lubricant composition, the hydrophobic portion can be increased and/or hydrophilic portion decreased. If greater aqueous emulsion breaking capability is required, the hydrophilic and/or hydrophobic portions can be adjusted to accomplish this.

Compounds illustrative of R4~(OH)q include aliphatic polyols such as the alkylene glycols and alkane polyols, e.g., ethylene glycol, propylene glycol, trimethylene glycol, glycerol, pentaerythritol, erythritol, sorbitol, mannitol, and the like and aromatic hydroxy compounds such as alkylated mono and polyhydric phenols and naphthols, e.g., cresols, heptylphenols, dodecylphenols, dioctylphenols, triheptylphenols, resorcinol, pyrogallol, etc.

Polyoxyalkylene polyol demulsifiers which have two or three hydroxyl groups and molecules consisting essentially of hydrophobic portions comprising

groups where R5 is lower alkyl of up to three carbon atoms and hydrophilic portions comprising -CH2CH2O- groups are particularly preferred.Such polyols can be prepared by first reacting a compound of the formula R4~(OH)q where q is 2-3 with a terminal alkylene oxide of the formula

and then reacting that product with ethylene oxide. R4~(OH)q can be, for example, TMP (trimethylolpropane), TME (trimethylolethane), ethylene glycol, trimethylene glycol, tetramethylene glycol, tri-(P-hydroxypropyl)amine, 1 ,4-(2-hydroxyethyl)-cyclohexane, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylene diamine, naphthol, alkylated naphthol, resorcinol, or one of the other illustrative examples mentioned hereinbefore.

The polyoxyalkylene alcohol demulsifiers should have an average molecular weight of 1000 to about 10,000, preferably about 2000 to about 7000. The ethyleneoxy groups (i.e., #H2CH2O-) normally will comprise from about 5% to about 40% of the total average molecular weight. Those polyoxyalkylene polyols where the ethyleneoxy groups comprise from about 10% to about 30% of the total average molecular weight are especially useful. Polyoxyalkylene polyols having an average molecular weight of about 2500 to about 6000 where approximately 1 0 /ó~20% by weight of the molecule is attributable to ethyleneoxy groups result in the formation of esters having particularly improved demulsifying properties. The ester and ether derivatives of these polyols are also useful.

Representative of such polyoxyalkylene polyols are the liquid polyols available from Wyandotte Chemicals Company under the name PLURONIC Polyols and other similar polyols. These PLURONIC Polyols correspond to the formula

wherein x, y, and z are integers greater than 1 such that the -CH2CH2O- groups comprise from about 10% to about 15% by weight of the total molecular weight of the glycol, the average molecular weight of said polyols being from about 2500 to about 4500. This type of polyol can be prepared by reacting propylene glycol with propylene oxide and then with ethylene oxide.

Another group of polyoxyalkylene alcohol demulsifiers illustrative of the preferred class discussed above are the commercially available liquid TETRONIC polyols sold by Wyandotte Chemicals Corporation. These polyols are represented by the general formula:

Such polyols are described in U.S. Patent No. 2,979,528 which is expressly incorporated herein by reference. Those polyols corresponding to the above formula having an average molecular weight of up to about 1 0,000 wherein the ethyleneoxy groups contribute to the total molecular weight in the percentage ranges discussed above are preferred. A specific example would be such a polyol having an average molecular weight of about 8000 wherein the ethyleneoxy groups accounts for 7.5%-1 2% by weight of the total molecular weight.Such polyols can be prepared by reacting an alkylene diamine such as ethylene diamine, propylene diamine, hexamethylene diamine etc., with propylene oxide until the desired weight of the hydrophobic portion is reached. Then the resulting product is reacted with ethylene oxide to add the desired number of hydrophilic units to the molecules.

Another commercially available polyoxyalkylene polyol demulsifier falling within this preferred group is Dow Polyglycol 112-2, a triol having an average molecular weight of about 4000~5000 prepared from propylene oxides and ethylene oxides, the ethyleneoxy groups comprising about 18% by weight of the triol. Such triols can be prepared by first reacting glycerol, TME, TMP, etc., with propylene oxide to form a hydrophobic base and reacting that base with ethylene oxide to add hydrophilic portions.

Alcohols useful in this invention also include alkylene glycols and polyoxyalkylene alcohols such as polyoxyethylene alcohols, polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. These polyoxyalkylene alcohols (sometimes called polyglycols) can contain up to about 150 oxyalkylene groups wherein the alkylene radical contains from 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols are generally dihydric alcohols. That is, each end of the molecule terminates with a -OH group. In order for such polyoxyalkylene alcohols to be useful, there must be at least one such -OH group.However, the remaining -OH group can be esterified with a monobasic, aliphatic or aromatic carboxylic acid of up to about 20 carbon atoms such as acetic acid, propionic acid, oleic acid, stearic acid, benzoic acid, and the like. The monoethers of these alkylene glycols and polyoxyalkylene glycols are also useful. These include the monoaryl ethers, monoalkyl ethers, and monoaralkyl ethers of these alkylene glycols and polyoxyalkylene glycols. This group of alcohols can be represented by the general formula HO+RAO4pRB~ORC where Rc is aryl such as phenyl, lower alkoxy phenyl, or lower alkyl phenyl; lower alkyl such as ethyl, propyl, tert-butyl, pentyl, etc.; and aralkyl such as benzyl, phenylethyl, phenylpropyl, p-ethylphenylethyl, etc.; p is zero to about eight, preferably two to four, carbon atoms.Polyoxyalkylene glycols where the alkylene groups are ethylene or propylene and p is at least two as well as the monoethers thereof as described above are very useful.

The monohydric and polyhydric alcohols useful in this invention include monohydroxy and polyhydroxy aromatic compounds. Monohydric and polyhydric phenols and naphthols are preferred hydroxyaromatic compounds. These hydroxy-substituted aromatic compounds may contain other substituents in addition to the hydroxy substituents such as halo, alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like. Usually, the hydroxy aromatic compound will contain 1 to 4 hydroxy groups.The aromatic hydroxy compounds are illustrated by the following specific examples: phenol, p-chlorophenol, p-nitrophenol, beta-naphthol, alpha-naphthol, cresols, resorcinol, catechol, carvacrol, thymol, eugenol, p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol, chloroglucinol, hexylresorcinol, orcin, guaiacol, 2-chlorophenol, 2,4-dibutylphenol, propenetetramer-substituted phenol didodecylphenol, 4,4'-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-naphthol, polyisobutenyl-(molecular weight (Mw) of about 1000)-substituted phenol, the condensation product of heptylphenol with 0.5 moles of formaldehyde, the condensation product of octylphenol with acetone, di(hydroxyphenyi)oxide, di(hydroxyphenyl)sulfide, di(hydroxyphenyl)disulfide, and 4-cyclohexylphenol.Phenol itself and aliphatic hydrocarbon-substituted phenols, e.g., alkylated phenols having up to 3 aliphatic hydrocarbon substituents are especially preferred. Each of the aliphatic hydrocarbon substituents may contain 100 or more carbon atoms but usually will have from 1 to 20 carbon atoms. Alkyl and alkenyl groups are the preferred aliphatic hydrocarbon substituents.

Further specific examples of monohydric alcohols which can be used include monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, beta-phenylethyl alcohol, 2-methylcyclohexanol, beta-chioroethanol, monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, monododecyl ether of triethylene glycol, monooleate of ethylene glycol, monostearate of diethylene glycol, sec-pentyl alcohol, tertbutyl alcohol, 5bromo-dodecanol, nitro-octadecanol, and dioleate of glycerol. Alcohols useful in this invention may be unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, 1-cyclohexene-3-ol and oleyl alcohol.

Other specific alcohols useful in this invention are the ether alcohols and amino alcohols including, for example, the oxyalkylene, oxy-arylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxyalkylene, aminoalkylene or amino-aryleneoxy-arylene radicals. They are exemplified by Cellosolve, carbitol, phenoxyethanol, heptylphenyl-(oxypropylene)6-OH, octyl (oxyethy!ene)30-OH, phenyl-(oxy,octylene)2-OH mono-(heptylphenyl-oxyprnpylene)-substituted glycerol, poly(styreneoxide), aminoethanol, 3-amino-ethylpentanol, di(hydroxyethyl)amine, paminophenol, tri(hydroxypropyl)amine, N-hydroxyethyl ethylenediamine, N,N,N',N'-tetrahydroxytrimethylenediamine, and the like.

The polyhydric alcohols preferably contain from 2 to about 10 hydroxy radicals. They are illustrated, for example, by the alkylene glycols and polyoxyalkylene glycols mentioned above such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols and polyoxyalkylene glycols in which the alkylene radicals contain 2 to about 8 carbon atoms.

Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, n-butyl ester of 9,1 0-dihydroxy stearic acid, methyl ester of 9,1 0-dihydroxy stearic acid, 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, celluloses, and so forth likewise can be used. The carbohydrates may be exemplified by glucose, fructose, sucrose, rhamose, mannose, glyceraldehyde, and galactose.

Polyhydric alcohols having at least 3 hydroxyl groups, some, but not all of which have been esterified with an aliphatic monocarboxylic acid having from about 8 to about 30 carbon atoms such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oil acid are useful. Further specific examples of such partially esterified polyhydric alcohols are the monooleate of sorbitol, distearate of sorbitol, monooleate of glycerol, monostearate of glycerol, di-dodecanoate of erythritol, and the like.

A preferred class of alcohols suitable for use in this invention are those polyhydric alcohols containing up to about twelve carbon atoms, and especially those containing three to ten carbon atoms. This class of alcohols includes glycerol, erythritol, pentaerythritol, dipentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose, 1 ,7-heptanediol, 2,4-heptanediol, 1 ,2,3-hexanetriol, 1,2,4hexanetriol, 1 ,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol, 1 ,2,4-butanetriol, quinic acid, 2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,1 0-decanediol, digitalose, and the like. Aliphatic alcohols containing at least three hydroxyl groups and up to ten carbon atoms are particularly preferred.

An especially preferred class of polyhydric alcohols for use in this invention are the polyhydric alkanols containing three to ten carbon atoms and particularly, those containing three to six carbon atoms and having at least three hydroxyl groups. Such alcohols are exemplified by glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl-1 ,3-propanediol(trimethylolethane), 2 hydroxymethyl-2-ethyl- 1 ,3-propanediol(trimethyloproprane), 1 ,2,4-hexanetriol, and the like.

From what has been stated above, it is seen that amines may contain alcoholic hydroxy substituents and alcohols can contain primary, secondary, or tertiary amino substituents. Thus, amino alcohols can be catagorized as both amine and alcohol provided they contain at least one primary or secondary amino group. If only tertiary amino groups are present, the amino alcohol belongs only in the alcohol catagory.

