BACKGROUND OF THE INVENTION

A functional fluid is a term which encompasses a variety of fluids including, but not limited to, tractor fluids, automatic transmission fluids, manual transmis¬ sion fluids, hydraulic fluids, power steering fluids, fluids related to power train components and fluids which have the ability to act in various different capacities. It should be noted that within each of these fluids such as, for example, automatic transmission fluids, there are a variety of different types of fluids due to the various transmissions having different designs which have led to the need for fluids of markedly different functional characteristics. One type of functional fluid is gener¬ ally known as a tractor fluid which can be used in connection with various types of tractor equipment in order to provide for the operation of the transmission, gears, bearings, hydraulics, power steering, mechanical power take off and oil immersed brakes of the tractor.

The components included within a functional fluid such as a tractor fluid must be carefully chosen so that the final resulting fluid composition will provide all the necessary characteristics required and pass a variety of different types of tests. In general, a tractor fluid

must act as a lubricant, a power transfer means and a heat transfer means.

Tractor fluids have a number of important specific characteristics which provide for their ability to operate within tractor equipment. Such characteristics include the ability to provide proper frictional proper¬ ties for preventing wet brake chatter of oil immersed brakes while simultaneously providing the ability to actuate wet brakes and provide power take-off (PTO) clutch performance. A tractor fluid must provide suffi¬ cient antiwear and extreme pressure properties as well as water tolerance/filterability capabilities.

The extreme pressure (EP) properties of tractor fluids are demonstrated by the ability of the fluid to pass a spiral bevel test as well as a straight spur gear test. The tractor fluid must pass wet brake chatter tests as well as provide adequate wet brake capacity when used in oil immersed disk brakes which are comprised of a bronze, graphitic composition, asbestos and paper. The tractor fluid must demonstrate its ability to provide friction retention for power shift transmission clutches such as those clutches which include graphitic and bronze clutches.

U.S. Patent 4,783,274 (Jokinen et al, November 8, 1988) is concerned with hydraulic fluids based on oily triglycerides of fatty acids. This reference relates to the need for fluids for hydraulic purposes which are based on renewable natural resources, and which are, at the same time, environmentally acceptable. One such a natural base component for hydraulic fluids would be the oily triglycerides, which are esters of natural fatty acids with straight-chained alkyl, alkenyl, alkylamines and alkatrienyl chains having a length of commonly C_-C ₂₂ , and of glycerol, which triglycerides have an iodine number illustrating their degree of unsaturation, of at least 50 and not more than 128. The possibilities

- 3 -

to make hydraulic fluids by using the said triglycerides as the base component were investigated.

U.S. Patent 3,776,847 (Pearson et al, December 4, 1973) relates to a lubricating oil composition for the hot rolling of metals comprising (a) from about 50 to about 85% by weight of a natural fatty oil, (b) from about 0.1 to about 10% by weight of an alkaline earth metal salt of an oil-soluble sulfonic acid and (c) from about 5 to about 49.9% by weight of a mineral lubricating oil having a viscosity index of at least 50.

U.S. Patent 2,330,773 (Zimmer et al, September 28, 1943) relates to adding to a suitable mineral oil base stock a small amount of a high molecular weight, oxygen- containing polymer which is depoly erizable at high temperature without charring. Small amount of fatty materials may be, and preferably are, also present.

The oxygen-containing polymer should be of a high molecular weight, e.g., at least 1000 and may be 50,000, 100,000, or even considerably higher, although it must not be so high in molecular weight as to be insoluble in the mineral oil base stocks referred to. In general, these polymers are obtained by polymerizing, unsaturated monomeric chemical compounds, such as, esters, ethers, acids, etc. A particularly preferred class of polymers are those produced from esters of acrylic acid and alkyl derivatives thereof, such as methacrylic acid containing a methyl substituent in the alpha position, or other higher alkyl groups, such as, ethyl, propyl, etc. , in a similar position; these esters should be derived from monohydric alcohols preferably containing more than 4 carbon atoms, such as amyl, hexyl, heptyl, octyl, lauryl, cetyl, octadecyl, etc. Such acrylic compounds contain the group CH -C, and have attached to this latter carbon atom a carboxylic ester group and either a hydrogen or a hydrocarbon group, such as, an alkyl or aryl group.

U.S. Patent 2,389,227 (Wright, November 20, 1945) involves the blending of a viscose hydrocarbon oil, such

as a petroleum lubricating oil fraction, with a non-dry¬ ing viscous oxidized or thickened fatty oil and with a small amount of an oxygen-containing high molecular weight polymer which normally is substantially solid. By a proper selection and proportioning of these ingredi¬ ents, a blend can be obtained having suitable viscosity and pour point characteristics to assure proper flowing and penetration and which protectively stays on rubbing surfaces under severe operating conditions.

