CA1215835A - Additive compositions containing aminophenol combinations useful as lubricant and fuel additives - Google Patents

Abstract

ADDITIVE COMPOSITIONS CONTAINING AMINOPHENOL
COMBINATIONS USEFUL AS LUBRICANT AND FUEL ADDITIVES

Abstract of Disclosure Disclosed are nitrogen-containing organic compo-sitions comprising the combination of amino phenols, wherein said phenols contain a substantially saturated hydrocarbon-based substituent of at least 10 carbon atoms with one or more of the following compositions:
(I) one or more carboxylic derivative composi-tions or post-treated carboxylic derivative compositions wherein said carboxylic derivative composition is produced by reacting at least one succinic acylating agent with a reactant selected from the group consisting of (a) amines, (b) alcohols, (c) reactive metal or reactive metal compo-unds, and (d) a combination of two or more of (a) through (c), 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 1,200 to about 5,000 and a Mw/Mn value of about 1.5 to about 6, said acylating agents being characterized by the presence of their structure of an average of at least 1.3 succinic groups for each equivalent weight of substituent groups, said post-treated carboxylic derivative compositions being prepared by reacting one or more post-treating reagents with said one or more carboxylic derivative compositions;
(II) at least one chlorine-containing compound selected from the group consisting of chloroaliphatic hydrocarbon-based compounds, chloroalicyclic hydrocarbon-based compounds or mixtures thereof;
(III) at least one sulfurized olefinically unsaturated compound.
Also disclosed are concentrates of these com-positions and lubricants and fuels containing these com-positions.

Description

I

ADDITIVE COMPOSITIONS CONTAINING AMINO PHENOL
-COMBINATIONS USEFUL US Lubricant END FUEL ADDITIVES
. , , _ , , .

Field of the Invention This invention relaxes 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 Libra-cant and fuel compositions comprising these compositions.
This invention also relates to a method for operating an 10 internal combustion engine by lubricating said engine during operation with these lubricating composition.
Summary 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 hollowing properties: detergent, dispersant, antioxidant, anticorrosive r antiwar, friction reducing and fluidity 20 modifying properties.
Another object it to provide novel concentrates comprising these novel nitrogen-containing organic combo-sessions Still another object is to provide novel lubricant 25 and fuel compositions containing these novel nitrogen-containing organic compositions.

.,~ ,~, I

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 (OKAY
c if - -(NH2)b wherein R is a substantially saturated, hydrocarbon-based suhstituent of at least 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 An with the proviso 15 that the sum of a, b and c does not exceed the unsatisfied valences of An; and An is an aromatic moiety having 0-3 optional ubstituen~s selected from the group consisting of lower alkyd, lower alkoxyl, vitro, halo or combinations of two or more of said substituentq; and (B) one or more carboxylic derivative commas-lions produced by reacting at least one substituted succinic acylatin~ agent with a reactant selected from the group consisting ox (a) an amine characterized by the presence within its structure of at least one H-N = group, (b) an 25 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 (do being reacted with said one or more substituted succinic assaulting agents simultaneously or sequentially it any order, wherein said substituted succinic 30 assaulting agents consist of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene, said polyalkene being characterized by a My value of 1200 to about 5000 and a Mom value of about 1.5 to about 6, said assaulting agents being characterized by the I

presence within their structure of an average of at least 1.3 succinic groups for each equivalent weight ox substitu-en groups.
One or more object of this invention art Allah accomplished by providing . nitrogen containing organic composition comprising a combination of (A) and (9) 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 mentionedjhereinabove and described in detail hereinafter are further combined with (C) at least one chlorine-con~aining compound selected from the group 15 consisting ox chloroaliphatic hydrocarbon-based compounds, chloxoalicyclic hydrocarbon-based compounds or mixtures thereof.
One or more objects of this invention are also accomplishes by providing a nitrogen-containing organic 20 composition comprising a combination of:
(A) at least one amino phenol of the general formula (OWE
(R) - -An - (NH2)b wherein R is a substantially saturated, hydrocarbon-based 25 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 ox aromatic nuclei present in An with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of An; and An is an aromatic moiety having 0-3 30 optional substituents selected from the group consisting of lower alkyd, lower alkoxyl, vitro, halo or combinations of two or more of said suhstituents; and (C) at least one chlorine-containing compound selected from the group consisting of chloroaliphatic I 3~ii hydrocarbon-based compounds, chloroalicyclic hydrocarbon-based compounds or mixtures thereof.
One or 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 herein-after are further combined with at least one sulfurized olefinically unsaturated compound.
DETAILED DESCRIPTION OF THE INVENTION
(A) The amino Phenol The Aromatic Moiety An The amino phenol useful for the purposes of this invention are of the general formula (lH)c c An - (NH2)b The aromatic moiety, An, can be a single aromatic nucleus such as a ensign nucleus, a pardon nucleus, a thiophene nucleus, a 1,2,3,4-tekrahydronaphthalene nucleus, etc., or a polynuclear aromatic moiety. Such polynuclear moieties can be ox the fused type; that is, wherein at least 20 one aromatic nucleus is fused at two points to another nucleus such a found in naphthalene, anthracene, the azanaphthalenes, etc. Alternatively, such polynuclear aromatic moieties can be of the linked type wherein a least two nuclei (either Monroe polynuclear) are linked through 25 bridging linkages to each other. Such bridging linkages can be chosen prom the group consisting of carbon-to-carkon single bonds, ether linkages, veto linkages, sulfide link-ages, polysulfide linkages of 2 to 6 sulfur atoms, sulfinyl linkages, sulfonyl linkages, Mullen linkages, alkaline 30 linkages, Delaware alkyl)methylene linkages, lower alkaline ether linkages, alkaline veto linkages, lower alkaline sulfur linkages, lower alkaline polysulfide linkages of 2 to 6 carbon atoms, amino linkage, palomino linkages and mixtures ox such diva lent bridging linkages. In certain 35 instances, more than one bridging linkage can be present in 12~Lr ~35 An between aromatic nuclei. For example, a fluorine nucleus has two Bunsen nuclei linked by both a ethylene linkage and a covalent bond. Such a nucleus may be considered to have 3 nuclei but only two of them are aromatic. Normally, however, An will contain only carbon atoms in the aromatic nuclei per so (plus any lower alkyd or alkoxy substituent present).
he number of aromatic nuclei, fused, linked or both, in An can play a role in determining the integer 10 values of a, b and c in Formula I. For example, when An contain a single aromatic nucleus, a, b and c are each independently 1 Jo JO When An contains two aromatic nuclei, a, b and c can each be an integer ox 1 to I that is, up to three times the number of aromatic nuclei present (in lo naphthalene, 2). With a tri-nuclear An moiety, a, b and c can each be an integer of 1 to 9. For example, when An is a biphenyl or a naphthyl moiety, a, b and c can each index pendently be an integer of 1 to 6. The values of a, b and c are obviously limited by the fax thaw their sum cannot 20 exceed the total unsatisfied valences of An, that is, the sum of a, b and c cannot exceed the number of carbon atoms in the aromatic moiety tar aye would otherwise be bonded to a hydrogen.
The single ring aromatic nucleus which can be the 5 An moiety can be represented by the general formula arm wherein en represents a single ring aromatic nucleus ego., Bunsen) of 4 to 10 carbons, each Q independently represents a lower alkyd group, lower alkoxy group, Norway group, or 30 halogen atom, and m is 0 to 3. As used in thus speci~ica lion and appended claims, "lower" refers to groups having 7 or less carbon atoms such as lower alkyd and lower alkoxyl groups. Halogen atoms include fluorine chlorine, bromide and iodine atoms; usually, the halogen atoms are fluorine 35 and chlorine atoms.

583~

Specific examples of single ring An moieties are the following:

r r To Me HUH H I H OH

I

= Me Of unit ~12 ` " r Ho --I / CH2-CH2 H I\ H 2 N H CH2-CH2 Ho wherein ye is methyl, Et is ethyl, Pry is n-propyl, and Kit I vitro.
When An is a polynuclear fused-ring aromatic 10 moiety, it can be represented by the general formula en en my (Q mm US
I .
wherein en, Q and m are as defined hereinabove, m' is 1 to 4 and '~~ 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 art-matte moieties An are:

I r H H H

Me Me Me Nit Ho H H OH

H f H ~l~LH
H Jo H

H H
eta .
I When the axiomatic moiety An is a linked polyp nuclear aromatic moiety it can be represented by the general formula ar-~-Lng-ar my wherein w it an integer of 1 to about 20, en is as described 15 above with the proviso that there are at least 3 unsatisfied (i.e., free) valences in the total of en groups, Q and m are as defined herein before, and each Lung is a bridging linkage individually chosen from the group consisting of carbonate-carbon single bonds, ether linkages (e.g. -O ), veto linkages (e.g./ -I ), sulfide linkage (e.g., -S-), polysulfide linkages of 2 to 6 sulfur atoms (e.g., -S2-6), sulfinyl linkages (e.g., -So-), sullenly linkages (e.g., us 2-) I.
lower alkaline linkages (e.g., -SHEA-, -CH2-CH2-, -SHEA-, R
etc.), Delaware alkyl)-methylene linkages (e.g., CRY-), lower alkaline ether linkage (e.g., -SHEA-, -CH20-CH2-, -CH2-CH20-, -CH2C~20OEIzCH2-, -OEI2CHOCH2~H-, -CH2~HO~HCH2-, Jo R I R
etc.), lower alkaline sulfide linkages (e.g., wherein one or more -0-'s in the lower alkaline ether linkages is replaced 10 with an -S- atom), lower alkaline polysulfide linkages (e.g., wherein one or more -0-'s is replaced with a ~S2-6 group), amino linkages (e.g., -I , -CHIN-, -CH2lCH2-, -alkali-, where elk is lower alkaline, etc.), palomino linkages (e.g., -rollick o where the unsatisfied free N
15 valences are taken up with H atoms or R groups), and mixtures ox such bridging linkages (each R being a lower alkyd group). It is alto possible that one or more of the en groups in the above-linked aromatic moiety can be no-placed by fused nuclei such a art a m' Specific example of linked moieties are-or H H H X
I J

go Ho H L H

My 1 0 H Me ye H H

J l-lot etc.

Usually all these An moieties are unsub~tituted except for the R, -OH and -NH2 group (and any bridging groups).
For such reasons as cost, availability, perform-ante, etc., the An moiety is normally a Bunsen nucleus, lower alkaline bridged Bunsen nucleus, or a naphthalene nucleus. Thus, a a typical An moiety is a Bunsen 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 units valences 15 being, insofar as possible, either ortho or pane to a hydroxyl group. Preferably, An is a Bunsen nucleus having so 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 pane Jo the hydroxyl group The Substantially Saturated Hydrocarbon-based Group R
The amino phenol of the present invention con-lain, directly bonded to the aromatic moiety An, a sub-staunchly 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 10 such group can be present, but usually, no more than 2 ox 3 such grollps are present for each aromatic nucleus in the aromatic moiety An. 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.
15 Usually, the hydrocarbon-based 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 20 from home- or inter polymers (ego, copolymers, terpolymers) of Mooney and dolphins having 2 to 10 carbon atoms, such as ethylene, propylene, buttonhole, isobutene, butadiene, is-prone, l-hexene, l-octene, etc. Typically, these olefins are l-monoolefins such a homopolymers of ethylene. The R
25 groups can be derived from the halogenated (e.g., chlorine-ted or brominated) analogs of such home- or inter polymers.
The R groups can, however, be made from other sources, such as monomeric high molecular weight alikeness (e.g., l-tetra-convene) and chlorinated analogs and hydrochlorinated 30 analogs thereof, aliphatic petroleum fractions, particularly paraffin waxes and cracked and chlorinated analogs and hydrochlorinated analogs thereof, white oils, synthetic alikeness such as those produced by the Ziegler-Natta process (e.g., polyethylene) greases) and other sources known to 35 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 ~58~

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 non-hydrocarbon 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 10 include, for example, hydroxyl, halo (especially sheller and Lowry), alkoxyl, alkyd Marquette, alkyd sulfoxy, etc.
Usually, however, the hydrocarbon-based groups R are purely hydrocarbyl and contain no such non-hydrocarbyl radicals.
The hydrocarbon-ba~ed groups R are substantially 15 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 non-aromatic unsaturated bond for every 50 carbo~-to-carbon 20 bonds present.
The hydrocarbon-baqed 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 25 or less carbon atoms fox 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.
30 Typically, these purely aliphatic R group are alkyd or alkenyl groups.
Specific examples of the substantially saturated hydrocarbon-based R groups are the following:
a tetra(propylene) group a tri(i~obutene) group a tetracontanyl group a henpentacontanyl group ~23~ 335i a mixture of polyethylene propylene groups of about 35 to about 70 carbon atoms a mixture of the oxidativeIy or mechanically degraded polyethylene propylene groups of about 35 to about 70 carbon atom a mixture of poly(propylene/l-hexene) groups of about 80 to about 150 carbon atoms a mixture ox poly~isobutene) group 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 butane content of 35 to 75 weight percent and isobutene 15 content of 15 to 60 weight percent in the presence of a Lewis acid catalyst such a aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than 50% of total repeating units) isobutene repeating units of the configuration SHEA
- SHEA C -C~3 The attachment of the hydrocar~on-based group R to the aromatic moiety An of the amino phenols of this invent lion can be accomplice by a number of techniques well known to those skilled in the art. One particularly suite 25 bye technique is the Friedel-Cra~ts reaction, wherein an olefin (e.g., a polymer containing an ole~inic bond), or halogenated or hydrohalogenated analog thereof, is reacted with a phenol. The reaction Occur in the presence of a Lewis acid catalyst (e.g., boron trifluoride and its come 30 plexus with ethers, phenols, hydrogen fluoride, etc.,aluminum chloride, aluminum bromide, zinc dichlorides etch).
Methods and conditions for carrying out such reactions are well known to those skilled in the art. See, for example, isle the discussion in the article entitled, "Alkylation of Phenols" in "Kirk-Othmer Encyclopedia of Chemical Tech-neology", Second Edition Vol. 1, pages 894-~95l Intrusions Publishers, a division of John Wiley and Company, NAY., 1963. Other equally appropriate and convenient techniques for attaching the hydroearbon-hased group R to the aromatic moiety An will occur readily to those skilled in the art.
The amino phenols of this invention contain at least one of each of the following subs~i~uents: a hydroxyl 10 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 An moiety. They need not, however t each be attached to the same aromatic ring if more than one aromatic nucleus is 15 present in the An moiety.
In a preferred embodiment, the amino phenols of this invention contain one each of the foregoing substitu-ens it a, b and c are each 1) and but a single aromatic ring, most preferably Bunsen. This preferred class of 20 amino phenols can be represented by the formula OH
(NH2)1-2 Al l IT (R")z I/
wherein the R' group it a substantially saturated hydra-carbon-based group of about 30 to about 400 aliphatic carbon atoms located ortho or pane to the hydroxyl group, R" is a 25 lower alkyd, lower alkoxyl, nitxo group or halogen atom and z is 0 or 1. Usually z is 0 and R' is a substantially saturated, purely hydrocarbyl aliphatic group. Often R' is an alkyd ox alkenyl group pane to the -OH substituent.
Often there is but one amino group, -NOAH, in these preferred 30 amino phenols but there can be two.
In a still more preferred embodiment of this invention, the amino phenol is of the formula I

OH

wherein R' is derived from homopolymerized or inter polymer-iced Clue l-olefins and has an average of from about 30 to about 400 alipha~ic carbon atom and R" and z are as defined above. Usually R' is derived from ethylene, propylene, battalion and mixtures thereof. T~plcally, it is derived from polymerized isobuteneO Often R' has a least about 50 aliphatic carbon atoms and z is 0.
The amino phenol of the present invention can be 10 prepared by a number of ~nythetic routes. These routes can vary in the type reactions used and the sequence in which they are employed. For example, an aromatic hydrocarbon, such as Bunyan, can be alkylated with an alkylating agent such as a polymeric olefin to form an alkylated aromatic 15 intermediate. This intermediate can then be nitrated, for example, to form a pollinator intermediate. The pollinator intermediate can in turn be reduced to a Damon, which can then be diazotized and reacted with water to convert one of the amino groups into a hydroxyl group and provide the 20 desired amino phenol. Alternatively, one of the vitro group in the pollinator intermediate can be converter to a hydroxyl group through fusion with caustic to provide a hydroxy-ni~ro 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 ole~inic alkylating agent to form an alXylated phenol. This alkylated phenol can then be nerd to form an inter mediate vitro phenol which can be converted to the desired 30 amino phenols by reducing at least some of the vitro groups to amino groups.