Amino alcohols contemplated as suitable for use in this invention have one or more amine groups and one or more hydroxy groups. Examples of suitable amino alcohols are the N-(hydroxy-lower alkyl) amines and polyamines such as 2-hydroxyethylamine, 3-hydroxybutylamine, di-(2-hydroxy-ethyl)amine, tri-(2-hydroxyethyl)amine, di-(2-hydroxypropyl)amine, N,N,N'-tri-(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetra-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, N,N'-di-(3hydroxypropyl)piperazine, N-(2-hydroxyethyl)morpholine, N-(2-hydroxyethyl)-2-morpholinone, N-(2hydroxyethyl)-3-methyl-2-morpholinone, N-(2-hydroxypropyl)-6-methyl-2-morpholinone, N-(2hydroxyethyl)-5-carbethoxy-2-piperidone, N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone, N-(2hydroxyethyl)-5-(N-butylcarbamyl)-2-piperidone, N-(2-hydroxyethyl)piperidine, N-(4hydroxybutylpiperidine, N,N-di-(2-hydroxyethyl)glycine, and ethers thereof with aliphatic alcohols, especially lower alkanols, N,N-di(3-hydroxypropyl)glycine, and the like. Also contemplated are other mono- and poly-N-hydroxyalkyl-substituted alkylene polyamines wherein the alkylene polyamines are as described above; especially those that contain two to three carbon atoms in the alkylene radicals and the alkylene polyamine contains up to seven amino groups such as the reaction product of about two moles of propylene oxide and one mole of diethylenetriamine.

Further amino alcohols are the hydroxy-substituted primary amines described in U.S. Patent 3,576,743 by the general formula Rd-N H2 where Rd is a monovalent organic radical containing at least one alcoholic hydroxy group, according to this patent, the total number of carbon atoms in Rd will not exceed about 20. Hydroxy-substituted aliphatic primary amines containing a total of up to about 10 carbon atoms are particularly useful.

Especially preferred are the polyhydroxy-substituted alkanol primary amines wherein there is only one amino group present (i.e., a primary amino group) having one alkyl substituent containing up to 10 carbon atoms and up to 6 hydroxyl groups. These alkanol primary amines correspond to Rd-NH2 wherein Rd is a mono- or polyhydroxy-substituted alkyl group. It is desirable that at least one of the hydroxyl groups be a primary alcoholic hydroxyl group. Trismethylolaminomethane is the single most preferred hydroxy-substituted primary amine.Specific examples of the hydroxy-substituted primary amines include 2-amino- 1 -butanol, 2-amino-2-methyl- 1 -propanol, p-(beta-hydroxyethyl)-analine, 2 amino-1-propanol, 3-amino-1 -propanol, 2-amino-2-methyl-1 ,3-propanediol, 2-amino-2-ethyl-1 ,3- propanediol, N-(beta-hydroxypropyl)-N'-(beta-a minoethyl)-piperazine, tris(hydroxymethyl)amino methane (also known as trismethylolamino methane), 2amino1 -butanol, ethanolamine, beta-(betahydroxy ethoxy)-ethyl amine, glucamine, glusoamine, 4-amino-3-hydroxy-3-methyl-1 -butene (which can be prepared according to procedures known in the art by reacting isopreneoxide with ammonia), N 3-(aminopropyl)-4-(2-hydroxyethyl)-piperadine, 2-amino-6-methyl-6-heptanol, 5-amino-1 -pentanol, N-(beta-hydroxyethyl)-1 ,3-diamino propane, 1 ,3-diamino-2-hydroxy-propane, N-(beta-hydroxy ethoxyethyl)ethylenediamine, and the like. For further description of the hydroxy-substituted primary amines contemplated as being useful as amines and/or alcohols, U.S. Patent 3,576,743 is expressly incorporated herein by reference for its disclosure of such amines.

The carboxylic derivative compositions produced by reacting the acylating agents of this invention with alcohols are esters. Both acidic esters and neutral esters are contemplated as being within the scope of this invention. Acidic esters are those in which some of the carboxylic acid functions in the acylating reagents are not esterified but are present as free carboxyl groups. Obviously, acid esters are easily prepared by using an amount of alcohol insufficient to esterify all of the carboxyl groups in the acylating reagents of this invention.

The acylating agents are reacted with the alcohols according to conventional esterification techniques. It normally involves heating the acylating agent of this invention with the alcohol, optionally in the presence of a normally liquid, substantially inert, organic liquid solvent/diluent and/or in the presence of esterification catalyst. Temperatures of at least about 1000C. up to the decomposition point are used (the decomposition point having been defined hereinbefore). This temperature is usually within the range of about 1000C. up to about 3000 C. with temperatures of about 1 400C to 2500C. often being employed. Usually, at least about one-half equivalent of alcohol is used for each equivalent of acylating agent.An equivalent of acylating agent is the same as discussed above with respect to reaction with amines. An equivalent of alcohol is its molecular weight divided by the total number of hydroxyl groups present in the molecule. Thus, an equivalent weight of ethanol is its molecular weight while the equivalent weight of ethylene glycol is one-half its molecular weight.

The amino-alcohols have equivalent weights equal to the molecular weight divided by the total number of hydroxy groups and nitrogen atoms present in each molecule.

Many issued patents disclose procedures for reacting high molecular weight carboxylic acid acylating agents with alcohols to produce acidic esters and neutral esters. These same techniques are applicable to preparing esters from the acylating agents of this invention and the alcohols described above. All that is required is that the acylating agents of this invention are substituted for the high molecular weight carboxylic acid acylating reagents discussed in these patents, usually on an equivalent weight basis. The following U.S. Patents are expressly incorporated herein by reference for their disclosure of suitable methods for reacting the acylating agents of this invention with the alcohols described above: 3,331,776; 3,381,022; 3,522,179; 3,542,680; 3,697,428; 3,755,169.

The reactive metals or metal compounds (c) Reactive metals or reactive metal compounds useful as (c) are those which will form carboxylic acid metal salts with the acylating agents of this invention and those which will form metal-containing complexes with the carboxylic derivative compositions produced by reacting the acylating reagents with amines and/or alcohols as discussed above. Reactive metal compounds useful as (c) for the formation of complexes with the reaction products of the acylating agents and amines are disclosed in U.S. Patent 3,306,908. Complex-forming metal reactants useful as (c) include the nitrates, nitrites, halides, carboxylates, phosphates, phosphites, sulfates, sulfites, carbonates, borates, and oxides of cadmium as well as metals having atomic numbers of 24 to 30 (including chromium, manganese, iron, cobalt, nickel, copper and zinc).These metals are the so-called transition or co-ordination metals, i.e., they are capable of forming complexes by means of their secondary or coordination valence. Specific examples of the complex-forming metal compounds useful as the reactant (c) in this invention are cobaltous nitrate, cobaltous oxide, cobaltic oxide, cobalt nitrite, cobaltic phosphate, cobaltous chloride, cobaltic chloride, cobaltous carbonate, chromous acetate, chromic acetate, chromic bromide, chromous chloride, chromic fluoride, chromous oxide, chromium dioxide, chromic oxide, chromic sulfite, chromous sulfate heptahydrate, chromic sulfate, chromic formate, chromic hexanoate, chromium oxychloride, chromic phosphite, manganous acetate, manganous benzoate, manganous carbanate, manganese dichloride, manganese trichloride, manganous citrate, manganous formate, manganous nitrate, manganous oxalate, manganese monooxide, manganese dioxide, manganese trioxide, manganese heptoxide, manganic phosphate, manganous pyrophosphate, manganic metaphosphate, manganous hypophosphite, manganous valerate, ferrous acetate, ferric benzoate, ferrous bromide, ferrous carbonate, ferric formate, ferrous lactate, ferrous nitrate, ferrous oxide, ferric oxide, ferric hypophosphite, ferric sulfate, ferrous sulfite, ferric hydrosulfite, nickel dibromide, nickel dichloride, nickel nitrate, nickel dioleate, nickel stearate, nickel sulfite, cupric propionate, cupric acetate, cupric metaborate, cupric benzoate, cupric formate, cupric laurate, cupric nitrite, cupric oxychloride, cupric palmitate, cupric salicylate, zinc benzoate, zinc borate, zinc bromide, zinc chromate, zinc dichromate, zinc iodide, zinc lactate, zinc nitrate, zinc oxide, zinc stearate, zinc sulfite, cadmium benzoate, cadmium carbonate, cadmium butyrate, cadmium chloroacetate, cadmium fumerate, cadmium nitrate, cadmium dihydrogenphosphate, cadmium sulfite, and cadmium oxide. Hydrates of the above compounds are especially convenient for use in the process of this invention.

U.S. Patent 3,306,908 is expressly incorporated herein by reference for its discussion of reactive metal compounds suitable for forming such complexes and its disclosure of processes for preparing the complexes. Basically, those processes are applicable to the carboxylic derivative compositions of the acylating agents of this invention with the amines as described above by substituting, or on an equivalent basis, the acylating reagents of this invention with the high molecular weight carboxylic acid acylating agents disclosed in U.S. Patent 3,306,908. The ratio of equivalents of the acylated amine thus produced and the complex-forming metal reactant remains the same as disclosed in 3,306,908 patent.

U.S. Reissue Patent 26,443 discloses metals useful in preparing salts from the reaction of acylating agents and amines as described hereinabove. Metal salts are prepared, according to this patent, from alkali metals, alkaline earth metals, zinc, cadmium, lead, cobalt and nickel. Examples of a reactive metal compound suitable for use as (c) are sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, sodium pentylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methylate, potassium pentylate, potassium phenoxide, lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, calcium ethylate, calcium propylate, calcium chloride, calcium fluoride, calcium pentylate, calcium phenoxide, calcium nitrate, barium oxide, barium hydroxide, barium carbonate, barium chloride, barium fluoride, barium methylate, barium propylate, barium pentylate, barium nitrate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesium propylate, magnesium chloride, magnesium bromide, barium iodide, magnesium phenoxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc methylate, zinc propylate, zinc pentylate, zinc chloride, zinc fluoride, zinc nitrate trihydrate, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium methylate, cadmium propylate, cadmium chloride, cadmium bromide, cadmium fluoride, lead oxide, lead hydroxide, lead carbonate, lead ethylate, lead pentylate, lead chloride, lead fluoride, lead iodide, lead nitrate, nickel oxide, nickel hydroxide, nickel carbonate, nickel chloride, nickel bromide, nickel fluoride, nickel methylate, nickel pentylate, nickel nitrate hexahydrate, cobalt oxide, cobalt hydroxide, cobaltous bromide, cobaltous chloride, cobalt butylate, cobaltous nitrate hexahydrate, etc. The above metal compounds are merely illustrative of those useful in this invention and the invention is not to be considered as limited to such.

U.S. Reissue 26,443 is expressly incorporated herein by reference for its disclosure of reactive metal compounds useful as (c) and processes for utilizing these compounds in the formation of salts.

Again, in applying the teachings of this patent to the present invention, it is only necessary to substitute the acylating agents of this invention on an equivalent weight basis for the high molecular weight carboxylic acylating agents of the reissue patent.