U.S. Patent 2,413,353 (Hunter et al, December 31, 1946) relates to improved cutting oil compositions.

Various types of fixed fatty oils may be used in the cutting oil compositions of this reference. These oils are intended primarily to increase the oiliness or lubricity of the resultant composition and are customari¬ ly used in amounts corresponding to 0.5 to 15.0 per cent by weight. Lard oil is particularly satisfactory for this purpose. However, other animal oils such as tallow oil, neat's-foot oil, sperm oil, wool oil, whale oil and the like may be used. Also certain fish and vegetable oils may be used. The fish oils are generally less advantageous due to their offensive odor and the vegeta¬ ble oils are likewise less advantageous because of their tendency to oxidize and form gum at the temperatures encountered in cutting operations. However, by the use of a sufficient amount of oxidation inhibitor this defect may be minimized, and vegetable oils such as olive oil, rapeseed oil, corn oil and castor oil may be used.

U.S. Patent 3,640,860 (Miller, February 8, 1972) is concerned with a lubricating composition suitable for use in the continuous casting of metals. More specifically, this reference is concerned with a composition useful for lubricating the metal-mold interface during the continu¬ ous casting of metals, which composition contains both dimer and trimer of an unsaturated fatty acid, a glyceride oil, especially a triglyceride, as a εolubilizing agent, and a mineral lubricating oil

component low in carbon residue and aromatic carbon content. The mineral lubricating oil can be made by a two-state catalytic hydrogenation process.

SUMMARY OF THE INVENTION A functional fluid, especially in the form of a tractor fluid, is disclosed which is comprised of

(A) at least one triglyceride;

(B) at least one detergent-inhibitor additive; and

(C) at least one viscosity modifying additive.

The functional fluid may also include (D) at least one synthetic ester base oil. Specific amounts and ranges of the above components are described below.

A primary object of this invention is to provide a functional fluid possessing a wide variety of different functional characteristics especially when used as a tractor fluid.

Another object of this invention is to provide a functional fluid capable of passing a wide variety of different tests with respect to characteristics such as EP/antiwear characteristics, water tolerance, brake capacity and chatter and filterability.

Still another object of the invention is to simulta¬ neously provide improved performance in the areas of improved low temperature fluidity/filterability, EP/antiwear performance, friction improving properties, wet brake chatter suppression, and capacity with respect to actuating hydraulics, transmissions, power steering and braking without harming performance in other areas.

Yet another object is to increase performance with respect to EP/antiwear performance without having an undesirable effect on corrosion testing and transmission performance.

Still another object is to provide improved water tolerance by including surfactants while not limiting EP performance.

Other objects of this invention include providing a functional fluid capable of passing a wide variety of different tests with respect to characteristics such as frictional characteristics, low temperature fluidity, seal swell characteristics, antifoaming characteristics, antioxidation characteristics and EP protection as demonstrated by spiral bevel and straight spur gear testing.

Another object is to provide sufficient power steering performance while simultaneously providing sufficient transmission performance as demonstrated in Turbo Hydra-matic oxidation testing (a General Motors Corp. test) .

Another object is to provide a fluid which provides sufficient friction retention for power shift transmis¬ sion clutches and provides corrosion inhibition particu¬ larly with respect to yellow metal (i.e., copper, brass, bronze) corrosion while simultaneously providing improved EP performance, proper frictional properties for wet brake chatter suppression and simultaneously providing wet brake capacity and power takeoff clutch performance.

A further object of this invention is to provide improved biodegradability by utilizing a triglyceride rather than a mineral oil to pass such industry wide tests as the CEC L33-T82.

A primary object of this invention is to provide a functional fluid which includes its essential components such that the fluid simultaneously provides a variety of desirable characteristics.

These and other objects of the invention will become apparent to those skilled in the art upon reading this disclosure.

DETAILED DESCRIPTION OF THE INVENTION The present invention is produced and sold in the form of the functional fluid final product which can be included in various mechanical devices such as tractors.

The essential components of the present functional fluid are: (A) at least one triglyceride; (B) at least one detergent-inhibitor additive; and (C) at least one viscosity modifying additive. An additional component (D) at least one synthetic ester base oil may also be included.

(A) The Triglyceride

The triclycerides of this invention are either a synthetic or naturally occurring triglyceride. Preferred is the naturally occurring triglyceride. The triglycerides are of the general formula

are are esters having a straight chain fatty acid moiety and a glycerol moiety wherein the fatty acid moiety contains R1, R2 and R3 which are saturated or unsaturated aliphatic hydrocarbon groups containing from about 8 to about 22 carbon atoms, preferably from about 12 to 22 carbon atoms.