~15-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" demon-striates. Techniques for nitrating phenols are also known.
See, for example, in Kirk Other "Encyclopedia of Chemical Technology", Second Edition, Vol. 13, the article entitled "Nitrophenols", page 888 en seq., as well as thy treatises "Aromatic Substitution; Nitration and Halogenation" by Pi B.
D. De La Mare and J. H. Rudy N. Y., Academic Press, 1959;
10 "Nitration and Aromatic Reactivity" by J. G. Hogged, London Cambridge University Press t 1961; and "Thy Chemistry of the Vitro and Nutrias Group", Henry Fever, Editor, In~erscience Publishers, NAY., 1969.
Aromatic hydroxy compounds can be nitrated with 15 nitric acid, mixtures of nitric acid with acids such as sulfuric acid or boron trifluoride, nitrogen tetraoxide, nitronium tetrafluoroborates and azalea nitrates. generally, nitric acid ox a concentration of, for example, about 30-90%
is a convenient nitrating reagent. substantially inert 20 liquid delineate and solvents such as acetic or butyric acid can aid in carrying out the reaction by improving reagent contact.
Condition and concentrations for nitrating hydroxy aromatic compounds are also well known in the art 25 For example, the reaction can be carried out at temperatures ox about -15C. to about 150C. Usually nitration is con-veniQntly carried out between about 25-75C.
Generally, depending on the particular nitrating agent about 0.5-4 moles of nitrating agent is used for every 30 mote of aromatic nucleus present in the hydroxy aromatic intermediate to be nitrated. If more than one aromatic nucleus is present in the An moiety, the amount of nitrating agent can be increased proportionately according to the number of such nuclei pronto. For example, a mole of 35 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 ~L2~3S

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 vitro compounds to the corresponding amine is also well known. See, for example r the article entitled lamination 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 cremate, etc. Co-catalysts such as alkali or alkaline earth metal hydroxides or amine (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.
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.

Vitro groups can also be reduced in the Xenon reaction, which is discussed in "Organic Reactions", Vol. 20, John Wiley &
Sons, NAY., 1973, page 455 et seq. Generally, the Xenon reaction involves reduction of a vitro group with diva lent negative sulfur compounds, such as alkali metal sulfides, polysulfides and hydrosulfides.

Lo ~17-The vitro groups can be reduced by electrolytic action; see, for example, the lamination by Reduction"
article, referred to above.
Typically the amino phenols of this invention are obtained by reduction of Nat phenols with hydrazine such as discussed above. This rewaken it generally carried out in the absence of a catalyst a temporaries of about 50-250C., typically, about 100 200C. The reaction time for reduction usually Aries between about 2-24 hours. Sub-10 staunchly inert liquid delineates 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 disk tillation, filtration, extraction, and so forth.
the reduction is carried out until at least about 50~, usually about 80%, ox the vitro groups present in thy vitro intermediate mixture are converted to amino groups.
The typical route Jo the amino phenols ox this invention just described can be summarized as (I) nitrating with at least one nitrating agent at least one compound of the formula (OH) I c c An wherein R is a substantially saturated hydrocarbon-based group of at least 10 aliphatic carbon atoms; a and c are 25 each independently an integer of 1 up to three times the number ox aromatic nuclei present in An with the proviso that An contains at least one carbon atom which is part of the axiomatic nucleus and which is bonded directly to a hydrogen atom and the sum ox a and c does no exceed the 30 remaining unsatisfied valences of An; and An is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyd, lower alkoxyl~ vitro, and halo, or combinations ox two or more optional sub~tituents, with the proviso that when An is a Bunsen having only one hydroxyl and one R substi~uent, the R substitu~nt is ortho or pane to said hydroxyl substituent, to form a first reaction mixture containing a vitro intermediate, and (II) reducing at least about 50% of the vitro groups in said first reaction mixture to amino groups.

Usually this means reducing at least about 50~ of the vitro groups to amino groups in a compound or mixture of compounds of the formula (Icky c An (Nub wherein R is a substantially saturated hydrocarbon-based substitutent 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 An with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of An; and An is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyd, lower alkoxyl, halo, or combinations of two or more of said optional substituents; with the proviso that when An is a Bunsen nucleus having only one hydroxyl and one R substituent, the R substituent is ortho or pane to said hydroxyl substituent.

The amino phenols useful for the purposes of this invention and processes for their preparation are described in US. Patent 4,100,082.
I (B) The Carboxylic Derivative Compositions and Post-Treated Carboxylic Derivative Compositions The Substituted Succinic Assaulting Agent The substituted succinic assaulting agent (hereinafter referred to as the "assaulting agent") useful for making composition (B) of this invention are those which can be characterized by the presence within their structure of two groups or moieties.
The first group or moiety is .....

referred to herein, for convenience, as the "substituent groups)" and is derived from a polyalkene. The polyalkene from which the substituted groups are derived is character-iced by a My (number average molecular weight) value of from 1200 to about 5000 and a Mom value of about 1.5 to about I
The second group or moiety is referred to herein as the "succinic group(s)". The succinic groups are those groups characterized by the structure O O
1 0 I c c 1 c x I J
wherein X and X' are the same or different provided at least one ox X and X' is such that the assaulting agent can lung-lion as carboxylic assaulting agents. That is, at feast one of X and X' must be such that the assaulting agent can I esterify alcohols, form asides or amine salts with ammonia or amine, form metal salts with reactive metals ox best-gaily reacting metal compounds, and otherwise function a a conventional carboxylic acid assaulting Agents. Transistor-ligation and tran~amidatisn reactions are considered, for 20 purposes of this invention, as conventional assaulting reactions.
Thus, X Andre X' is usually OH, -O-hydrocarbyl, -O My where My represents one equivalent of a metal ammo-I'm or amine cation, -NOAH -Of, Brie, and together, X and X' 25 be -O- so as to form the android. 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 prom entering into acylation reactions.
Preferably, however, X and X' are each such that both I carboxyl functions of the succinic group (i.e., both I
and -C-X') can enter into acylation reactions.

~2~L5~3~
-20~

One ox the unsatisfied valences in the grouping -C-C- of the succinic group structure hereinabove worms 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 aifferen~
substituent group, all but the said one such valence is usually satisfied by hydrogen; it -H.
The substituted ~uccinic assaulting agents are characterized by the presence within their structure of at 10 least 1,3 succinic groups or each equivalent weigh of substituent groups. For purposes of this invention, the number of equivalent weights of substituent groups it deemed to be the number corresponding Jo the quotient obtained by dividing the My value of the polyalkene from which the 15 subsequent it derived into the total weight ox the siesta-tent groups present in the assaulting agents. Thus, if a assaulting agent it characterized by a total weight of sub-stituent group of 40~000 and the My value for the polyalkene from which the ~ubstituent groups are derived is 2000, then 20 what assaulting agent is characterized by a total of 20 (40,000/2000 = 203 equivalent weights of ~ubstituent groups.
Therefore, that particular assaulting agent must also be characterized by the presence within its structure of a least 26 succinic groups to meet one of the requirements of 25 the succinic assaulting agents of this invention.
nether requirement for the assaulting agents within this invention it that the substituent groups must have been derived from a polyalkene characterized by a Mom value of about 1.5 to about 6, My being the conventional 30 symbol representing weight average molecular weight.
Before proceeding, it should be pointed out that the My and My values for polyalkene, for purposes of this invention, are determined by gel permeation chromatography (GPC). This separation method involves column chxomatogra-35 pry in which the stationary phase is a heteroporous, sol-vent-swollen polymer network of a polystyrene gel varying in permeability over many orders of magnitude. As the liquid phase (te~rahydrofuran) containing the polymer sample passes through the gel, the polymer molecule diffuse into all parts of the gel not mechanically barred Jo them. The smaller molecules "permeate' more completely and spend more 5 time in the column; the larger molecules "permeate" less and pass through the column more rapidly. The My and ow 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 10 standards of polymers of known molecular weight disturb-lion. For purposes of this invention a series of free-shunted polymers of isobutene, polyisobut~ne being the preferred embodiment, is used as the calibration standard.
For example, the My values disclosed herein are 15 obtained using a Water Associates model 20Q gel permeation chromatography equipped with a 2.5 ml siphon, a 2 ml sample injection loop and four stainless steel columns 7.8 mm in r diameter by 120 centimeters long a Each column was packed A with STYROGEL~ a commercially available, rigid, porous gel 20 (in particle form) of cros~linked styrene/divinyl Bunsen copolymers. These gels are also obtained from Waters Associates. The first column contains STYROGEL having a retention volume of AYE. The second and third column contain 5TYROGEL having a retention size of 500 A. The 25 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 stain-less steel tubing. The second and third columns are each I 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 ~0F.
35 (15 5C.) of 0.89 and a viscosity at 210F. t99C.) of 12.50 SUP. A sample of this polymer is fractionated by dialysis using a rubber membrane and a sixty extraction apparatus do ok SUE

with refluxing petroleum ether as solvents. Eleven free-lions are taken; one sample each hour for the first seven hours, then three samples each four hours, and finally ha residue which did not permeate the membrane over a four-hour period and the My of each was measured using vapor phase osmometry and Bunsen solvent Each calibration sample is then chromatographedO
Approximately 7 my of sample is weighed into a small bottle which is then filled with 4 ml of reagent grade tetrahydro-10 Furman. The sealed bottle is stored overnight before an-aliases. The afore-described liquid phase chroma~ograph is degassed at 5gC. and a flow rate of 2.0 ml per minute of tetrahydrofuran maintained. Sample pressure is 180 psi and the reference pressure 175 psi. The retention time of each 15 sample is measure. The My of each calibration sample is calculated from the My assuming the relationship 2 My = ow.
The retention times and My for each sample, which are shown in the following table, are plotted to provide a standard-ration curve. The My and My for sample polymers is then 20 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, numkaxs 7 and 8, ~1966).
Polyalkenes having the My and My values discussed above are known in the art and can be prepared according to conventional procedures. Several such polyalkenes, en-specially polybutenes, are commercially available.

aye Rut* My Rut* My Rut* My 42Z40 40 ~38 50 229 32 16~85 42 453 52 202 33 1~780. 43 400 53 18 4180 45 33~ 55 167 36 2640 I 304. 56 156 39 865 49 2~6 Again, turning to the characteristics of the succinic assaulting agents of this invention, the succinic 15 groups will normally correspond to the formula O
- I - C - R
. I .

I
wherein Al and R2 are each independently Selected from the group consisting of -OH, -Of, Oilier alkyd, and when taken together, Al and R2 are O . In the latter case, the _ _ art - retention time in units of number of times siphon (2.5ml) empties The siphon empties every 2.5 minutes.

~5~3~i succinic group is a succinic android group. ~11 the succinic groups in a particular assaulting agent need not be the same, but they can be the: same. Preferably, the sue-cynic groups will correspond to - oh_ c ox ; OH - C
C~2 - C OH , ¦ O
O COOK

and mixtures thereof. Providing assaulting agents wherein the sexing groups are the same or different is within the ordinary skill of the art and canoe accomplished through conventional procedures such as treating the assaulting 10 agents themselves (for example, hydrolyzing the android to the free acid or converting the free acid to an acid color-ire with thinly chloride) and/or selecting the appropriate malefic or fumaric reactants, As previously mentioned, the minimum number of 15 succinic groups for each equivalent weight of substituent group is 1.3. Preferably, however, the minimum will be 1.4;
usually lo to about 3.5 succinic groups for each equivalent weight of ~ub~tituent group. An especially preferred minimum is at least 1.5 ~uccinic groups for each equivalent 20 weight of ~ubstituent 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 sub-stituted succinic assaulting agents of this invention can be 25 represented by the symbol Al ,. (X2 ) y where Al represents one equivalent weight of substituent group, X2 represents one succinic group, as discussed above, and y it a number equal to or greater than 1.3, ivy 30 1.3. The more preferred embodiments of the invention could be similarly represented by, for example, letting Al and X2 I 33~i represent more preferred substituent groups and succinic groups, respectively, as disc sod elsewhere herein and by letting the value of y vary as discussed above; e.g., y is equal to or greater than 1.4 (y > 1.4); y is equal to or greater than 1.5 (y > 1.5); y equals 1.4 to about 3.5 (yo-yo); and y equals 1.5 to about 3.5 yo-yo.
In addition to preferred substituted succinic groups where the preference depends on the number and identity ox succinic groups for each equivalent weight of 10 substituent group, 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 My, for example, a minimum of about 1200 is preferred with an My value in the 15 range of from about 1200 to about 3200 also being preferred A more preferred My value is one in the range of from about 1500 to about 2800. A most preferred range of My values is from about lS00 to about 2400. With polybutenes, an en-specially preferred minimum value or My it about 1700 and an 20 especially preferred range of My values is from about 1700 to about 2400.
As to the values of the ratio Mom, there are also several preferred values. A minimum Mom value of about I 8 it preferred with a range of values of about 1.8 25 up to about 3.5 also being preferred. A still more pro-furred monomania value of Mom 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 Mom is about 2.5 with a range of values of about 2.5 to 30 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 characters-tics of the assaulting agents are, for lack ox better terming 35 olagy to describe the situation contemplated ho this in-mention, intended to be understood as being both independent and dependent. They are intended to be independent in the 5~3~

sense that, for example, a preference for a minimum of I
or 1.5 succinic group per equivalent weight of substituent groups is no tied to a more preferred value of My or Mom.
They axe 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 My and/or Mom, the combination of preferences does in fact describe still further more preferred embodiment of the invention Thus, the various parameters are intended to stand alone with respect to the particular parameter bring discussed but can also ye combined with other parameters to identify further preference. This some concept is intended to apply throughout the specification with respect to the description of preferred values, ranges, ratios, reactants, 15 and the like unless a contrary intent is clearly demonstra-ted or apparent.
The polyalkene~ from which the substituent groups in (B) are derived are homopolymers and inter polymers of polymerizable olefin monomers of 2 to about 16 carbon atoms;
20 usually 2 to about 6 carbon atoms. The inter polymers are those in which two or more olefin monomers are inter polymer-iced 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, "inter-25 polymer' 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 polyp alikeness from which the ~ubstituent groups are derived are of tell conventionally referred to as "polyolefin(s)".
The olefin monomers from which the polyalkenes are derived are polymerizable Olin monomers characterized by the presence of one or more ethylenically unsaturated groups (i.e., ~C=C _); that is, they are monoolefinic monomers such as ethylene, propylene, buttonhole, isobutene, and octene-l or polyolefinic monomers (usually diolefinic monomers) such as butadiene-1,3 and isoprene.