U.S. Patent 3,271,310 discloses the preparation of metal salt of high molecular weight carboxylic acid acylating agents, in particular alkenyl succinic acids. The metal salts disclosed therein are acid salts, neutral salts, and basic salts. Among the illustrative reactive metal compounds used to prepare the acidic, neutral and basic salts of the high molecular weight carboxylic acids disclosed in 3,271 310 are lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methylate, silver oxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesium propyllate, magnesium phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, calcium propylate, calcium pentylate, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, barium oxide, barium hydroxide, barium hydrate, barium carbonate, barium ethylate, barium pentylate, aluminum oxide, aluminum propylate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butylate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide, and nickel carbonate. The present invention is not to be considered as limited to the use of the above metal compounds; they are presented merely to illustrate the metal compounds included with the invention.

U.S. Patent 3,271,310 is expressly incorporated herein by reference for its disclosure of suitable reactive metal compounds for forming salts of the acylating reagents of this invention as well as illustrative processes for preparing salts of these acylating reagents. As will be apparent, the processes of 3,271,310 are applicable to the acylating reagents of this invention merely by substituting on an equivalent weight basis, the acylating reagents of this invention for the high molecular weight carboxylic acids of the patent.

(d) The combination of two or more of (a), (b) and (c) From the foregoing description, it is apparent that the acylating reagents of this invention can be reacted with any individual amine, alcohol, reactive metal, reactive metal compound or any combination of two or more of any of these; that is, for example, one or more amines, one or more alcohols, one or more reactive metals or reactive metal compounds, or a mixture of any of these. The mixture can be a mixture of two or more amines, a mixture of two or more alcohols, a mixture of two or more metals or reactive metal, compounds, or a mixture of two or more components selected from amines and alcohols, from amines and reactive metals or reactive metal compounds, from alcohols and reactive metal compounds, or one or more components from each of the amines, alcohols, and reactive metal or reactive metal compounds.Furthermore, the acylating reagents of this invention can be reacted with the amines, alcohols, reactive metals, reactive metal compounds, or mixtures thereof, as described above, simultaneously (concurrently) or sequentially in any order of reaction.

Canadian Patent 956,397 is expressly incorporated herein by reference for its disclosure of procedures for reacting the acylating reagents of this invention with amines, alcohols, reactive metal and reactive metal compounds, or mixtures of these, sequentially and simultaneously. All that is required to apply the processes of that patent to this invention is to substitute, on an equivalent weight basis, the acylating agents of this invention for the high molecular weight carboxylic acid acylating agents disclosed in that Canadian patent. Carboxylic derivative compositions of this invention prepared utilizing the processes disclosed in the Canadian patent constitute a preferred class of carboxylic acids or carboxylic acid derivative compositions. The following U.S.Patents are also incorporated herein by reference, being counterparts of the incorporated Canadian patent, for the same reasons given for incorporating the Canadian patent: 3,836,469; 3,836,470; 3,836,471,3,838,050; 3,838,052; 3,879,308; 3,957,854; 3,957,855; 4,031,118. The Canadian patent and the U.S. patents, which are counterparts thereof as identified above, are also incorporated herein to illustrate that the amount of polyoxyalkylene alcohol demulsifier utilized in preparing dispersant/detergents from the acylating reagents of this invention is normally quite small on an equivalent basis.

It is also pointed out that, among the more preferred carboxylic derivative compositions of this invention are those prepared according to the Canadian patent and corresponding U.S. patent identified above in which the polyoxyalkylene alcohol demulsifier has been omitted. In other words, a preferred class of carboxylic derivative compositions of this invention are the various reaction products of the high molecular weight carboxylic acid acylating agents of the Canadian patent with one or more amines, alcohols, and reactive metal compounds as disclosed therein differing only in that the acylating agents of this invention are substituted on an equivalent weight basis and, further, that the polyoxyalkylene alcohol demulsifier reactant is omitted.

In addition, U.S. Patent 3,806,456 is expressly incorporated herein by reference for its disclosure of processes useful in preparing products from the acylated reagents of this invention and polyoxyalkylene polyamines as described hereinbefore. Substitution of the acylated reactants of this invention for the high molecular weight carboxylic acid acylating agents disclosed in 3,806,456 on an equivalent weight basis produces compounds further characterized by the viscosity index improving properties.

U.S. Patent 3,576,743 is also incorporated herein by reference for its disclosure of a process for preparing carboxylic derivative compositions from both polyhydric alcohols and amine; in particular, hydroxy-substituted primary amines. Again, substitution of the acylating reagents of this invention on an equivalent weight basis fcr the high molecular carboxylic acid acylating agents disclosed in 3,576,743 provides compositions having the desired dispersant/detergent compositions and V.l.

improving properties.

U.S. Patent 3,632,510 is expressly incorporated herein by reference for its disclosure of processes for preparing mixed ester-metal salts. Mixed ester-metal salts derived from acylating reagents of this invention, the alcohols, and the reactive metal compounds can be prepared by following the processes disclosed in 3,632,510 but substituting, on an equivalent weight basis, the acylating reagents of this invention for the high molecular weight carboxylic acid acylating agents of the patent. The carboxylic acid derivative compositions thus produced also represent a preferred aspect of this invention.

Commonly assigned U.S. Patent Application Ser. No. 1 60,751 , filed June 1 8, 1 980, is expressly incorporated herein by reference for its disclosure of processes for preparing polyamine modified estercarboxylic derivative compositions useful as (B) in the present invention.

Generally, the process comprises: (I) Reacting, to form a polyester intermediate, (A) at least one polyhydric alcohol with (B) a substituted succinic acid acylating agent, the substituent thereon being derived from at least one alkene polymer having a number average molecular weight (i in) of at least about 1200 and a ratio of weight average to number average molecular weight (Mw/Mn) of about 1.5~6.0, said acylating agent having within its molecular structure an average of at least about 1.3 succinic groups per substituent group; and (II) subsequently reacting said polyester intermediate with (C) at least one acylatable polyamine to form said amine-modified polyester composition; the process comprises carrying out said steps I and II in such a way that: a first solution of 35% by weight of said amine-modified polyester in a first mineral oil having a kinematic viscosity at 1000C. of 3.6 4.3 centistokes has a nitrogen content of at least 0.0175% by weight and a first kinematic viscosity at 1000C. of at least about 300 centistokes; and a second solution prepared by dissolving said first solution in a second mineral oil having a kinematic viscosity at 1000C. of about 6.1 centistokes, at a level to provide 7% by weight of said amine modified polyester in said second solution, has a second kinematic viscosity of at least about 9 centistokes.

Finally, U.S. Patents 3,755,169; 3,804,763; 3,868,330; and 3,948,800 are expressly incorporated herein by reference for their disclosure of how to prepare carboxylic acid derivative compositions. By following the teachings of these patents and substituting the acylating agents of this invention for the high molecular weight carboxylic acylating agents of the patents, a wide range of carboxylic derivative compositions within the scope of the present invention can be prepared.

Incorporation of so many patents is done because, it is felt, that the procedures necessary to prepare the carboxylic derivative compositions from the acylating agents and the amines, alcohols, and reactive metals and reactive metal compounds, as well as mixtures thereof, is well within the skill of the art, such that a detailed description herein is not necessary.

Of the carboxylic derivative compositions described hereinabove, those prepared from the acylating agents and the alkylene polyamines, especially polyethylene polyamines, and/or polyhydric alcohols, especially the polyhydric alkanols, are especially preferred. As previously stated, mixtures of polyamines and/or polyhydric alcohols are contemplated. Normally, all the carboxyl functions on the acylating reagents of this invention will either be esterified or involved in formation of an amine salt, amide, imide or imidazoline in this preferred group of carboxylic derivative compositions.

In addition to detergent/dispersant properties, the carboxylic derivative compositions and posttreatments thereof discussed herein function as Vl improvers and these viscosity index improving capabilities are enhanced when prepared from the reaction of the acylating agents with polyfunctional reactants. For example, polyamines having two or more primary and/or secondary amino groups, polyhydric alcohols, amino alcohols in which there are one or more primary and/or secondary amino groups and one or more hydroxy groups, and polyvalent metal or polyvalent metal compounds. It is believed that the polyfunctional reactants serve to provide "bridges" or cross-linking in the carboxylic derivative compositions and this, in turn, is somehow responsible for the viscosity index-improving properties.

However, the mechanism by which viscosity index improving properties is obtained is not understood and applicants do not intend to be bound by this theory. Since the carboxylic derivative compositions derived, in whole or in part, from polyhydric alcohols appear to be particularly effective in permitting a reduction of V.l. improver in lubricating compositions, the polyfunctionality of reactants (a), (b), and (c) may not fully explain the V.l. improving properties of the carboxylic derivative compositions.

Obviously, however, it is not necessary that all of the amine, alcohol, reactive metal, or reactive metal compound reacted with the acylating reagents be polyfunctional. Thus, combinations of mono and polyfunctional amines, alcohols, reactive metals and reactive metal compounds can be used; for example, monoamine with a polyhydric alcohol, a monohydric alcohol with polyamine, an amino alcohol with a reactive metal compound in which the metal is monovalent, and the like.

While the parameters have not been fully determined as yet, it is believed that acylating reagents of this invention should be reacted with amines, alcohols, reactive metals, reactive metal compounds, or mixtures of these which contain sufficient polyfunctional reactant, (e.g., polyamine, polyhydric alcohol) so that at least about 25% of the total number of carboxyl groups (from the succinic groups or from the groups derived from the maleic reactant) are reacted with a polyfunctional reactant. Better results, insofar as the viscosity index-improving facilities of the carboxylic derivative compositions is concerned, appear to be obtained when at least 50% of the carboxyl groups are involved in reaction with such polyfunctional reactants.In most instances, the best viscosity index improving properties seem to be achieved when the acylating reagents of this invention are reacted with a sufficient amount of polyamine and/or polyhydric alcohol (or amino alcohol) to react with at least about 75% of the carboxyl group. It should be understood that the foregoing percentages are "theoretical" in the sense that it is not required that the stated percentage of carboxyl functions actually react with poly functional reactant. Rather these percentages are used to characterize the amounts of polyfunctional reactants desirably "available" to react with the acylating reagents in order to achieve the desired viscosity index improving properties.

Post-treated carboxylic derivative compositions Another aspect of this invention, (B), may be post-treated carboxylic derivative compositions prepared by reacting one or more post-treating reagents with one or more carboxylic derivative compositions. Additionally, (B) includes mixtures of one or more carboxylic derivative compositions and one or more post-treated carboxylic derivative compositions.

The process for post-treating the carboxylic acid derivative compositions is analogous to the post-treating processes used with respect to similar derivatives of the high molecular weight carboxylic acid acylating agents of the prior art. Accordingly, the same reaction conditions, ratio of reactants and the like can be used.

Acylated nitrogen compositions prepared by reacting the acylating agents of this invention with an amine (a) as described above are post-treated by contacting the acylated nitrogen compositions thus formed (e.g., the carboxylic derivative compositions) with one or more post-treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulfide, hydrogen sulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents such as terephthalic acid, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols, and sulfur plus phenols.

