WO1989009812A1

WO1989009812A1 - Lubricating oil additives

Info

Publication number: WO1989009812A1
Application number: PCT/US1989/001359
Authority: WO
Inventors: Alan C. Clark
Original assignee: The Lubrizol Corporation
Priority date: 1988-04-11
Filing date: 1989-03-31
Publication date: 1989-10-19
Also published as: AU3530189A

Abstract

A lubricating oil additive for lubricating compositions is disclosed. The composition is essentially comprised of a lubricating base oil having dissolved therein a combination of: (A) a metal salt of a dihydrocarbylphosphorodithioic acid of formula (I), wherein at least one of the hydrocarbyl groups R is a neohydrocarbyl group of formula (II), wherein R1, R2 and R3 are hydrocarbyl groups selected from the groups consisting of aliphatic or aromatic groups; (B) a metal overbased composition; and (C) a reaction product of a composition prepared by reacting (i) a hydrocarbon substituted succinic acid producing compound with at least about one-half equivalent, per equivalent of acid producing compound with (ii) one or more amines, one or more alcohols, or a mixture of one or more amines and/or one or more alcohols.

Description

LUBRICATING OIL ADDITIVES

FIELD OF THE INVENTION

This invention relates to lubricating oil additives and lubricating compositions containing them. More particularly, this invention relates to a formulation having utility as an additive in hydraulic fluids, tractor transmission fluids, diesel engine oils and crankcase oils for passenger cars.

BACKGROUND OF THE INVENTION

It is well known that the metal salts of the diesters of phosphorothiolthionic acids, generally known as dithiophosphoric acids, are useful as additives for lubricants. The diesters may be prepared by the reaction of alcohols or phenols with phosphorus pentasulfide and then converted into metal salts by direct reaction with a metal oxide or hydroxide.

Though salts of a wide variety of metals have been suggested as additives for lubricants and are effective to a greater or lesser degree, the zinc salts are almost universally preferred on account of their greater oil-solubility and ease of preparation.

It has been well known for some time that organic zinc dithiophosphates when used as additives for lubri- cants, are effective inhibitors of oxidation and corrosion of composite metal, e.g, copper-lead, bearings and enhance the load-carrying capacity of the oil. These compounds — —

have the valuable property of reducing wear of valve tappets which sometimes takes place under heavy load.

DESCRIPTION OF RELATED ART U.S. Patent 3,595,792 (Elliott et al, July 27, 1971) provides a lubricating oil additive consisting essentially of a mixture of at least one bismuth dihydrocarbyl dithiophosphate and at least one salt of a dihydrocarbyl dithiophosphoric acid and a metal of Group lib of the Periodic Table selected from the group consisting of zinc dihydrocarbyl dithiophosphates and cadmium dihydrocarbyl dithiophosphates, which additive may be admixed with an oil of lubricating viscosity, for example, in an amount of from 0,01% to 10% by weight based on the total weight of the oil and additive. U.S. Patent 4,094,800 ( arne, June 13, 1978) disclos¬ es lubricating oil compositions having improved anti-wear properties, comprising a major portion of a lubricating oil and an effective amount of an oil soluble additive combination comprising a basic zinc alkyl dithiophosphate having alkyl groups made from primary alcohols containing from about 6 to about 20 carbon atoms and a non-acidic lubricating oil anti-rust compound comprising a succinic anhydride substituted with an alkenyl group which has about 8 to about 50 carbon atoms reacted with an alcohol, an amine, or mixtures thereof.

The zinc dithiophosphate is generally made from primary alcohol containing about 7 to about 12 carbon atoms and generally has a zinc to phosphorus ratio of about 1.15-1.5:1.

SUMMARY OF THE INVENTION

The present invention is a composition comprising: (A) a metal salt of a dihydrocarbylphosphoro dithioic acid of the formula

H

wherein each R is independently a hydrocarbyl group containing from 1 to about 50 carbon atoms and wherein at least one of the hydrocarbyl groups R is a neo hydrocarbyl group of the formula

wherein R, , R₂ and R₃ are independently aliphatic or aromatic groups;

(B) a metal overbased organic acid composition; and

(C) a reaction product of a composition prepared by reacting

(i) a hydrocarbon substituted succinic acid producing compound with at least about one-half equiva¬ lent, per equivalent of acid producing compound with

(ii) one or more amines, one or more alcohols, or a mixture of one or more amines and/or one or more alcohols.

• A primary objective of this invention is to provide lubricating oil compositions which meet or exceed engine qualification standards of dispersancy for both gasoline and diesel or compression ignition engines.

A feature of this invention is that the lubricating oil compositions can be easily and economically manufactured.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

Before the present compositions and processes for making such are described, it is to be understood that this invention is not limited to the particular compositions, materials or processes described as such, compositions and processes may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular preferred embodi¬ ments only, it is not intended to be limiting since the scope of the present invention will be limited only by the appended claims.

In order to clarify the following description of the lubricant compositions of the invention, individual components of the composition will be described followed by specific examples of the compositions including the individual components.

It must be noted that as used in this specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context.clearly dictates otherwise. Thus, for example, a reference to "a composition" includes mixtures of such compositions, reference to "a salt" includes reference to mixtures of such salts, and reference to "an overbased material" includes mixtures of overbased materials and so forth. (A) The Metal Salt

The metal salts which are included in the compositions of the present invention are metal salts of a dihydrocarbylphosphorodithioic acid of the formula

RO ^SH

wherein R, , R₂ and R₃ are hydrocarbyl groups selected from the groups consisting of aliphatic or aromatic groups; and the other hydrocarbyl group R, if not a neohydrocarbyl group, is selected from the group consisting of aliphatic or aromatic groups.

As used in this specification and appended claims, the terms "hydrocarbyl" or "hydrocarbon-based" denote a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydro¬ carbon character within the context of this invention. Such groups include the following: (1) Hydrocarbon groups; that is, aliphatic (e.g., alkyl or alkenyl) , alicyclic (e.g., cycloalkyl or cycloalkenyl) , aromatic, aliphatic- and alicyclic- substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like, as well as cyclic groups wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form an alicyclic group) . Such groups are known to those skilled in the art. Examples include methyl, ethyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, etc. (2) Substituted hydrocarbon groups, that is groups containing non-hydrocarbon substituents which, in the context of this invention, do not alter^' the predominantly hydrocarbon character of the group. Those skilled in the art will be aware of suitable substituents. Examples include halo, hydroxy, nitro, cyano, alkoxy, acyl, etc.

(3) Hetero groups; that is, groups which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suit- able hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.

In general, no more than about three substituents or hetero atoms, and preferably no more than one, will be present for each 10 carbon atoms in the hydrocarbyl group.

Terms such as "alk l-based group", "aryl-based group" and the like have meaning analogous to the above with respect to alkyl and aryl groups and the like.

The non-neo hydrocarbyl group R may be an aliphatic or aromatic group selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl and mixtures thereof. The hydrocarbyl groups are alkyl or alkenyl groups containing from 1 to about 50 carbon atoms, prefer¬ ably from 3 to about 22 carbon atoms, and most preferably from 3 to about 12 carbon atoms. Preferably the non-neo hydrocarbyl group R is an alkyl group containing from 3 to 12 carbon atoms. Specific examples of alkyl groups containing from 3 to about 12 carbon atoms are n-propyl, isopropyl, n-butyl, 2-butyl, 2-methyl-l-propyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-l-butyl, 3-methyl-1-butyl, 4-me hyl-2-pentyl, 2-ethyl-l-hexyl, decyl and dodecyl. When one R is an aryl group, the preferred hydrocarbyl groups are phenyl, alpha-naphthyl and beta-naphthyl. When one R is an alkaryl group, the preferred hydrocarbyl groups are mono, di or tri alkyl-substituted phenyl, alkyl-substituted alpha-naphthyl and alkyl- substituted beta-naphthyl wherein each alkyl group is from 1 to about 22 carbon atoms, and most preferably from 2 to about 12 carbon atoms.

The hydrocarbyl groups R., R_ and R₃ may be alkyl groups containing from 1 to about 16 carbon atoms, prefer¬ ably 1 to about 10 carbon atoms, and most preferably 1 to about 6 carbon atoms. Specific examples of alkyl groups of R, , R_ and R^ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and t-butyl. Non-limiting examples of neoalcohols that may be employed in the practice of this invention are: 2,2-dimethyl-l- propanol, 2,2-dimethyl-l-butanol, 2,2-dimethyl-l-pentanol, 2,2-dimethyl-l-hexanol, 2,2-dimethyl-l-heptanol, 2,2-di- methyl-1-octanol, 2-methyl-2-ethyl-l-butanol, 2-methyl-2- ethyl-1-pentanol, 2-methyl-2-ethyl-l-hexanol, 2-methyl-2- ethyl-1-heptanol, 2-methyl-2-ethyl-l-octanol, 2,2-diethyl- 1-butanol, 2,2-diethyl-l-pentanol, 2,2-diethyl-l- hexanol,2,2-diethyl-l-heptanol, 2,2-diethyl-1-octanol, 2,2,3-trimethyl-l-butanol, 2,2,3,-trimethyl-1-pentanol, 2,2,3-trimethyl-l-hexanol, 2,2,3-trimethyl-l-heptanol,

2,2,3-trimethyl-l-octanol, 2,3-dimethyl-2-ethyl-l-butanol,

2,2,4-trimethyl-l-pentanol, 2,2,4-trimethyl-l-hexanol,

2,2,4-trimethyl-l-heptanol and 2,2,4-trimethyl-l-octanol.

The hydrocarbyl groups R, , R- and , may be alkenyl groups containing from 2 to about 16 carbon atoms, prefer¬ ably 2 to about 10 carbon atoms, and most preferably 2 to about 6 carbon atoms. Specific examples of alkenyl groups of R,, R- and R, include ethenyl, the various propenyls, the various butenyls and the various pentenyls. Non-limiting examples of such neoalcohols that may be employed in the practice of this invention are: 2,2-dimethyl-3-butene-l-ol, 2,2,3-trimethyl-4-pentene- l-ol, 2,2,3-trimethyl-3-pentene-l-ol, 2,2,4-trimethyl-4- pentene-1-ol, 2,2,4-trimethyl-3-pentene-l-ol, 2,2- dimethyl-5-hexene-l-ol, 2,2-dimethyl-4-hexene-l-ol and 2 ,2-dimethyl-3-hexene-l-ol.

Preferred acids of the formula

S (I)

R °*-*-_^ .P SH

R ^

are readily obtainable by the reaction of phosphorus pentasulfide (P₂S₅) and an alcohol or an alcohol and a phenol. The reaction involves mixing at a temperature of about 20 to about 200°C, four moles of alcohol or a phenol with one mole of phosphorus pentasulfide. Hydrogen sulfide is liberated in this reaction. Component (A) is a metal salt of a dihydrocarbylphosphorodithioic acid. The metals for component (A) are the alkali metals, the alkaline earth metals, antimony, tin, zinc and transition metals as well as mixtures of two or more of these metals. The preferred salts are those of zinc. The metal salt can be prepared by reacting the dihydrocarbylphosphorodithioic acid with a suitable metal base.

The following examples illustrate the preparation of the metal salt of the dihydrocarbylphosphorodithioic acid represented by formula (I) . Unless otherwise indicated in the examples and elsewhere in this specification and claims, all parts and percentages are by weight, and all temperatures are in degrees Centigrade.

Example A-l To a 5-liter, 4-necked flask fitted with a stirrer, thermowell, powder addition funnel with nitrogen inlet and water-cooled condenser vented and aspirated to caustic traps are added 1716 parts (13.2 moles) 2,2,4-trimethyl-l-pentanol and 1188 parts (19.8 moles) isopropyl alcohol. The contents are heated to 61°C and 1665 parts (7.5 moles) P..S.. are incrementally added over 4.5 hours while sweeping with nitrogen. The contents are filtered to give a dithiophosphoric acid with the follow¬ ing analyses: acid neutralization number to phenolphthalein 186; acid neutralization number to bromophenol blue 167. In preparing a metal salt of this acid, 618 parts (15.2 equivalents) zinc oxide and 516 parts diluent oil are added to a flask. While stirring at room temperature, 4156 parts (13.8 equivalents) of the above generated acid is added over 2.5 hours. The addi¬ tion is exothermic to 54°C. The contents are stirred and heated to 80°C and 20 millimeters mercury. The residue is filtered to give a product having the following analyses: % zinc 9.73; % sulfur 18.4; % phosphorus 9.02.

Example A-2 Charged to a reaction flask as described in Example A-l are 3250 parts (25 moles) 2,2,4-trimethyl-l-pentanol. At 75°C, 1261 parts (5.68 moles) ^S5 ^re slowly added with nitrogen sweeping at 1 cubic foot per hour. After the P-_jS_c addition is complete, the temperature is maintained at 80°C for 2 hours. The contents are filtered to give a dithiophosphoric acid having the following analyses: acidic neutralization number to phenolphthalein 140; acidic neutralization number to bromophenol blue 140. In preparing a metal salt of this acid, 448 parts (11 equivalents) zinc oxide and 459 parts mineral oil are added to a flask. At 50°C, 4010 parts (10 equivalents) of the above prepared acid is added over a three-hour period. After the addition is completed the temperature is increased to 77°C and held for three hours. Volatiles are removed at 110°C and 15 millimeters mercury. The residue is filtered to give a product having the following analyses: % sulfur 14.4; % phosphorus 7.04; % zinc 7.28.