Naturally occurring triglycerides having utility in this invention are exemplified by corn oil, cottonseed oil, peanut oil, olive oil, palm oil, palm kernel oil, sunflower oil, high oleic sunflower oil, coconut oil, safflower oil, rapeseed oil, low erucic rapeseed oil, canola oil, soybean oil, lard oil, beef tallow oil, and menhaden oil. Preferred is rapeseed oil, especially low erucic rapeseed oil.

(B) The Deterσent-Inhibitor Additive

This invention contemplates utilizing a detergent- inhibitor additive that preferably is free from phospho¬ rus and zinc and comprises at least one metal overbased composition B-l and/or at least one carboxylic dispersant composition B-2, diary1 amine B-3, sulfurized composition B-4 and metal passivator B-5. The purpose of the detergent-inhibitor additive is to provide a multi¬ purpose power transmission fluid capable of maintaining cleanliness of mechanical parts, providing anti-wear and extreme pressure gear protection, anti-oxidation performance and corrosion while also effecting proper frictional properties on all clutches and wet brakes.

fB-l) The Metal Overbased Composition

These overbased salts of organic acids are widely known to those of skill in the art and generally 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" "neu¬ tral" 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, mix¬ tures 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 basically 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 used as (B-l) in this invention usually have metal ratios of at least about 3:1. Typi¬ cally, they have ratios of at least about 12:1. Usually they have metal ratios not exceeding about 40:1. Typi¬ cally salts having ratios of about 12:1 to about 20:1 are used.

The basically reacting metal compounds used to make these overbased salts are usually an alkali or alkaline earth metal compound (i.e., the Group IA, IIA, and IIB metals excluding francium and radium and typically excluding rubidium, cesium and beryllium) although other basically reacting metal compounds can be used. Com¬ pounds of Ca, Ba, Mg, Na and Li, 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 be used in the present invention.

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

The carbocylic sulfonic acids 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:

[R _χ -T-(S0 ₃ ) _y ] ₂ M _b (II)

_[R 4 (S0 ₃ ) _a ] _dMb (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, R in

Formula III is an aliphatic radical containing at least about 15 carbon atoms and M is either a metal cation or

4 hydrogen. Examples of type of the R radical are alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R are groups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including polymerized C ₂ , C_, C., C _g , C _g , etc. , olefins containing from about 15 to 7000 or more carbon atoms.

4 . The groups T, R, and R n 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 are 210*F; petrolatum sulfonic acids; mono- and poly-wax substituted

sulfonic and polysulfonic acids of, e.g., benzene, naphthalene, phenol, diphenyl ether, napthalene 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 "bottoms" 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 12 substituents on the benzene ring. Dodecyl benzene bottoms, principally mixtures of mono-and di-dodecyl benzenes, are available as by-products from the manufac¬ ture of household detergents. 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 manufac¬ ture-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-Oth er "Encyclopedia of Chemical Technology", Second Edition, Vol. 19, pp. 291 at 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 intended that the term "petroleum sulfonic acids" or "petroleum sulfonates" includes all sulfonic acids or the salts thereof derived from petroleum products. A partic¬ ularly valuable group of petroleum sulfonic acids are the mahogany 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 IA, IIA and IIB overbased salts of the above-described synthetic and petroleum sulfonic acids are typically useful in making (B-l) of 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 8 carbon atoms and preferably at least 12 carbon atoms. Usually they have no more than about 400 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 aleic 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, commer¬ cially 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 400 aliphatic carbon atoms, g 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 f is an integer of from one to four with the proviso that R* and g 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 radical represented by Ar* will be a polyvalent nucleus derived from benzene or naphthalene such as phenylenes and naphthylene, e.g..

methyphenylenes, ethoxyphenylenes, nitrophenylenes, isopropylenes, hydroxyphenylenes, mercaptophenylenes, N, -diethylaminophenylenes, chlorophenylenes,

N,N-diethylaminophenylenes, chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes, and similar tri-, tetra-, pentavalent nuclei thereof, etc.

The R* groups are usually hydrocarbyl groups, preferably groups such as alkyl or alkenyl radicals. However, the R* groups can contain small number 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—, —0—, —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 ethylene-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*, f and g 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:

wherein R** in Formula VI is an aliphatic hydrocarbon i _t 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, i _t

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 salicyclic 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 salicyclic acids wherein the aliphatic hydrocarbon substituents are derived from polymerized ole ins, particularly polymer¬ ized lower 1-mono-olefins such as polyethylene, polypropylene, polyisobutylene, ethylene/-propylene copolymers and the like and having average carbon con¬ tents of about 30 to about 400 carbon atoms.

The carboxylic acids corresponding to Formulae IV-V 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.

Another type of overbased carboxylate salt used in making (B-l) of this invention are those derived from alkenyl succinates of the general formula:

(VII) R*—CHCOOH CH ₂ C00H

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-described 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 considered organic acids. Thus, overbased salts of phenols (generally known as phenates) are also useful in

making (B-l) of this invention are well known to those skilled in the art. The phenols from which these phenates are formed are of the general formula:

(VIII) (R*) _g (Ar*)—(XH) _f

wherein R*, g, Ar*, X and f have the same meaning and preferences are described hereinabove with reference to Formula IV. The same examples described with respect to Formula IV also apply.