The same post-treating reagents are used with carboxylic derivative compositions prepared from the acylating agents of this invention and a combination of amines (a) and alcohols (b) as described above.

However, when the carboxylic derivative compositions of this invention are derived from alcohols (b) and the acylating agents, that is, when they are acidic or neutral esters, the post-treating reagents are usually selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, sulfur, sulfur chlorides, phosphorus sulfides, phosphorus oxides, carboxylic acid acylating agents such as terephthalic acid, epoxides, and episulfides.

Since post-treating processes involving the use of these post-treating reagents is known insofar as application to reaction products of high molecular weight carboxylic acid acylating agents of the prior art and amines and/or alcohols, detailed descriptions of these processes herein is unnecessary. In order to apply the prior art processes to the carboxylic derivative compositions of this invention, all that is necessary is that reaction conditions, ratio of reactants, and the like as described in the prior art, be applied to the novel carboxylic derivative compositions of this invention.The following U.S. patents are expressly incorporated herein by reference for their disclosure of post-treating processes and posttreating reagents applicable to the carboxylic derivative compositions of this invention: 3,087,936; 3,200,108; 3,254;025; 3,256,185; 3,278,550; 3,281,428; 3,282,955; 3,284,410; 3,338,832; 3,344,069; 3,366,569; 3,373,111; 3,367,943; 3,403,102; 3,428,561; 3,502,677; 3,513,093; 3,533,945; 3,541,012 (use of acidified clays in post-treating carboxylic derivative compositions derived from the acylating reagents of this invention and amines); 3,639,242; 3,708,522; 3,859,318; 3,865,813; 3,470,098; 3,369,021; 3,184,411; 3,185,645; 3,245,908; 3,245,909; 3,245,910; 3,573,205; 3,269,681; 3,749,695; 3,865,740; 3,954,639; 3,459,530; 3,390,086; 3,367,943; 3,185,704; 3,551,466; 3,415,750; 3,312,619; 3,280,034; 3,718,663; 3,652,616; UK 1,085,903; UK 1,162,436; U.S. 3,558,743. The processes of these incorporated patents, as applied to the carboxylic derivative compositions of this invention, and the post-treated carboxylic derivative compositions thus produced constitute a further aspect of this invention.

Furthermore, the carboxylic derivative compositions, the post-treated carboxylic derivative compositions, the acylating agents described hereinabove and processes for their preparation are described in U.S. Patent 4,234,435, which is expressly incorporated herein by reference for its teachings in this regard.

(c) Chlorine-containing compounds The chlorine-containing compounds useful for the purposes of this invention are selected from the group consisting of chloroaliphatic hydrocarbon-based compounds, chloroalicyclic hydrocarbonbased compounds or mixtures thereof.

The chloroaliphatic hydrocarbon-based compounds useful for the purpose of this invention are compounds which comprise chlorine atoms and aliphatic hydrocarbon-based radicals. As used herein, the term "aliphatic hydrocarbon-based radical" denotes a radical having an aliphatic carbon atom directly attached to the chlorine atom and having predominantly aliphatic hydrocarbon character within the context of this invention. Such radicals include the following: (1) Aliphatic hydrocarbon radicals: e.g., alkyl, alkenyl, and aromatic- and alicyclic-substituted alkyl and alkenyl radicals, and the like. Such radicals are known to those skilled in the art; examples include ethyl, propyl, butyl, pentyl, octyl, decyl, stearyl, dodecenyl and oleyl (all isomers being included).

(2) Substituted aliphatic hydrocarbon radicals; that is, radicals containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominantly aliphatic hydrocarbon character of the radical. Those skilled in the art will be aware of suitable substituents (e.g., alkoxy, hydroxy, alkylthio, carbalkoxy, nitro).

(3) Heteroaliphatic hydrocarbon radicals; that is, radicals which, while predominantly aliphatic hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, oxygen and nitrogen.

In general, no more than about three substituents or heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in the aliphatic hydrocarbon-based radical.

Preferably, the aliphatic hydrocarbon-based radical present in the chlorine compounds of this invention is free from acetylenic and usually also from ethylenic unsaturation and contains at least five carbon atoms. Most often it is an alkyl-based radical, usually an alkyl radical.

The term " alkyl-based radical", as used herein, denotes an alkyl radical within the description of the term "aliphatic hydrocarbon-based radical" and includes alkyl radicals analogous to the "aliphatic hydrocarbon-based radicals" described hereinabove and such radicals are alkyl-hydrocarbon radicals, substituted alkyl-hydrocarbon radicals and hetero-alkyl hydrocarbon radicals.

The chloroalicyclic hydrocarbon-based compounds useful for the purposes of this invention are compounds comprising chlorine atoms and alicyclic hydrocarbon-based radicals. As used herein, the term "alicyclic hydrocarbon-based radical" denotes a radical having an alicyclic carbon atom directly attached to the chlorine atom and having predominantly alicyclic hydrocarbon character within the context of this invention. Such radicals include the following: (1) Alicyclic hydrocarbon radicals; e.g., cycloalkyl or cycloalkenyl, and aromatic- and aliphaticsubstituted alicyclic radicals, and the like. Such radicals are known to those skilled in the art; examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methycyclohexyl, cyclopentenyl, cyclopentadienyl and cyclohexenyl.

(2) Substituted alicyclic hydrocarbon radicals; that is, radicals containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominantly alicyclic hydrocarbon character of the radical. Those skilled in the art will be aware of suitable substituents (e.g., alkoxy, hydroxy, alkylthio, carbalkoxy, nitro).

(3) Heteroalicyclic hydrocarbon radicals; that is, radicals which, while predominantly alicyclic hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, oxygen and nitrogen.

In general, no more than three substituents or heteroatoms, and preferably no more than one, will be present for each ten carbon atoms in the alicyclic hydrocarbon-based radical.

Preferably, the alicyclic hydrocarbon-based radical present in the chlorine-containing compounds of this invention is free from acetylenic and usually also free from ethylene unsaturation and contains at least five carbon atoms.

As previously stated, the chlorine-containing compounds may also be mixtures of one or more of the chloroaliphatic hydrocarbon-based compounds and/or the chloroalicyclic hydrocarbon-based compounds. Furthermore, the chlorine-containing compounds usually contain approximately from about 30 to about 70 percent by weight chlorine. The preparation of the chlorine-containing compounds (c) is well known to those of ordinary skill in the art and a detailed description of the process is unnecessary. Briefly, such compounds are prepared by reacting chlorine gas with the appropriate hydrocarbon-based compound until the desired weight gain of chlorine is obtained.

The preferred chlorine-containing compounds are the chlorinated paraffin wax compositions. The molecular weight of these chlorinated paraffin wax compositions usually ranges from about 300 up to about 1100, preferably from about 350 to about 700 and, preferably, contains from about 35 up to about 50% by weight of chlorine These preferred chlorine-containing compounds are commercially available from Diamond Chemicals under the trademark Chlorowax.

Sulfurized olefinically unsaturated compound The compositions of this invention may be further combined with at least one sulfurized olefinically unsaturated compound.

The olefinically unsaturated compounds which are sulfurized to provide the sulfurized olefinically unsaturated compounds useful for the purposes of this invention are diverse in nature. They contain at least one olefinic double bond, which is defined as a non-aromatic double bond; that is, one connecting two aliphatic carbon atoms. In its broadest sense, the olefin may be defined by the formula R7R8C=R9R10, wherein each of R7, Rs, R9 and R10 is hydrogen or an organic radical.In general, the R groups in the above formula which are not hydrogen may be satisfied by such groups as-C(R11)3, -CON(R11)2, -COON(R11)4, #OOM, -CN,

R11, -X, -YR11 or -Ar, wherein: Each R11 is independently hydrogen, alkyl, alkenyl, aryl, substituted alkyl, substituted alkenyl or substituted aryl, with the proviso that any two R11 groups can be alkylene or substituted alkylene whereby a ring of up to about 12 carbon atoms is formed; M is one equivalent of a metal cation (preferably Group I or II, e.g., sodium, potassium, barium, calcium); X is halogen (e.g., chloro, bromo, or iodo); Y is oxygen or divalent sulfur; Ar is an aryl or substituted aryl radical of up to about 12 carbon atoms in the substituent.

Any two of R7, R8, R9 and R10 may also together form an alkylene or substituted alkylene group, i.e., the olefinic compound may be alicyclic.

The nature of the substituents in the substituted moieties described above are not normally a critical aspect of the invention and any such substituent is useful so long as it is or can be made compatible with lubricating environments and does not interfere under the contemplated reaction conditions. Thus, substituted compounds which are so unstable as to deleteriously decompose under the reaction conditions employed are not contemplated. However, certain substituents such as keto or aldehydo can desirably undergo sulfurization. The selection of suitable substituents is within the skill of the art or may be established through routine testing. Typical of such substituents include any of the above-listed moieties as well as hydroxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, nitro, phosphate, phosphite, alkali metal mercapto and the like.

The olefinically unsaturated compound is usually one in which each R group which is not hydrogen is independently alkyl, alkenyl or aryl, or (less often) a corresponding substituted radical.

Monoolefinic and diolefinic compounds, particularly the former, are preferred, and especially terminal monoolefinic (~-olefins) hydrocarbons; that is, those compounds in which R7 and R8 are hydrogen and R9 and R' are alkyl or aryl, especially alkyl (that is, the olefin is aliphatic). Olefinic compounds having from about 8 up to about 36 and especially from about 8 up to about 20 carbon atoms are particularly desirable.

The C8#38 aliphatic a-olefin (i.e., terminal olefin) is usually one which is unbranched on the olefinic carbon atoms; that is, which contains the moiety CH2=CH-. It also usually contains substantially no branching on the aliylic carbon atoms; that is, it preferably contains the moiety CH2=CHCH2-. The preferred olefins are those in the C8#20 range. Mixtures of these olefins are commercially available and such mixtures are suitable for use in this invention.

Also, fatty acid esters derived from one or more unsaturated carboxylic acids are particularly useful as the olefinically unsaturated compounds.

The term "fatty acid" as used herein refers to acids which may be obtained by hydrolysis of a naturally occurring vegetable or animal fat or oil. These are usually in the C16#20 range and include oleic acid, linoleic acid and the like.

Fatty acid esters which are useful are primarily esters of aliphatic alcohols, including monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, the butanols, etc., and polyhydric alcohols including ethylene glycol, propylene glycol, trimethylene glycol, neopentyl glycol, glycerol and the like.

Particularly preferred are fatty oils derived predominantly from unsaturated acids, that is, naturally occurring triglycerides of long chain unsaturated carboxylic acids, especially linoleic and oleic acids.

These fatty oils include such naturally occurring animal and vegetable oils are lard oil, peanut oil, cotton seed oil, soybean oil, corn oil and the like.