Example A-3

^■ Following essentially the same procedure as Example A-l, 193.6 parts (2.2 moles) 2,2-dimethyl-l-propanol, 286 parts (2.2. moles) isooctyl alcohol and 222 parts (1 mole)

P_S_r are reacted. The dithiophosphoric acid obtained has 0 an acid neutralization number to phenolphthalein of 172 and an acid neutralization number to bromophenol blue of 160. The zinc salt is prepared utilizing 490 parts (1.5 equivalents) of the above prepared acid, 67.2 parts (165 equivalents) zinc oxide and 60 parts mineral oil. The metal salt obtained has the following analyses: % sulfur 16.9, % phosphorus 8.23 and % zinc 8.90. Example A-4

Following essentially the same procedure of Example

A-l, 972 parts (7.48 moles) 2,2,4-trimethyl-l-pentanol,

920 parts (7.48 moles) Cresylic acid 33 (a low hydrocarbyl-substituted phenol from Merichem Company of

Houston, Texas, having an average number of carbon atoms in the hydrocarbyl substituents of 2.07), and 755 parts

(3.40 moles) P^S-. are reacted. The dithiophosphoric acid obtained has an acid neutralization number to phenolphthalein of 151 and an acid neutralization number to bromophenol blue of 138. The zinc salt is prepared utilizing 372 parts (1 equivalent) of the above prepared acid, 45 parts (1.1 equivalents) zinc oxide and 104 parts diluent oil. The metal salt obtained has the following analyses: % zinc 6.57, % sulfur 11.8 and % phosphorus 5.93.

Example A-5 Charged to a flask are 455 parts (3.5 moles) 2-ethylhexanol and 455 parts (3.5 oles) 2,2,4-trimethyl-l-pentanol. At 55°C, 353 parts (1.59 moles) ^P ₂ ^S ₅ ^are added over a two-hour period. The contents are heated to 65°C and held for two hours. Upon filtration a dithiophosphoric acid is obtained with the following analyses: acid neutralization number to phenolphthalein 156, acid neutralization number to bromophenol blue 161. A copper salt is prepared utilizing 359 parts (1 equivalent) of the above prepared acid, 45 parts mineral oil and 78.7 parts (1.1 equivalents) of cuprous oxide.

Example A-6

Charged to a flask are 18.7 parts (0.99 moles) 2,2,4-trimethyl-l-pentanol and 113.9 (1.2 moles) phenol. At 90°C, 111 parts (0.5 moles) P₂S are added incrementally while maintaining the temperature at 90°C and blowing with nitrogen at 1 centigrade per hour. After - li ¬

the addition is complete, the contents are held at 90°C for two hours. Upon filtration a dithiophosphoric acid is obtained with the following analyses: acid neutralization number to phenolphthalein 164; acid neutralization number to bromophenol blue 150. A cobalt salt is prepared utilizing 343 parts (1 equivalent) of the above prepared acid, 75 parts oil and 65.5 parts (1.1 equivalents) of cobaltous carbonate.

(B) The Metal Overbased Composition Overbased salts of organic acids are widely known to those of skill in the art and include metal salts wherein the amount of metal present in them exceeds the stoichiometric amount. Such salts are said to have conversion levels in excess of 100% (i.e., they comprise more than 100% of the theoretical amount of metal needed to convert the acid to its "normal" "neutral" salt) . Such salts are often said to have metal ratios in excess of one

(i.e., the ratio of equivalents of metal to equivalents of organic acid present in the salt is greater than that required to provide the normal or neutral salt which required only a stoichiometric ratio of 1:1) . They are commonly referred to as overbased, hyperbased or superbased salts and are usually salts of organic sulfur acids, organic phosphorus acids, carboxylic acids, phenols or mixtures of two or more of any of these. As a skilled worker would realize, mixtures of such overbased salts can also be used.

The terminology "metal ratio" is used in the prior art and herein to designate the ratio of the total chemi- cal equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the salt which would be expected to result in the reaction between the organic acid to be overbased and the basic reacting metal compound according to the known chemical reactivity and stoichiometry of the two reactants. Thus, in a normal or neutral salt the metal ratio is one and in an overbased salt the metal ratio is greater than one.

The overbased salts (B) in this invention usually have metal ratios of at least about 1.5:1. Typically, they have ratios of at least about 12:1. Usually they have metal ratios not exceeding about 40:1. Typically, salts having ratios of about 12:1 to about 20:1 are used. The basic reacting metal compounds used to make these overbased salts are selected from the metals of Groups IIA, I IA and IVB. Compounds of calcium, barium, magnesium, aluminum, titanium and zirconium, such as their hydroxides and alkoxides of lower alkanols, are usually used as basic metal compounds in preparing these overbased salts but others can be used as shown by the prior art incorporated by reference herein. Overbased salts containing a mixture of ions of two or more of these metals can also be used in the present invention.

These overbased salts can be of oil-soluble organic sulfur acids such as sulfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosulfuric acid. Generally they are salts of aliphatic substituted aromatic sulfonic acids.

The alkyl substituted aromatic or aliphatic sulfonates include the mono- or poly-nuclear aromatic or cycloaliphatic compounds. The oil-soluble sulfonates can be represented for the most part by the following formulae:

[(R₄) — -(S0₃)_γ]₂M_b (II)

[R₅—(S0₃)_a]_dM_b (III)

In the above formulae, M is either a metal cation "as described hereinabove or hydrogen; T is a cyclic nucleus such as, for example, benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, petroleum naphthenes, decahydro-naphthalene, cyclopentane, etc.: R. in Formula II is an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc; x is at least 1, and (R.) + T contains a total of at least about 15 carbon atoms, R₅ in Formula III is an aliphatic group containing at least about 15 carbon atoms and M is either a metal cation or hydrogen. Examples of type of the R_g group are alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R₅ are groups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including polymerized C₂, C_ , C. , C_g, C, , etc., olefins containing from about 15 to 7000 or more carbon atoms. The groups T, R. , and R_ in the above formulae can also contain other inorganic or organic substituents in addi¬ tion to those enumerated above such as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide, etc. In Formula II, x, y, z and b are at least 1, and likewise in Formula III, a, b and d are at least 1.

Specific examples of sulfonic acids useful in this invention are mahogany sulfonic acids; bright stock sulfonic acids; sulfonic acids derived from lubricating oil fractions having a Saybolt viscosity from about 100 seconds at 100°F to about 200 seconds at 210°F; petrolatum sulfonic acids; mono- and poly-wax substituted sulfonic and polysulfonic acids of, e.g., benzene, naphthalene, phenol, diphenyl ether, naphthalene disulfide, diphenylamine, thiophene, alpha-chloronaphthalene, etc.; other substituted sulfonic acids such as alkyl benzene sulfonic acids (where the alkyl group has at least 8 carbons), cetylphenol mono-sulfide sulfonic acids, dicetyl thianthrene disulfonic acids, dilauryl beta naphthyl sulfonic acid, dicapryl nitronaphthalene sulfonic acids, and alkaryl sulfonic acids such as dodecyl benzene "bot¬ toms" sulfonic acids. The latter acids derived from benzene which has been alkylated with propylene tetramers or isobutene trimers to introduce 1,2,3, or more branched-chain C-₂ substituents on the benzene ring. Dodecyl benzene bottoms, principally mixtures of mono- and di-dodecyl benzenes, are available as by-products from the manufacture of household deter¬ gents. Similar products obtained from alkylation bottoms formed during manufacture of linear alkyl sulfonates (LAS) are also useful in making the sulfonates used in this invention.

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

Other descriptions of overbased sulfonate salts and techniques for making them can be found in the following U.S. Pat. Nos. 2,174,110; 2,174,506; 2,174,508; 2,193,824

2,197,800 2,202,781 2,212,786 2,213,360 2,228,598 2,223,676 2,239,974 2,263,312 2,276,090 2,276,297 2,315,514 2,319,121 2,321,022 2,333,568 2,333,788 2,335,259 2,337,552 2,346,568 2,366,027 2,374,193 2,383,319 3,312,618; 3,471,403; 3,488,284; 3,595,790; and 3,798,012. These are hereby incorporated by reference for their disclosures in this regard.

Also included are aliphatic sulfonic acids such as paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, hexapropylene sulfonic acids, tetra-amylene sulfonic acids, polyisobutene sulfonic acids wherein the polyisobutene contains from 20 to 7000 or more carbon atoms, chloro-substituted paraffin wax sulfonic acids, nitroparaffin wax sulfonic acids, etc.; cycloaliphatic sulfonic acids such as petroleum naphthene sulfonic acids, cetyl cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, bis-(di-isobutyl) cyclohexyl sulfonic acids, etc.

With respect to the sulfonic acids or salts thereof described herein and in the appended claims, it is intend- ed that the term "petroleum sulfonic acids" or "petroleum sulfonates" includes all sulfonic acids or the salts thereof derived from petroleum products. A particularly valuable group of petroleum sulfonic acids are the mahoga¬ ny sulfonic acids (so called because of their reddish-brown color) obtained as a by-product from the manufacture of petroleum white oils by a sulfuric acid process.

Generally Group IIA metal overbased salts of the above-described synthetic and petroleum sulfonic acids are typically useful in this invention.

The carboxylic acids from which suitable overbased salts for use in this invention can be made include aliphatic, cycloaliphatic, and aromatic mono- and polybasic carboxylic acids such as the napthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, alkyl- or alkenyl-substituted aromatic carboxylic acids. The aliphatic acids generally contain at least 12 carbon atoms. Usually they have no more than about 30 carbon atoms. Generally, if the aliphatic carbon chain is branched, the acids are more oil-soluble for any given carbon atoms content. The cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, a-linolenic acid, propylene-tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclopentane carboxylic acid, myristic acid, dilauryldecahydronaphthalene carboxylic acid, stearyl-octahydroindene carboxylic acid, palmitic acid, commercially available mixtures of two or more carboxylic acids such as tall oil acids, rosin acids, and the like. A typical group of oil-soluble carboxylic acids useful in preparing the salts used in the present inven- tion are the oil-soluble aromatic carboxylic acids. These acids are represented by the general formula:

wherein R* is an aliphatic hydrocarbon-based group of at least 4 carbon atoms, and no more than about 100 aliphatic carbon atoms, a is an integer from one to four, Ar* is a polyvalent aromatic hydrocarbon nucleus of up to about 14 carbon atoms, each X is independently a sulfur or oxygen atom, and m is an integer of from one to four with the proviso that R* and a are such that there is an average of at least 8 aliphatic carbon atoms provided by the R* groups for each acid molecule represented by Formula IV. Examples of aromatic nuclei represented by the variable Ar* are the polyvalent aromatic radicals derived from benzene, napthalene anthracene, phenanthrene, indene, fluorene, biphenyl, and the like. Generally, the group represented by Ar* will be a polyvalent nucleus derived from benzene or naphthalene such as phenylenes and naphthylenes, e.g., methylphenylenes, ethoxyphenylenes, nitrophenylenes, isopropylenes, hydroxyphenylenes, mercaptophenylenes , N,N-diethylaminophenylenes, chloro- phenylenes, N,N-diethylaminophenylenes, chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes, and similar tri-, tetra-, pentavalent nuclei thereof, etc. The R* groups are usually hydrocarbyl groups, prefer¬ ably groups such as alkyl or alkenyl radicals. However, the R* groups can contain a small number of substituents such as phenyl, cycloalkyl (e.g., cyclohexyl, cyclopentyl, etc. ) and nonhydrocarbon groups such as nitro, amino, halo (e.g., chloro, bromo, etc.), lower alkoxy, lower alkyl mercapto, oxo substituents (i.e., =0), thio groups (i.e., =S) , interrupting groups such as —NH—, —o— , —S—, and the like provided the essentially hydrocarbon character of the R* group is retained. The hydrocarbon character is retained for purposes of this invention so long as any non-carbon atoms present in the R* groups do not account for more than about 10% of the total weight of the R* groups.

Examples of R* groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyl- octyl, 4-(p-chlorophenyl)-octyl, 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl, and substituents derived from polymerized olefins such as polychloroprenes, polyethyl- enes, polypropylenes, polyisobutylenes, ethylene-propylene copolymers, chlorinated olefin polymers, oxidized ethyl¬ ene-propylene copolymers, and the like. Likewise, the group Ar* may contain non-hydrocarbon substituents, for example, such diverse substituents as lower alkoxy, lower alkyl mercapto, nitro, halo, alkyl or alkenyl groups of less than 4 carbon atoms, hydroxy, mercapto, and the like.

Another group of useful carboxylic acids are those of the formula:

wherein R*, X, Ar*, m and a are as defined in Formula IV and p is an integer of 1 to 4, usually 1 or 2. Within this group, an especially preferred class of oil-soluble carboxylic acids are those of the formula:

(OH)

wherein R** in Formula VI is an aliphatic hydrocarbon group containing at least 4 to about 400 carbon atoms, a is an integer of from 1 to 3, b is 1 or 2, c is zero, 1, or 2 and preferably 1 with the proviso that R** and a are such that the acid molecules contain at least an average of about 12 aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule. And within this latter group of oil-soluble carboxylic acids, the aliphatic-hydrocarbon substituted salicylic acids wherein each aliphatic hydrocarbon substituent contains an average of at least about 16 carbon atoms per substituent and 1 to 3 substituents per molecule are particularly useful. Salts prepared from such salicylic acids wherein the aliphatic hydrocarbon substituents are derived from polymerized olefins, particularly polymerized lower 1-πtono-olefins such as polyethylene, polypropylene, polyisobutylene, ethylene/-propylene copolymers and the like and having average carbon contents of about 30 to about 400 carbon atoms. The carboxylic acids corresponding to Formulae IV-VI above are well known or can be prepared according to procedures known in the art. Carboxylic acids of the type illustrated by the above formulae and processes for preparing their overbased metal salts are well known and disclosed, for example, in such U.S. Pat. Nos. as 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092; 3,410,798 and 3,595,791 which are incorporated by refer¬ ence herein for their disclosures of acids and methods of preparing overbased salts. Component (B) may also be a borated complex of either an alkali metal overbased sulfonic acid or an alkaline earth metal overbased carboxylic acid such as described hereinabove. borated complexes of this type may be prepared by heating the overbased sulfonic acid or overbased carboxylic acid with boric acid at about 50°-100°C, the number of equivalents of boric acid being roughly equal to the number of equivalents of alkali metal in the salt. U.S. Patent No. 3,929,650 is incorporated by reference herein for its disclosure of borated complexes.

Another type of overbased carboxylate salt used as component (B) in this invention are those derived from alkenyl succinic acids of the general formula:

(VII)

R*—CHC00H I CH₂COOH

wherein R* is as defined above in Formula IV. Such salts and means for making them are set forth in U.S. Pat. Nos. 3,271,130, 3,567,637 and 3,632,510, which are hereby incorporated by reference in this regard.