~51~35 They Olin monomers are usually polymerizable terminal olefins, that is, olefins characterized by the presence in their structure of the group C=C~2. ivory, polymerizable internal olefin monomers (sometimes referred to in the patent literature as medial olefins) characterized by the presence within their structure of the group COO C__ can also be use to form the polyalkenes. When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which 10 era inter polymers. 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 it piperylene) is deemed to be a terminal olefin for purpose 15 Of this invention.
White the polyalkenes from which the substituent groups of the assaulting agents are derived generally are hydrocarbon polyalkene~, they can contain non-hydrocarbon group such a lower alkoxy, lower alkyd Marquette, hydroxy, 20 Marquette, ox (i.e., 11 as in veto an alluded groups; e.g., O O
~C-~-C=~and ~C-C-H), vitro, halo, cyan, carboalkoxy (i.e., -~-O-alkyl where "alkyd" is usually lower alkyd) alkanoyloxy (i.e., alkyd -C-O- where alkyd is usually lower alkyd) and the like provided the non-hydrocarbon substituents do not substantially interfere with formation of the assaulting agents of this invention. When present, such non-hydro-carbon 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, 30 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 Shari groups which usually ~5~3~;i I
facilitate the formation of the substituted succinic cay-feting agents ox this invention. (us used herein, the text "lower" when used with a chemical group such as in "lower alkyd" or "lower alkoxy" is intended to describe groups having up to and including seven carbon atoms) Although the polyalkenes may include aromatic groups (especially phenol groups and lower alkyd- and/or lower alkoxy-substituted phenol groups such as portrait-butyl)-phenyl~ and cycloaliphatic groups such as would be obtained from polymerizable cyclic olefins or cycloaliphatic substituted-polymerizable cyclic olefins t the polyalkenes usually will ye tree from such groups Nevertheless, polyp alikeness derived from inter polymers of both Dennis and styrenes such as butadiene-1,3 and styrenes or portrait-butyl)-styrene are exceptions to this generalization.
Again, because aromatic an cycl~aliphatic group 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 dine-styrenes inter polymer exception already noted). Within this general preference, there is a further preference for polyalkenes which are derived from the group consisting of homopolymers and inter polymers of terminal hydrocarbon olefins ox 2 to about 16 carbon atoms. This further prefer-once is qualified by the proviso that, while inter polymers of terminal olefins are usually preferred, inter polymers optionally containing up to about 40% of polymer units derived prom internal olefins of up to about 16 carbon atoms are also within a preferred group. A more pre~errPd class of polyalkenes are those selected from the group consisting of homopolymers and inter polymers of terminal olefins of 2 to about 6 carbon atoms, more preferably 2 to 4 carbon atoms. However, another preferred class of polyalkenes are Sue the latter more preferred posy lkenes optionally containing up to about 25% of polymer unit 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 tech-piques include ethylene; propylene; buttonhole; button;
isobutene; pentene-l; hexene-l; heptene-l; octene-l; nonene-l; disannul; pontoon; propylene-tetramer; diisobutylene;
isobutylene triter; butadiene-1,2; butadiene-1,3; pent-Dunn; pentadiene-1,3; pentadiene-1,4; isoprene; hex-Dunn; 2-chloro-butadiene-1,3; 2~mekhyl-heptene-1; 3 cyclohexyl-butene-l; 2-methyl-5-propyl-hexenerl; octane;
3,3-dimethyl-pentene~ Turin; 2,4-dichloro styrenes divinylbenzene; vinyl acetate; ally alcohol; l-methyl-vinyl acetate; acrylonitrile; ethyl acrylate; methyl methacrylate;
ethyl vinyl ether; and methyl vinyl kitten. I these, the hydrocarbon polymerizable monomer are preferred and of these hydrocarbon monomers, the terminal olefin monomers are particularly preferred.
Specific examples of polyalkenes include polyp propylene, polybutenes, ethylene-propylene copolymers, styrene-isobutene copolymers, isobutene-butadiene-1,3 copolymers, propene-isoprene copolymers, isobutene sheller-prone copolymers, isobutene-(para-methyl)styrene copol~mers, copol~mers of hexene-l with hexadiene-1,3, copolymers of oatene-l with hexene-l, copolymers of heptene~l with pen-tunnel, copolymers of 3-methyl-butene-1 with octene-l, copolymers ox 3,3-dimethyl pentene-l with hexene-l, and terpolymers of i30butene, styrenes and pip~rylene. More specific examples of such inter polymers include copolymer of 95% (by weight) of isobutene with 5% (by weight) of Turin;
terpolymer of 98% of isobuten~ with 1% of piperylene and 1 of chloroprene; terpolymer of 95% of isobutene with 2% of buttonhole and 3% of hexene~l; terpolymer of 60~ of isobutene with 20~ of pentene-l and 20% of octene-l; copolymer of 80%
of hexene-l and 20% of heptene-l; terpolymer of 90% of isobutene with I ox cyclohexene and I of propylene; and copolymer of 80% ox ethylene Rand 20~ ox propylene A pro-furred source of polyalkenes are the polytisobutene~s obtained by polymerization of I refinery stream having a butane content of about 35 Jo about 75 percent by weight and : an isobutene content of about pa to about 60 percent by weigh in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polyp butanes contain predominantly greater than at least about 50% of the total repeating units) of isobutene repeating units of the configuration _ SHEA - f SHEA
Obviously, preparing polyalkenes as described above which meet the various criteria for My and Mom 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 a stripping (including vacuum stripping) a very light end Andre oxidatively or mechanically degrading high molecular weight polyalkene Jo produce lower molecular weight polyalkenes can also be used In preparing the assaulting agents of this invent lion, one or more of the above-described polyalkenes is reacted with one or more acidic reactants selected from the group consisting of m~leic or fumaric reactants of the general formula O o If 11 X-C-CH=C~-C-X' ~S~3S
I

wherein X and X' are as defined hereinbeforeO Preferably the malefic an fumaric reactants will be one or more come pounds corresponding to the formula O
I CH=CH ~=R2 wherein Al and R2 are as previously defined herein. Ordain-aridly the malefic or fumaric reactants will be malefic acid, fumaxic acid, malefic android, or a mixture of two or more of these The malefic 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 sub-stituted succinic assaulting agents of the present invention.
The especially preferred reactants are malefic acid, malefic android, and mixtures of these. Due to availability and ease of reaction, malefic android will usually be employed.
The one or more polyalkenes and one or more malefic or fumaric reactants can be reacted according to any of several known procedures in order to produce the assaulting agents useful in the present invention. Basically, the procedures are analogous to procedures used to prepare the high molecular weight succinic androids and other equiva-lent succinic assaulting analog whereof except that the polyalkenes (or polyolefins) of the prior art are replaced with the particular polyalkenes described above and the amount of malefic or fumaric reactant used must be such that there is at least 1.3 su~cinic groups for each equivalent weigh ox the substituent group in the final substituted succinic assaulting agent produced.
The process presently deemed to be best for preparing the substituted succinic assaulting agents of this invention from the standpoint of efficie~y, overall economy, and the performance of the acylatiny agents thus produced, as well as the performance ox the derivatives whereof, is the so-called "one-step" process. This process is described l35 in US. Patents 3t215,707 and 3,231,587.

Basically, the one-step process involves preparing a mixture of the polyalkene and the malefic reactant it the malefic and fumaric reactants of the formula O O O O
X-C-CH=CH-C~X' and Rl-C-CH=CH-C-R2~
wherein X, X', Al and R2 are as previously defined containing the necessary amounts of both to provide the desired assaulting agents of this invention. This means that there must be at least 1.3 moles of malefic 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 1~0C.

A variation on this process involves adding additional malefic 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 malefic reactant are first mixed before the introduction of chlorine Usually, where the polyalkene is sufficiently fluid at 1~0C., and above, there is no need to utilize an additional substantially inert, normally liquid solvent/diluent in the one-I step process. However, if a solvent/diluent is employed, it ispxeferably one that resists chlorination. Again, the polyp and per-chlorinated and/or -fluorinated alikeness, 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 .....

AYE, :~2~S1~3S
I
maximum tltilization of the chlorine, the rate should be about the same a the rate of consumption of chlorine in -the course of the reaction. When the introduction rate of chlorine exceeds the rate ox consumption, chlorine is evolved from the reaction mixture It is often advantageous to use a closed system including super atmospheric pressure, in order to prevent loss of chorine 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 140C. Thus, the minimum temperature at which the process is normally carried out is in the neighborhood of 140C~ The preferred temperature range it usually between about 160C~ and about 2203C. Higher temperatures such as 250C. or even higher may be used but usually with little advantage In fact, temperature in excess of 220C. are often disadvantageous with respect to preparing the par-titular assaulting 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 malefic reactant. For this reasons, maximum temperatures of about 200 to about 210C. are normally not exceeded.
The upper limit of the useful temperature in the one-step process it determined primarily by the decomposition point of the components in the reaction mixture inducing the reactants and the desired products. The decomposition point is that temperature at which there is sufficient decompo-session of any reactant or product such as to interfere with the production of the desired products.
In the octopi process, the molar ratio of malefic reactant to chlorine is such what there is at least about one mole ox chlorine or each mole of malefic 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 chorine, is utilized in order to offset any loss of chlorine from the reaction mixture. Laxer amounts of excess chlorine may be use but do not appear to produce any beneficial results.

~2~83S

As mentioned previously, the molar ratio of polyalkene to malefic reactant it such that therm is at least about 1.3 moles of malefic reactant for each mole of posy alkeneY This is necessary in order that there can be at least 1.3 succinic groups per equivalent weight of sub-stituent group in the product. Preferably, however, an excess of malefic reactant is used. Thus, ordinarily about a 5% to about 25% excess of malefic rear ant 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 azalea-tying agents with a reactant selected from the group con-sitting of (a) an 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 (a) through (c), the coupon-ens of (d) being reacts with said assaulting reagents simultaneously or sequentially in any order.
The amine, (a), useful for reacting with the assaulting agent useful for this invention are toss kirk-terraced by the presence within their structure of at least one H-N - _ group can be a monoamine or polyamide compound.
US For purposes of this invention, hydrazine and substituted hydrazines containing up to three substituents are included as amine suitable for prepaying carboxylic derivative compositions. Mixtures of two or more amine can be used in the reaction with one or more assaulting 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 polyamide, especially a polyamide containing at least two H-N - _ groups, either or both of which are primary or secondary amine. the polyamides result in carboxylic derivative compositions which are usually more effective as dispersant/detergent additives, relative to 5~33~;

derivative compositions derived from monoamine. Suitable monoamine and polyamides are described in greater detail hereinafter.
Alcohol, (b), which can be reacted with the assaulting agents useful for this invention include the mandrake and polyhydric alcohols. Again, the polyhydric alcohols are preferrer since they usually result in car-boxlike derivative compositions which are more effective dispersant/detergents relative to caxboxylic derivative compositions derived from mandrake 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 assaulting agents. These metals and metal compounds are described further hereinafter.
The Amine (a) The monoamine and polyamides 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., HEN-) or secondary amino (i.e., H-N=) group. The amine can be aliphatic, cycle-aliphatic, aromatic, or heterocyclic, including aliphatic-substituted aromatic, aliphatic-substituted cycloaliphatic, aliphatic-substituted aromatic t aliphatic-substituted heterocyclic, cycloaliphatic-substituted aliphatic, cycle-aliphatic-substituted aromatic, cycloaliphatic-3ubstituted heterocyclic, aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic, aromatic-substituted hotter-cyclic, heterocyclic-substituted aliphatic~ heterocyclic-substituted cycloaliphatic, and heterocyclic-substituted aromatic amine and may be saturated or unsaturated. If unsaturated, the amine will be free from acetylenic unset unction (i.e., -C-C-). The amine may also contain non-hydrocarbon substituents or groups as long a these groups do not significantly interfere with the reaction of the ~L2~5~335 amine with the assaulting reagents of this invention. Such non-hydrocarbon substitusnta an groups include lower alkoxy, lower alkyd Marquette, vitro, interrupting groups such as -O-and -S- (e . g ., as in such groups as -CH2C~2-X-CH2CH2-where X is -O- or -S-).
With the exception of the branched polyalkylene polyamide, the polyoxyalkyl~ne polyamides, and the high molecular weight hydrocarbyl-substitu~ed amine described more fully hereafter, the amine used in this invention ordinarily contain less Han about 40 carbon atoms in total and usually not more than about 20 carbon atoms in total.
Alipha~ic monoamine include mono-aliphatic and di-aliphatic substituted amine wherein the aliphatic groups can be saturated or unsaturate and straight or branched chain. Thus, they are primary or secondary aliphatic ammonias Such amine include, for example, moo- and at-alkyl-substituted amine, moo- and do alkenyl-substituted amine, and amine having one N alkenyl substituent and one N-alkyl substituent and the like. The total number of carbon atoms in these aliphatic monoamine will, as men-toned before, normally not exceed about 40 and usually not exceed about 20 carbon atoms. Specific examples of such monoamine include ethyl amine, diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoa mine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, octadecylamine, and the like. Examples of cycloaliphatic-substituted aliphatic amine, aromatic-substituted aliphatic amine, and hotter-cyclic-substituted aliphatic amine, include 2-(cyclohexyl)-e~hylamine, benzylamine, phenylethylamine, and furl-propyl)amine~
Cycloaliphatic monoamine are those monoamine wherein there is one cycloaliphatic substituent attached directly to the amino nitrogen through a carbon atom in the cyclic ring structure. Examples of cycloaliphatic moo-amine include cyclohexylamines, cyclopentylamines, cycle-hexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamine, ~2~5~

dicyclohexylamines, and the like Example-s of aliphatic-substituted, aromatic-substLtuted, and hete~ocyclic-sub-stituted cycloaliphatic monoamine include propyl~substi-tuned cyclohexylamine~, phenyl-~ubstituted cyclopentyl-amine, and pyranyl-substituted cyclohexylamine~
Suitable aromatic amine include those monoamine 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 Bunsen) but can include fused aromatic rings, especially those derived from naphthylene. Examples of aromatic monoamine include aniline, di(para-methylphenyl)-amine, naphthylamine, N-~n-butyl)anilinet and the like.
Examples of aliphatic-~ubstituted, cycloaliphatic-substi~
tuned, and he~erocyclic-subs~ituted aromatic monoamine are para-ethoxyaniline, para-dodecylaniline/ cyclohexyl-sub-stituted naphthylamine, and thienyl-substituted aniline.
Suitable polyamides are aliphatic, cycloaliphatic and aromatic polyamides analogous to the above-described monoamine 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 polyamides include N-aminopropyl-cyclohaxylamines, N-N'-di-n-butyl-para-phenylene Damon, bis-(para-aminophenyl)-methane, 1,4-diaminocyclohexana, and the like.
Heterocyclic moo- and polyamides can also be used in making the substituted carboxylic acid assaulting agent derivative compositions ox this invention. As used herein, the terminology "heterocyclic moo- and polyamide" is intended to describe those heterocyclic amine containing at least one primary or secondary amino group and at least one nitrogen as a heteroatom in the haterocyclic ring. However, as long as there is present in the heterocyclic moo- and polyamides at least one primary or secondary amino group, the hetero-N atom in the ring can be a tertiary amino nitrogen; that it, one that does not have hydrogen attached directly to the ring nitrogen. Heterocyclic amine can be ~2~5~35 saturated or unsaturated and can contain various subset-tents such as vitro, alkoxy, alkyd Marquette, alkyd, at-Kenya, aureole, alkaryl, or aralkyl substituents. Generally, the total number of carbon atoms in the subs~ituents will 5 not exceed about 20. Heterocyclic amine can contain heteroatoms other than nitrogen, especially oxygen and sulfur. Obviously whey can contain more than one nitrogen he~eroatom. The five- and six-membered heterocyclic rings are preferred.
among the suitable heterocyclics are assurance, azetidinas, azolidines, twitter- and dodder pardons, pyrolyze, insoles, piperidines, imidazoles, dip and twitter-hydroimidazoles, piperazines, isGindoles, urines, morph-links, thiomorpholine , N-aminoalkylmorpholines, N-amino-alkylthiomorpholines, N-aminoalkylpiperazine~, N!N'-di-aminoalkylpiperazines, aspens, assassins, assonance, aye-cones and twitter-, dip and pPrhydro-derivatives of each of the above and mixtures of two or more of these heterocyclic amine. Preferred heterocyclic amine are the saturated 5-and 6-membered heterocyclic amine containing only nitrogen, oxygen and/or sulfur in the hotter ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like. Piperidine, aminoalkyl-sub-s-tituted piperidines, pipexazine, aminoalkyl-substituted piperazines, morpholine, aminoalkyl-su~stituted morpholines, pyrrolidine, and aminoalkyl-substituted pyxrolidines, are especially preferred. Usually the aminoalkyl substituents are substituted on a nitrogen atom forming part of the hotter ring. Specific examples of such heterocyclic amine include N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-di-aminoethylpiperazine.
ydroxyamines both moo- and polyamides, analogous to those described above are also useful in this invention provided they contain at least one primary or secondary amino group Hydroxy-substituted amine having only ton-tiara amino nitrogen such as in tri-hydroxyethyl amine, are thus excluded as an amine, but can ye used as an alcohol as ~L5~33~

disclosed hereafter The hydroxy-substituted amine con-template 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 amine include ethanol amine, di-(3-hydroxypropyl)-amine, 3 hydroxy-butyl-amine, 4-hydroxybutyl-amine, diethanolamine, Dow-hydroxypropyl)-amine, ~-(hydroxypropyl)propylamine, No hydroxyethyl)-cyclohexylamine, 3-hydroxycycl~pentylamine, para-hydroxyaniline, N-hydroxyethyl piperazine, and the like.
The terms hydroxyamine and amino alcohol describe the same class or compounds and, therefore, can be used interchangaab7y. Hereinafter, in the specification and appended claims, the term hydroxyamine will be understood to include amino alcohols as well as hydroxyamines.
Also suitable as amine are the aminosulfonic acids and derivatives thereof corresponding to the general formula:

arc N 3x ( Ray ) Ire wherein R3 is -OH, -NH2, ONE, etc., Ray is a polyvalent organic radical having a valence equal to zoo; Rub and I are each independently hydrogen, hydrocarbyl, and substituted hydrocarbyl with the proviso that at least one of Rub or Arc is hydrogen per aminosulfonic acid molecule; x and y are each integers equal to or greater than one From the for-mute, it is apparent that each aminosulfonic reactant is characterized by at least one HO = or HEN group and a o least one -~-R3 group. These sulfonic acids can be elf-phatic, cycloaliphatic, or aromatic aminosulfonic acids and the corresponding functional derivatives of the sulfa group.
Specifically, the aminosulfonic acids can be aromatic aminosulfonic acids, that is, where Ray is a polyvalent ~2~5~35 aromatic radical such as phenylene where at least one -S-R3 o group is attached directly to a nuclear carbon atom of the aromatic radical. the aminosulfonic acid may also be a monomania aliphatic sulfonic acid; that is, an acid where x is one and Ray is a polyvalent aliphatic radical such as ethylene, propylene, trim ethylene, and 2-methylene propylene. Other suitable amino-sulfonic acids and derivatives thereof useful as amine in this invention are disclosed in US. Patents 3l926,820; 3,029,250; and 3,367,864.