The composition and nature of fatty oils is well known to those of ordinary skill in the art and can be found in more detail in M.P. Doss, Properties of the principal, FATS, Fatty Oils, Waxes, Fatty Acids and Their Salts, The Texas Company, 1 952, which is hereby incorporated by reference for its description of the fatty oils and unsaturated carboxylic acids useful for this invention.

The sulfurization of olefinically unsaturated compounds can be prepared by reacting, for example, elemental sulfur with one or more of the olefinically unsaturated compounds described above at a temperature of from about 1 000C up to about 2500C., preferably, from about 1250 C. up to about 2000C. The amounts of sulfur per mole of olefinically unsaturated compound are usually from about 0.3 to about 2.0 gram-atoms, preferably from about 0.5 to about 1.5 gram-atoms.

The following U.S. patents are illustrative of the sulfurized olefinically unsaturated compounds useful for this invention and the processes for their preparation, and are expressly incorporated herein by reference for their teachings in this regard: 3,796,661; 3,919,187; 3,850,825; 3,986,966; 4,053,427; 4,119,550.

The following specific illustrative examples describe how to make the amino phenols (A) and the carboxylic derivative and post-treated carboxylic derivative compositions (B) which comprise the combination compositions of this invention.

In these examples, as well as in this specification and the appended claims, all percentages, parts and ratios are by weight, unless otherwise expressly stated to the contrary. Temperatures are in degrees centigrade (OC.) unless expressly stated to the contrary.

Example 1A A mixture of 4578 parts of a polyisobutene-substituted phenol prepared by boron trifluoridephenol catalyzed alkylation of phenol with a polyisobutene having a number average molecular weight of approximately 1000 (vapor phase osmometry), 3052 parts of diluent mineral oil and 725 parts of textile spirits is heated to 600 to achieve a homogenity. After cooling to 300,319.5 parts of 16 molar nitric acid in 600 parts of water is added to the mixture. Cooling is necessary to keep the mixture's temperature below 400. After the reaction mixture is stirred for an additional two hours, an aliquot of 3710 parts is transferred to a second reaction vessel. This second portion is treated with an additional 127.8 parts of 16 molar nitric acid in 130 parts of water at 25#300.The reaction mixture is stirred for 1.5 hours and then stripped to 2200/30 tor. Filtration provides an oil solution of the desired intermediate (IA).

Example 1 B A mixture of 810 parts of the oil solution of the (IA) intermediate described in Example 1 A, 405 parts of isopropyl alcohol and 405 parts of toluene is charged to an appropriate sized autoclave.

Platinum oxide catalyst (0.81 part) is added and the autoclave is evacuated and purged with nitrogen four times to remove any residual air. Hydrogen is fed to the autoclave at a pressure of 29~55 psig while the content is stirred and heated to 27--920 for a total of thirteen hours. Residual 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 stripped to provide an oil solution of the desired amino phenol. This solution contains 0.578% nitrogen.

Example 2 An alkylated phenol is prepared by reacting phenol with polybutene having a number average molecular weight of about 1000 (vapor phase osmometry) in the presence of a boron trifluoride/phenol catalyst. The catalyst is neutralized and removed by filtration. Stripping of the product filtrate first to 2300/760 tor (vapor temperature), then to 2050/50 tor (vapor temperature), provides purified alkylated phenol as a residue.

To a mixture of 265 parts of purified alkyl phenol, 1 76 parts blend mineral oil and 42 parts of petroleum naphtha having a boiling point of approximately 200 is slowly added a mixture of 18.4 parts concentrated nitric acid (69~70%) and 35 parts water. The reaction mixture is stirred for 3 hours at about 30--450, stripped to 1200/20 tor (vapor temperature) and filtered to provide an oil solution of the desired nitro phenol intermediate.

Example 3 A mineral oil solution (1900 parts) of an alkylated, nitrated phenol as described in Example 2 containing 43% mineral oil is heated under a nitrogen atmosphere to 1450. Then 70 parts of hydrazine hydrate is slowly added to the mixture over 5 hours while its temperature is held at about 1450. The mixture is then heated to 1 600 for one hour while 56 parts of aqueous distillate is collected. An additional 7 parts of hydrazine hydrate is added and the mixture is held at 1400 for an additional hour.

Filtration at 1 300 provides an oil solution of the desired amino phenol product containing 0.5% nitrogen.

Example 4 To a mixture of 800 parts of polybutene-substituted phenol prepared essentially as described in Example 2, and 944 parts of diluent mineral oil at 590 is added 72 parts of concentrated nitric acid.

The reaction is controlled so as to keep the reaction temperature between 59 and 680. The reaction mixture is stirred for two hours at 69--730 and then heated to 1400 while nitrogen is slowly passed through it and water is removed by distillation. Hydrazine hydrate (90 parts) is then slowly added to the mixture at 1300 to 1370 over 3 hours. The mixture is stirred for 0.5 hour at this temperature and then heated to 1 600 while nitrogen is slowly passed through the mixture and provision is made for collecting the aqueous distillate. The residue is an oil solution of the desired amino phenol product.

Example 5 A mixture of 609 parts of polybutene-substituted phenol prepared essentially as described in Example 2 and 454 parts of mineral diluent oil is blended at 570. To this mixture is added, over 8 hours, 46.5 parts of concentrated nitric acid (66.3% nitric acid). The mixture is stirred for 1.5 hours at 58--63 0 and then heated to 1420 for 1.7 hours while nitrogen is slowly passed through the mixture.

The mixture is held at 143~145 for 0.5 hour and then cooled to 1 140. During the reaction, 23 parts of distillate is collected. Filtration of the mixture at 1 1 3--1260 provides an oil solution of the desired nitro intermediate having a nitrogen content of 0.64%.

Example 6 To 320 parts of the oil solution of the polybutene-substituted nitrated phenol described in Example 5 is added 12 parts of aqueous hydrazine (64% hydrazine) over 6.25 hours at a temperature of 1600. Filtration provides an oil solution of the desired amino phenol product having a nitrogen content of 0.59%.

Example 7 To a mixture of 3000 parts of an alkylated phenol made essentially as described in Example 2 having a polybutene substituent of about 70 carbon atoms and 3000 parts of glacial acetic acid at 51 0 is added 540 parts of concentrated nitric acid over three hours. During the addition, the mixture is held at 5 1#630. The mixture is stored at room temperature for 18 hours and then heated to 1200 for 6 hours while nitrogen is slowly passed through the mixture. Provision is made for collecting the aqueous distillate. The reaction is then stripped to 1 400/28 tor (vapor temperature) and the residue filtered at 1200 to provide the desired final product having a nitrogen content of 2.55%. On this basis, it is calculated that the product contains an average of two nitro groups per alkylated phenol.

Example 8 To a mixture of 545 parts of the alkylated dinitro phenol described in Example 7 and 340 parts of diluent mineral oil at 1250 is added 100 parts of hydrazine hydrate. This addition is carried out under a nitrogen atmosphere for a 2.5 hour period while the temperature is held at 122--1250. The reaction mixture is then refluxed at 1230 for 2.5 hours and heated for an additional 2 hours to 1550 while provision is made for collecting aqueous distillate. A slow stream of nitrogen is passed through the reaction mixture at 150--1 550 for an additional 2 hours and the residue is filtered to provide an oil solution of the desired amino phenol product having a nitrogen content of 1.16%.

Example 9 To a mixture of 361 parts of tetrapropenyl-substituted phenol and 271 parts of glacial acetic acid at 7---170 is added a mixture of 90 parts concentrated nitric acid (70% HNO3) and 90 parts of glacial acetic acid. The addition is carried out over 1.5 hours while the reaction mixture is cooled externallv to 7-1 70 The cooling bath is removed and the reaction stirred for 2 hours at room temperature.

Stripping to 1 340/?5 tor (vapor temperature) and filtration provides as a residue the desired nitrated intermediate having a nitrogen content of 4.65%.

Example 10 To 303 parts of the nitrated intermediate described in Example 9 at 1250 under a nitrogen atmosphere is added 100 parts of hydrazine hydrate over a 2.4 hour period. The mixture is refluxed for 2.5 hours and then distilled to a vapor temperature of 1550. A slow stream of nitrogen is passed through the reaction mixture while it is kept at a temperature of 1 55 to 1900. Filtration of the residue provides the desired amino phenol product which has a nitrogen content of 4.89%.

Example 11 A mixture of 510 parts (0.28 mole) of polyisobutene (Mn=1 845; Mw=5325) and 59 parts (0.59 mole) of maleic anhydride is heated to 1100. This mixture is heated to 1900 in seven hours during which 43 parts (0.6 mole) of gaseous chlorine is added beneath the surface. At 1900--1920 an additional 11 parts (0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is stripped by heating at 1900--1930 with nitrogen blowing for 10 hours. The residue is the desired polyisobutenesubstituted succinic acylating agent having a saponification equivalent number of 87 as determined by ASTM procedure D-94.

Example 12 A mixture of 1000 parts (0.495 mole) of polyisobutene (Mn=2020; Mw=6049) and 11 5 parts (1.17 moles) of maleic anhydride is heated to 1100. This mixture is heated to 1840 in 6 hours during which 85 parts (1.2 moles) of gaseous chlorine is added beneath the surface. At 1840--1890 an additional 59 parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is stripped by heating at 1860--1900 with nitrogen blowing for 26 hours. The residue is the desired polyisobutenesubstituted succinic acylating agent having a saponification equivalent number of 87 as determined by ASTM procedure D-94.

Example 13 A mixture of 3251 parts of polyisobutene chloride, prepared by the addition of 251 parts of gaseous chlorine to 3000 parts of polyisobutene (Mn=1 696; Mw=6594) at 800 in 4.66 hours, and 345 parts of maleic anhydride is heated to 2000 in 0.5 hour. The reaction mixture is held at 200 ~ 2240 for 6.33 hours, stripped at 2100 under vacuum and filtered. The filtrate is the desired polyisobutene-substituted succinic acylating agent having a saponification equivalent number of 94 as determined by ASTM procedure D-94.

Example 14 A mixture is prepared by the addition of 10.2 parts (0.25 equivalent) of a commercial mixture of ethylene polyamines having from about 3 to about 10 nitrogen atoms per molecule to 11 3 parts of mineral oil and 161 parts (0.25 equivalent) of the substituted succinic acylating agent prepared in Example 11 at 1380. The reaction mixture is heated to 1 500 in 2 hours and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.

Example 15 A mixture is prepared by the addition of 57 parts (1.38 equivalents) of a commercial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms per molecule to 1067 parts of mineral oil and 893 parts (1.38 equivalents) of the substituted succinic acylating agent prepared in Example 12 at 1400 to 1450. The reaction mixture is heated to 1550 in 3 hours and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.

Example 16 A mixture is prepared by the addition of 18.2 parts (0.433 equivalent) of a commercial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms per molecule to 392 parts of mineral oil and 348 parts (0.52 equivalent) of the substituted succinic acylating agent prepared in Example 12 at 1400. The reaction mixture is heated to 1 500 in 1.8 hours and stripped by blowing with nitrogen.