Other patents specifically describing techniques for making overbased salts of the hereinabove-αescribed sulfonic acids, carboxylic acids, and mixtures of any two or more of these include U.S. Pat. Nos. 2,501,731

2,616,904; 2,616,905; 2,616,906 2,616,911; 2,616,924 2,616,925; 2,617,049; 2,777,874 3,027,325; 3,256,186 3,282,835; 3,384,585; 3,373,108 3,365,296; 3,342,733 3,320,162; 3,312,618; 3,318,809 3,471,403; 3,488,284 3,595,790; and 3,629,109. The disclosures of these patents are hereby incorporated in this present specifi¬ cation for their disclosures in this regard as well as for their disclosure of specific suitable basic metal salts. In the context of this invention, phenols are consid¬ ered organic acids. Thus, overbased salts of phenols (generally known as phenates) are also useful as component (B) of this invention and are well known to those skilled in the art. The phenols from which these phenates are formed are of the general formula:

(VIII)

wherein R*, a, Ar*, X and m have the same -meaning and preferences are described hereinabove with reference to Formula IV. The same examples of these groups described with respect to Formula IV also apply.

A commonly available class of phenates are those made from phenols of the general formula:

(IX)

wherein a is an integer of 1-3, b is of 1 or 2 , z is 0 or 1, R is a hydrocarbyl-based substituent having an average of from 4 to about 400 aliphatic carbon atoms and R_ is selected from the group consisting of lower hydrocarbyl, lower alkoxyl, nitro, amino, cyano and halo groups.

One particular class of phenates for use in this invention are the overbased, Group IIA metal sulfurized phenates made by sulfurizing a phenol as described herein¬ above with a sulfurizing agent such as sulfur, a sulfur halide, or sulfide or hydrosulfide salt. Techniques for making these sulfurized phenates are described in U.S. Pat. Nos. 2,680,096; 3,036,971; and 3,775,321 which are hereby incorporated by reference for their disclosures in this regard.

Other phenates that are useful are those that are made from phenols that have been linked through alkylene (e.g., methylene) bridges. These are made by reacting single or multi-ring phenols with aldehydes or ketones, typically, in the presence of an acid or basic catalyst. Such linked phenates as well as sulfurized phenates are described in detail in U.S. Pat. No. 3,350,038; particu¬ larly columns 6-8 thereof, which is hereby incorporated by reference for its disclosures in this regard.

Generally Group IIA metal overbased salts of the above-described carboxylic acids are typically useful as component (B) of this invention.

The method of preparing metal overbased compositions is illustrated by the following examples.

Example B-l A mixture consisting essentially of 480 parts of a sodium petrosulfonate (average molecular weight of about 480) , 84 parts of water, and 520 parts of mineral oil is heated at 100°C. The mixture is then heated with 86 parts of a 76% aqueous solution of calcium chloride and 72 parts of lime (90% purity) at 100°C for two hours, dehydrated by heating to a water content of less than about 0.5%, cooled to 50°C, mixed with 130 parts of methyl alcohol, and then blown with carbon dioxide at 50°C until substantially neutral. The mixture is then heated to 150°C to distill off methyl alcohol and water and the resulting oil solu¬ tion of the basic calcium sulfonate filtered. The fil¬ trate is found to have a calcium sulfate ash content of 16% and a metal ratio of 2.5.

Example B-2 A mixture of 1305 parts of the above carbonated calcium petrosulfonate of Example B-l, 930 parts of mineral oil, 220 parts of methyl alcohol, 72 parts of isobutyl alcohol, and 38 parts of amyl alcohol is pre¬ pared, heated to 35°C, and subjected to the following operating cycle four times: mixing with 143 parts of 90% commercial calcium hydroxide (90% calcium hydroxide) and treating the mixture with carbon dioxide until it has a base number of 32-39. The resulting product is then heated to 155°C during a period of nine hours to remove the alcohol and filtered at this temperature. The filtrate is characterized by a calcium sulfate ash content of about 40% and a metal ratio of about 12.2.

Example B-3 A mineral oil solution of a basic, carbonated calcium complex is prepared by carbonating a mixture of an alk lated benzene sulfonic acid (molecular weight of 470) an alkylated calcium phenate, a mixture of lower alcohols (methanol, butanol, and pentanol) and excess lime (5.6 equivalents per equivalent of the acid) . The solution has a sulfur content of 1.7%, a calcium content of 12.6% and a base number of 336. To 950 grams of the solution, there is added 50 grams of a polyisobutene (molecular weight of 1000)-substituted succinic anhydride (having a saponification number of 100) at 25°C. The mixture is stirred, heated to 150°C, held at that temperature for 0.5 hour, and filtered. The filtrate has a total base number to bromophenol blue of 315 and contains 35.4% of mineral oil.

Example B-4 To 950 grams of a solution of a basic, carbonated, calcium salt of an alkylated benzene sulfonic acid (aver¬ age molecular weight 425) in mineral oil (base number 406, calcium 15.2% and sulfur 1.4%) there is added 50 grams of the -polyisobutenyl succinic anhydride of Example B-3 at 57°C. The mixture is stirred for 0.65 hour at 55°-57°C, then at 152°-153°C for 0.5 hour and filtered at 105°C. The filtrate has a total base number to bromophenol blue of 387 and contains 43.7% of mineral oil.

Example B-5 A mixture comprising 753 parts (by weight) of mineral oil, 1440 parts of xylene, 84 parts of a mixture of a commercial fatty acid mixture (acid number of 200, 590 parts of an alkylated benzene sulfonic acid (average molecular weight 500) , and 263 parts of magnesium oxide is heated to 60°C. Methanol (360 parts) and water (180 parts) are added. The mixture is carbonated at 65°C-98°C while methanol and water are being removed by azeotropic distillation. Additional water (180 parts) is then added and carbonation is continued at 87°-90°C for three and a half hours. Thereafter, the reaction mixture is heated to 160°C at 20 ^'torr and filtered at 160°C to give a basic, carbonated magnesium sulfonate-carboxylate complex (78.1% yield) containing 7.69% of magnesium and 1.67% of sulfur and having a base number of 336. To 950 parts of the above basic, carbonated magnesium complex, there is added 50 parts of the polyisobutenyl succinic anhydride of Example B-3 and the mixture is heated to 150°C for one-half hour and then filtered to give a composition having a total base number to bromophenol of 315.

Example B-6 A mixture comprising 906 grams (1.5 equivalents) of an oil solution of an alkylbenzene sulfonic acid (average molecular weight 460-480) , 564 grams of mineral oil, 600 grams of toluene, 95.7 grams of magnesium oxide (4.4 equivalents) , and 120 grams of water is carbonated at a temperature of about 78°-85°C for about 7 hours at a rate of about 3 cubic feet of carbon dioxide per hour. The carbonated product is stripped by heating to 165°C at a pressure of 20 torr and filtered. The filtrate is an oil solution of a basic, carbonated magnesium sulfonate complex having a metal ratio of 3.1 and containing 15.27% of magnesium sulfate ash, 2.66% of sulfur and a total base number to bromophenol blue of 98. To 95 grams of this complex there is added 5 grams of the polyisobutenyl succinic anhydride of Example B-3 and the mixture is stirred at 150^CC and filtered.

Example B-7 A mixture of 1000 parts (3.6 equivalents) of a tall oil fatty acid, 1799 parts of mineral oil, 292 parts isobutyl alcohol, 187 parts n-amyl alcohol and 5.3 parts calcium chloride dissolved in 240 parts water are charged to a reactor. At 40°C, 158 parts (4.27 equivalents) calcium hydroxide is added and the temperature is in- creased to 90°C and held at this temperature for 1.5 hours. The contents are cooled to 50°C and added are 73 parts isobutyl alcohol, 47 parts n-amyl -alcohol, 467 parts methyl alcohol and 108 parts (2.93 equivalents) of calcium hydroxide. The contents are carbonated at 50°C to a basic neutralization number to phenolphthalein of 0-5. The contents are heated to 150°C and filtered. The filtrate has the following analyses: Sulfate ash (%) 15.5 Metal ratio 2.0 Total base number to bromophenol blue 125

Example B-8 To a mixture comprising 125 parts of low viscosity mineral oil and 66.5 parts of heptylphenol heated to about 38°C there is added 3.5 parts of water. Thereafter, 16 parts of paraformaldehyde are added to the mixture at a uniform rate over 0.75 hour. Then 0.5 parts of hydrated lime are added and this mixture is heated to 80°C over a 1 hour period. The reaction mixture thickens and the temperature rises to about 116°C. Then, 13.8 parts of hydrated lime are added over 0.75 hour while maintaining a temperature of about 80°-90°C. The material is then heated to about 140°C for 6 to 7 hours at a reduced pressure of about 2-8 torr to remove substantially all water. An additional 40 parts of mineral oil are added to the reaction product and the resulting material is fil¬ tered. The filtrate is a concentrated oil solution (70% oil) of the substantially neutral calcium salt_< of the heptylphenol-formaldehyde condensation product. It is characterized by calcium content of about 2.2% and a sulfate ash content of 7.5%. Example B-9 To a mixture comprising 125 parts of low viscosity mineral oil and 66.5 parts of heptylphenol heated to about 38°C there is added 3.5 parts of water. Thereafter, 16 parts of paraformaldehyde are added to the mixture at a uniform rate over 0.75 hour. Then 0.5 parts of hydrated lime are added and this mixture is heated to 80°C over a 1 hour period. The reaction mixture thickens and the temperature rises to about 116°C. Then, 13.8 parts of hydrated lime are added over 0.75 hour while maintaining a temperature of about 80°-90°C. The material is then heated to about 140°C for 6 to 7 hours at a reduced pressure of about 2-8 torr to remove substantially all water. An additional 40 parts of mineral oil are added to the reaction product and the resulting material is fil¬ tered. The filtrate is a concentrated oil solution (70% oil) of the substantially neutral calcium salt of the heptylphenol-formaldehyde condensation product. It is characterized by calcium content of about 2.2% and a sulfate ash content of 7.5%.

Example B-10 To a reactor is added 1797 parts (6.75 equivalents) of a dodecyl-substituted phenol and heated to 60°C. Added is 92 parts water, 126 parts (3.4 equivalents) calcium hydroxide, 173 parts (5.4 moles) sulfur and 33.8 parts of a 50% aqueous sodium hydroxide solution. The contents are heated to reflux of 112°C while blowing with nitrogen at 1 cfh. The contents are held at reflux for 8 hours and then stripped to 155°C. At 120°C, 719 parts oil is added and at 60°C, 133 parts (3.6 equivalents) calcium hydroxide, 66 parts (1.1 equivalents) acetic acid is added and an exotherm to 68°C is noted. At 57°C, 965 parts methyl alcohol, 351 parts (9.5 equivalents) calcium hydroxide, and 130 parts blend oil are added. The contents are carbonated at 63-68°C to a neutralization number to phenolphthalein of 35-40. The contents are stripped to 155°C while blowing with nitrogen at 1.5 cfh. At 120°C, 66 parts blend oil and 180 parts of the polyisobutenyl succinic anhydride of Example B-3 is added. The contents are stirred for an additional hour and filtered giving a product with the following analyses:

Sulfate ash (%) 25.5

Sulfur (%) 2.52

Metal Ratio 2.30

Example B-ll A reaction mixture comprising about 512 parts by weight of a mineral oil solution containing about 0.5 equivalent of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl group has an average of about 18 aliphatic carbon atoms and about 30 parts by weight of an oil mixture containing about 0.037 equivalent of an alkylated benzenesulfonic acid together with about 15 parts by weight (about 0.65 equivalent) of a magnesium oxide and about 250 parts by weight of xylene is added to a flask and heated to a temperature of about 60°C to 70°C. The reaction mass is subsequently heated to about 85°C and approximately 60 parts by weight of water are added. The reaction mass is held at a reflux tempera¬ ture of about 95°C to 100°C for about 1-1/2 hours and subsequently stripped at a temperature of 155°C-160°C, under a vacuum, and filtered. The filtrate comprises the basic carboxylic magnesium salt characterized by a sulfated ash content of 12.35% (ASTM D-874, IP 163), indicating * that the salt contains 200% of the stoichiometrically equivalent amount of magnesium.

Example B-12

A reaction mixture comprising about 506 parts by weight of a mineral oil solution containing about 0.5 equivalent of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have an average of about 16 to 24 aliphatic carbon atoms and about 30 parts by weight of an oil mixture containing about 0.037 equivalent of an alkylate benzenesulfonic acid together with about 22 parts by weight (about 1.0 equiva¬ lent) of a magnesium oxide and about 250 parts by weight of xylene is added to a flask and heated to temperatures of about 60°C to 70°C. The reaction is subsequently heated to about 85°C and approximately 60 parts by weight of water are added to the reaction mass which is then heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 95°-100°C for about 1-1/2 hours and subsequently stripped at about 155°C, under 40 torr and filtered. The filtrate comprises the basic carboxylic magnesium salt and is characterized by a sulfated ash content of 15.59% (sulfated ash) corre- sponding to 274% of the stoichiometrically equivalent amount.

Example B-13 To a reactor is charged 1000 parts of a neutral barium sulfonate and heated to 75°C. 119 parts of barium hydroxide monohydrate is added and the contents are dried by heating to 150°C and carbonated to obtain a neutraliza¬ tion number to phenolphthalein in the range of 0-1. The filtrate is an overbased barium sulfonate having the following analyses: Sulfate ash (%) 20.0 Metal ratio 2.5 Sulfur 2.0

Example B-l4

A mixture consisting essentially of 4.1 parts calcium chloride dissolved in 141.6 parts water, 306.7 parts of an alcohol mixture of 61% isobutyl alcohol and 39% n-amyl alcohol and 89.3 parts calcium hydroxide are added to a reaction vessel. 1000 parts of a sulfonic acid obtained by sulfonating with sulfur trioxide, a bright stock obtained from Mobil Oil Corporation identified as Prorex

1300 is added over -a 2 hour period between 50-S0°C. Volatiles are removed at 150°C with nitrogen being passed through the system. The contents are filtered to obtain the desired product having a % calcium sulfate ash of 5.2.