Hydrazine and substituted-hydrazine can also be used as amine 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 hydrogen bonded directly to hydrazine nitrogen and, more preferably, both hydrogen are on the same nitrogen.
The substituents which may be present on the hydrazine include alkyd, alkenyl, aureole, aralkyl, alkaryl, and the like. Usually, the substituents are alkyd, especially lower alkyd, phenol, and substituted phenol such as lower alkoxy-substituted phenol or lower alkyl-substituted phenol. Specific examples of substituted hydrazines are methylhydrazine, N,N-dimethylhydrazine, NUN'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine, N-lpara-tolyl)-NI-(n-butyl)-hydrazine, N-(para-nitrophenyl)-hydrazine, N-(para-nitrophenyl)-N-methylhydrazine, N/N'-di-(para-chlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine, and the I like.

The high molecular weight hydrocarbyl amine, both monoamine and polyamides, which can be used as amine 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 amine and their methods of preparation are known in the art and described, for example, in US. Patent 3,~75,554 and 3,438,757.

PA

S

All that is required for use of these amine is that they possess at least one primary or secondary amino group.

- Another group of amine suitable for use in this invention are branched polyalkylene polyamides. The branched polyalkylene polyamides are polyalkylene polyamides wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene r Hi tire-/ NN2 t R N R
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 groups and at least one tertiary amino group.

These reagents may be expressed by the formula:
H _ _ NH2 -(R Nix -[RN~RHl Z RN~2 _ _ Y
wherein R is an alkaline group such as ethylene, propylene, battalion and other homology (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 polyamides includes those of the formula:

I

NH2 RUN I RN - (R-N - H

wherein n is an integer, for example, 1-20 or more but preferably 1-3, wherein R is preferably ethylene, but may be propylene, battalion, etc. (straight chained or branched.
The preferred embodiments are presented by the following formula:
H H
NH2 (CH2CH2 I CH2CH2 1 - (Chic 2 I - H

SHEA

15 (n = 1-3). _ _ n 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 Polyamides N-400 N-800, N-1200, etc. Polyamide N-400 has the above formula wherein nil.
USE patents 3,200,106 and 3,259,578 disclose how to make such polyamides and processes for reacting them with carboxylic acid assaulting agents, and analogous processes can be used with the assaulting reagents of this invention.
Suitable amine also include polyoxyalkylene polyamides, e.g., polyoxyalkylene dominoes and polyoxyalkylene trimness, having average molecular weights ranging from about 200 to 4000 and preferably from about 400 to 2000. Illustrative examples of these polyoxyalkylene polyamides may be characterized by the formulae:
NH~-Alkylene - O-Alkylene )mNH2 Jo ~5~35 43- .
where m has a value of about 3 to 70 and preferably about 10 to 35;
R alkaline O~Alkylene nun 2]3-6 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 it 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 hazing a valence of 3 to 6. The alkaline 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 alkaline groups present within the above for-mule may be the same or different.
More specific examples of these polyamides in-elude:
NH2fH-CH2~ OCH2CH I NH2 SHEA SHEA
wherein x has a value of from about 3 to 70 and preferably from about 10 to 35 and:
CH2-------~0CH~CH OX NH2 ¦ SHEA

CH3-CH2--C~-CH2- OCH2CH NH2 SHEA- -~OCH2CH - I _NH2 SHEA
wherein x y z have a total value ranging from about 3 to 20 30 and preferably from about 5 to 10.
The preferred polyoxyalkylene polyamides for purposes of this invention include the polyoxyethylene and polyoxypropylene dominoes and the polyoxypropylene trimness having average molecular weights ranging from about 200 to 2000. The polyoxyalk~lene polyamides are commercially available and may be obtained, for example, from the Jeff person Chemical Company, Inc. under the trade name "Jeff-amine D-230, D-400, D-1000, D-20001 T-403, etc.", - I -US. patents 3,~04,763 and 3,948~800 disclose such polyoxyalkylene polyamides and processes for assaulting them with carboxylic acid assaulting agents which processes can be applied to their reaction with the assaulting reagents of this invention.
The most preferred amine for use in this invention are the alkaline polyamides, including the polyalkylene polyamides, as described in more detail hereafter. The alkaline polyamides include those conforming to the formula:
H-N ~Alkylene-Nt R" R"
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 "Alkaline"
group has from about 1 to about 10 carbon atoms but the preferred alkaline is ethylene or propylene. specially preferred are the alkaline polyamides where each R" is hydrogen with the ethylene polyamides and mixtures of ethylene polyamides being the most preferred. Usually n will have an average value of from about 2 to about 7. Such alkaline polyamides include ethylene polyamides, ethylene polyamides, battalion polyamides, propylene polyamides, pentylene polyamides, hexylene polyamides, heptylene polyamides, etc. The higher homology of such amine and related aminoalkyl-substituted piperazines are also included.
~lkylene polyamides useful in preparing the carboxylic I derivative compositions include ethylene Damon, triethylene tetramine, propylene Damon, trim ethylene Damon, hexamethylene Damon, decamethylene Damon, octamethylene Damon, Dwight-methylene)triamine, tripropylene tetramine, tetraethylene pent amine, trim ethylene Damon, pantaethylene examine, di(trimethylene)triamine, N-(2-aminoethyl)piperazine, Boyce-aminoethyl)piperazine, and the like. Higher homology as are obtained by condensing two or more of the above-illustrated alkaline amine are useful as amine in this invention as are mixturesQf two or more of any of the afore-described polyamides.

' I

Ethylene polyamides, such as those mentioned above, are especially useful for reasons of cost and effectiveness Such polyamides are described in detail under the heading "Dominoes and Higher Amine" in The Encyclopedia of Chemical Technology, Second Edition, Kirk and Other, Volume 7, pages 27-39, Intrusions Publishers, Division of John Wiley and Sons, 1966. Such compounds are prepared most conveniently by the reaction of an alkaline chloride with ammonia or by reaction of an ethylene mine with a ring-opening reagent such as ammonia, etc. These reactions result in the production of the somewhat complex mixtures of alkaline polyamides, including cyclic condensation products such as piperazines.

Hydroxyalkyl alkaline polyamides having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in preparing compositions of the present invention Preferred hydroxyalkyl-substituted alkaline polyamides 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 polyamides include N-(2-hydroxyethyl~ethylene Damon, N,N-bis(2-hydroxyethyl~ethylene Damon, 1 (~-hydroxyethyl)-piperazine, monohydroxypropyl-substituted diethylene thiamine, dihydroxypropyl-substituted tetraethylene pent amine, No hydroxybutyl)tetramethylene Damon, etch Higher homology as are obtained by condensation of the above-illustrated hydroxy alkaline I polyamides through amino radicals or through hydroxy radicals are likewise useful as amine 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 assaulting agents and the amine described herein before yield assaulted amine which US

include amine salts, asides, immediacy and imidazolines as well as mixtures thereof, To prepare carboxylic derivative composition from the assaulting agents and the amine, one or more assaulting agents and one or more amine are heated, optionally in the presence of a normally liquid, suntan tidally inert organic liquid solven~/diluent, at temperatures in the range of about 80C. up Jo the decomposition point (the decomposition point is the temperature at which there is sufficient decomposition of any reactant or product such 10 as to interfere with the production of the desired product) but normally at temperature in the range of about 100C. up to about 300C. provided 300C. does not exceed the decompo-session point. Temperatures of about 125C. to about 250C.
are normally used. The assaulting agent and the amine are 15 reacted in amounts sufficient to provide from about one-half equivalent to about 2 mole of amine per equivalent of assaulting reagent. For purposes of this invention an equip valet of amine it that amount of the amine corresponding to the total weight of amine divided by the total number of 20 nitrogens present. Thus, octylamine has an equivalent weight equal to its molecular weight; ethylene Damon has an equivalent weigh equal to one half its molecular weight;
and aminoethylpiperazine has an equivalent weight to one-third its molecular weight. Also, for example, the equip I valet weight of a commercially available mixture of polyp alkaline polyamide can be determined by dividing the atomic weight of nitrogen (14) by the ON contained in the polyp amine. Therefore, a polyamide mixture having a ON of 34 would have an equivalent weight of 41.2. The number of 30 equivalents of assaulting agent depends on the number of carboxylic functions (ego carboxylic acid groups or lung-tonal derivatives thereof) present in the assaulting no-agent. Thus, the number of equivalents of assaulting agents will vary with the number of car boxy groups present therein.
35 In determining the number of equivalents of assaulting agents, those carboxyl functions which are not capable of reacting as a assaulting agent are excluded In general, 83~
- I -however, there is one equivalent of assaulting agent or each car boxy group in the assaulting agents. For example, there would be two equivalents in the assaulting agents derived prom the reaction of one mole of olefin polymer and one mole of malefic android.
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 assaulting agent available to react with amine.
US. Patents 3,172,~92; 3,219,666; and 3,272,746 describe the preparation of assaulted amine from high molecular assaulting agents and procedures applicable to reacting the substituted succinic assaulting agents of this invention with the amine as described above. In applying the disclosures of these patents to the substituted assaulting agents of this invention, the latter can be substituted for the high molecular weight carboxylic acid assaulting agents disclosed in these patents on an equivalent basis.
That is, where one equivalent of the high molecular weight carboxylic assaulting agent disclosed in these incorporated patents is utilized, one equivalent of the assaulting agent of this invention can be used.

The Alcohols (b) Alcohols (b) useful in preparing carboxylic derivative compositions of this invention from the assaulting agents previously described include those compounds of the general formula:

3 (Ohm"

wherein R3 is a monovalent or polyvalent organic radical joined to the -OH groups through carbon-to-oxygen bonds (that is, -COY
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, us _ .

~s~35 aliphatic-substituted aromatic alcohols, aliphatic-substi-tuned heterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols cycloaliphatic substituted aromatic alcohols, cycloaliphatic-substituted heterocyclic alcohols t heterocyclic-substituted aliphatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols. Except for the polyoxy-alkaline alcohols, the moo- and polyhydric alcohols cores-pounding to the formula Rome" will usually contain not 10 more than about 40 carbon atoms and generally not more than about 20 carbon atoms. The alcohols may contain non hydra-carbon substituents of the same type mentioned with respect to the amine above, that is, non-hydrocarbon substituents which do not interfere with the reaction of the alcohols 15 with the assaulting agents of this invention. In general, polyhydric alcohols are preferred.
Among the polyoxyalkylene alcohols suitable for use in the preparation of the carboxylic derivative compost-lions of this invention are the polyoxyalkylene alcohol I emulsifiers for aqueous emulsions. The terminology "demur-sifter for aqueous emulsions" as used in the present specie ligation and claims it intended to describe those polyp oxyalkylene alcohols which are capable of preventing or retarding the formation of aqueous emulsions or "breaking"
25 aqueous emulsions. The terminology "aqueous emulsion" is generic to oil-in-water and water-in-oil emulsions.
Many commercially available polyoxyalkylene at cool emulsifiers can be used. Useful emulsifiers are the reaction products of various organic amine, carboxylic acid 30 asides, and qua ternary ammonium salts with ethylene-oxide.
Such pol~oxyethylated amine, asides, and qua ternary salts . I era available from Armour Industrial Chemical Co. under the names E~HODUOMEEN an ethylene oxide condensation product of an N-alkyl alkylenediamine under the name DAMON I;
35 ETHOMEEN tertiary amine which are ethylene oxide condense-lion products of primary fatty amine; ETHOMIDS~k ethyl-eneoxide condensates of fatty acid asides; and ETHOQUAD
to us i83~i polyoxyethylated qua ternary ammonium salts such as qua-ternary ammonium chloride.
The preferred demu~sifiers are liquid polyoxyalky-tone 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 alkyd, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyd, etch containing up to about forty carbon atom. Specific 10 hydrocarbyl groups are methyl, bottle, dodecyl, toll, phenol, naphthyl, dodecylphenyl, p-octylphenyl ethyl, cyclohexyl, and the like. Carboxylic acids useful in preparing the ester derivatives are moo- or polycarboxylic acids such as acetic acid, Valerie acid, Laurie acid, 15 Starkey acid, succinic acid, and alkyd or alkenyl-substi-tuned succinic acids wherein the alkyd or alkenyl group contains up to about twenty carbon atoms. Members of this class of alcohols are Marshall available from various sources; erg, PLURONIC polyols from Wyandotte Chemicals 20 Corporation; POLYGLYCOL 112-2~ a liquid trio derived from ethylene oxide and ~ropyleneoxide available from Dow Chemical Co.; and TERGITOL5~ dodecylphenyl or nonylphenyl polyethyl-one glycol ethers, and ICONS polyalkylene glycols and various derivatives thereof, both available from Union 25 Carbide Corporation However, the emulsifiers 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 demulslfiers, an alcoholic hydroxyl group is one attached to 30 a carbon atom that does not form part of an aromatic nucleus.
In this class of proofer polyoxyalkylene Alcoa hots are those polyols prepared as "block" copolymers.
Thus, a hydroxy-substituted compound, Wreck (where q is 1 to 6, preferably 2 to 3, and R4 is the residue of a moo- or 35 polyhydric alcohol ox Mooney or polyhydroxy phenol, naphthol, etc.) it reacted with an alkaline oxide, Rs-CH-/H~R6, to -Trudy I