The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.

Example 17 A mixture of 334 parts (0.52 equivalent) of the polyisobutene-substituted succinic acylating agent prepared in Example 11, 548 parts of mineral oil, 30 parts (0.88 equivalent) of pentaerythritol and 8.6 parts (0.0057 equivalent) of Polyglycol 112-2 demulsifier from Dow Chemical Company is heated at 1 500 for 2.5 hours. The reaction mixture is heated to 2100 in 5 hours and held at 2100 for 3.2 hours. The reaction mixture is cooled to 1 900 and 8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines having an average of about 3 to about 10 nitrogen atoms per molecule is added. The reaction mixture is stripped by heating at 2050 with nitrogen blowing for 3 hours, then filtered to yield the filtrate as an oil solution of the desired product.

Example 18 A mixture of 3225 parts (5.0 equivalents) of the polyisobutene-substituted succinic acylating agent prepared in Example 1 2, 289 parts (8.5 equivalents) of pentaerythritol and 5204 parts of mineral oil is heated at 2250--2350 for 5.5 hours. The reaction mixture is filtered at 1300 to yield an oil solution of the desired product.

Example 19 A mixture of 631 parts of the oil solution of the product prepared in Example 18 and 50 parts of anthranilic acid is heated at 195~212 for four hours. The reaction mixture is then filtered at 1300 to yield an oil solution of the desired product.

Example 20 A mixture is prepared by the addition of 14 parts of aminopropyl diethanolamine to 867 parts of the oil solution of the product prepared in Example 1 8 at 190~200 . The reaction mixture is held at 1950 for 2.25 hours, then cooled to 1200 and filtered. The filtrate is an oil solution of the desired product.

Example 21 A mixture of 62 parts of boric acid and 2720 parts of the oil solution of the product prepared in Example 14 is heated at 1 500 under nitrogen for six hours. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired boron-containing product.

Example 22 An oleyl ester of boric acid is prepared by heating an equimolar mixture of oleyl alcohol and boric acid in toluene at the reflux temperature while water is removed azeotropically. The reaction mixture is then heated to 1 500 under vacuum and the residue is the ester having a boron content of 3.2% and a saponification number of 62. A mixture of 344 parts of the ester and 2720 parts of the oil solution of the product prepared in Example 14 is heated at 1500 for six hours and then filtered. The filtrate is an oil solution of the desired boron-containing product.

Example 23 Boron trifluoride (34 parts) is bubbled into 21 90 parts of the oil solution of the product prepared in Example 1 5 at 800 within a period of three hours. The resulting mixture is blown with nitrogen at 7O#800 for two hours to yield the residue as an oil solution of the desired product.

Example 24 A mixture of 3420 parts of the oil-containing solution of the product prepared in Example 1 6 and 53 parts of acylonitrile is heated at reflux temperature from 1250 to 1450 for 1.25 hours, at 1450 for three hours and then stripped at 1250 under vacuum. The residue is an oil solution of the desired product.

Example 25 A mixture is prepared by the addition of 44 parts of ethylene oxide over a period of one hour to 1460 parts of the oil solution of the product prepared in Example 15 at 1500. The reaction mixture is held at 1 500 for one hour, then filtered to yield the filtrate as an oil solution of the desired product.

Example 26 A mixture of 3880 parts of the oil solution of the product of Example 14 and 120 parts of terephthalic acid is heated at 1 500--1 600 and filtered. The filtrate is an oil solution of the desired product.

Example 27 A decyl ester of phosphoric acid is prepared by adding one mole of phosphorus pentaoxide to three moles of decyl alcohol at a temperature within the range of 320 to 550 and then heating the mixture at 60--63 0 until the reaction is complete. The product is a mixture of the decyl esters of phosphoric acid having a phosphorus content of 9.9% and an acid number of 250 (phenolphthalein indicator). A mixture of 1 750 parts of the oil solution of the product prepared in Example 14 and 112 parts of the above decyl ester is heated at 145-1 500 for one hour. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.

Example 28 A mixture of 2920 parts of the oil solution of the product prepared in Example 1 5 and 69 parts of thiourea is heated to 800 and held at 800 for two hours. The reaction mixture is then heated at 1 501550 for four hours, the last of which the mixture is blown with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.

Example 29 A mixture of 1460 parts of the oil solution of the product prepared in Example 15 and 81 parts of a 37% aqueous formaldehyde solution is heated at reflux for three hours. The reaction mixture is stripped under vacuum at 1500. The residue is an oil solution of the desired product.

Example 30 A mixture of 1160 parts of the oil solution of the product prepared in Example 14 and 67 parts of sulfur monochloride is heated for one hour at 1 500 under nitrogen. The mixture is filtered to yield an oil solution of the desired sulfur-containing product.

Example 31 A mixture is prepared by the addition of 11.5 parts of formic acid to 1 000 parts of the oil solution of the product prepared in Example 1 5 at 600. The reaction mixture is heated at 60--1 000 for two hours, 92-i 000 for 1.75 hours and then filtered to yield an oil solution of the desired product.

Example 32 A mixture is prepared by the addition of 58 parts of propylene oxide to 11 70 parts of the oil solution of the product prepared in Example 18 and 10 parts of pyridine at 80--900. The reaction mixture is then heated at 100~120 for 2.5 hours and then stripped to 1700 under vacuum. The residue is an oil solution of the desired product.

Example 33 A mixture of 1170 parts of the oil solution of the product prepared in Example 18 and 36 parts of maleic anhydride is heated to 2000 over a 1.5 hour period and maintained at 200~210 for 5.5 hours. During the last 1.5 hour period of heating, the reaction mixture is blown with nitrogen. The reaction mixture is stripped to 1 900 under vacuum, then filtered to yield the filtrate as an oil solution of the desired product.

As previously indicated, the nitrogen-containing organic compositions of this invention comprise the combination of (A) and (B) or (C). Also, a combination of (A), (C) and at least one sulfurized olefinicially unsaturated compound is a preferred embodiment of this invention. The nitrogencontaining organic compositions comprising a combination of (A), (B) and (C) is another preferred embodiment of this invention. An additional preferred embodiment of the present invention are the nitrngen-containin'g organic compositions comprising a combination of (A), (B), (C) and at least one sulfurized olefinically unsaturated compound.

Accordingly, the above compositions may be combined simultaneously or sequentially in any order.

The nitrogen-containing organic compositions are preferably prepared by combining the abovedescribed component compositions through the use of conventional blending techniques which include, for example, mixing the component compositions at a temperature sufficient to insure homogeneous blending and/or the use of a solvent/diluent such as mineral oil, xylene, naphtha or a normally liquid fuel to facilitate handling and to insure a homogeneous mixture of the component compositions.

Such techniques are well known to those of ordinary skill in the art and, therefore, further discussion is unnecessary. Generally, the weight ratio of the component compositions (B), (C) and the sulfurized olefinically unsaturated compounds to the amino phenol compounds (A) is about 0.1 to about 10.0 parts to one part amino phenol.

The examples in the following table illustrate the nitrogen-containing compositions of the present invention.

Table Ex. Suffurized** no. Ex. 3 Ex. 14 Ex. 26 Chlorowax~4O* C15#18 a-olefin I 16.5 --- 70 10 3.5 II 16.5 70 --- 10 3.5 lil 65 --- --- 35 IV 20 --- 80 V 20 80 --- *Commercially available chlorinated paraffin wax from Diamond Chemicals containing about 40% by weight chlorine.

**Prepared by reacting 1 mole of elemental sulfur with 1 mole of C15#18 a-olefin at 1 700C for 9 hours under a blanket of nitrogen gas.

As previously indicated, the compositions of this invention are also useful as additives for lubricants, in which they function as antioxidants, anticorrosives, detergents, dispersants, fluidity modifiers and, in particular, impart one or more of the following properties to lubricants: anticorrosive, antiwear and friction reducing properties. These particular properties are unexpected and are especially effective in protecting silver, copper and lead parts in diesel engines. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, stationary power engines and turbines and the like. Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions can also benefit from the incorporation therein of the compositions of the present invention.

Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins [e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers, chlorinated polybutylenes, poly( 1 -hexenes), poly( 1 -octenes), poly( 1 -decenes), etc. and mixtures thereof]; alkylbenzenes [e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes, etc.]; polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500~1000, diethyl ether of polypropylene glycol having a molecular weight of 1 000-1 500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C13 Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic 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, diisooctyl azelate, diisodecyl azelate, dioctyl phthaiate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants [e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes, poly-(methylphenyl)siloxanes, etc.]. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahydrofurans and the like.

Unrefined, refined and rerefined oils (and mixtures of each with each other) of the type disclosed hereinabove can be used in the lubricant compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those of skill in the art such as solvent extraction, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.

Generally, the lubricants of the present invention contain an amount of the nitrogen-containing organic compositions of this invention sufficient to provide it with antioxidant, antiwear, anticorrosive, detergent, dispersant, friction reducing or fluidity modifying properties. Normally this amount will be about 0.05% to about 20%, preferably about 0.1% to about 10% of the total weight of the lubricant. In lubricating oils operated under extremely adverse conditions, such as lubricating oils for marine diesel engines, the compositions of this invention may be present in amounts of up to about 30% by weight.

The term "minor amount" as used in the specification and appended claims is intended to mean that when a composition contains a "minor amount" of a specific material that amount is less than 50% by weight of the composition.

The term "major amount" as used in the specification and appended claims is intended to mean that when a composition contains a "major amount" of a specific material that amount is more than 50% by weight of the composition.

The invention also contemplates the use of other additives in combination with the compositions of this invention. Such additives include, for example, auxiliary detergents and dispersants of the ashproducing or ashless type, auxiliary corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, copper deactivators, color stabilizers and antifoam agents.

The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, phenols or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.

The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 500 C. and filtering the resulting mass. The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known.Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-P- naphthylamine, and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60#2OO0 C.

The basic alkali and/or alkaline earth metal carbonate sulfonate and/or phenate useful in combination with the nitrogen-containing organic compositions of this invention, are well known to those of ordinary skill in the art and are described in detail in U.S. Patent 3,779,920 which is expressly incorporated herein by reference for its teaching in regard to these compositions and the processes for their preparation.

Auxiliary ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for use in the lubricants of this invention. The following are illustrative: (1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms with nitrogen-containing compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic materials.Examples of these "carboxylic dispersants" are described in British Patent 1,306,529 and in many U.S. patents including the following: 3,163,603 3,351,552 3,541,012 3,184,474 3,381,022 3,542,678 3,215,707 3,399,141 3,542,680 3,219,666 3,415,750 3,567,637 3,271,310 3,433,744 3,574,101 3,272,746 3,444,170 3,576,743 3,281,357 3,448,048 3,630,904 3,306,908 3,448,049 3,632,510 3,311,558 3,451,933 3,632,511 3,316,177 3,454,607 3,697,428 3,340,281 3,467,668 3,725,441 3,341,542 3,501,405 Re 26,433 3,346,493 3,522,179 (2) Reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines, preferably polyalkylene polyamines.These may be characterized as "amine dispersants" and examples thereof are described for example in the following U.S. patents: 3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines), which may be characterized as "Mannich dispersants". The materials described in the following U.S.