Example B-l5 The following is charged to a reactor: a 1000 part blend of mineral oil and the product of Example W such that the calcium sulfonate content is 22%, 2.0 parts calcium chloride dissolved in 5.4 parts water, 132 parts of the mixed alcohol of Example B-14, 34 parts of methyl alcohol and 44 parts of the product of Example Q. The contents are stirred and 58 parts calcium hydroxide is charged and carbon dioxide is blown below the surface until the neutralization number is between 20 and -30. An additional 36 parts of calcium hydroxide is charged with carbon dioxide blowing to a neutralization number of 20-30. The contents are then dried and filtered to obtain a product with the following analyses: Calcium sulfate ash (%) 14.6 Total base number to bromophenol blue 100 Sulfur (%) 1.3

Example B-16 The following is charged to a reactor: a 100 part blend of mineral oil and the product of Example W such that the calcium sulfonate content is 19.3%, 118.2 parts of the mixed alcohol of Example B-14, 2.0 parts calcium chloride dissolved in 44.1 parts methyl alcohol, 79.5 parts of the product of Example Q and 88.1 parts of calcium hydroxide. Carbon dioxide is blown at between 44-56°C until the neutralization number is 40-50. 5 additional portions of calcium hydroxide at 58.3 parts each are added with carbon dioxide blowing to a neutral¬ ization number of 40-50. Oil is added and the contents are stripped to 150°C with nitrogen blowing. The analyses are: Calcium sulfate ash (%) 38.0

Total base number to bromophenol blue 300

Sulfur (%) 0.8

Example B-17 While maintaining a temperature of 55°C, 1000 parts phenol and 68 parts sulfonated polystyrene catalyst (marketed as Amberlyst-15 by Rohm and Haas Company) are charged to a reactor equipped with a stirrer, condenser, thermometer and subsurface gas inlet tube. The reactor contents are then heated to 120°C while nitrogen blowing for 2 hours. 1232 parts propylene tetramer is charged, and the reaction mixture is stirred at 120°C for 4 hours. Agitation is stopped, and the batch is allowed to settle for 0.5 hour. The crude supernatant reaction mixture is filtered and vacuum stripped until a minimum of 0.5 percent residual propylene tetramer remains.

A reactor equipped with a stirrer, condenser, ther¬ mometer and subsurface addition tube is charged with 1000 parts of the reaction product obtained above. The temper- ature is adjusted to 48-49°C and 175 parts sulfur dichloride is added while the temperature is kept below 60°C. The batch is then heated to 88-93°C while nitrogen blowing until the acid number (using bromophenol blue indicator) is less than 4.0. 400 parts diluent oil is then added, and the mixture is mixed thoroughly to obtain a sulfurized phenol.

A basic calcium salt of a phenol sulfide is prepared by reacting the sulfurized phenol with calcium hydroxide in the presence of acetic acid, methanol and polyisobutenyl succinic anhydride and blowing with CO . The product obtained has a metal ratio of 2.3, % sulfated ash of 24.5 and a total base number to bromophenol blue of 200. Example B-l8 To a flask fitted with a stirrer, thermowell, water reflux condenser and submerged gas inlet tube is added 1355 parts (2.4 equivalents) of an alkylated sulfonic acid, 1679 parts mineral oil, 280 parts of the polyisobutenyl succinic anhydride of Example B-3 and 3100 parts xylene. The contents are heated and stirred to 35°C and 105 parts (175 equivalents) acetic acid is added. At 45°C, added are 200 parts (9.5 equivalents) magnesium oxide, 160 parts methyl alcohol and 80 parts water. C0₂ is blown below the surface at 3 cubic feet per hour for 15 hours. Three additional increments of MgO, methyl alcohol and water are added with the portions being 200:160:80; 200:160:80 and 150:120:60 parts MgO:methyl alcohol:water, respectively. Each increment is C0_ blown at 3 cubic feet per hour for 1.5 hours, 4 hours, respectively. The contents are stripped to 105°C with C0₂ blowing at 3 cubic feet per hour and later to 10 mm mercury. The contents are filtered to give a product of the following analyses: total base number to bromophenol blue, 390; % sulfate ash, 43.7; % sulfur 1.66.

The Hydrocarbyl-substituted Succinic Acid Producing Compcund (C) (i)

The hydrocarbyl-substituted succinic acid producing compound (C) (i) of the present invention is an olefin polymer substituted carboxylic acid acylating agents made by reacting one or more alpha-beta olefinically unsa urated carboxylic acid reagents containing two to about 20 carbon atoms, exclusive of the carboxyl-based groups, with one or more olefin polymers containing at least 30 carbon atoms, as described more fully hereinafter.

The alpha-beta olefinically unsaturated carboxylic acid reagents may be either the acid per se or functional derivatives thereof, e.g., anhydrides, esters, acylating nitrogen, acyl halide, nitrileε, metal salts. These carboxylic acid reagents may be either monobasic or polybasic in nature. When they are polybasic they are preferably dicarboxylic acids, although tri- and tetracarboxylic acids can be used. Exemplary of the monobasic alpha-beta olefinically unsaturated carboxylic acid reagents are the carboxylic acids corresponding to the formula

wherein R„ is hydrogen, or a saturated aliphatic or alicyclic, aryl, alkylaryl or heterocyclic group, prefera¬ bly hydrogen or a lower alkyl group, and R_g is hydrogen or a lower alkyl group. The total number of carbon atoms in

Ro₀ and R_Qy should not exceed 18 carbon atoms. Specific examples of useful monobasic alpha-beta olefinically unsaturated carboxylic acids are acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, 3-phenyl propenoic acid, 2-decenoic acid, etc. Exemplary polybasic acids include maleic acid, fumaric acid, mesaconic acid, itaconic acid and citraconic acid. The alpha-beta olefinically unsaturated reagents can also be functional derivatives of the foregoing acids. These functional derivatives include the anhydrides, esters, amides, imides, acid halides, nitriles, amine salts and metal salts of the aforedescribed acids. A preferred alpha-beta olefinically unsaturated carboxylic acid reagent is maleic anhydride. Methods of preparing such functional derivatives are well known to those of ordinary skill in the art, and they can be satisfactorily described by noting the reactants used to produce them. Thus, for example, derivative esters for use in the present invention can be made by esterifying monohydric or polyhydric alcohols or epoxides with any of the aforedescribed acids. Amines and alcohols described hereinafter can be used to prepare these functional derivatives. The nitrile functional derivatives of the aforedescribed carboxylic acid useful in making the products of the present invention can be made by the conversion of a carboxylic acid to the corresponding nitrile by dehydration of the corresponding amide. The preparation of the latter is well known to those skilled in the art and is described in detail in The Chemistry of the Cyano Group edited by Zvi Rappoport, Chapter 2 , which is hereby incorporated by reference for its relevant disclosures pertaining to methods for preparing nitriles. Ammonium salt acylated nitrogen functional deriva¬ tives can also be made from any of the amines described hereinafter as well as from tertiary amino analogs of them (i.e., analogs wherein the -NH groups have been replaced with -N-hydrocarbyl or -N-hydroxy hydrocarbyl groups) , ammonia or ammonium compounds (e.g., NH.C1, NH.OH, etc.) by conventional techniques well known to those of ordinary skill in the art.

The metal salt functional derivatives of the forego¬ ing carboxylic acid reagents can also be made by conven- tional techniques well known to those of ordinary skill in the art. Preferably, they are made from a metal, mixture of metals, or a basically reacting metal derivative such as a metal salt or mixture of metal salts where the metal is chosen from Group la, lb, Ila or lib of the periodic table although metals from Groups IVa, IVb, Va, Vb, Via, Vlb, V lb and VIII can also be used. The counter ion of the metal salt can be inorganic such as halide, sulfide, oxide, carbonate, hydroxide, nitrate, sulfate, thiosulfate, phosphite, phosphate, etc., or organic such as lower alkanoate, sulfonate, alcoholate, etc. The salts formed from these metals and the acid products can be "acidic," "normal" or "basic" salts. An "acidic" salt is one in which the equivalents of acid exceed the stoichiometric amounts required to neutralize the number of equivalents of metal. A "normal" salt is one wherein the metal and acid are present in stoichiometrically eσuivalent amounts. A "basic" salt (sometimes referred to as "overbased", "superbased" or "hyperbased" salts) is one wherein the metal is present in a stoichiometric excess relative to the number of stoichiometric equivalents of carboxylic acid compounds from which it is produced. The production of the latter are well known to those of ordinary skill in the art and are described in detail in "Lubricant Additives" by M. W. Ranney, pages 67-77, which is hereby incorporated by reference for its relevant disclosures pertaining to methods for preparing overbased salts.

The acid halide functional derivative of the aforedescribed olefinic carboxylic acids can be prepared by the reaction of the acids and their anhydrides with a halogenation agent such as phosphorus tribromide, phospho- rus pentachloride, or thionyl chloride. Esters can be prepared by the reaction of the acid halide with the aforesaid alcohols or phenolic compounds such as phenol, naphthol, octyl phenol, etc. Also, amides and imides and other acylated nitrogen derivatives can be prepared by reacting the acid halide with the above-described a ino compounds. These esters and acylated nitrogen derivatives can be prepared from the acid halides by conventional techniques well known to those of ordinary skill in the art. The olefin polymers are selected from the group consisting of homopolymers and/or interpolymers of mono-olefins of from 2 to 30 carbon atoms. The chlori¬ nated or brominated analogs of the olefin polymers are also within the scope of the present invention. These olefin polymers are aliphatic in nature. The description of these olefin polymers as being aliphatic is intended to denote that, of the total number of carbon atoms in the polymer, no more than about 20% are non-aliphatic carbon atoms; that is, carbon atoms which are part of an alicyclic or aromatic ring. Thus, a polymer containing, e.g., 5% of its carbon atom in alicyclic ring structures and 95% of its carbon atom in aliphatic structures would be an aliphatic polymer within the context of this invention.

The mono-olefins useful in preparing the olefin polymers can be internal olefins (i.e., when the olefinic unsaturation is not in the "-1-" or alpha position) or preferably 1-olefins. These mono-olefins can be either straight or branched chain, but preferably they are straight chain. Exemplary of such mono-olefins which can be used to prepare the olefin polymers of this invention are ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-l-butene, 3-methyl-l-butene, the 1-hexenes, the 1-heptenes, the 1-octenes and styrene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene , 1-eicosene, 1-henicosene, 1-docosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-octacosene, 1-nonacosene, etc. Preferred mono-olefins are ethylene, propylene, 1-butene, and especially isobutene, commercially available alpha olefin fractions such as ^ci5_i8 alpha-olefins, C,₂_₁₆ alpha-olefins, ^c-₍4_i6 alpha-olefins, C, , ,_g alpha-olefins, ^C16-18 alpha-olefins, ^ci6_20 alpha-olefins, ^C22-28 alpha-olefins, etc.

Mono-olefins which are useful in the preparation of the olefin polymers can be derived from the cracking of paraffin wax. The wax cracking process yields both even and odd number C_g_₂₀ liquid olefins of which 85 to 90 percent are straight chain 1-olefins. The balance of the cracked wax olefins is made up of internal olefins, branched olefins, diolefins, aromatics and impurities. Distillation of the C_g_₂₀ liquid olefins obtained from the wax cracking process yields fractions (e.g., C.

15—18 alpha-olefins) which are useful in preparing the olefin polymers of this invention.

Other mono-olefins which are useful in preparing the olefin polymers can be derived from the ethylene chain growth process. This process yields even numbered straight chain-1-olefins from a controlled Ziegler polymerization.

Other methods for preparing the mono-olefins of this invention include chlorination-dehydrochlorination of paraffin and catalytic dehydrogenation of paraffins.

The above procedures for the preparation of mono-olefins are well known to those of ordinary skill in the art and are described in detail under the heading "Olefins" in the Encyclopedia of Chemical Technology, Second Edition, Kirk and Othmer, Supplement, Pages 632-657, Interscience Publishers, Div. of John Wiley and Son, 1971, which is hereby incorporated by reference for its relevant disclosures pertaining to methods for prepar¬ ing mono-olefins. The olefin polymers used in this invention can contain small amounts of alicyclic carbon atoms. Such alicyclic carbon atoms can be derived from such monomers as cyclopentene, cyclohexene, ethylene cyclopentane, methylene cyclohexene, 1,3-cyclohexene, norbornene, norboradiene and cyclopentadiene.

The olefin polymers used in this invention are also substantially saturated in nature. That is, their mole¬ cules contain no more than 10% olefinic or acetylenic unsaturation. In other words, there is no more than one olefinic or acetylenic carbon-carbon bond for every ten monovalent carbon-carbon bonds in the molecules of the polymers. Normally, the polymers are free from acetylenic unsaturation.

The olefin polymers used in this invention each contain a least about 30 aliphatic carbon atoms; prefera¬ bly, they contain an average of up to about 3500 carbon atoms; preferably, an average of about 50 to about 700 carbon atoms. In terms of molecular weight, the polymers used in this invention^* have number average molecular weights as determined by gel permeation chromatography of at least about 420, more preferably, they have a maximum number average molecular weight as determined by gel permeation chromatography of no more than about 50,000; an especially preferred range for number average molecular weights of the polymers used in this invention is about 750 to about 10,000. A particularly preferred range of number average molecular weights is from about 750 to about 3,000. The preferred weight average molecular weight as determined by gel permeation chromatography is at least about 420 up to about 100,000, more preferably about 1,500 to about 20,000. The molecular weight of the polymers used in this invention can also be defined in terms of inherent viscos¬ ity. The inherent viscosity (n. .) of these polymers generally is at least about 0.03, preferably at least about 0.07, no more than about 1.5, and preferably no more than 0.2 deciliters per gram. These inherent viscosities are determined at concentrations of 0.5 gram of polymer in 100 ml. of carbon tetrachloride or tetrachloroethylene at 30°C.

The olefin polymers of this invention are most conveniently obtained by the polymerization of the olefins with Friedel-Crafts polymerization catalyst such as aluminum chloride, boron trifluoride, titanium tetrachloride, or the like. The polymers could also be obtained by the use of "Ziegler Type" catalysts. These catalysts generally include a transition metal compound such as the halide, oxide or alkoxide and an organo-metallic compound wherein the metal is of the Group

I-III of the Periodic Chart. Generally, titanium tri- or tetrachloride or vanadium trichloride or oxychloride is combined with a trialkyl or dialkyl aluminum halide such as triethyl aluminum, triisobutyl aluminum or diethyl aluminum chloride.