I
. -50-form a hydrophobic base Us being a lower alkyd group of up to four carbon atom, R6 being H or the same as R5 with the proviso that the alkaline oxide does not contain in excess of ten carbon atoms. This base is then reacted with ethyl-one oxide to provide a hydrophilic portion resulting in 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 10 skill of the art to prepare such polyols whose molecules are characterized by hydrophobic and hydrophilic moieties pro-sent in a ratio rendering them suitable as emulsifiers for aqueous emulsion in various lubricant compositions and thus suitable as alcohols in this invention. Thus, if more oil-15 volubility is needed in a given lubricant composition, the hydrophobic portion can be increased and/or hydrophilic portion decreased. If greater aqueous emulsion breaking capability it required, the hydrophilic and/or hydrophobic portions can be adjusted to accomplish this.
Compound illustrative of Wreck include elf-phatic polyols such as the alkaline glycols and Al Kane polyols, e.g., ethylene glycol, propylene glycol, trim ethyl-one glycol, glycerol, pentaexythritol, erythritol, sorbitol, minutely, and the like and aromatic hydroxy compounds such 25 as alkylated moo- and polyhydric phenols and naphthols, e.g., chrysalis, heptylphenols, dodecylphenols, dioctylphenols, triheptylphenols, resorcinol, pyrogallol, etc.
Polyoxyalkylene polyol emulsifiers which have two or three hydroxyl groups and molecules consisting Essex-0 tidally of hydrophobic portions comprising -SHEA group where R5 is lower alkyd of up Jo three carbon atoms and hydrophilic portions comprising -CH2CH2O- groups are part-ocularly preferred. Such polyols can be prepared by first 35 reacting a compound of the formula Wreck where q is 2-3 with a terminal alkaline oxide of the formula Us SHEA

So and then reacting that product with ethylene oxide R4~~0H)q can be, for example, TOP (trimethylolpropane), TOME
ttrimethylolethane), ethylene glycol, trim ethylene glycol, tetramethylane glycol, trip hydroxypropyl)amine, 1,4-(2-hydroxyethyl)-cyclohexane, N,N,N',N'-tetrakis(2-hydroxy-propyl)ethylene Damon, N,N,N',N'-tetraki 5 ( 2-hydroxyethyl)-ethylene Damon, naphthol, alkylated naphthol, resorcinol, or one of the other illustrative examples mentioned here-in before The polyoxyalkylene alcohol emulsifiers should have an average molecular weight of 1000 to about 10,000, preferably about 2000 to about 7000. The ethyleneoxy groups (i.e., -CH2CH20-) normally will comprise from about 5% to about 40% of the total average molecular weight. Those 15 polyoxyalkylene polyols where the ethyleneoxy groups come prose 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 10%-20% by weight of the 20 molecule is attributable to ethyleneoxy groups result in the formation of esters having particularly improved demulsi-lying properties. The ester and ether derivatives of these polyols are also useful.
Representative of such polyoxyalkylene polyols are 25 the liquid polyols available from Wyandotte Chemicals Come puny under the name PLURONIC Polyols and other similar polyols. These PLURONIC Polyols correspond to the formula HG-(CH2CH2O)X(lHCH20)y(CH2CH~O)z-H
SHEA
wherein x, y, and z are integers greater than 1 such that 30 the -CH2CH2O- groups comprise prom 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 35 ethylene oxide.

5~3~i Another group of polyoxyalkylene alcohol emulsifiers 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:
H(C2H4O)b(c3H6o)a \ / (C3H6O~a~c2H4O~b H(C2~4O)b(c3H6o)a (C3H6O)a(c2H4o~b Such polyols are described in US. Patent No. 2,979,528. Those polyols corresponding to the above formula having an average molecular weight of up to about 10,000 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 account for 7.5%-12% by weight of the total molecular weight. Such polyols can be prepared by reacting an alkaline Damon such as ethylene Damon, propylene Damon, hexamethylene Damon etc., with propylene oxide until the desired weight ox the hydrophobic portion is reached. Then the resulting product is reacted with ethylene oxide to add the desired number ox hydrophilic units to the molecules.

Another commercially available polyoxyalkylene polyol emulsifier falling within this preferred group is Dow Polyglycol

2, a trio having an average molecular weight of about US 4000-5000 prepared from propylene oxides and ethylene oxides, the ethyleneoxy groups comprising about 18% by weight of the trio.
Such trios can be prepared by first reacting glycerol, TOME, TOP, 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 alkaline glycols and polyoxyalkylene alcohols such as polyoxyethylene alcohols, polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. These polyoxyalkylene * trade mark ~2~33~i alcohols (sometimes called polyglycol~) can contain up to about 150 oxyalkylene groups wherein the alkaline radical contains from 2 to about 8 carbon atoms. Such polyoxy alkaline 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 remain-in -OH group can be esterified with a monobasic, aliphatic or aromatic carboxylic acid of up to about 20 carbon atoms 10 such as acetic acid, prop ionic acid, oleic acid, Starkey acid, benzoic acid, and the like. The monoethers of these alkaline ylycols and polyoxyalkyl~ne glycols are also useful. These include the monorail ether, monoalkyl ethers, and monoaralkyl ethers of these alkaline glycols and 15 polyoxyalkylene glycols. This group of alcohols can be represented by the general formula HO RHO RUB OR
where ARC is aureole such as phenol, lower alkoxy phenol, or lower alkyd phenol, lower alkyd such a ethyl, propel, left-20 bottle, pinwheel, etc.; and aralkyl such as bouncily, phenol-ethyl, phenylpropyl, p-ethylphenylethyl, etc.; p is zero to about eight, preferably two to four, carbon atoms. Polyp oxyalkylene glycols where the alkaline groups are ethylene or propylene and p is at least two as well as the monoethers I thereof as described above are very useful.
The mandrake and polyhydric alcohols useful in this invention include monohydroxy and polyhydroxy aromatic compounds. Mandrake and polyhydric phenols and naphthols are preferred hydroxyaromatic compounds. These hydroxy-30 substituted aromatic compounds may contain other subset-tents in addition to the hydroxy substituents such as halo, alkyd, alkenyl, alkoxy, alkylmercapto, vitro an the like Usually, the hydroxy aromatic compound will contain 1 to 4 hydroxy groups. The aromatic hydroxy compounds are thus-35 treated by the following specific examples: phenol, p-chlorophenol, p-nitrophenol, beta-naphthol, alpha-naphthol, chrysalis, resorcinol, catcall, caxvacrol, thymol, euyenol, p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol, sheller-glucinol, hexylresorcinol, orison, gawkily, 2-chlorophenol, 2,4-dibutylphenol, propenetetramer-substituted phenol t didodecylphenol, 4 t 4'-methylene-bis-me~hylene~bis-phenol, alpha-decyl-be~a naphthol, polyisobutenyl-(mol~cular weight (My) of about substituted phenol the condensation product of heptylphenol with Owe moles of formaldehyde, the condensation product of octylphenol with acetone, dodder-10 xyphenyl)oxide, di(hydroxyphenyl)sulfide, di(hydroxyphenyl)-disulfide, and 4-cyclohexylphenol. Phenol itself and elf-phatic hydrocarhon-substituted phenols, e.g., alkylated phenols having up to 3 aliphatic hydrocarbon substituents are especially preferred. Each of the aliphatic hydrocarbon lo substituents may contain 100 or more carbon atoms but usually will have from 1 to 20 carbon atoms. Alkyd and alkenyl groups are the preferred aliphatic hydrocarbon substituents.
Further specific examples of mandrake alcohols 20 which can be used include mandrake alcohols such as methanol, ethanol, i~ooctanol, dodecanol, cyclohexanol, cyclopentanol, Bunnell alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, ensoul alcohol, beta-phenylethyl alcohol, 2-methyLcyclohexanol, beta-chloroethanol, moo-25 methyl ether of ethylene glycol, monobutyl ether of ethyleneglycol, monopropyl ether of diethylene glycol, monododecyl ether of triethylene glycol~ moonlit of ethylene glycol, menstruate of diethylene glycol, sec-pentyl alcohol, tertbutyl alcohol, 5-bromo-dodecanol, nitro-octadecanol, and dwelt of glycerol. Alcohols useful in this invention may be unsaturated alcohols such as ally alcohol, cinnamyl alcohol, l-cyclohexene-3-ol and of ye 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 ox-alkaline, aminoalkylene or amino-aryleneoxy~arylene radicals.

A They are exemplified by CeIlosolve, carbitol, phenoxyethanol, heptylphenyl-(oxypropylene)6-OH, octyl-(oxyethylene)~o-O~, phenyl-(oxyoctylene) 2 I mono-(heptylphenyl-oxypropylene) substituted glycerol, polystyrene oxide amino ethanol, 3-amino-e~hylpentanol, di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine, N-hydroxyethyl ethylenediamine, N,N,N',N'-tetrahydroxy-trimethylenediamine, and the like.
The polyhydric alcohols preferably contain from 2 to about 10 hydroxy radicals. They are illustrated, for example, by the alkaline glycols and polyoxyalkylene glycols mentioned above such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene guy-got, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkaline glycols and polyoxyalkylene glycols in which the alkaline radicals contain 2 to about 8 carbon atoms.
Other useful polyhydric alcohols include glycerol, moonlit of glycerol, menstruate of glycerol, monomethyl ether of glycerol, pentaerythritol~ n-butyl ester of 9,10-20 dihydroxy Starkey acid, methyl ester of 9,10-dihydroxy Starkey acid, l,2-butanediol, 2,3-hexanediol, 2,4-hexane-Doyle pinnacle, erythritol, arabitol, sorbitol, minutely, 1,2-cyclohexanediol, and zillion glycol. Carbohydrates such as sugars, starches, cellulose, and so forth likewise can 25 be used. The carbohydrates may be exemplified by glucose, fructose, sucrose, Remus, muons, ylyceraldehyde, and galactose~
Polyhydric alcohols having at least 3 hydroxyl groups, some, but not all of which have been esterified with 30 an aliphatic monocarboxylic acid having from about 8 to about 30 carbon atoms such as octanoic acid, oleic acid, Starkey acid, linoleic acid, dodecanoic acid or tall oil acid are useful. Further specific examples of such par-tidally esterified polyhydric alcohols are the moonlit of 35 sorbitol, distrait of sorbitol, moonlit of glycerol menstruate of glycerol, di-dodecanoate of erythritol, and the like.
I toe we ~Z3~35 A preferred class of alcohol suitable for use in this invention are those polyhydric alcohols containing up to about twelve carbon atoms, and especially those contain-in three to ten carbon atoms. This class of alcohols includes glycerol, erythritol, pen~aerythritol, Dupont-erythritol, gluconic acid, glyceraldehyde, glucose, era-buoyancy, 1~7-heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol, 2,3,4-hexanetriol~
1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid, 2,2,6,~
10 tetrakis-(hydroxymethyl)cyclohexanol, 1,10 decanediol, digitals, 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 Alcoa 15 hots for use in this invention are the polyhydric alkanolscontaining 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-, minutely, sorbitol, 20 2hydroxymethyl-2-methyl-1,3-propanediol~trimethylolmethane), 2-hydroxymethyl-2-ethyl-1,3-propanediol(trimethylopropane), 1,2,4-hexanetriol, and the like.
From what has been stated above, it is seen thaw amine may contain alcoholic hydroxy substituents and Alcoa 25 hots can contain primary, secondary, or tertiary aminosubstituents. Thus, amino alcohols can be catagoriæed as both amine and alcohol provided they contain a least one primary our secondary amino group. If only tertiary amino groups are present, the amino alcohol belongs only in the 30 alcohol category.
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 polyamides such as 2-35 hydroxyethylamine, 3-hydroxybutylamine, di-(2-hydroxyethyl)-amine, tri-(2~hydroxyethyl~amine, di-(2-hydroxypropyl)amine, So I
N,N,N'-tri-(2-hydroxyethyl)ethylenedlamine, N,N,N',N'-tetra-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piper-amine, N,N'-di-(3-hydroxypropyl)pipexazine, N-(2-hydroxy-ethyl)morpholine, N-(2~hydroxyethyl)-2-morpholinone, No S hydroxyethyl~-3-methyl-2-morpholinone, N~(2-hydroxypropyl~-6-methyl-2-morpholinone, N-(~hydroxyethyl)-5-carbethoxy-2-piperidone, N-(2-hydroxypropyl)-5-carbethoxy-2-piperiaone, N-(2-hydroxyethyl)-5~(N-butylcarbamyl)-2-piperidonno, No hydroxyethyl~piperidinP, N (4-hydroxyhu~yl)piperidine, NUN-10 di-(2-hydroxyethyl)glycine, and ether thereof with elf-phatic alcohols, especially lower alkanols, N,N-di(3 ho-droxypropyl)glycine, and the Mike. Also contemplated are other moo- and poly-N-hydroxyalkyl-substituted alkaline polyamides wherein the alkaline polyamides are as described 15 above; especially those that contain two to three carbon atoms in the alkaline radicals and the alkaline polyamide 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 amine described in US. Patent 3,576,743 by the general formula where Ray is a monovalent organic radical containing at least 25 one alcoholic hyrax group, according to this patent, the total number of carbon atoms in Rod will not exceed about 20.
Hydroxy-substituted aliphatic primary amine containing a total of up to about 10 carbon atoms are particularly use-us Especially preferred are the polyhydroxy-substituted 30 alkanol primary amine wherein there is only one amino group present (i.e., a primary amino group) having one alkyd substituent containing up to 10 carbon atoms and up to 6 hydroxyl groups. These alkanol primary amine correspond to Rd-NH2 wherein I is a moo- or polyhydroxy-substituted 35 alkyd group. It is desirable that at least one of the hydroxyl groups be a primary alcoholic hydroxyl group.

I 33~

Trismethylolaminomethane is the single most preferred hydroxy-substituted primary amino Specific examples of the hydroxy-substituted primary amine 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-aminoethyl)-piperazine, tris(hydroxymethyl)amino methane also known as trismethylolamino methane, 2-amino-1-butanol, ethanol amine, beta-(beta-hydroxy 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-hydroxy-ethyl)-piperadine, 2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol, N-~beta-hydroxyethyl)-1,3-diamino propane, Damon-2-hydroxy-propane, N-(beta-hydroxy ethoxyethyl)-ethylenediamine, and the like. For further description of the hydroxy-substituted primary amine contemplated as being useful as amine and/or alcohols, see US. Patent 3,576,743.

The carboxylic derivative compositions produced by reacting the assaulting 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 assaulting reagents are not esterified but are present as free carboxyl croups. Obviously, acid esters are easily prepared by using an amount of alcohol insufficient to esterify all of the corbel groups in the assaulting reagents of this invention.

The assaulting agents are reacted with the alcohols according to conventional esterification techniques. It normally involves heating the assaulting 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.

5~3~

Temperatures of at least about 100C. up to the decomposition point are used Tithe decomposition point having been defined herein before). This temperature is usually within the range of about 100C. up to about 300C. with temperatures of about 140C.
to 250C. often being employed. Usually, at least about one-half equivalent of alcohol is used for each equivalent of assaulting agent. An equivalent of assaulting agent is the same as discussed above with respect to reaction with amine. 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 assaulting agents with alcohols to produce acidic esters and neutral esters. These same techniques are applicable to preparing esters from the assaulting agents of this invention and the alcohols described above. All that is required is that the assaulting agents of this invention are substituted for the high molecular weight carboxylic acid assaulting reagents discussed in these patents, usually on an equivalent weight basis. The following US. Patents disclose suitable methods for reacting the assaulting agents of this invention with the alcohols described above: 3,331,776; 3,381,022;

3,522,179; 3,542,680; 3,697,428; 3,755,1690 The Reactive Metals or Metal Compounds I
Reactive metals or reactive metal compounds useful as (c) are those which will form carboxylic acid metal salts with the assaulting agents of this invention and those which will form metal-containing complexes with the carboxylic derivative compositions produced by reacting the assaulting reagents with amine and/or alcohols as discussed above.

.