Patents are illustrative: 2,459,112 3,442,808 3,591,598 2,962,442 3,448,047 3,600,372 2,984,550 3,454,497 3,634,515 3,036,003 3,459,661 3,649,229 3,166,516 3,461,172 3,697,574 3,236,770 3,493,520 3,725,277 3,355,270 3,539,633 3,725,480 3,368,972 3,558,743 3,726,882 3,413,347 3,586,629 3,980,569 (4) Products obtained by post-treating the carboxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbonsubstituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like.Exemplary materials of this kind are described in the following U.S. patents: 3,036,003 3,282,955 3,493,520 3,639,242 3,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,093 3,649,659 3,216,936 3,367,943 3,533,945 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,536 3,280,234 3,455,831 3,591,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522 (5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates.These may be characterized as "polymeric dispersants" and examples thereof are disclosed in the following U.S. patents: 3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 The above-noted patents are incorporated by reference herein for their disclosures of ashless dispersants.

Extreme pressure agents and auxiliary corrosion- and oxidation-inhibiting agents are exemplified by sulfurized alkylphenol, phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentyiphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate;Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol.

Still another additive which may be combined with the nitrogen-containing compositions of the invention are the 2,5-bis-C5-C20 alkyldithio thiodiazoles, such as 2,5-bis(octyldithio)thiadiazole, which function as antioxidants, sulfur deactivators and antiwear agents. The dithiothiadiazoles are advantageously employed in an amount of between 0.01 and 1 wt.%, and preferably between 0.02 and 0.1 wt.% of the finished oil composition.

The compositions of this invention can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concentrates usually contain about 20~90% by weight of the composition of this invention and may contain, in addition, one or more other additives known in the art or described hereinabove.

The fuel compositions of the present invention contain a major proportion of a normally liquid fuel, usually a hydrocarbonaceous petroleum distillate fuel such as motor gasoline as defined by ASTM Specification D 439~73 and diesel fuel or fuel oil as defined by ASTM Specification D-396.

Normally liquid fuel compositions comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) are also within the scope of this invention as are liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale and coal. Normally liquid fuels which are mixtures of one or more hydrocarbonaceous fuels and one or more nonhydrocarbonaceous materials are also contemplated. Examples of such mixtures are combinations of gasoline and ethanol, and diesel fuel and ether. Particularly preferred is gasoline, that is, a mixture of hydrocarbons having an ASTM boiling point of about 600 C. at the 10% distillation point to about 2050C. at the 90% distillation point.

Generally, these fuel compositions contain an amount of the nitrogen-containing organic composition of this invention sufficient to impart antioxidant, antiwear, anticorrosive, friction reducing, detergent or dispersant properties to the fuel; usually this amount is about 0.001 to about 5% (based on the weight of the final composition), preferably 0.001% to 1%.

The fuel compositions of this invention can contain, in addition to the compositions of this invention, other additives which are well known to those of skill in the art. These can include antiknock agents such as tetraalkyl lead compounds, lead scavengers such as haloalkanes (e.g., ethylene dichloride and ethylene dibromide), deposit preventors or modifiers such as triaryl phosphates, dyes, cetane improvers, auxiliary antioxidants such as 2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants, anti-icing agents and the like.

In certain preferred fuel compositions of the present invention, the afore-described compositions are combined with an ashless dispersant in gasoline. Such ashless dispersants are preferably esters of a mono- or polyol and a high molecular weight mono- or polycarboxylic acid acylating agent containing at least 30 carbon atoms in the acyl moiety. Such esters are well known to those of skill in the art. See, for example, French patent 1,396,645, British patents 981,850 and 1,055,337 and U.S. patents 3,255,108; 3,311,558; 3,331,776; 3,346,354; 3,522,179; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428; 3,708,522; and British Patent Specification 1,306,529. These patents are expressly incorporated herein by reference for their disclosure of suitable esters and methods for their preparation.Generally, the weight ratio of the compositions of this invention to the aforesaid ashless dispersants is about 0.1 to about 10.0, preferably about 1 to about 10 parts of composition to 1 part ashless dispersant. In still another embodiment of this invention, the inventive additives are combined with Mannich condensation products formed from substituted phenols, aldehydes, polyamines, and substituted pyridines. Such condensation products are described in U.S. patents 3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,725,277.

The compositions of this invention can be added directly to the fuel to form the fuel compositions of this invention or they can be diluted with a substantially inert, normally liquid organic solvent/diluent such as mineral oil, xylene, or a normally liquid fuel as described above, to form an additive concentrate which is then added to the fuel in sufficient amounts to form the inventive fuel composition described herein. These concentrates generally contain about 20 to 90 percent of the compositions of this invention and can contain in addition any of the above-described conventional additives, particularly the afore-described ashless dispersants in the aforesaid proportions. The remainder of the concentrate is the solvent/diluent.

The lubricant, fuel and additive concentrate compositions of this invention are exemplified by the following: Example A A gasoline having a Reid vapor pressure of 8.4 psi and containing 24 parts per million parts of gasoline of the nitrogen-containing product described in Example V.

Example B A diesel fuel oil containing 40 parts per million parts of fuel of the nitrogen-containing product described in Example IV.

Example C A solvent-refined, neutral SAE 10 mineral oil containing 7% of the nitrogen-containing product described in Example II.

Example D A solvent-refined, SAE 40 mineral oil containing 6% of the nitrogen-containing composition described in Example I.

Example E A synthetic lubricant comprised predominantly of Cs~Cg normal alcohol esters of a 50/50 molar mixture of adipic and glutaric acids containing 5% of the nitrogen-containing product described in Example II.

Example F A concentrate comprising 50% of the mineral oil and 50% of the product described in Example I.

The lubricant and fuel compositions of this invention and the nitrogen-containing organic compositions of this invention and the processes for preparing these products have been specifically exemplified above to aid those skilled in the art in understanding and practicing the invention. Many obvious variations and departures from the specific disclosure will be apparent to those of skill in the art based on principles and teachings herein and in the prior art. Such variations and departures are contemplated as being within the scope of the present invention unless clearly excluded by the

Claims (107)

appended claims. Claims

1. A nitrogen-containing organic composition comprising a combination of: (A) at least one amino phenol of the general formula

wherein R is a substantially saturated, hydrocarbon-based substituent of at least 8 aliphatic carbon atoms; a, b and c are each independently an integer of one up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic moiety having 0--3 optional substituents selected from the group consisting of lower alkyl, lower alkoxy, nitro, halo or combinations of two or more of said substituents; and (B) one or more carboxylic derivative compositions produced by reacting at least one substituted succinic acylating agent with a reactant selected from the group consisting of (a) an amine characterized by the presence within its structure of at least one

group, (b) an alcohol, (c) a reactive metal or reactive metal compound, and (d) a combination of two or more of any of (a) through (c), the components of (d) being reacted with said one or more substituted succinic acylating agents simultaneously or sequentially in any order, wherein said substituted succinic acylating agents consist of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene, said polyalkene being characterized by a Mn value of 1200 to about 5000 and a Mw/Mn value of about 1.5 to about 6, said acylating agents being characterized by the presence within their structure of an average of at least 1.3 succinic groups for each equivalent weight of substituent groups.

2. A composition as claimed in claim 1 wherein R contains up to about 750 carbon atoms and there are no optional substituents attached to Ar.

3. A composition as claimed in claim 2 wherein R is an alkyl or alkenyl group.

4. A composition as claimed in claim 1 wherein R contains from about 30 to about 750 aliphatic carbon atoms and is made from a homo- or interpolymer of C2-C10 olefins.

5. A composition as claimed in claim 4 wherein said olefins are selected from the group consisting of ethylene, propylene, butylene and mixtures thereof.

6. A composition as claimed in claim 1 wherein a, b and c are each 1, there are zero optional substituents attached to Ar, and Ar is a benzene nucleus.

7. A composition as claimed in claim 6 wherein R is an alkyl or alkenyl group of at least about 30 carbon atoms and up to about 750 carbon atoms and is derived from a homo- or interpolymer of C2- C10 1 -monoolefins.

8. A composition as claimed in claim 1 wherein the amino phenol is of the formula

wherein R' is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic carbon atoms, R" is a member selected from the group consisting of lower alkyl, lower alkoxy, nitro, and halo; and z is O or 1.

9. A composition as claimed in claim 8 wherein R' is a purely hydrocarbyl aliphatic group of at least about 50 carbon atoms and is made from a polymer or interpolymer of an olefin selected from the group consisting of C2#10 1 -monoolefins and mixtures thereof.

10. A composition as claimed in claim 9 wherein z is 0.

11. A composition according to claim 1 wherein the succinic groups correspond to the formula

wherein R1 and R2 are each independently selected from the group consisting of --OH, --CI, -O- lower alkyl and, when taken together, Rr and 2 are -0-, with the proviso that all the succinic groups need not be the same.

12. A composition according to claim 11 wherein the substituent groups in (B) are derived from one or more polyalkene selected from the group consisting of homopolymers and interpolymers of terminal olefins of two to about sixteen carbon atoms, with the proviso that said interpolymers can optionally contain up to about 40% of polymer units derived from internal olefins of up to about sixteen carbon atoms.

13. A composition according to claim 12 wherein said value of Mn is at least about 1500.

14. A composition according to claim 13 wherein said value of Mw/Mn is at least about 1.8.

1 5. A composition according to claim 14 wherein the substituent groups in (B) are derived from one or more polyalkene selected from the group consisting of homopolymers and interpolymers of terminal olefins of two to about six carbon atoms, with the proviso that said interpolymers can optionally contain up to about 25% of polymer units derived from internal olefins of up to about six carbon atoms.

16. A composition according to claim 15 wherein the substituent groups in (B) are derived from a member selected from the group consisting of polybutene, ethylene propylene copolymer, polypropylene, and mixtures of two or more of any of these.

17. A composition according to claim 16 wherein (B) is characterized by the presence within its structure of an average of at least 1.4 succinic groups for each equivalent weight of the substituent groups.

18. A composition according to claim 17 wherein said value of Mn is about 1 500 to about 2800.

19. A composition according to claim 18 wherein said value of Mw/Mn is about 2.0 to about 3.4.

20. A composition according to claim 19 wherein (B) is characterized by the presence within its structure of at least 1.5 up to about 2.5 succinic groups for each equivalent weight of the substituent groups.

21. A composition according to claim 20 wherein the substituent groups in (B) are derived from polybutene in which at least about 50% of the total units derived from butenes is derived from isobutene.