Additionally, the olefin polymers of this invention can be obtained by chain polymerization of the olefins by the use of free-radical initiators. The free-radical initiators commonly used are organic peroxides. The preferred organic peroxides are di-t-butyl peroxide and benzoyl peroxide. Chain polymerization is well known to those of ordinary skill in the art and is discussed more fully in Schildknecht, C.E., Allyl Compounds and Their Polymers, Wiley-Interscience, 1973, pp. 62-63 which is incorporated by reference for its relevant disclosure pertaining to methods of chain polymerization and free-radical initiators useful in chain polymerization. The hydrocarbyl substituted succinic acid producing compound (C) (i) of the present invention can be prepared by directly contacting in a first step one or more alpha-beta olefinically unsaturated carboxylic reagents with one or more olefin polymers at a temperature in the range of, for example, about 140°C to about 300°C. The processes for preparing the hydrocarbyl-substituted succinic acid producing compound (C) (i) are well known to those of ordinary skill in the art and have been described in detail, for example, in U.S. Patents 3,087,936

3,163,603 3,172,892; 3,189,544; 3,219,666; 3,231,587

3,272,746 3,288,714; 3,306,907; 3,331,776; 3,340,281 3,341,542 3,346,354; and 3,381,022 which are incorporated herein by reference.

The hydrocarbyl-substituted succinic acid producing compound (C) (i) of this invention can also be prepared by reacting one or more alpha-beta olefinically unsaturated carboxylic reagents with one or more olefin polymers, respectively, in the presence of chlorine or bromine at a temperature within the range of about 100°C to about 300°C according to the techniques disclosed in U.S. Patents 3,215,707, 3,231,587, and 3,912,764, which are incorporat- ed herein by reference.

The chlorinated or brominated analogs of the olefin polymer can be prepared by conventional techniques well known to those of ordinary skill in the art. For example, the chlorinated analogs of the olefin polymers can be prepared by contacting (i.e., reacting) a 1:1 mole ratio of the olefin polymer with chlorine at 100°-200°C. Excess chlorine may be used; for example, about 1.1 to about 3 moles of chlorine for each mole of olefin polymer.

The olefin polymer or chlorinated or brominated analogs thereof are generally reacted at a ratio of one equivalent of olefin polymers or chlorinated or brominated analog thereof (for purposes of this invention the equiva¬ lent weight of the olefin polymers is equal to their total number average molecular weight, as determined by gel permeation chromatography) to f om about 0.1 to about 5 moles, usually 0.1 to about 1 mole, with the unsaturated carboxylic reagent, respectively.

When the olefin polymers and the unsaturated carboxylic reagents are reacted in the presence of chlo¬ rine or bromine, the ratios of the reactants are the same as hereinabove-described. The molar ratio of unsaturated carboxylic reagent to chlorine or bromine is generally one mole of to about 0.5 up to about 1.3 mole, usually, from about 1 up to about 1.05 mole, of chlorine or bromine. Reaction Products of the Hydrocarbyl-substituted Succinic Acid Producing Compound (c) (i) with Amines and/or Alcohols (C) (ii) :

Also included in this invention are the compositions made by reacting (C) (i) a hydrocarbyl-substituted succinic acid producing compound ("carboxylic acid acylating agent") as described above with (C) (ii) one or more amines, or one or more alcohols, or mixtures of one or more amines and/or one or more alcohols.

The amines useful as (C) (ii) for reacting with (C) (i) the hydrocarbyl-substituted succinic acid producing compound are characterized by the presence within their structure of at least one H-N<group. These amines can be monoa ines or polyamines. Hydrazine and substituted hydrazines containing up to three substituents are included as amines suitable for preparing carboxylic derivative compositions. Mixtures of two or more amines can be used in the reaction with one or more of the acylating agents of the present invention. Preferably, the amine contains at least one primary amino group (i.e., -NH₂) . Advantageously, the amine is a polyamine, especially a polyamine containing at least two H-N groups, either or both of which are primary or secondary amines. The use of polyamines result in succinic acid derivative compositions which are usually more effective as dispersant/detergent additives, than are derivative compositions derived from monoamines. Suitable monoamines and polyamines are described in greater detail hereinafter.

Alcohols (C) (ii) which can be reacted with (C) (i) the hydrocarbyl-substituted succinic acid producing compound include monohydric and polyhydric alcohols. Polyhydric alcohols are preferred since they usually result in succinic acid derivative compositions which are more effective as dispersant/detergents than succinic acid derivative compositions derived from monohydric alcohols. Alcohols suitable for use in this invention are described in greater detail hereinafter. The monoamines and polyamines useful in this inven¬ tion are characterized by the presence within their structure of at least one H-N<_ group. Therefore, they have at least one primary (i.e., H₂N-) or secondary amino (i.e., H-N .) group. The amines can be aliphatic, cycloaliphatic, aromatic, or heterocyclic, including aliphatic-substituted aromatic, aliphatic-substituted cycloaliphatic, aliphatic-substituted aromatic, aliphatic- substituted heterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphatic-substituted aromatic, cyclo- aliphatic-substituted heterocyclic, aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic, aromatic- substituted heterocyclic, heterocyclic-substituted aliphatic, heterocyclic-substituted cycloaliphatic, and heterocyclic-substituted aromatic amines and may be saturated or unsaturated. If unsaturated, the amine is preferably free from acetylenic unsaturation (i.e., -C≡C-) . The amines may also contain non-hydrocarbon substituents or groups as long as these groups do not significantly interfere with the reaction of the amines with the acylating reagents of this invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl mercapto, nitro, interrupting groups such as -O- and -S- (e.g., as in such groups as -CH₂ CH₂-X-CH₂-CH - where X is -0- or -S-.

With the exception of the branched polyalkylene polyamines, the polyoxyalkylene polyamines and the high molecular weight hydrocarbyl-substituted amines described more fully hereafter, the amines used in this invention ordinarily contain less than about 40 carbon atoms in total and usually not more than about 20 carbon atoms in total. Aliphatic monoamines include mono-aliphatic and di-aliphatic substituted amines wherein the aliphatic groups can be saturated or unsaturated and straight or branched chain. Thus, they are primary or secondary aliphatic amines. Such amines include, for example, mono- and di-alkyl-substituted amines, mono- and di-alkenyl-substituted amines, and amines having one N-alkenyl substituent and one N-alkyl substituent and the like. The total number of carbon atoms in these aliphatic monoamines preferably does not exceed about 40 and usually does not exceed about 20 carbon atoms. specific examples of such monoamines include ethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, octadecyl- amine, and the like. Examples of cycloaliphatic- substituted aliphatic amines, aromatic-substituted aliphatic amines, and heterocyclic-substituted aliphatic amines, include 2-(cyclohexyl)-ethylamine, benzylamine, phenylethylamine, and 3-(furylpropyl)amine. Cycloaliphatic ^* monoamines are those monoamines wherein there is one cycloaliphatic substituent attached directly to the amino nitrogen through a carbon atom in the cyclic ring structure. Examples of cycloaliphatic monoamines include cyclohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclo- hexylamine, dicyclohexylamines, and the like. Examples of aliphatic-substituted, aromatic-substituted, and hetero¬ cyclic-substituted cycloaliphatic monoamines include propyl-substituted cyclohexylamines, phenyl-substituted cyclopentylamines, and pyranyl-substituted cyclohexyl¬ amines. Suitable aromatic amines include those monoamines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The aromatic ring will usually be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthalene. Exam¬ ples of aromatic monoamines include aniline, di(para- methylphenyl)amine, naphthylamine, N-(n-butyl)aniline, and the like. Examples of aliphatic-substituted, cyclo¬ aliphatic-substituted, and heterocyclic-substituted aromatic monoamines are para-ethoxyaniline, para-dodecyl- aniline, cyclohexyl-substituted naphthylamine, and thienyl-substituted aniline.

Suitable polyamines are aliphatic, cycloaliphatic and aromatic polyamines analogous to be above-described monoamines except for the presence within their structure of another amino nitrogen. The other amino nitrogen can be a primary, secondary or tertiary amino nitrogen. Examples of such polyamines include N-aminopropyl-cyclo- hexylamines, N-N'-di-n-butyl-para-phenylene diamine, bis-(para-aminophenyl) -methane,1,4-diaminocyclohexane, and the like.

Heterocyclic mono- and polyamines can also be used in . making the substituted carboxylic acid acylating agent derivative compositions of this invention. As used herein, the terminology "heterocyclic mono- and polyamine(s) " is intended to describe those heterocyclic amines containing at least one primary or secondary amino group and at least one nitrogen as a heteroatom in the heterocyclic ring. However, as long as there is present in the heterocyclic mono- and polyamines at least one primary or secondary amino group, the hetero-N atom in the ring can be a tertiary amino nitrogen; that is, one that does not have hydrogen attached directly to the ring nitrogen. Heterocyclic amines can be saturated or unsatu¬ rated and can contain various substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the total number of carbon atoms in the substituents will not exceed about 20. Heterocyclic amines can contain heteroatoms other than nitrogen, especially oxygen and sulfur. Obviously they can contain more than one nitrogen heteroatom. The five- and six-membered heterocyclic rings are preferred.

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

Hydroxyamines both mono- and polyamines, analogous to those described above are also useful in this invention provided they contain at least one primary or secondary amino group. Hydroxy-substituted amines having only tertiary amino nitrogen such as in tri-hydroxyethyl amine, are thus excluded as an amine, but can be used as an alcohol as disclosed hereafter. The hydroxy-substituted amines contemplated are those having hydroxy substituents bonded directly to a carbon atom other than a carbonyl carbon atom; that is, they have hydroxy groups capable of functioning as alcohols. Examples of such hydroxy- substituted amines include ethanolamine, di- (3-hydroxy- propyl)amine, 3-hydroxybutylamine, 4-hydroxybutylamine, diethanolamine, di-(2-hydroxypropyl)-amine, N-(hydroxy- propyl)propylamine, N-(2-hydroxyethyl)-cyclohexylamine, 3-hydroxycyclopentylamine, para-hydroxyaniline, N-hydroxy- ethyl piperazine, and the like. The terms hydroxyamine and aminoalcohol describe the same class of compounds and, therefore, can be used interchangeably. Hereinafter, in the specification and appended claims, the term hydroxyamine will be understood to include aminoalcohols as well as hydroxyamines. Also suitable as amines are the aminosulfonic acids and derivatives thereof corresponding to the formula

0 ^,Ec^Eb^N-»x •- ^Ra-—> ^■— ^{" E}'y

wherein R is -OH, -NH , ONH₄, etc., R is a polyvalent organic radical having a valence equal to x+y; r and R are each independently hydrogen, hydrocarbyl, and substi¬ tuted hydrocarbyl with the proviso that at least one of R, and R is hydrogen per aminosulfonic acid molecule; x and y are each integers equal to or greater than one. From the formula, it is apparent that each aminosulfonic rreeaaccttaanntt iiss cchhaarraacctteerr:ized by at least one NH or H_N- group and at least one

0 II -S-R

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

group is attached directly to a nuclear carbon atom of the aromatic radical. The aminosulfonic acid may also be a mono-amino aliphatic sulfonic acid; that is, an acid where x is one and R is a polyvalent aliphatic radical such as ct ethylene, propylene, trimethylene, and 2-methylene propylene. Other suitable aminosulfonic acids and deriva¬ tives thereof useful as amines in this invention are disclosed in U.S. Patents 3,926,820; 3,029,250; and 3,367,864; which are incorporated herein by reference. Hydrazine and substituted-hydrazine can also be used as amines in this invention. At least one of the nitro¬ gens in the hydrazine must contain a hydrogen directly bonded thereto. Preferably there are at least two hydro¬ gens bonded directly to hydrazine nitrogen and, more preferably, both hydrogens are on the same nitrogen. The substituents which may be present on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the substituents are alkyl, especially lower alkyl, phenyl, and substituted phenyl such as lower alkoxy-substituted phenyl or lower alkyl-substituted phenyl. specific examples of substituted hydrazines are methylhydrazine, N,N-dimethylhydrazine, N,N'-dimethy1- hydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine, N-(para-tolyl)-N*-(n-butyl)-hydrazine, N-(para-nitro- phenyl)-hydrazine, N-(para-nitrophenyl) -N-methylhydrazine, N,N'-di-(para-chlorcphenol) -hydrazine, N-phenyl-N'-cyclo- hexylhydrazine, and the like. The high molecular weight hydrocarbyl amines, both monoamines and polyamines, which can be used as amines in this invention are generally prepared by reacting a chlorinated polyolefin having a molecular weight of at least about 400 with ammonia or amine. Such amines are known in the art and described, for example, in U.S. Patents 3,274,554, and 3,438,757, both of which are expressly incorporated herein by reference for their disclosure in regard to how to prepare these amines. All that is required for use of these amines is that they possess at least one primary or secondary amino group.

Another group of amines suitable for use in this invention are branched polyalkylene polyamines. The branched polyalkylene polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene

group per nine ^* amino units present on the 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

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

wherein n is an integer, for example, 1-20 or more but preferably 1-3, and R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched) . The preferred embodiments are presented by the following formula H

The groups in the brackets may be joined in a head-to-head or a head-to-tail fashion. Compounds de¬ scribed by this formula wherein n = 1-3 are manufactured and sold as Polyamines N-400, N-800, N-1200, etc. Polyamine N-400 has the above formula wherein n=l.

U.S. patents 3,200,106 and 3,259,578 are incorporated herein by reference for their disclosure of how to make such polyamines and processes for reacting them with carboxylic acid acylating agents.