Reactive metal compounds useful as (c) for the formation of complexes with the reaction products of the assaulting agents and amine are disclosed in US. Patent 3,306,908.
Complex-forming metal reactants useful as (c) include the nitrates, nitrites, halides, carboxylates, phosphates, phosphates, sulfates, sulfites, carbonates, borate, 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 10 transition or coordination metals, it whey are capable of forming complexes by means of their secondary or co-ordination valence. Specific examples of the complex-forming metal compounds useful as the reactant lo) in this invention are cobaltous nitrate, cobaltous oxide, cobaltic 15 oxide, cobalt nitrite, cobaltic phosphate, cobaltous color-ides cobaltic chloride, cobaltous carbonate, crimes acetate, chronic acetate, chronic bromide, crimes color-ides chronic fluoride, crimes oxide, chromium dioxide, chronic oxide, chronic sulfite, crimes sulfate Hyatt-20 hydrate, chronic sulfate, chronic format, chronic hexano-ate, chromium oxychloride, chronic phosphate, manganese acetate, manganese bonniest, manganese carbonate, manganese dichlorides manganese trichloride, manganese citrate, muggins format, manganese nitrate, manganese oxalate, 25 manganese monoxide, manganese dioxide, manganese trioxides manganese heptoxide, manganic phosphate, manganese pyre-phosphate, manganic metaphosphate, manganese hypophosphite, manganese vale rate, ferrous acetate, ferris bonniest, ferrous bromide, ferrous carbonate, ferris ornate ferrous lactate, ferrous nitrate, ferrous oxide, ferris oxide, ferris hypophosphite, ferris sulfate, ferrous sulfite, eureka hydrosulfite, nickel dibromide, nickel dichlorides nickel nitrate, nickel dwelt, nickel Stewart, nickel sulfite, cupric preappoint, cupric acetate, cupric mote-borate, cupric bonniest, cupric format, cupric laurate,cupric nitrite, cupric oxychIoride, cupric palpitate 9 cupric salicylate, zinc bonniest, zinc borate, zinc bromide, zinc ~2~5i835 chromates zinc dichromate, zinc iodide, zinc lactate, zinc nitrate, zinc oxide, zinc Stewart, zinc sulfite, cadmium bonniest cadmium carbonate, cadmium bitterroot, cadmium chloroacetatel cadmium Enumerate, 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.

US. Patent 3,306,908 discloses reactive metal compounds suitable for forming such complexes and processes for preparing the complexes. Basically, those processes are applicable to the carboxylic derivative compositions of the assaulting agents of this invention with the amine as described above by substituting, or on an equivalent basis, the assaulting reagents of this invention with the higher molecular weight earboxylic acid allotting agents disclosed in US. Patent 3,306,908. The ratio of equivalents of the assaulted amine thus produced and the complex-forming metal reactant remains the same as disclosed in 3,306,908 patent.

US. Reissue Patent 26,443 discloses metals useful in preparing salts from the reaction of allotting agents and amine 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 methyl ate, sodium propylate, sodium pentylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate potassium methyl ate, potassium pentylate, potassium phenoxide, lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, calcium oxide, calcium hydroxide, calcium carbonate, calcium methyl ate, calcium ethyl ate, calcium replete, calcium chloride, calcium fluoride, calcium pentylate, calcium phenoxide, calcium nitrate, barium oxide, barium hydroxide, barium earonbate, barium chloride, barium fluoride, barium methyl ate, barium propylate, barium pentylate, barium nitrate, magnesium oxide, magnesium hydroxide, magnesium I I

carbonate, magnesium ethyl ate, magnesium propylate, magnesium chloride, magnesium bromide, barium iodide, magnesium phenoxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc methyl ate, zinc propylate, zinc pentylate, zinc chloride, zinc fluoride, zinc nitrate trihydrate, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium methyl ate, cadmium propylate, cadmium chloride, cadmium bromide, cadmium fluoride, lead oxide, lead hydroxide, lead carbonate, lead ethyl ate, lead pentylate, lead chloride, lead fluoride lead iodide, lead nitrate, nickel oxide, nickel hydroxide, nickel carbonate, nickel chloride, nickel bromide, nickel fluoride, nickel methyl ate, nickel pentylate, nickel nitrate hexahydrate, cobalt oxide, cobalt hydroxide, cobaltous bromide, cobaltous chloride, cobalt butyla-te, 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.

US. Reissue 26,443 discloses 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 assaulting agents of this invention on an equivalent weight basis for the high molecular weight carboxylic assaulting agents of the reissue patent.

US. Patent 3,271,310 discloses the preparation of metal I salt of high molecular weight carboxylic acid assaulting 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 methyl ate, sodium propylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methyl ate, silver .

- 63 5~35 oxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium elite, magnesium propyllate, magnesium phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, calcium methyl ate, calcium propylate, calcium pentylate, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethyl ate, barium oxide, barium hydroxide, barium hydrate, barium carbonate, barium ethyl ate, 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.

US. Patent 3,271,310 discloses suitable reactive metal compounds for forming salts of the assaulting reagents of this invention as well as illustrative processes for preparing salts of these assaulting reagents. As will be apparent, the processes of 3,271,310 are applicable to the assaulting reagents of this invention merely by substituting on an equivalent weight basis, the assaulting reagents of this invention for the high molecular weight carboxylic acids of the patent.

Ed) The Combination of Two or More of (a), (b) and (c) -From the foregoing description, it is apparent that the assaulting 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 amine, 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 amine, 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 amine and alcohols, from amine and reactive metals or reactive metal compounds, from alcohols and reactive metal compounds, or one or more components from each of the amine, alcohols, and reactive metal or reactive metal compounds.
Furthermore, the assaulting reagents of this invention can be reacted with the amine, alcohols, reactive metals, reactive metal compounds, or mixtures thereof, as described above, simultaneously (concur-gently) or sequentially in any order of reaction.

Canadian Patent 956,397 discloses procedures for reacting the assaulting reagents of this invention with amine, 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 assaulting agents of this invention for the high molecular weight carboxylic acid assaulting 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 US. Patents are counterparts of the above Canadian patent: 3,836,469; 3,836,470; 3,836,471; 3,838,050;
3,838,052; 3,879,308; 3,957,85~; 3,957,855; 4,031,118. The Canadian patent and the US. patents illustrate that the amount of polyoxyalkylene alcohol emulsifier utilized in preparing ~ispersant/detergents from the assaulting 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 US.
patent identified above in which the polyoxyalkylene alcohol emulsifier has been omitted. In other words, a preferred class it So of carboxylic derivative compositions of this invention are the various reaction products of the high molecular weight carboxylic acid assaulting agents of the Canadian patent with one or more amine, alcohols, and reactive metal compounds as disclosed therein differing only in that the assaulting agents of this invention are substituted on an equivalent weight basis and, further, that the polyoxyalkylene alcohol emulsifier reactant is omitted.

In addition, US. Patent 3,806,456 discloses processes useful in preparing products from the assaulted reagents of this invention and polyoxyalkylene polyamides as described herein before. Substitution of the assaulted reactants of this invention for the high molecular weight carboxylic acid assaulting agents disclosed in 3,806,456 on an equivalent weight basis produces compounds further characterized by the viscosity index improving properties.

US. Patent 3,576,743 discloses a process for preparing carboxylic derivative compositions from both polyhydric alcohols and amine; in particular, hydroxy-substituted primary amine. Again, substitution of the assaulting reagents of this invention on an equivalent weight basis for the high molecular carboxylic acid assaulting agents disclosed in 3,576,743 provides compositions having the desired dispersant/detergent compositions and V.I. improving properties.

I US. Patent 3,632,510 discloses processes for preparing mixed ester-metal salts. Mixed ester-metal salts derived from assaulting 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 assaulting reagents of this invention for the high molecular weight carboxylic acid assaulting do, 58~

agents of the patent The carboxylic acid derivative compositions thus produced also represent a preferred aspect of this invention.

Processes for preparing polyamide modified ester-carboxylic derivative compositions useful as (B) in the present invention generally comprise:
(I) Reacting, to form a polyester intermediate, (A) at least one polyhydric alcohol with (B) a substituted succinic acid assaulting agent, the substituent thereon being derived from at least one alkene polymer having a number average molecular weight (My) of at least about 1200 and a ratio of weight average to number average molecular weight (Mom) of about 1.5-6.0, said assaulting agent having within its molecular structure an average of at least about 1.3 succinic groups per substitutent group; and (II) subsequently reacting said polyester intermediate with (C) at least one acylatable polyamide 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-I modified polyester in a first mineral oil having a kinematic viscosity at 100C. of 3.6-~.3 centistokes has a nitrogen content of at least 0.0175% by weight and a first kinematic viscosity at 100C. of at least about 300 centistokes; and a second solution prepared by dissolving said first I solution in a second mineral oil having a kinematic viscosity at 100C. 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.

Jo ~2~5~35 Finally, USE Patents 3,755,169; 3,804,763; 3r868,330;
and 3,948,800 disclose how to prepare carboxylic acid derivative compositions. By following the teachings of these patents and substituting the assaulting agents of this invention for the high molecular weight carboxylic assaulting agents of the patents, a wide range of carboxylic derivative compositions within the scope of the present invention can be prepared.

Reference to so many patents has been made because, it is felt, the procedures necessary to prepare the carboxylic derivative compositions from the assaulting agents and the amine, alcohols, and reactive metals and reactive metal compounds, as well as mixtures thereof, are 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 assaulting agents and the allcylene polyamides, especially polyethylene polyamides, and/or polyhydric alcohols, especially the polyhydric alkanols, are especially preferred. As previously stated, mixtures of polyamides and/or polyhydric alcohols are contemplated.
I Normally, all the carboxyl functions on the assaulting reagents of this invention will either be esterified or involved in formation of an amine salt, aside, imide or imidazoline in this preferred group of carboxylic derivative compositions.

In addition to detergent/dispersant properties, the I carboxylic derivative compositions and post-treatments thereof discussed herein function as VI improvers and these viscosity index improving capabilities are enhanced when prepared from the reaction or the assaulting agents with polyfunctional reactants.
For example, polyamides having two or more primary and/or secondary amino groups, polyp .....

~2~3~i hydric alcohols, amino alcohols in which where are one or more primary and/or secondary amino groups and one or more hydroxy groups, and polyvalent metal or polyvalent metal compounds. It it believed what the polyunctional reactants serve to provide "bridges" or cross-linking in the car-boxlike 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 10 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.I. improver in lubricating compositions, the polyfunctionallty of reactants 15 (a), (b), and (c) may not fully explain the V.I. 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 assaulting reagents be polyphonic-20 tonal. Thus, combinations of moo- and polyfunctional amine, alcohols, reactive metals and reactive metal come pounds can be used; for example, monoamine with a polyhydric alcohol, a mandrake alcohol with polyamide, an amino alcohol with a reactive metal compound in which the metal is 25 monovalent, and the like.
While the parameters have not been fully deter-mined as yet, it is believed that assaulting reagents of this invention should be reacted with amine, alcohols, reactive metals, reactive metal compounds, or mixtures of these which 30 contain sufficient polyfunctional reactant (e.g., polyp amine, 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 malefic reactant) are reacted with a polyfunctional reactant. Better results 35 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 pro-pexties seem to be achieved when the assaulting reagents of this invention are reacted with a sufficient amount of polyamide 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 10 stated percentage ox car~oxyl functions actually react with polyfunctional reactant. Rather these percentages are used to characterize the amounts of polyfunctional reactants desirably "available" to react with the assaulting reagents in order to achieve the desired viscosity index improving 15 properties.
Post-t_eated_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 20 carboxylic derivative compositions Additionally, (B) includes mixtures of one or more carboxylic derivative compositions and one or more post-treated carboxylic don-ivative compositions.
The process for post-treating the carboxylic acid I derivative compositions is analogous to the post-treating processes used with respect to similar derivatives of the high molecular weight carboxylic acid assaulting agents of the prior art. Accordingly, the same reaction conditions, ratio of reactants and the like can be used.
Assaulted nitrogen compositions prepared by react-in the assaulting agents ox this invention with an amine (a as described above are post-treated by contacting the assaulted nitrogen compositions thus formed (ago., the carboxylic derivative compositions) with one or more post-35 treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron I

acids, esters ox boron acids, carbon disulfide, hydrogen sulfide, sulfur, sulfur chlorides, alkenyl cyanides, car-boxlike acid assaulting agents such as terephthalic acid, aldehydes, kittens, urea, Thor, guanidine, Dyson-doomed, hydrocarbyl phosphates, hydrocarbyl phosphates, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydra-corbel isothiocyanates, epoxies, 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 azalea-cling agents of this invention and a combination of amine (a) and alcohols (b) as described above. However, when the carboxylic derivative compositions of this invention are derived from alcohols (b) and the assaulting 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 assaulting agents such as terephthalic acid, epoxies, 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 assaulting agents of the prior art and amine 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 ox this invention. The following US. patents disclose post-treating processes and post-treating reagents apply-cable 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 assaulting reagents of this invention and amine); 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
1,0~35,903; UK 1,162,436; US. 3,558,743. The processes of these 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 assaulting' agents described hereinabove and processes for their preparation are described in US. Patent 4,234,435 (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 hydrocarbon-based compounds or mixtures thereof.

The chloroaliphatic hydrocarbon-based compounds useful for the purposes 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 ....

I
.. i ~2~35i and having predominantly aliphatic hydrocarbon character within the context of this invention. Such radicals include the following:
(1) Aliphatic hydrocarbon radicals: e.g., alkyd, alkenyl, and aromatic- and alicyclic-substituted alkyd and alkenyl radicals, and the like. Such radicals are known to those skilled in the art; examples include ethyl, propel, bottle, ponytail, octal, decal, stroll, dodecenyl and oilily (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 radix eel. Those skilled in the art will be aware of suitable 15 substituents (erg., alkoxy, hydroxy, alkylthio, carbalkoxy, vitro).
(3) Heteroaliphatic hydrocarbon radicals; that is, radicals which, while predominantly allphatic hydra-carbon in character within the context of this invention, 20 contain atoms other than carton 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 25 or heteroatoms, and preferably no more than one, will be present fox each 10 carbon atoms in the aliphatic hydra-carbon-based radical.
Preferably, the aliphatic hydrocarbon-based radical present in the chlorine compounds of this invention 30 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 alkyd radix eel.
The term "alkyl-based radical", as used herein, 35 denotes an alkyd radical within the description of the term "aliphatic hydrocarbon-based radical" and includes alkyd 3 2~L5~3S

radicals analogous to the "aliphatic hydrocarbon-based radicals" described hereinabove and such radicals are alkyd-hydrocarbon radicals, substituted alkyd 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 hydrocarbGn-based radicals. As used herein, the term "alicyclic hydrocarbon-based radical" denotes a radical having an alicyclic carbon 10 atom directly attached to the chlorine atom and having predominantly alicyclic hydrocarbon character within the context of this invention. Such radicals include the following:
I Alicyclic hydrocarbon radicals; e.g., cry;
15 cloalkyl or cycloalkenyl, and aromatic- and aliphatic-substituted alicyclic radicals, and the like. Such radicals are known to those skilled in the art examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycle-hotly, cyclooctyl, methylcyclohexyl, cyclopentenyl, cycle-20 pentadienyl 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 radix 25 eel. Those skilled in the art will be aware of suitablesubstituents ego., alkoxy, hydroxy, alkylthio, carbalkoxy, Norway).
3) Heteroalicyclic hydrocarbon radicals; that is, radicals which, while predominantly alicyclic hydra-30 carbon in character within the context of this inven~ion,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.