22. A composition according to claim 21 wherein said value of Mn is about 1500 to about 2400.

23. A composition according to claim 22 wherein said value of Mw/Mn is about 2.5 to about 3.2.

24. A composition according to claim 23 wherein the succinic groups correspond to the formulae

and mixtures of these.

25. A composition as claimed in claim ii, 1 6, 22 or 24 wherein R contains up to about 750 carbon atoms and there are no optional substituents attached to Ar.

26. A composition as claimed in claim 25 wherein R is an alkyl or alkenyl group.

27. A composition as claimed in claim 11, 1 6, 22, or 24 wherein R contains about 30 to about 750 aliphatic carbon atoms and is made from a homo- or interpolymer of C2-C10 olefins.

28. A composition as claimed in claim 27 wherein said olefins are selected from the group consisting of ethylene, propylene, butylene and mixtures thereof.

29. A composition as claimed in claim 11, 1 6, 22 or 24 wherein a, b and c are each 1 , there are zero optional substituents attached to Ar, and Ar is a benzene nucleus.

30. A composition as claimed in claim 29 wherein R is an alkyl or alkenyl group of at least about 30 carbon atoms and up to about 750 carbon atoms and is derived from a homo-or interpolymer of C2-C10 1 -monoolefins.

31. A composition as claimed in claim 11 wherein the amino phenol is of the formula

wherein R' is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic carbon atoms, R" is a member selected from the group consisting of lower alkyl, lower alkoxyl, nitro and halo; and z is O or 1.

32. A composition according to claim 1, 3, 5, 7, 8, 11, 1 6, 22 or 24 wherein, said (B) is a posttreated carboxylic derivative composition prepared by reacting one or more post-treating reagents with said one or more carboxylic derivative compositions.

33. A composition according to claim 32 wherein, when said carboxylic derivative compositions are prepared from reactant (a), said post-treated carboxylic derivative compositions are prepared by reacting said carboxylic derivative composition with one or more post-treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulfide, hydrogen sulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols, and sulfur plus phenols.

34. A composition according to claim 32 wherein, when said carboxylic derivative compositions are prepared from reactant (b), said post-treated carboxylic derivative compositions are prepared by reacting said carboxylic derivative composition with one or more post-treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, sulfur, sulfur chlorides, phosphorus sulfides, phosphorus oxides, carboxylic acid acylating agents, epoxides, and episulfides.

35. A composition according to claim 32 wherein, when said carboxylic derivative compositions are prepared from a combination of reactant (a) and (b), said post-treated carboxylic derivative compositions are prepared by reacting said carboxylic derivative composition with one or more posttreating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulfide, hydrogen sulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols, and sulfur plus phenols.

36. A composition according to claim 31 wherein, said (B) is a post-treated carboxylic derivative composition prepared by reacting one or more post-treating reagents with said one or more carboxylic derivative compositions.

37. A composition according to claim 36 wherein, when said carboxylic derivative compositions are prepared from reactant (a), said post-treated carboxylic derivative compositions are prepared by reacting said carboxylic derivative composition with one or more post-treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulfide, hydrogen sulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyantes, hydrocarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehydeproducing compounds plus phenols and sulfur plus phenols.

38. A composition according to claim 36 wherein, when said carboxylic derivative compositions are prepared from reactant (b), said post-treated carboxylic derivative compositions are prepared by reacting said carboxylic derivative composition with one or more post-treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, sulfur, sulfur chlorides, phosphorus sulfides, phosphorus oxides, carboxylic acid acylating agents, epoxides, and episulfides.

39. A composition according to claim 36 wherein, when said carboxylic derivative compositions are prepared from a combination of reactant (a) and (b), said post-treated carboxylic derivative compositions are prepared by reacting said carboxylic derivative composition with one or more posttreating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulfide, hydrogen sulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyantes, hydrocarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols and sulfur plus phenols.

40. A composition according to claims 1, 3, 5, 7, 8, 11, 1 6, 22, 24, 31 or 36 wherein the nitrogen-containing organic composition is further combined with at least one chlorine-containing compound selected from the group consisting of chloroaliphatic hydrocarbon-based compounds, chloroalicyclic hydrocarbon-based compounds and mixtures thereof which contain from about 30 up to about 70% by weight chlorine therein.

41. A composition according to claim 32 wherein the nitrogen-containing organic composition is further combined with at least one chlorine-containing compounds selected from the group consisting of chloroaliphatic hydrocarbon-based compounds, chloroalicyclic hydrocarbon-based compounds and mixtures thereof which contain from about 30 to about 70% by weight chlorine therein.

42. A nitrogen-containing organic composition comprising a combination of: (A) at least one amino phenol of the general formula

wherein R is a substantially saturated, hydrocarbon-based substituent of at least 8 aliphatic carbon atoms; a, b, and c are each independently an integer of one up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic moiety having 0--3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, halo or combinations of two or more of said substituents; and (C) at least one chlorine-containing compound selected from the group consisting of chloroaliphatic hydrocarbon-based compounds, chloroalicyclic hydrocarbon-based compounds or mixtures thereof.

43. A composition as claimed in claim 42 wherein R contains up to about 750 carbon atoms and there are no optional substituents attached to Ar.

44. A composition as claimed in claim 43 wherein R is an alkyl or alkenyl group.

45. A composition as claimed in claim 42 wherein R contains about 30 to about 750 aliphatic carbon atoms and is made from a homo- or interpolymer of C2~C10 olefins.

46. A composition as claimed in claim 45 wherein said olefins are selected from the group consisting of ethylene, propylene, butylene and mixtures thereof.

47. A composition as claimed in claim 42 wherein a, b, and c are each 1, there are 0 optional substituents attached to Ar, and Ar is a benzene nucleus.

48. A composition as claimed in claim 47 wherein A is an alkyl or alkenyl group of at least about 30 carbon atoms and up to about 750 carbon atoms and is derived from a homo-or interpolymer of C2#10 1 -monoolefins.

49. A composition as claimed in claim 42 wherein the aminophenol is of the formula

wherein R' is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic carbon atoms, R" is a member selected from the group consisting of lower alkyl, lower alkoxy, nitro, and halo; and z is O or 1.

50. A composition according to claims 42, 44, 46, 48 or 49 wherein the chlorine-containing compound contains up to about 70 percent by weight chlorine.

51. A composition according to claim 50 wherein the chlorine-containing compound is a chlorinated paraffin wax.

52. A composition according to claim 51 wherein the chlorinated paraffin wax contains from about 35 up to about 50 percent by weight of chlorine.

53. A composition according to claims 42, 44, 46, 48 or 49 wherein the nitrogen-containing organic composition is further combined with at least one sulfurized olefinically unsaturated compound.

54. A composition according to claim 53 wherein the sulfurized olefinically unsaturated compound is derived from an olefin defined by the formula R7R8C=CR9R10, wherein each of R7, Rs, R9 and R10 is hydrogen or an organic radical.

55. A composition according to claim 54 wherein the olefin contains from about 8 up to about 36 carbon atoms.

56. A composition according to claim 55 wherein the olefin is an a-olefin and contains from about 8 up to about 20 carbon atoms.

57. A composition according to claim 50 wherein the nitrogen-containing organic composition is further combined with at least one sulfurized olefinically unsaturated compound.

58. A composition according to claim 57 wherein the sulfurized olefinically unsaturated compound is derived from an olefin defined by the formula R7R8C=CRgR10, wherein each of R7, R8, R9 and R10 is hydrogen or an organic radical.

59. A composition according to claim 58 wherein the olefin contains from about 8 up to about 36 carbon atoms.

60. A composition according to claim 59 wherein the olefin is an a-olefin and contains from about 8 up to about 20 carbon atoms.

61. A composition according to claim 52 wherein the nitrogen-containing organic composition is further combined with at least one sulfurized olefinically unsaturated compound.

62. A composition according to claim 61 wherein the sulfurized olefinically unsaturated compound is derived from an olefin defined by the formula R7R8C=CR9R10, wherein each of R7, R8, R9 and R10 is hydrogen or an organic radical.

63. A composition according to claim 62 wherein the olefin contains from about 8 up to about 36 carbon atoms.

64. A composition according to claim 63 wherein the olefin is an -olefin and contains from about 8 up to about 20 carbon atoms.

65. An additive concentrate comprising about 20~90% of at least one composition of claims 1, 3, 5, 7, 8, 11, 16, 22, 24, 31, 36, 42, 44, 46, 48 or 49 and a substantially inert, normally liquid organic diluent.

66. An additive concentrate comprising about 20~90% of at least one composition of claim 32 and a substantially inert, normally liquid organic diluent.

67. An additive concentrate comprising about 20~90% of at least one composition of claim 40 and a substantially inert, normally liquid organic diluent.

68. An additive concentrate comprising about 20~90% of at least one composition of claim 41 and a substantially inert, normally liquid organic diluent.

69. An additive concentrate comprising about 20~90% of at least one composition of claim 50 and a substantially inert, normally liquid organic diluent.

70. An additive concentrate comprising about 20~90% of at least one composition of claim 52 and a substantially inert, normally liquid organic diluent.

71. An additive concentrate comprising about 20~90% of at least one composition of claim 53 and a substantially inert, normally liquid organic diluent.

72. An additive concentrate comprising about 20~90% of at least one composition of claim 56 and a substantially inert, normally liquid organic diluent.

73. An additive concentrate comprising about 20~90% of at least one composition of claim 57 and a substantially inert, normally liquid organic diluent.

74. An additive concentrate comprising about 20~90% of at least one composition of claim 60 and a substantially inert, normally liquid organic diluent.

75. An additive concentrate comprising about 20~90% of at least one composition of claim 61 and a substantially inert, normally liquid organic diluent.

76. An additive concentrate comprising about 20~90% of at least one composition of claim 64 and a substantially inert, normally liquid organic diluent.

77. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claims 1, 3, 5, 7, 8, 11, 1 6, 22, 24, 31, 36, 42, 44, 46, 48, or 49.

78. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 32.

79. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 40.

80. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 41.

81. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 50.

82. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 52.

83. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 53.

84. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 56.

85. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 57.

86. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 60.

87. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 61.

88. A lubricant composition comprising a major amount of an-oil of lubricating viscosity and a minor amount of at least one composition of claim 64.

89. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of at least one composition of claims 1, 3, 5, 7, 8, ii, 16, 22, 24, 31, 36, 42, 44,46,48 or 49.

90. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of at least one composition of claim 32.

91. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of at least one composition of claim 40.

92. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of at least one composition of claim 41.

93. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of at least one composition of claim 50.

94. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of at least one composition of claim 52.

95. A method for operating an internal combustion engine which comprises lubricating said engine during operation and with the lubricating composition of claim 77.

96. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 78.

97. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 79.

98. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 80.

99. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 81.

100. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 82.

101. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 83.

102. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 84.

103. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 85.

104. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 86.

105. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 87.

106. A method for operating an internal combustion engine which comprises lubricating said engine during operation with the lubricating composition of claim 88.

107. The invention in all its novel aspects.