Suitable amines also include polyoxyalkylene polyamines, e.g., polyoxyalkylene diamines and polyoxyalkylene tria ines, having average molecular weights ranging from about 200 to 4000 and preferably from about 400 to 2000. Illustrative examples of these polyoxyalkylene polyamines may be characterized by the formulae

NH₂-Alkylene ( O-Alkylene m 2

where m has a value of about 3 to 70 and preferably about 10 to 35; and

[Alkylene -- ^■O-Alkylene ^n^KH2^]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 is from about 3 to about 70 and generally from about 6 to about 35, and R is a polyvalent saturated hydrocarbyl radical of up to ten carbon atoms having a valence of 3 to 6. The alkylene groups may be straight or branched chains and contain from 1 to 7 carbon atoms, and usually from 1 to 4 carbon atoms. The various alkylene groups present within the above formulae may be the same or different. More specific examples of these polyamines include:

NH_nCH-CH„ {— OCH Δ_CjH ) X NH„

CH₃ CH₃

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

CH₂ (0CH₂CH τ- NH₂ CH₃

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

Preferred polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2000. The polyoxyalkylene ,polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under the trade name "Jeff-amines D-230, D-400, D-1000, D-2000, T-403, etc.".

U.S. Patents 3,804,663 and 3,948,800 are incorporated herein by reference for their disclosure of such polyoxyalkylene polyamines and process for acylating them with carboxylic acid acylating agents. Preferred amines are the alkylene polyamines, includ¬ ing the polyalkylene polyamines, as described in more detail hereafter. The alkylene polyamines include those conforming to the formula _H__N (Alkylene-N-) R"

R ^■ „" R ' ⁿ

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

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

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

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in preparing compositions of the present invention. Preferred hydroxyalkyl-substituted alkylene polyamines are those in which the hydroxyalkyl groups is a lower hydroxyalkyl group, i.e., having less than eight carbon atoms. Examples of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethy1)ethylene diamine, N,N-bis (2-hydroxyethyl)ethylene diamine, 1-(2-hydroxy- ethyl) -piperazine, monohydroxypropyl-substituted diethylene triamine, dihydroxypropyl-substituted tetra- ethylene pentamine, N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as are obtained by condensation of the above-illustrated hydroxy alkylene polyamines through amino radicals or through hydroxy radicals are likewise useful as amines in this invention. Condensation through amino radicals results in a higher amine accompanied by removal of ammonia and condensation through the hydroxy radicals results in products con¬ taining ether linkages accompanied by removal of water. The reaction products produced from the reaction of _v the hydrocarbyl-substituted succinic acid producing compound of this invention and the amines described hereinbefore are acylated amines which include amine salts, amides, imides and imidazolines as well as mixtures thereof. To prepare carboxylic derivatives from the acylating agents and amines, one or more of each of the succinic acid producing compounds and one or more amines are heated, optionally in the presence of a normally liquid, substantially inert, organic liquid solvent/ diluent, at temperatures in the range of about 80°C up to the decomposition point (the decomposition point is the temperature at which there is sufficient decomposition of any reactant or product such as to interfere with the production of the desired product) but normally at temper- atures in the range of about 100°C to about 300"C, provid¬ ed 300°C does not exceed the decomposition point. Temperatures of about 125°C to about 250°C are normally used. The succinic acid producing compound and the amine are reacted in amounts sufficient to provide from about one-half equivalent to about 2 moles of amine per equiva¬ lent of the succinic acid producing compound. For purpos¬ es of this invention an equivalent of amine is that amount of the amine corresponding to the total weight of amine divided by the total number of nitrogens present. Thus, octylamine has an equivalent weight equal to its molecular weight; ethylene diamine has an equivalent weight equal to one-half its molecular weight; and aminoethylpiperazine has an equivalent weight equal to one-third its molecular weight. Also, for example, the equivalent weight of a commercially available mixture of polyalkylene polyamine can be determined by dividing the atomic weight of nitro¬ gen (14) by the %N contained in the polyamine times 100. Therefore, a polyamine mixture having a %N of 34 would have an equivalent weight of 41.2. The number of equivalents of the succinic acid producing compound depends on the total number of carboxylic functions (e.g., carboxylic acid groups or functional derivatives there) present in the succinic acid producing compound. Thus, the number of equivalents of succinic acid producing compound will vary with the number of carboxy groups present therein. In determining the number of equivalents of succinic acid producing compound, those carboxyl functions which are not capable of reacting as a carboxylic acid acylating agent are excluded. In general, however, there is one equivalent of acylating agent for each carboxy group in the acylating agents. For example, there would be two equivalents in the acylating agents derived from the reaction of one mole of olefin polymer and one mole of maleic anhydride. Conventional techniques are readily available for determining the number of carboxyl functions (e.g., acid number, saponification number) and, thus, the number of equivalents of acylating agent available to react with amine.

Because the succinic acid producing compound can be used in the same manner as the high molecular weight acylating agents of the prior art in preparing acylated amines suitable as additives for lubricating oil compositions, U.S. patents 3,172,892; 3,219,666; and 3,272,746 are incorporated herein by reference for their disclosures with respect to the procedures applicable to reacting the substituted carboxylic acid acylating agents with the amines as described above. In applying the disclosures of these patents to the hydrocarbyl-substituted succinic acid producing compound of this invention, the latter can be substituted for the high molecular weight carboxylic acid acylating agents disclosed in these patents on an equivalent basis. That is, where one equivalent of the high molecular weight acylating agent disclosed in these incorporated patents is utilized, one equivalent of succinic acid producing compound of this invention can be used. These patents are also incorporated by reference for their disclosure of how to use the acylated amines thus produced as additives in lubricating oil compositions. Dispersant/detergent properties can be imparted to lubricating oils by incorpo¬ rating the acylated amines produced by reacting the succinic acid producing compound with the amines described above on an equal weight basis with the acylated amines disclosed in these patents. Alcohols useful in preparing carboxylic derivative compositions of this invention from the acylating agents previously described include those compounds of the general formula

wherein R,_n is a monovalent or polyvalent organic groups joined to the -OH groups through carbon-to-oxygen bonds (that is, -C-OH wherein the carbon is not part of a carbonyl group) and t is an integer of from 1 to about 10, preferably 2 to about 6. As with the amine reactants, the alcohols can be aliphatic, cycloaliphatic, aromatic, and heterocyclic, including aliphatic-substituted cyclo¬ aliphatic alcohols, aliphatic-substituted aromatic alcohols, aliphatic-substituted heterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols, cyclo¬ aliphatic-substituted aromatic alcohols, cycloaliphatic- substituted heterocyclic alcohols, heterocyclic- substituted aliphatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols. Except for the polyoxyalkylene alcohols, the mono- and polyhydric alcohols corresponding to the formula R, _n-(0H) will usually contain not more than about 40 carbon atoms and generally not more than about 20 carbon atoms. The alcohols may contain non- hydrocarbon substituents of the same type mentioned with respect to the amines above, that is, non-hydrocarbon substituents which do not interfere with the reaction of the alcohols with the acylating reagents of this inven¬ tion. In general, polyhydric alcohols are preferred. Among the polyoxyalkylene alcohols suitable for use in the preparation of the carboxylic derivative composi¬ tions of this invention are the polyoxyalkylene alcohol demulsifiers for aqueous emulsions. The terminology "demulsifier for aqueous emulsions" as used herein is intended to describe those polyoxyalkylene alcohols which are capable of preventing or retarding the formation of aqueous emulsions or "breaking" aqueous emulsions. The terminology "aqueous emulsion" is generic to oil-in-water and water-in-oil emulsions.

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

Preferred demulsifers are liquid polyoxyalkylene alcohols and derivatives thereof. The derivatives contem¬ plates are the hydrocarbyl ethers and the carboxylic acid esters obtained by reacting the alcohols with various carboxylic acids. Illustrative hydrocarbyl groups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc., containing up to about 40 carbon atoms. Specific hydrocarbyl groups are methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenyl ethyl, cyclohexyl, and the like. Carboxylic acids useful in preparing the ester derivatives are mono- or polycarboxylic acids such as acetic acid, lauric acid, stearic acid, succinic acid, and alkyl or alkenyl- substituted succinic acids wherein the alkyl or alkenyl group contains up_^to about 20 carbon atoms. Members of this class of alcohols are commercially available from various sources; e.g., PLURONIC polyols from Wyandotte Chemicals Corporation; POLYGLYCOL 112-2, a liquid triol derived from ethylene oxide and propylene oxide available from Dow Chemical Co.; and TERGITOLS, dodecylphenyl or nonylphenyl polyethylene glycol ethers, and UCONS, poly¬ alkylene glycols and various derivatives thereof, both available from Union Carbide Corporation. However, the demulsifers used must have an average of at least one free alcoholic hydroxyl group per molecule of polyoxyalkylene alcohol. For purposes of describing these polyoxyalkylene alcohols which are demulsifiers, an alcoholic hydroxyl group is one attached to a carbon atom that does not form part of an aromatic nucleus.

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

to form a hydrophobic base, R₁₂ being a lower alkyl group of up to about 4 carbon atoms, R_._ being H or the same as R-_ with the proviso that the alkylene oxide does not contain in excess of 10 carbon atoms. This base is then reacted with ethylene oxide to provide a hydrophilic portion resulting in a molecule having both hydrophobic and hydrophilic portions. The relative sizes of these portions can be adjusted by regulating the ratio of reactants, time of reaction, etc., as is obvious to those skilled in the art. It is within the skill of the art to prepare such polyols whose molecules are characterized by hydrophobic and hydrophilic moieties present in a ratio rendering them suitable as demulsifiers for aqueous emulsions in various lubricant compositions and thus suitable as alcohols in this invention. Thus, if more oil-solubility is needed in a given lubricant composition, the hydrophobic portion can be increased and/or hydrophilic portion decreased. If greater aqueous emul¬ sion breaking capability is required, the hydrophilic and/or hydrophobic portions can be adjusted to accomplish this. Compounds illustrative of R..-(0H) include aliphatic polyols such as the alkylene glycols and alkane polyols, e.g., ethylene glycol, propylene glycol, trimethylene glycol, glycerol, pentaerythritol, erythritol, sorbitol, mannitol, and the like and aromatic hydroxy compounds such as alkylated mono- and polyhydric phenols and naphthols, e.g., cresols, heptylphenols, dodecylphenols, dioctylphenols, triheptylphenols, resorcinol, pyrogallol, etc.

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

-CHCH_0- I

^R14

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

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

The polyoxyalkylene alcohol demulsifers should have an average molecular weight of 1000 to about 10,000, preferably about 2000 to about 7000. The ethyleneoxy groups (i.e,, -CH_CH_0-) normally will comprise from about 5 % to about 40% of the total average molecular weight. Those polyoxyalkylene polyols where the ethyleneoxy groups comprise from about 10% to about 30% of the total average molecular weight are especially useful. Polyoxyalkylene polyols having an average molecular weight of about 2500 to about 6000 where approximately 10%-20% by weight of the molecule is attributable to ethyleneoxy groups result in the formation of esters having particularly improved demulsifying properties. The ester and ether derivatives of these polyols are also useful.

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

H0-(CH2_oCH2_0)x(CiHCH_20)y(CH2„CH20) z-H

CH

wherein x, y and z are integers greater than 1 such that the -CH-CH-O- groups comprise from about 10% to about 15% by weight of the total molecular weight of the glycol, the average molecular weight of said polyols being from about 2500 to about 4500. This type of polyol can be prepared by reacting propylene glycol with propylene oxide and then with ethylene oxide. Another group of polyoxyalkylene alcohol demulsifiers illustrative of the preferred class discussed above are the commercially available liquid TETRONIC polyols sold by Wyandotte Chemicals Corporation. These polyols are represented by the general formula

Such polyols are described in U.S. patent No. 2,979,528 which is incorporated herein by reference. 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 alkylene diamine such as ethylene diamine, propylene diamine, hexamethylene diamine, etc., with propylene oxide until the desired weight of the hydropho¬ bic portion is reached. Then the resulting product is reacted with ethylene oxide to add the desired number of hydrophilic units to the molecules. Another commercially available polyoxyalkylene polyol demulsifier falling within this preferred group is Dow Polyglycol 112-2, a triol having an average molecular weight of about 4000-5000 prepared from propylene oxides and ethylene oxides, the ethyleneoxy groups comprising about 18% by weight of the triol. Such triols can be prepared by first reacting glycerol, TMC, TMP, etc., with propylene oxide to form a hydrophobic base and reacting that base with ethylene oxide to add hydrophilic portions.

Alcohols useful in this invention also include alkylene glycols and polyoxyalkylene alcohols such as polyoxyethylene _ alcohols, polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. These polyoxyalkylene alcohols (sometimes called polyglycols) can contain up to about 150 oxyalkylene groups and the alkylene radical contains from 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols are generally dihydric alcohols. That is, each end of the molecule terminates with a -OH group. In order for such polyoxyalkylene alcohols to be useful, there must be at least one such -OH group. However, the remaining -OH group can be esterified with a monobasic, aliphatic or aromatic carboxylic acid of up to about 20 carbon atoms such as acetic acid, propionic acid, oleic acid, stearic acid, benzoic acid, and the like. The monoethers of these alkylene glycols and polyoxyalkylene glycols are also useful. These include the monoaryl ethers, monoalkyl ethers, and monoaralkyl ethers of these alkylene glycols and polyoxyalkylene glycols. This group of alcohols can be represented by the general formula