I

In general, no more than three substituents or heteroatoms, and preferably no more than one, will be present for each Zen carbon atoms in the alicyclic hydra-carbon-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 ethylenic unsatura~ion and contains at least five carbon atoms.
As previously stated, the chlorine-containing compounds may also be mixtures of one or more of the sheller-aliphatic hydrocarbon-based compounds and/or the sheller alicyclic hydrocarbon-based compounds. Furthermore, the chlorine-containing compounds usually contain approximately lo from about 30 to about 70 percent by weight chlorine The preparation of the chlorine-containing compounds (c3 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 20 appropriate hydrocarbon-based compound until the desired weight gain of chlorine is obtained.
The preferred chlor~ne-containing compounds are the chlorinated paraffin wax compositions. The molecular weight of these chlorinated paraffin wax compositions 25 usually range 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 Chemical under the trademark Sheller-30 wax, The compositions of this invention may be further combined with at least one sulfurized olefinically unset-unrated compound.
The olefinically unsaturated compounds which are sulfurized to provide the sulfurized olefinically unset-unrated compounds useful for the purposes of this invention are diverse in nature. They contain at least one olefinic double bond, which it 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=CRgRlo, wherein each of R7, Ray Rug and Rio 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 -Creole, Conrail, Conrail, -COO, Al 1 10 -ON, -1, Roll, -X, -Yell or An, wherein:
Each Roll is independently hydrogen, alkyd, at-Kenya, aureole, substituted alkyd, substituted alkenyl or substituted aureole, with the proviso that any two Roll groups can be alkaline or substituted alkaline whereby a ring of up 15 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., sheller, broom, or idea);
Y is oxygen or diva lent sulfur;
An is an aureole or substituted aureole radical of up to about 12 carbon atoms in the substituent.
Any two of R7, R8, R9 and Rl may also together Norm an alkaline or substituted alkaline group, i.e., the olefinic compound may be alicyclic.
The nature of the substituents in the substituted moieties described above are no normally a critical aspect of the invention and any such substituent is useful Jo long as it it or can be made compatible with lubricating environ-mints and does not interfere under the contemplated reaction 30 conditions. Thus, substituted compounds which are so us-stable as to deleteriously decompose under the reaction con-dictions employed are not contemplated. However, certain substituents such as veto or alluded can desirably undergo sulfurization. the selection of suitable substituents is 35 within the skill of the art or may be established through 1;2 ~L5~35;
Jo routine testing. Typical of such substituents include any of the above-listed moieties as well as hydroxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, vitro, phosphate, phosphate, alkali metal Marquette and the like.
The olefinically unsaturated compound is usually one in which each R group which is not hydrogen is indepen-deftly alkyd, alkenyl or aureole, or (less often) a coxes-pounding substituted radical. Monoolefinic and diolefinic compounds, particularly the former, are preferred, and espy-10 Shelley terminal moncolefinic (Alphonse) hydrocarbons; that is, those compounds in which R7 and R8 are hydrogen and R9 and Rl are alkyd or aureole, especially alkyd that is, the olefin it aliphatic). Olefinic compounds having from about 8 up to about 36 and especially from about 8 up to about 20 15 carbon atoms are particularly desirable.
The C8-36 aliphatic ~-olefin it terminal Olin is usually one which is unbranched on the ole~inic carbon atoms; that it which contains the moiety CH2=CH-.
It also usually contains substantially no branching on the 20 allylic carbon atoms; that is, it preferably contains the moiety CH2=CHCH2-~ The preferred oleflns are those in the Kiwi 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 oLeinically unsaturated compounds.
The term "fatty azalea" as used herein refers to acids which may be obtained by hydrolysis of a naturally 30 occurring vegetable or animal fat or oil. These are usually in the Of 6-2 o range and include oleic acid linoleic acid and the like.
Fatty acid esters which are useful are primarily esters of aliphatic alcohols, including mandrake alcohols I

such as methanol, ethanol, n-propanol, isopropanol, the buttonless, etc., and polyhydric alcohols including ethylene glycol, propylene glycol, trim ethylene luckily, 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 as 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 MOP. Doss, Properties of the Principal, FATS, Fatty Oils, Waxes, Fatty Acids and Their Salts, The Texas Company, 1952, which describes 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 100C. up to about 250C., preferably, from about 125C. up to about 200C. 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 US. patents are illustrative of the sulfurized olefinically unsaturated compounds useful for this invention and the processes for their preparation 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 car-boxlike derivative and post-treated carboxylic derivative compositions (By which comprise the combination compositions of this inven~ionA
In these examples, as well as in this specific cation and the appended claims, all percentages, parts and ratios are by weight, unless otherwise expressly stated to the contrary. Temperatures are in degrees centigrade (C.) 10 unless expressly stated to the contrary.
EXAMPLE lo A mixture of 4578 pats of a polyisobutene~sub-~tituted phenol prepared by boron trifluoride-phenol catalyzed alkylation of phenol with a polyisobutene having a 15 number average molecular weight of approximately Lowe (vapor phase osmometry), 3052 parts of delineate mineral oil and 725 parts of textile spirits is heated to 60 to achieve home-join. After cooling Jo 30, 319.5 parts of 16 molar nitric acid in 600 parts of water is added to the mixture.
20 Cooling is necessary to keep the mixture's temperature below 40. After the reaction mixture is stirred for an add-tonal two hours, an Alcott 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 25 130 parts of water at 25-30. the reaction mixture is stirred for 1.5 hours and when stripped o 220~30 ion.
Filtration provides an oil solution of the desired inter-mediate tip).
ExamF~e lo A mixture of 810 parts of the oil solution of the (IA) intermediate described in Example lay 405 parts of isopropyl alcohol and 405 parts of Tulane is charged to an appropriate sized autoclave. Platinum oxide catalyst (0.81 part) is added and the autoclave is evacuated and purged 35 with nitrogen four times to remove any residual air. Hydra-gun is fed to the autoclave at a pressure of 29-55 prig isle while the content is stirred and heated to 27-92 or a total of thirteen hours. Residual excess hydrogen is removed from the reaction mixture by evacuation and purging with nitrogen four time. 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.

An alkylated phenol it prepared by reacting phenol 10 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 neutral-iced and removed by filtration. Stripping of the product filtrate first to 230~/760 ion (vapor temperature), then to 15 205/50 ion (vapor temperature), provides purified alkylated phenol as a residue.
To a mixture of 265 parts of purified alkyd phenol, 176 parts blend mineral oil and 42 parts of pew trillium naphtha having a boiling point of approximately 20 20 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 30-45, stripped to 120~/20 ion vapor temperature) and filtered to provide an oil solution of the desired vitro phenol intermediate.

A mineral oil solution ~1900 parts of an alkyd-axed, nitrated phenol as described in Example 2 containing 43% mineral oil is heated under a nitrogen atmosphere to 145. Then 70 parts of hydrazine hydrate is slowly added to 30 the mixture over 5 hours while its temperature is held at about 145. The mixture is then heated to 160 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 140 for an additional hour. Filtration 35 at 130 provides an oil solution of the desired amino phenol product containing 0.5~ nitrogen.

~583S

_ _ _ To a mixture of 800 parts of polybutene-substi tuned phenol prepared essentially as described in Example 2 and 944 parts of delineate mineral oil at 59 is added 72 5 parts of concentrated nitric acid. The reaction is con-trolled so as to keep the reaction temperature between 59 and 68. The reaction mixture is stirred for two hours at 69-73 and then heated to 140 while nitrogen is slowly passed through it and water is removed by distillation.
10 ~ydrazine hydrate (90 parts) is then slowly added to the mixture at 130 to 137 over 3 hours. The mixture is stirred for 0.5 hour at this temperature and then heated to 160 while nitrogen is slowly passed through the mixture and provision is made for collecting the aqueous distillate.
15 The residue is an oil solution of the desired amino phenol product.

. . .
A mixture of 609 parts of polybutene-substituted phenol prepared essentially as described in Example 2 and 20 454 parts of mineral delineate oil is blended at 57. 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 and then heated to 142 for 1.7 hours while nitrogen is slowly passed through the mixture. The I mixture is held a 143-145 for 0.5 hour and then cooled to 114. During the reaction, 23 parts of distillate is collected. Filtration of the mixture at 113-126 provides an oil solution of the desired vitro intermediate having a nitrogen content of 0.64~.

_. .
To 320 parts of the oil solution of the polyp butene-substituted nitrated phenol described in Example 5 is added 12 parts of aqueous hydrazine t64% hydrazlne) over 6.25 hours at a temperature of aye. Filtration provides an 35 oil solution of the desired amino phenol product having a nitrogen content of 0.59%.

~æ~ss3~

To a mixture of 3000 parts of an alkylated phenol made essentially as described in example 2 having a polyp butane substation of about 70 carbon atoms and 3000 parts of glacial acetic acid at 51 is added 540 parts of con-cent rated nitric acid over three hours. During the add-lion, the mixture is held at 51-63. The mixture is stored at room temperature for 18 hours and when heated to 120 for 5 hours while nitrogen is slowly passed through the mixture 10 Provision is made for collecting the aqueous distillate.
The reaction it then stripped to 140~28 tot vapor temper azure) and the residue filtered at 120~ to provide the desired final product having a nitrogen content of 2.55%.
On this basis, it is calculated that the product contains an 15 average of two vitro groups per alkylated phenol.

To a mixture of 545 parts of the alkylated donator phenol described in Example 7 and 340 parts ox delineate mineral oil at 125 is added 100 parts of hydrazine hydrate.
20 This addition is carried out under a nitrogen atmosphere for a 2.5 hour period while the temperature is held a 122-125.
The reaction mixture is when reflexed at 123 for 2.5 hours and heated for an additional 2 hours to 155 while provision is made for collecting aqueous distillate. A slow stream of 25 nitrogen is passed through the reaction mixture at 150-155 or 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%.

Jo a mixture of 361 parts of tetrapropenyl-sub-stituted phenol and 271 parts of glacial acetic acid at 7-17 is added a mixture of 90 parts concentrated nitric acid ~70% HNO3) and 90 parts of glacial acetic acid. The add-lion is carried out over 1.5 hours while the reaction mix-35 lure is cooled externally to 7-17. The cooling bath is removed and the reaction stirred or 2 hours at room temper-. . .

~2~35 azure. Stripping to 134/ 35 ion vapor temperature) and filtration provides as a residue the desired nitrated intermediate having a nitrogen content of 4.65%.

To 303 parts of the nitrated intermediate desk cried in Example 9 at 125 under a nitrogen atmosphere is added 100 parts of hydrazine hydrate over a 2.4 hour period, The mixture is reflexed for 2.5 hours and then distilled to a vapor temperature of 155. A slow stream of nitrogen is 10 passed through the reaction mixture while it is kept at a temperature of 155 to 190. Filtration of the residue provides the desired amino phenol product which has a nitrogen content of 4.89%.

A mixture of 510 pyres (0.28 mole) of pulse-butane (My = 1845; My = 5325) and 59 parts (0.59 mole) of malefic android is heated to 110~. This mixture is heated to 190. in seven hours during which 43 part (0.6 mole) of gaseous chlorine it added beneath the surface. At 190-20 192. an additional 11 parts (OWE mole) of chlorine is added over 3.5 hours. The reaction mixture is stripped by heating at 190-193 with nitrogen blowing for 10 hours.
The residue is the desired polyisobutene-substituted sue-Seneca assaulting agent having a saponification equivalent 25 number of 87 as determined by ASTM procedure D-94.

A mixer of Lowe parts (0~495 mole of pulse-button (My = 2020; My = 6049) and 115 parts (1017 moles of malefic android is heated to 110. This mixture is heated 30 to 184 in 6 hours during which 85 parts ~1.2 moles) of gaseous chlorine is added beneath the surface. At 184-189 an additional 59 parts (0.83 mole) of chlorine is added over

4 hours. The reaction mixture it stripped by heating at 186-190 with nitrogen blowing for 26 hours. The residue 35 is the desired polyisobutene-substituted succinic assaulting agent having a saponficiation equivalent number of 87 as determined by ASSET procedure D-94.

~5~335 A mixture of 3251 parts of polyisobutene chloride, prepared by the addition of 251 parts of gaseous chlorine to 3000 pats of polyi~obutene (My = 1696; My = 6S94) at 80 in 4.66 hours, and 345 par s of malefic android is heated to 200 in 0.5 hour the reaction mixture it held at 200-224 for 6.33 hours, stripped at 210 under vacuum and filtered.
The filtrate is the desired polyisobutene-substituted succinic assaulting agent having a saponification equivalent 10 number of 94 as determined by ASSET procedure D-94.

A mixture is prepared by the addition of 10.2 parts (0.25 equivalent of a commercial mixture of ethylene polyamides having from about 3 to about 10 nitrogen atoms 15 per molecule Jo 113 parts of mineral oil and 161 parts (0.25 equivalent) of the substituted succinic assaulting agent prepared in Example 11 at 138. The reaction mixture is heated to 150 in 2 hours and stripped by blowing with nitrogen, the reaction mixture is filtered to yield the 20 filtrate a an oil solution of the desired product.

_ A mixture is prepared by the addition of 57 parts (1.38 equivalents) of a commercial mixture of ethylene polyp amine having from about 3 to 10 nitrogen atoms per molecule I to 1067 parts of mineral oil and 893 parts (1.38 equiva-lunate) of the substituted succinic assaulting agent prepared in Example 12 at 140 to 145. The reaction mixture is heated to 155 in 3 hours and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the rate as an oil solution of the desired product.
EXAMPLE it A mixture is prepared by the addition of 18.2 parts (0.433 equivalent) of a commercial mixture of ethylene polyamides having from about 3 to 10 nitrogen atoms per 35 molecule to 392 parts of mineral oil and 348 parts (0~52 equivalent) of the substituted succinic assaulting agent I
prepared in Example 12 at 140. The reaction mixture is heated Jo 150 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.

A mixture of 334 parts (0.52 equivalent) of the polyisobutene-substituted succinic assaulting agent prepared in Example 11, 548 part of mineral oil, 30 parts (0.88 equivalent) of pentaerythritol and 8.6 parts (0.0057 equiva~
10 lent) of Polyglycol 112 2 demulslfier from Dow Chemical Company is heated at 150 for 2.5 hours. The reaction mixture is heated to 210 in 5 hours and held at 210 for 3.2 hours. The reaction mixture is cooled Jo 190 and US
parts (0.2 equivalent) of a commercial mixture of ethylene 15 polyamides having an average of about 3 to about 10 nitrogen atoms per molecule is added The reaction mixture it stripped by heating at 205 with nitrogen blowing for 3 hours, then filtered to yield the filtrate as an oil soul-lion of the desired product.

.
A mixture of 3225 parts (5.0 equivalents) of the polyisobutene-substituted succinic assaulting agent prepared in Example 12, 289 parts (8.5 equivalents) of punter-throttle and 5204 parts of mineral oil is heated at 225-235 25 for So hours. The reaction mixture is filtered at 130 to yield an oil solution of the desired product EN _ LYE 19 A mixture of 631 parts of the oil solution of the product prepared in Example 18 and 50 part ox anthranilic 30 acid is heated at 195-212 for four hours. The reaction mixture is then filtered at 130 to yield an oil solution of the desired product.
Example` 20 .
A mixture is prepared by the addition of 14 parts 35 of aminopropyl diethanolamine to 867 parts of the oil soul-lion of the product prepared in Example 18 at 190 200. The ~2~3~i reaction mixture is held at 195 for 2.25 hours, then cooled to 120 and filtered. the filtrate is an oil solution of the desired product.

A mixture of 62 parts of boric acid and 2720 parts of top oil solution of the product prepared in Example 14 is heated at 150 under nitrogen for six hours. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired boron-containing product.

__ n oilily ester of boric acid is prepared by heating an equimolar mixture of oilily alcohol and boric acid in Tulane at the reflex temperature while water is removed azeotropicallyO The reaction mixture is then heated to 150 15 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 15~ for six hours and then filtered. The filtrate is an 20 oil solution of the desired boron-containing product.

Boron trifluoride (34 parts) is bubbled into 2190 parts of the oil solution of the product prepared in example 15 at 80 within a period of three hours. The resulting 25 mixture is blown with nitrogen at 70-80 D for two hours to yield the residue as an oil solution of the desired product.
EXl~PLE 24 A mixture of 3420 parts of the oil-containing solution of the product prepared in Example 16 and 53 parts 30 of acylonitrile is heated at reflex temperature from 1~5 to 145 for 1.25 hours, at 145 for three hours and then stripped at 125 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 I ii83~i the oil solution of the product prepared in Example 15 at 150. The ration mixture is held at 150 for one hour, then filtered to yield the flltxate as an oil solution of the desired product.

-A mixture of 3880 parts of the oil solution of the product of Example 14 and 120 parts of terephthalic acid is heated at 150-160 and filtered. The filtrate is an oil solution of the desired product.