where R and R are independently alkylene radicals of 2 to 8 carbon atoms; and R is aryl such as phenyl, lower alkoxy phenyl, or lower alkyl phenyl; lower alkyl such as ethyl, propyl, tertbutyl, pentyl, etc.; and aralkyl such as benzyl, phenylethyl, phenylpropyl, p-ethylphenylethyl, etc.; p is zero to about eight, preferably two to four. Polyoxyalkylene glycols where the alkylene groups are ethylene or propylene and p is at least two as well as the monoethers thereof as described above are very useful. The monohydric and polyhydric alcohols useful in this invention include monohydroxy and polyhydroxy aromatic compounds. Monohydric and polyhydric phenols and naphthols are preferred hydroxyaromatic compounds. These hydroxy-substituted aromatic compounds may contain other substituents in addition to the hydroxy substituents such as halo, alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like. Usually, the hydroxy aromatic compound will contain 1 to 4 hydroxy groups. The aromatic hydroxy compounds are illustrated by the following specific examples: phenol, p-chlorophenol, p-nitrophenol, beta-naphthol, alpha-naphthol, cresols, resorcinol, catechol, carvacrol, thymol, eugenol, p,p'-dihydroxy- biphenyl, hydroquinone, pyrogallol, phloroglucinol, hexylresorcinol, orcin, quaiacol, 2-chlorophenol, 2,4-dibutylphenol, propenetetramer-substituted phenol, didodecylphenol, 4,4'-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-naphthol, polyisobutenyl-(molecular weight of about 1000)-substituted phenol, the condensation product of heptylphenol with 0.5 moles of form ldehyde, the condensation product of octylphenol with acetone, di(hydroxyphenyl)oxide, di(hydroxyphenyl) sulfide, di(hydroxyphenyl)disulfide, and 4-cyclohexylphenol. Phenol itself and aliphatic hydrocarbon-substituted phenols, e.g, alkylated phenols having up to 3 aliphatic hydrocarbon substituents are especially preferred. Each of the aliphatic hydrocarbon substituents may contain 100 or more carbon atoms but usually will have from 1 to 20 carbon atoms. Alkyl and alkenyl groups are the preferred aliphatic hydrocarbon substituents. Further specific examples of monohydric alcohols which can be used include monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, 2,2,4-trimethyl-l-pentanol, behenyl alco¬ hol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, beta-phenylethyl alcohol, 2-methylcyclohexanol, beta-chloroethanol, monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, monododecyl ether of triethylene glycol, monooleate of ethylene glycol, monostearate of diethylene glycol, sec-pentyl alcohol, tertbutyl alcohol, 5-bromo-dodecanol, nitro-octadecanol, and dioleate of glycerol. Alcohols useful in this inven¬ tion may be unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, l-cyclohexene-3-ol, oleyl alcohol, 2,2,4-trimethyl-3-pentene-l-ol and 2,2,4-trimethyl-4- pentene-1-ol. Other specific alcohols useful in this invention are the ether alcohols and amino alcohols including, for example, the oxyalkylene, oxyarylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxyalkylene, aminoalkylene or amino-aryleneoxy-arylene radicals. They are exemplified by Cellosolve, carbitol, phenoxyethanol, heptylphenyl- (oxypropylene) ,--OH, octyl- (oxyethylene) -OH, phenyl- (oxyoctylene) ₂-OH, mono- (heptylphenyloxypropylene) -substituted glycerol, poly- (styreneoxide) , aminoethanol, 3-amino-ethylpentanol, di (hydroxyethyl) amine, p-aminophenol, tri (hydroxypropyl) amine, N-hydroxyethyl ethylenediamine, N,N,N' ,N'-tetra- hydroxy-trimethylenediamine, and the like.

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

Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glyerol, monomethyl ether of glycerol, pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methyl ester of 9, 10-dihydroxy stearic acid, neopentyl glycol, 2,2,4-trimethyl-l,3-pentanediol, 2 ,3-butanediol,

2,3-hexanediol, 2,4-hexanediol, pinacol , erythritol, arabitol, sorbitol, mannitol, 1 ,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugar, starches, celluloses, and so forth likewise can be used. The carbohydrates may be exemplified by glucose, fructose, lactose, sucrose, rhamnose, mannose, glyceraldehyde, and galactose.

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

A preferred class of alcohols suitable for use in this invention are those polyhydric alcohols containing up to about 12 carbon atoms, and especially those containing three to ten carbon atoms. This class of alcohols in¬ cludes glycerol, erythritol, pentaerythritol, dipenta- erythritol, glyconic acid, glyceraldehyde, glucose, arabinose, 2,2,4-trimethyl-l,3-pentanediol, 1,7-heptane- diol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexane- triol, 1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid, 2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decane- diol, digitalose, and the like. Aliphatic alcohols containing at least three hydroxyl groups and up to ten carbon atoms are particularly preferred.

Another preferred class of polyhydric alcohols for use in this invention are the polyhydric alkanols contain- ing three to ten carbon atoms and particularly, those containing three to six carbon atoms and having at least three hydroxyl groups. Such alcohols are exemplified by glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl-l,3-propanediol(tri- methylolethane) , 2-hydroxymethyl-2-ethyl-l,3-propanediol-

(trimethylolpropane) , 1,2,4-hexanetriol, and the like.

The amines useful in accordance with the present invention may contain alcoholic hydroxy substituents and alcohols that are useful can contain primary, secondary, or tertiary amino substituents. Thus, hydroxyamines can be categorized as both amine and alcohol provided they contain at least one primary or secondary amino group. If only tertiary amino groups are present, the amino alcohol belongs only in the alcohol category. Typically, the hydroxylamines are primary, secondary or tertiary alkanol amines or mixtures thereof. Such amines can be repre- sented, respectfully, by the formulae:

H₂N-R'-OH,

H

N-R'-OH and

R

N-R'-OH

wherein each R is independently a hydrocarbyl group of one to about eight carbon atoms or hydroxyl-substituted hydrocarbyl group of two to about eight carbon atoms and R' is a divalent hydrocarbyl group of about two to about 18 carbon atoms. The group -R'-OH in such formulae represents the hydroxyl-substituted hydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group. Typical- ly, it is an acyclic straight or branched alkylene group such as an ethylene,1,2-propylene,1,2-butylene,1,2- octadecylene, etc. group. Where two R groups are present in the same molecule they can be joined by a direct carbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples of such hetrocyclic amines include N-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and the like. Typically, however, each R is a lower alkyl group of up to 7 carbon atoms.

The hydroxyamines can also be ether N-(hydroxyl- substituted hydrocarbyl)amines. These are hydroxyl- substituted poly(hydrocarbyloxy) analogs of the above-described hydroxy amines (these analogs also include hydroxyl-substituted oxyalkylene analogs. Such N-(hydroxyl-substituted hydrocarbyl) amines can be conve¬ niently prepared by reaction of epoxides with afore- described amines and can be represented by the formulae:

H₂N-(R-O) H,

H

N- (R*0) H and

R-

R..

N (R'O) H

wherein x is a number from 2 to about 15 and R and R' are as described above. Polyamine analogs of these hydroxy amines, particu¬ larly alkoxylated alkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine) can also be used in accordance with the present invention. Such polyamines can be made by reacting alkylene amines (e.g., ethylenediamine) with one or more alkylene oxides (e.g., ethylene oxide, octadecene oxide) of two to about 20 carbons. Similar alkylene oxide-alkanol amine reaction products can also be used such as the products made by reacting the aforedescribed primary, secondary or tertiary alkanol amines with ethylene, propylene or higher epoxides in a 1:1 or 1:2 molar ratio. Reactant ratios and tempera¬ tures for carrying out such reactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines include N-(2-hydroxyethyl)ethylene diamine, N,N-bis(2- hydroxyethyl)-ethylene diamine, 1-(2-hydroxyethyl)pipera¬ zine, mono(hydroxypropyl)-substituted diethylene triamine, di (hydroxypropyl)-substituted tetraethylene pentamine, N- (3-hydroxybutyl)-tetra ethylene diamine, etc. Higher homologs obtained by condensation of the above illustrated hydroxy alkylene polyamines through amino radicals or through hydroxy radicals are likewise useful. Condensa- tion through amino radicals results in a higher amine accompanied by removal of ammonia while condensation through the hydroxy radical results in products containing ether linkages accompanied by removal of water. Mixtures of two or more of any of the aforedescribed mono- or polyamines are also useful.

Particularly useful examples of N-(hydroxy- substituted hydrocarbyl)amines include mono-, di-, and triethanol amine, diethylethanol amine, di- (3-hydroxy¬ propyl) amine, N-(3-hydroxybutyl) amine, N-(4-hydroxy- butyl) amine, N,N-di-(2-hydroxypropyl) amine, N-(2-hydroxyethyl) orpholine and its thio analog, N-(2-hydroxyethyl) cyclohexyl amine, N-3-hydroxycyclo- pentyl amine, o-, - and p-aminophenol, N-(hydroxyethyl) piperazine, N,N'-di(hydroxyethyl) piperazine, and the like. Preferred hydroxy amines are diethanolamine and triethanolamine.

Further amino alcohols are the hydroxy-substituted primary amines described in U.S. Patent 3,576,743 by the general formula

where R is a monovalent organic radical containing at least one alcoholic hydroxy group, according to this patent, the total number of carbon atoms in Ra will not exceed about 20. Hydroxy-substituted aliphatic primary amines containing a total of up to about 10 carbon atoms are particularly useful. Especially preferred are the polyhydroxy-substituted alkanol primary amines wherein there is only one amino group present (i.e., a primary amino group) having one alkyl substituent containing up to 10 carbon atoms and up to 6 hydroxyl groups. These alkanol primary amines correspond to Ra-NH z_. wherein Ra is a mono- or polyhydroxy-substituted alkyl group. It is desirable that at least one of the hydroxyl groups be primary. Trismethylolaminomethane is a particularly preferable hydroxy-substituted primary amine. Specific examples of the hydroxy-substituted primary amines include 2-amino-l-butanol, 2-amino-2-methyl-l-propanol, p-(beta- hydroxyethyl)-analine, 2-amino-l-propanol, 3-amino-l- propanol, 2-amino-2-methyl-l,3-propanediol, 2-amino-2- ethyl-1,3-propanediol, N-(beta-hydroxypropyl)-N'-(beta- aminoethyl)-piperazine, tris(hydroxymethyl)amino methane (also known as trismeth lolamino methane) , 2-amino-l- butanol, ethanolamine, 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-hydroxyethyl)-piperadine, 6-amino- 2-methyl-2-heptanol, 5-amino-l-pentanol, N-(beta-hydroxy- ethyl)-3,3-diamino propane, l,3-diamino-2-propanol, N-(beta-hydroxy ethoxyethyl)-ethylenediamine, and the like. For further description of the hydroxy-substituted primary amines contemplated as being useful as amines and/or alcohols, U.S. Patent 3,576,743 is incorporated herein by reference for its disclosure of such amines.

The reaction products produced by reacting the hydrocarbyl substituted succinic acid producing compound of this invention with alcohols are esters. Both acidic esters and neutral esters are contemplated as being within the scope of this invention. Acidic esters are those in which some of the carboxylic acid functions in the acylating reagents are not esterified but are present as free carboxyl groups. Obviously, acid esters are easily prepared by using an amount of alcohol insufficient to esterify all. of the carboxyl groups in the acylating reagents of this invention. The hydrocarbyl substituted succinic acid producing compound is reacted with the alcohols according to conventional esterification techniques. It normally involves heating a mixture of the hydrocarbyl substituted succinic acid producing compound of this invention with the alcohol, optionally in the presence of a normally liquid, substantially inert, organic liquid solvent/diluent and/or in the presence of esterification catalyst. Temperatures of at least about 100°C up to the decomposition point are used (the decomposition point having been defined hereinbefore) . This temperature is usually within the range of about 100°C up to about 300°C with temperature of about 140°C to 250°C often being employed. Usually, at least about one-half equivalent of alcohol is used for each equivalent of the acylating agents. An equivalent of such acylating reagents is the same as discussed above with respect to reaction with amines. An equivalent of alcohol is its molecular weight divided by the total number of hydroxyl groups present in the molecule. Thus, an equivalent weight of ethanol is its molecular weight while the equivalent weight of ethylene glycol is one-half its molecular weight. The amino-alcohols have equivalent weights equal to the molecular weight divided by the total number of hydroxy groups and nitrogen atoms present in each molecule.

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

Suitable substantially inert, organic liquid solvents or diluents may be used in the reaction processes of the present invention and include such relatively low boiling liquids as hexane, heptane, benzene, toluene, xylene, etc., as well as high boiling materials such as solvent neutral oils, bright stocks, and various types of synthet¬ ic and natural lubricating oil base stocks. Factors governing the choice and use of such materials are well known to those of skill in the art. Normally such diluents will be used to facilitate heat control, han¬ dling, filtration, etc. It is often desirable to select diluents which will be compatible with the other ateri- als, which are to be present in the environment where the product is intended to be used.

As used in the specification and appended claims, the term "substantially inert" when used to refer to solvents, diluents, and the like, is intended to mean that the solvent, diluent, etc., is inert to chemical or physical change under the conditions in which it is used so as not to materially interfere in an adverse manner with the preparation, storage, blending and/or functioning of the compositions, additives, compounds, etc., of this invention in the context of its intended use. For exam¬ ple,- small amounts of a solvent, diluent, etc., can undergo minimal reaction or degradation without preventing the making and using of the invention as described herein. In other words, such reaction or degradation, while technically discernible, would not be sufficient to deter the practical worker of ordinary skill in the art from making and using, the invention for its intended purposes. "Substantially inert" as used herein is, thus, readily understood and appreciated by those of ordinary skill in the art.

As previously described, substantially inert organic liquid solvents or diluents may be used in this reaction. The compositions of this invention can be recovered from such solvent/diluents by such standard procedures as distillation, evaporation, and the like, when desired. Alternatively, if the solvent/diluent is, for example, a base oil suitable for use in a functional fluid, the product can be left in the solvent/diluent and used to form the lubricating, fuel or functional fluid composition as described below. The reaction mixture can be purified by conventional means (e.g., filtration, centrifugation, etc.), if desired.

The preparation of component (C) is illustrated by the following specific examples. In these examples, as well as elsewhere in the specification and appended claims, the molecular weights are number average molecular weights (Mn) as determined by gel permeation chromatography (GPC) .

Example C-l

A mixture of 5365 parts of a commercial Cl.o _c—l .o_ alpha-olefin available from Gulf Oil Company and 108 parts of di-t-butyl peroxide is heated to 130°C for 4 hours. 54 parts of di-t-butyl peroxide are added to the reaction mixture which is maintained at 130°C. 54 part samples of di-t-butyl peroxide are added to the reaction mixture seven more times at two-hour intervals between each addition. The reaction mixture is heated to 150°C for one hour. The resulting product is a polymer of C.l,—l_.₀ alpha-olefins (n_inh=0.063 (0.5 grams/100 ml. CC1₄, 30°C)).

Example C-2

A mixture of 1800 parts of the polymer prepared in Example C-l and 211 parts of maleic anhydride is heated to

190°C. The reaction mixture is maintained at 190-235°C for 20 hours. The reaction mixture is blown with nitrogen at 230°C to remove unreacted maleic anhydride. Example C-3 A mixture of 4800 parts of polyisobutylene with a number average molecular weight of 300 and 1568 parts of maleic anhydride are heated at 220°C to 240°C for 30 hours. The reaction mixture is vacuum distilled at 200-320°C and 0.4-0.7 mm. Hg. to yield the desired product.