A decal ester of phosphoric acid i prepared by adding one mole of phosphorus pentaoxide to three moles of decal alcohol at a temperature within the range of 3~ to 55 and then heating the mixture at 60-~3 until the react 15 lion is complete. The product is a mixture of the decylesters of phosphoric acid having a phosphorus content of 9.9% and an acid number of 250 ~phenolphthaleln indicator.
A mixture of 1750 parts of the oil solution of the product prepared in Example 14 and 112 parts of the above decal 20 ester is heated at 145-150 for one hour. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.
EXAMPLE
A mixture of 2920 parts of the oil solution of the 25 product prepared in Example 15 and 69 parts of Thor us heated to 80 and held at 80 for two hours. The reaction mixture is then heated at 150-155 for four hours, the last ox which the mixture is blown with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution 30 of the desired product.

A mixture of 1460 parts of the oil solution ox the product prepared in Example 15 and 81 parts of a 37% aqueous formaldehyde solution is heated at reflex for three hours.
35 The reaction mixture is stripped under vacuum at 150. The residue is an oil solution of the desired product.

~5~35 _ __ A mixture of 1160 parts of the oil solution of the product prepared in Employ 14 and 67 parts of sulfur moo-chloride is heated for one hour at 150 under nitrogen. The S mixture is filtered to yield an oil solution of the desired sulfur-containing product.

___ A mixture is prepared by the addition of 11~5 parts of foxmlc acid to 1000 parts of the oil solution of 10 the product prepared in Example 15 at 60. The reaction mixture is heated at 60-100 for two hours, g2-lOG~ for 1.75 hours and then filtered to yield an oil solution of the desired product.

.
A mixture is prepared by the addition of 58 parts of propylene oxide to 1170 parts ox the oil solution of the product prepared in Example 18 and 10 parts of pardon at 80-90. The reaction mixture is then heated at 100-120 for 2.5 hours and then stripped to 170 under vacuum. The 20 residue is an oil solution of the desired product.

-A mixture of 1170 parts of the oil solution of the product prepared in Example 18 and 36 parts of malefic ashy-drive is heated to 200 over a 1.5 hour period and main-25 twined 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 190~ 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 come bination of PA) and (B) or (C). Also, a combination of (A), (C) and at least one sulfurized olefinically unsaturated compound is a preferred embodiment of this invention. The 35 nitrogen containing organic compositions comprising a combination of (A), (B) and (C) is another preferred em-bodimen of this invention. An additional preferred em-bodiment of the present invention are the nitrogen-con-twining organic composition comprising a combination of (A), (B), (C) and at least one sulfurized olefinically unsaturated compound.
Accordingly, the above compositions may be come brined simultaneously or sequentially in any order.
The nitrogen-containing organic compositions are preferably prepared by combining the above-described come 10 potent compositions through the use of conventional blending techniques which include, for example, mixing the component compositions at a temperature sufficient to insure home-generous blending and/or the US of a solvent/diluent such as mineral oil, xylenel 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 composi~lons tub), I and the sulk foreside olefinically unsaturated compound to the aminoph~nol compounds PA) is about 0.1 to about 10.0 parts to one part amino phenol.
Toe examples in the following table illustrate the nitrogen-containing compositions of the present invention.
table En. Sulfurized**
Nooks. Rex. 14 En. 26 Sheller* I 5-18 ~-Olefin I 16~5 --- 70 10 3.5 ~I16.5 70 --- 10 3.5 commercially available chlorinated paraffin wax from Diamond Chemicals containing about 40~ by weight chlorine.
**Prepared by reacting 1 mole ox elemental sulfur with 1 mole 35 of Claus 18 ~-olefin at 170~C. 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 an~ioxidants, anticorrosives, deter gents, dispersants, fluidity modifiers and, in particular, impart one or more of the following properties to Libra-cants- anticorrosive, antiwar and friction reducing properties. These particular properties are unexpected and are especially effective in protecting silver, copper and lead parts in diesel engines. whey can be employed in a 10 variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereon. these lubricants include crankcase lubricating oils for spark-ignited and compression ignited internal combustion engines, including automobile and truck 15 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, transsexual lubricants, gear lubricants, metal-working lubricants, 20 hydraulic fluids and other lubricating oil and grease combo-sessions 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 pew US trillium oils and solvent-treated or acid-treated mineral lubricating oils of the paranoiac, naphthenic and mixed para~inic-n~phthenic types. Oils ox lubricating viscosity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include hydrocarbon oils and 30 halo-substituted hydrocarbon oils such as polymerized and interpolyrnerized olefins rug., polybutylenesl pulpier-pylons, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes~, polyp octanes), polyp doziness), etc. and mixtures thereof; alkylbenzenes ego., 35 dodecylbenzenes, tetradecylbenzenesO dinonylbenzenes, Dow-ethylhexyl)benzenes, etc.]; polyphenyls (e.g., biphenyls, ~5~33S

-so terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkaloid diphenyl sulfides and the derivatives, analogs and homology thereof and the like.
Alkaline oxide polymers and inter polymers and derivatives thereof where the terminal hydroxyl groups have bee modified by es~erification, etherification, etc. con-statute another class of known synthetic lubricating oils.
These are exemplified by the oils prepared through polyp merization of ethylene oxide or propylene oxide, the alkyd 10 and aureole ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, deathly ether of polypropylene glycol having a molecular weight of 1000-15 1500, etc.) or moo- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed Coca fatty acid esters, or the Of 3 Ox acid divester of tetraethylena glycol.
Another suitable class ox synthetic lubricating oils comprises the esters of dicarboxylic acids ego., 20 phthalic acid, succinic acid, alkyd succinic acids and alkenyl succinic acids, malefic acid, azelaic acid, sub Eric acid, sebacic acid, fumaric acid adipic acid, linoleic acid dimmer Masonic acid, alkyd Masonic acids, alkenyl Masonic acids, etc.) with a variety of alcohols ego, bottle Alcoa 25 hot, Huxley 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) subacute, di-n-hexyl umarate, ductile subacute, disquietly assault, deciduously 30 assault, ductile phthalate, didecyl phthalate, dieicosyl subacute, the ~-ethylhexyl divester of llnoleic acid diver, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two mole of 2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those made from Us to Of 2 monocarboxylic acids and polyols and I 33~

polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythrltol, tripentaPrythritol, etc.
Silicon-based oils such as the polyalkyl-, polyp aureole-, polyalkoxy-, or polyaryloxy~siloxane oils and sift-gate oils comprise another useful class of synthetic Libra-cants [ego, tetraethyl silicate, tetraisopropyl silicate, twitter (2-ethylhexyl) silicate, tetra-t4-methyl-2-ethylhexyl) silicate, tetra-(p~tert-bu~ylphenyl) silicate, hooks-methyl-~-pentoxy)-disiloxane, poly~methyl)-5iloxanes~ polyp 10 ~methylphenyl)siloxanes, etc.]. Other synthetic lubricating oils include liquid esters ox phosphorus-containing acids ego., tricresyl phosphate, trioctyl phosphate, deathly ester of decylphosphonic acid, etch polymeric tetrahydro-furriness and the like.
Unrefined, refined and redefined oils (and mix-lures of each with each other) of the type disclosed here-in above 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 20 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 25 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 extract ton, acid or base extraction, filtration, percolation, etc.
30 Redefined 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 redefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of 35 spent additives and oil breakdown products.

33~i Generally, the lubricants of the present invention contain an amount of the nitrogan-containing organic coy positrons of this invention sufficient to provide it with antioxidant, antiwar anticorrosive, detergent, dispersant, friction reducing or fluidity modifying properties. Norm-ally this amount will be about 0.05% to about 20~, pro-fireball about 0.1% to about 10% of the total weight of the lubricant. In lubricating oil operated under extremely adverse conditions, such as lubricating oils for marine 10 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 specie ligation and appended claims is intended to mean that when a composition contains a "minor amount" of a specific material 15 that amount is less than 50% by weight of the composition.
The term 'major amount" as used in the specific cation 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 ash-producing or cashless type, auxiliary corrosion- and oxidation-inhibiting agents, pyre point depressing agents, extreme pressure agents, copper deactivators, color stabilizers and anti foam 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 o'er organic phosphorus acids characterized by at least one direct coronet phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of Lowe) with a phosphorizing agent such as phosphorus trichloride, phosphorus Hyatt-35 sulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphor-thwack 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 educe 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 50C. 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 finlike substances such as phenol, naphthol, alkylphenol, tiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a finlike substance; alcohols such as methanol, 2-propanol, octal alcohol, cello solve, carbitol, ethylene glycol, stroll alcohol, and cyclohexyl alcohol and amine such as aniline, phenylenediamine, phenothiazine, phenol-~-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 60-200C. The basic alkali and/or alkaline earth metal carbonate sulfonate and/or fount useful in combination with the nitrogen-containing organic compositions ox this invention, are well known to those of ordinary skill in the art and are described in detail in US.
Patent 3,779~920, as well as processes for their preparation.
auxiliary cashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a non-volatile ....

Sue material such as boric oxide or phosphorus pent oxide;
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-10 containing compounds such as amine, organic hydroxy come pounds such as phenols and alcohols, and/or basic inorganic materials. Examples of these "carboxylic dispersants" are described in British Patent 1,306,5~9 and in many USE
patents including the following:
3,1~3,603 3,351,552 3,541,012 3,184,474 3,381,022 3,542,678 3,215,707 3,39~,141 3,542,~8~
3,219,~66 3,~15,750 3,567,637 3,271,310 3,433,744 3,574,101 3,272,746 3,44~,170 3,576,743 3,281,357 3,44~,048 3,630,904 3,306,90~ 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 3,4~7,668 3,725,441 3,341,542 3,501,405 Rye 26,433 3,346,~93 3,52~,179 2) Reaction products of relatively high mole-ular weight aliphatic or alicyclic halides with amine, 30 preferably polyalkylene polyamides. These may be kirk-terraced as "amine dispersants" and examples thereof are described for example in the following USE patents:
3,275,554 3,45~,555 3,438,757 3,565,804 (3) Reaction products of alkyd phenols in which the alkyd group contains at least about 30 carbon atoms with Swahili aldehydes (especially formaldehyde) and amine especially polyalkylene polyamides), which may be characterized as "Mannish dispersants". The materials described in the following US. patents are illustrative:
2,459,112 3,4~2,~08 3,591,598 2,962,442 3,~48,047 3,~00,372 2,984,550 3,454,497 3,634,515 3,036 t 003 3,459,661 3,64g,229 3,166,516 3,461,172 3,697,574 3,236,770 3,493,5~0 3,725~277 3~355,270 3,~39,633 3,725,~80 3,368,972 3,558,743 3,726,~82 3,413,347 3,586,629 3,980,569 (4) Products obtained by post-treating the car-15 boxlike, amine or Mannish dispersants with such reagents as urea, Thor, carbon disulfide, aldehydes, kittens, car-boxlike acids, hydrocarbon-subskituted succinic androids, nitrites, epoxies, boron compounds phosphorus compounds or the like. Exemplary materials of this kind are described in 20 the following US. patents:
3,036,003 3,282,955 3,493,520 3,639,~42 3,~87,936 3,312,619 3,502,677 3,649,2~9 3,~00,10~ 3,36~,569 3,513,093 3,649,659 3,216,93~ 3,367,9~3 3,533,945 3,658,836 25 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,~42,808 Sue 3,703,536 3,280,~34 3,455,~31 3,591,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522

(5) Inter polymers ox oil-solubilizing monomers such as decal methacrylate, vinyl decal 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 35 characterized as "polymeric dispersals and examples thereof are disclosed in the following US. patents:

Sue 3,32g,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 Extreme pressure agents and auxiliary corrosion- and oxidation-inhibiting agents are exemplified by sulfurized alkyd-phenol, phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl owlet;
phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphates such as dibutyl phosphate, doughtily phosphate, dicyclohexyl phosphate, pentylphenyl phosphate, dipentylphenyl phosphate, tridecyl phosphate, distearyl phosphate, dim ethyl naphthyl phosphate, oilily 4-pentylphenyl phosphate, polypropylene (molecular weight substituted phenol phosphate, diisobutyl-substituted phenol phosphate;
metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphoro dithioate, 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(octyl~
dithio)thiadiazole, which functions as antioxidant, sulfur deactivators and antiwar 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 I.

diluted with a substantially inert normally liquid organic delineate such as mineral oil, naphtha, Bunsen, Tulane or zillion, to form an additive concentrate. These concentrates usually contain about guy% by weight of the composition of 5 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 10 as motor gasoline as defined by ASTM Specification D-439-73 and diesel fuel or fuel oil as defined by ASTM Specification D-3960 Normally liquid fuel compositions comprising non-hydrocarbonaceous materials such a alcohols, ethers organo-nitro compounds and the like (e.g., methanol, ethanol, 15 deathly 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 20 more nonhydrocarbonaceous materials era 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 60C. at the 10% distillation punt to about 205C. 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, antiwar, anticorrosive, friction reducing, detergent or dispersant proprieties to the fuel; usually this amount is about 0.001 to about I (based on the weight of the final composition), preferably 0.001% to I
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 twitter-~Z~S~33~

alkyd lead compounds, lead scavengers such as haloalkanes (e.g., ethylene dichlorides and ethylene dibromide~, deposit preventers or modifiers such as triaryl phosphates, dyes, octane improvers, auxiliary antioxidant such as 2,6-ditertiary-butyl-4-methyl-phenol, rust inhibitors such as alkylating succinic acids andanhydrides, bacteriostatic agents, gum inhibitors, metal deactivators/ emulsifiers, 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 cashless dispersant in gasoline. such cashless dispersants are preferably esters of a moo- or polyol and a high molecular weight moo- or polycarboxylic acid assaulting agent containing at least 30 carbon atoms in the azalea moiety. Such esters and methods for their preparation 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 US. patents 3,255,10B; 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. Generally the weight ratio of the compositions of this invention to the aforesaid cashless dispersants is about 0.1 to about 10.0l preferably about 1 to about 10 parts of composition to 1 part cashless dispersant. In still another embodiment of this invention, the inventive I additives are combined with Mannish condensation products formed from substituted phenols, aldehydes, polyamides, and substituted prudence. Such condensation products are described in US.
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, I.

33~ii zillion, 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 con-ventional additives, particularly the afore-described cashless dispersants in the aforesaid proportions. The remainder of the concentrate is the solvent/dlluent.
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 15 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 20 in example IV.

A ~ol~ent-refined, neutral SUE 10 mineral oil containing 7% of the nitrogen-containing product described in Example II.
25 Example D
A soLvent-refined, SUE 40 mineral oil containing

6% of the nitrogen containing composition described in Example I.
Example E
A synthetic lubricant comprised predominantly of C5-Cg normal alcohol esters of a 50/50 molar mixture of adipic and glutaric acids containing I 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.

~2~5~335 --10~--The lubricant and fuel compositions of this invent lion and the nitrogen containing organic compositions of this invention and the processes for preparing these pro-ducts 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 10 as being within the scope of the present invention unless clearly excluded by the appended claims

Claims (106)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

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 alkoxyl, nitro, halo or combinations of two ox more of said substituents; and (B) one or more carboxylic derivative compo-sitions 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 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 charac-terized 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 0 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, -Cl, -O-lower alkyl and, when taken together, R1 and R2 are -O-, 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 homopoly-mers and interpolymers of terminal olefins of two to about sixteen carbon atoms, with the proviso that said inter-polymers 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.

15. 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 homopoly-mers 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 1500 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 substitutent 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 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 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 24 wherein a, b and c are each 1, there are zero optional substitutents 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 inter-polymer 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 0 or 1.

32. A composition according to claim 1 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.

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 thiophos-phites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulfides, formal-dehyde 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 post-treating reagents selected from the group con-sisting 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, hy-drocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydro-carbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-producing com-pounds 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 acyl-ating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phos-phites, hydrocarbyl thiophosphates, hydrocarbyl thiophos-phites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulfides, form-aldehyde or formaldehyde-producing 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 post-treating reagents selected from the group con-sisting 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, hydrcarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols and sulfur plus phenols.

40. A composition according to claim 1 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 compound 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-l0 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 0 or 1.

50. A composition according to claim 42 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 claim 42 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, R8, 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 .alpha.-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=CR9R10, 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 .alpha.-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 compositoin 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 .alpha.-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, 22 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 substnatially 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 claim 1.

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, 22 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 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 opertion 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.