Example C-4

A mixture of 800 parts of the product of Example C-2, 89 parts of the product of Example C-3, 92.4 parts of ethylene polyamine with a nitrogen content of 32.3%, and 264 parts xylene are heated at the reflux of xylene for 5 hours. Xylene is gradually removed until the temperature reaches 170°C. The temperature is maintained at 170°C for two hours. The mixture is diluted with toluene. A solvent refined 100 neutral oil is added and the mixture is filtered to yield an oil-containing solution of 60% of the desired nitrogen-containing product.

Example C-5 A mixture of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020; Mw = 6049) and 115 parts (1.17 moles) of maleic anhydride is heated to 110°C. This mixture is heated to 184^CC in 6 hours during which 85 parts (1.2 moles) of gaseous chlorine is added beneath the surface. At 184°-189°C an additional 59 parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is stripped by heating at 186°-190°C with nitrogen blowing for 26 hours. The residue is the desired polyisobutene-substituted succinic acylating agent having a saponification equivalent number of 87 as determined by ASTM procedure D-94.

Example C-6 A mixture is prepared by the addition of 57 parts (1.38 equivalents) of a commercial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms per molecule to 1,067 parts of mineral oil and 893 parts (1.38 equivalents) of the substituted succinic acylating agent prepared in Example C-2 at 140° to 145°C. The reaction mixture is heated to 155°C in 3 hours and stripped by blowing with'' nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.

As previously indicated, the compositions of this invention are also useful as additives for lubricants, in which they function primarily as detergent/dispersants. These compositions can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, stationary power engines and turbines and the like. Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions- can also benefit from the incorporation therein of the compositions of the present invention. .

Natural oils include animal oils and vegetable oils (e.g., lard oil, castor oil) as well as solvent-refined or acid-refined mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffin-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils. Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.); alkyl benzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl) benzenes, etc.); polyphenols (e.g., biphenyl, terphenyls, etc.); and the like. Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubri¬ cating oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic diester of tetraethylene glycol. Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol,, dodecyl alcohol, 2-ethylhexyl alcohol, pentaerythritol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid, and the like. Silicon-based oils such as the^* polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants (e.g., tetraethyl-silicate, tetraisopropyl-silicate, tetra- (2-ethylhexyl)-silicate, tetra-(4-methyl-2-tetraethyl)- silicate, tetra-(p-tert-butyphenyl)-silicate, hexyl-(4-methyl-2-pentoxy)-di-siloxane, poly(methyl) - siloxanes, poly-(methylphenyl)-siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans, and the like. Unrefined, refined and rerefined oils (and mixtures of each with each other) of the type disclosed hereinabove can be used in the lubricant compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purifi¬ cation treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except that they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those of skill in the art such as solvent extraction, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by process¬ es similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or repro¬ cessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.

The compositions of the present invention also comprise mixtures of the above described metal salt of a dihydrocarbylphosphorodithioic acid (A) and the metal overbased composition (B) with

(C) a reaction product of a composition pre¬ pared by reacting (i) a hydrocarbyl substituted succinic acid producing compound with at least about one-half equivalent, per equivalent of acid producing compound with

(ii) one or more amines, one or more alcohols, or a mixture of one or more amines and/or one or more alcohols. In a blend that contains a lubricating base oil, (A) , (B) and (C) are generally present in the following levels (A) at a phosphorus level from about 0.05% up to about 2%; (B) at a total base number level from about 0.1 up to about 10 and (C) when (C) (ii) is an amine at a nitrogen level of 0.01 to 0.5 and when (C) (ii) is an alcohol at a saponification number level of 0.5 to 10.

Preferably the % phosphorus level of (A) , the total base number of (B) and the nitrogen level of (C) when

(C) (ii) is an amine are 0.05 to 0.75, 1 to 10 and 0.01 to

0.25 respectively. When (C) (ii) is an alcohol, (C) is present at a saponification number level of 0.5 of 7.5.

Most preferably, these levels are 0.05 to 0.5, 2 to 10 and 0.01 to 0.1 respectively when (C) (ii) is an amine; or 0.5 to 5 when (C) (ii) is an alcohol.

The invention also contemplates the use of other additives. Such additives include, for example, auxiliary detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, viscosity improving agents, extreme pressure agents, color stabilizers and anti-foam agents

An API SF/CC, oil blend is prepared by blending the following into a mineral oil (SAE 15W40 base):10% hydrogenated styrene/isoprene non-dispersant viscosity improver, 0.2% pour point depressant, 4.2% of the product of Example C-6 , 0.45% zinc salt of mixed isobutyl- and primary amyl phosphorodithioic acids, 0.1% alkylated aryl amine, 1.8% of the product of Example B-17, 1.15% of the product of Example B-18, 1.1% of the product of Example A-2 and 100 ppm of a silicone anti-foam agent. When evaluated in the Caterpillar 1G-2 engine test, a TGF = 77 and WTD = 233.0 rating is observed after a 480 hour test period.

While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

CLAIMS :

1. A composition comprising a lubricating base oil having dissolved therein a combination of:

(A) a metal salt of a dihydrocarbylphosphoro- dithioic acid of the formula

R— C— CH₂— R₃

wherein R, , R₂ and R₃ are independently aliphatic or aromatic groups;

(B) a metal overbased organic acid composition, and (C) a composition prepared by reacting

(i) a hydrocarbyl substituted succinic acid producing compound with

2. The composition according to claim 1 wherein R, , R₂ and R_ are alkyl groups containing from 1 to about 16 carbon atoms.

3. The composition according to claim 2 wherein R, , R and R, are alkyl groups containing from 1 to about 10 carbon atoms.

4. The composition according to claim 3 wherein R, , R₂ and R, are alkyl groups containing from 1 to about

6 carbon atoms.

5. The composition according to claim 4 wherein R, and R^ are methyl or ethyl groups.

6. The composition according to claim 5 wherein R₁ and R., are methyl groups and R₂ is an isobutyl group.

7. The composition according to claim 1 wherein the metal for (A) is selected from the group consisting of alkali metals, alkaline earth metals, antimony, tin, transition metals and combinations thereof.

8. The composition according to claim 7 wherein the transition metals are selected from the group consisting of zinc, manganese, nickel, cobalt, copper, iron and combinations thereof.

9. The composition according to claim 1 wherein the metal overbased composition (B) is a sulfonate, a carboxylate, a phenate, a salicylate, or mixtures thereof.

10. The composition according to claim 9 wherein (B) is a metal overbased sulfonate derived from an alkylated aryl sulfonic acid wherein the alkyl group has at least about 15 carbon atoms.

11. The composition according to claim 10 wherein the metal is an alkali or alkaline earth metal.

12. The composition according to claim 11 wherein the alkaline earth metal is calcium or magnesium.

13. The composition according to claim 11 wherein the alkali metal is sodium.

14. The composition according to claim 9 wherein (B) is a metal overbased carboxylate derived from fatty acids having at least about 12 aliphatic carbon atoms.

15. The composition according to claim 14 wherein the metal is calcium, magnesium or zinc.

16. The composition according to claim 9 wherein (B) is a metal overbased phenate derived from the reaction of an alkylated phenol wherein the alkyl group has at least about 6 carbon atoms with formaldehyde.

17. The composition according to claim 16 wherein the metal is sodium, calcium or magnesium.

18. The composition according to claim 16 wherein the phenate is derived from the reaction of an alkylated phenol wherein the alkyl group has at least about 6 aliphatic carbon atoms, with a sulfurization agent.

19. The composition according to claim 18 wherein the metal is sodium, calcium or magnesium.

20. The composition according to claim 16 wherein the phenate is derived from the reaction of an alkylated phenol having at least about 6 aliphatic carbon atoms with a sulfurization agent and formaldehyde.

21. The composition according to claim 20 wherein the metal is sodium, calcium or magnesium.

22. The composition according to claim 1 wherein the succinic acid-producing compound of (C) (i) contains an average of at least about 50 aliphatic carbon atoms in the hydrocarbyl substituent.

23. The composition according to claim 1 wherein the succinic acid-producing compound of (C) (i) is selected from the group consisting of succinic acids, anhydrides, esters and halides.

24. The composition according to claim 1 wherein the hydrocarbyl substituent of the succinic acid-producing compound of (C) (i) is derived from a polyolefin having an Mn value within the range of from about 700 to about 10,000.

25. The composition according to claim 1 wherein component (C) (ii) is an alkylene polyamine of the formula

_H__N (Alkylene-N-) - R" 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 "Alkylene" group has from about 1 to about 10 carbon atoms.

26. The composition according to claim 1 wherein component (C) (ii) is a polyoxyalkylene alcohol wherein a hydroxy-substituted compound, which is represented by the formula

wherein q is an integer of from 1 to 6 and R.. is the residue or a mono- or polyhydric alcohol or mono- or polyhydroxy phenol or naphthol, is reacted with an alkylene oxide, which is represented by the formula CH CH-

^{^}12 \ / ^13

O

wherein R..- is an alkyl group of up to about 4 carbon atoms and R. _ is hydrogen or an alkyl group of up to about 4 carbon atoms with the proviso that the alkylene oxide does not contain in excess of about 10 carbon atoms, to form a hydrophobic base, said hydrophobic base then being reacted with ethylene oxide to produce said polyoxyalkylene alcohol.

27. The composition according to claim 1 wherein component (C) (ii) is a monohydroxy aromatic compound or a polyhydroxy aromatic compound.

28. The composition according to claim 1 wherein component (C) (ii) is a hydroxy-substituted primary amine of the formula

wherein Rct is a monovalent organic group containing at least one hydroxy group, the total number of carbon atoms in Rct not exceeding about 20.

29. The composition according to claim 1 wherein component (C) (ii) is selected from the group consisting of (a) primary, secondary and tertiary alkanol amines which can be represented correspondingly by the formulae

H H R —R'—-OH, N—R'—OH and N—R^»—OH

H-^^ R-^ -BT

(b) hydroxyl-substituted oxyalkylene analogs of said alkanol amines represented by the formulae

wherein each R is independently a hydrocarbyl group of 1 to about 8 carbon atoms or hydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms or hydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms, R' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, (c) mixtures of two or more thereof and x is a number from 2 to about 15.

30. A composition comprising a lubricating base oil having dissolved therein a combination of

(A) a metal salt of a dihydrocarbylphosphoro¬ dithioic acid of the formula

aliphatic

wherein the aliphatic group contains from about 3 to aobut 22 carbon atoms; R-, R_ and R_ are aliphatic groups and independently contain from 1 to about 10 carbon atoms,

(B) a metal overbased composition selected from the group consisting of a sulfonate and a carboxylate, and

(C) a composition prepared by reacting

(i) a hydrocarbyl substituted succinic acid producing compound with

31. The composition according to claim 30 wherein R.. , R₂ and R_ are alkyl groups containing from 1 to 6 carbon atoms.

32. The composition according to claim 31 wherein R_ and R_ are methyl groups and R₂ is an isobutyl group.

33. The composition according to claim 30 wherein the metal for (A) is a transition metal.

34. The composition according to claim 33 wherein the metal is copper.

35. The composition according to claim 30 wherein the metal overbased composition (B) is a sulfonate derived from an alkylated aryl sulfonic acid wherein the alkyl group has at least about 15 carbon atoms.

36. The composition according to claim 35 wherein the metal is an alkali or alkaline earth metal.

37. The composition according to claim 36 wherein the alkali metal is sodium.

38. The composition according to claim 36 wherein the alkaline earth metal is magnesium or calcium.

39. The composition according to claim 30 wherein the metal overbased carboxylate (B) is derived from fatty acids having at least about 12 aliphatic carbon atoms.

40. The composition according to claim 39 wherein the metal is calcium, magnesium or zinc.

41. The composition according to claim 30 wherein the succinic acid producing compound (C) (i) contains an average of at least about 50 aliphatic carbon atoms.

42. The composition according to claim 30 wherein the succinic acid producing compound (C) (i) is a succinic acid or anhydride.

43. The composition according to claim 30 wherein component (C) (ii) is an alkylene polyamine of the formula

H-N (Alkylene-N-) R"

R" R

44. The composition according to claim 30 wherein component (C) (ii) is a polyoxyalkylene alcohol wherein a hydroxy-substituted compound, which is represented by the formula

11 q

wherein q is an integer of from 1 to 6 and R is the residue or a mono- or polyhydric alcohol or mono- or polyhydroxy phenol or naphthol, is reacted with an alkylene oxide, which is represented by the formula

R.1"Tϊ CsHT—— yCH———R.1. 0

wherein R₁₂ is an alkyl group of up to about 4 carbon atoms and R, , is hydrogen or an alkyl group of up to about 4 carbon atoms with the proviso that the alkylene oxide does not contain in excess of about 10 carbon atoms, to form a hydrophobic base, said hydrophobic base then being reacted with ethylene oxide to produce said polyoxyalkylene alcohol.

45. The composition according to claim 30 wherein component (C) (ii) is a monohydroxy aromatic compound or a polyhydroxy aromatic compound.

46. The composition according to claim 30 wherein component (C) (ii) is a hydroxy-substituted primary amine of the formula

R_a-NH₂

47. The composition according to claim 30 wherein component (C) (ii) is selected from the group consisting of (a) primary, secondary and tertiary alkanol amines which can be represented correspondingly by the formulae

X H

48. A lubricating composition according to claim 1 comprising an oil of lubricating viscosity, a phosphorus level of (A) of from about 0.05-2.0%, a total base number level of (B) of from about 0.1-10, a nitrogen level of (C) of from about 0.01-0.5 when (C) (ii) is an amine or a saponification number level of (C) of from about 0.5-10 when (C) (ii) is an alcohol.

49. A lubricating composition according to claim 30 comprising an oil of lubricating viscosity, a phosphorus level of (A) of from about 0.05-2.0%, a total base number level of (B) of from about 0.1-10, a nitrogen level of (C) of from about 0.01-0.5 when (C) (ii) is an amine or a saponification number level of (C) of from about 0.5-10 when (C) (ii) is an alcohol.