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

(IX)

it it it wherein a is an integer of 1-3, b is of 1 or 2, z is 0 or 1, R in Formula IX is a hydrocarbyl-based substituent having an average of from 4 to about 400 aliphatic carbon

5 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 hereinabove with a sulfurizing agent such as sulfur, a sulfur halide, or sulfide or hydrosulfide salt. Tech¬ niques 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 overbased salts of the above- described carboxylic acids are typically useful in making (B-l) of this invention.

Component (B-l) may also be a borated complex of an overboard metal sulfonate, carboxylates or phenate. Borated complexes of this type may be prepared by heating the overboard metal sulfonate, carboxylate or phenate with boric acid at about 50"-100°C, the number of equivalents of boric acid being roughly equal to the number of equivaletnts of metal in the salt.

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

Example fB-D-1 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 solution of the basic calcium sulfonate filtered. The filtrate is found to have a calcium sulfate ash content of 16% and a metal ratio of 2.5. A mixture of 1305 parts of the above carbonated calcium petrosulfonate, 930 parts of mineral oil, 220 parts of methyl alcohol, 72 parts of isobutyl alcohol, and 38 parts of amyl alcohol is prepared, 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 character¬ ized by a calcium sulfate ash content of about 40% and a metal ratio of about 12.2.

Example (B-l)-2 A mineral oil solution of a basic, carbonated calcium complex is prepared by carbonating a mixture of an alkylated 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 suσcinic anhydride (having a saponification number of 100) at 25°C. The mixture is stirred, heated to 150 ^β C, held at that temper¬ ature for 0.5 hour, and filtered. The filtrate has a base number of 315 and contains 35.4% of mineral oil.

Example (B-l)-3 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-2 at 57*C. The mixture is stirred for 0.65 hour at 55 ^β -57*C, then at 152*-153*C for 0.5 hour and filtered at 105*C. The filtrate has a base number of 387 and con¬ tains 43.7% of mineral oil.

Example (B-l)-4 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 ^β -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 complex, there is added 50 parts of the polyisobutenyl succinic anhydride of Example B-2 and the mixture is heated to 150"C for one-half hour and then filtered to give a composition having a base number of 315.

Example (B-l)-5 A mixture comprising 1000 grams (1.16 equivalents) of an oil solution of an alkylbenzene sulfonic acid, 115 grams of mineral oil, 97 grams of lower alcohols de¬ scribed in Example (B-l)-l, 57 grams of calcium hydroxide (1.55 equivalents), and a solution of 3.4 grams CaCl_ in 7 grams water is reacted at a temperature of about 55"C for about 1 hour. The product is stripped by heating to 165*C at a pressure of 20 torr and filtered. The fil¬ trate is an oil solution of a basic, carbonated calcium sulfonate complex having a metal ratio of 1.2 and con¬ taining 8.0% of calcium sulfate ash, 3.4% of sulfur and a base number of 10.

Example (B-l)-6 A mixture of 2,576 grams of mineral oil, 240 grams (1.85 equivalents) of octyl alcohol, 740 grams (20.0 equivalents) of calcium hydroxide, 2304 grams (8 equiva¬ lents) of oleic acid, and 392 grams (12.3 equivalents) of

methyl alcohol is heated with stirring to a temperature about 50*C in about 0.5 hour. This mixture then is treated with C0 ₂ (3 cubic feet per hour) at 50'-60 ^β C for a period of about 3.5 hours. The resulting mixture is heated to 150*C and filtered. The filtrate is a basic calcium oleate complex having the following analyses:

Sulfate ash (%) 24.1

Metal ratio 2.5

Neutralization No. (acidic) 2.0

Example (B-l)-7

A reaction mixture comprising 1044 grams (about 1.5 equivalents) of an oil solution of an alkylphenyl sulfonic acid (average molecular weight -500) , 1200 grams of mineral 981, 2400 grams of xylene, 138 grams (about 0.5 equivalents) of tall oil acid mixture (oil-soluble fatty acid mixture sold by Hercules under the name PAMAK-4) , 434 grams (20 equivalents) of magnesium oxide, 600 grams of methanol, and 300 grams of water is carbon¬ ated at a rate of 6 cubic feet of carbon dioxide per hour at 65°-70 ^β C. (methanol reflux). The carbon dioxide introduction rate was decreased as the carbon dioxide uptake diminished. After 2.5 hours of carbonation, the methanol is removed and by raising the temperature of the mixture to about 95 ^β C with continued carbon dioxide blowing at a rate of about two cubic feet per hour for one hour. Then 300 grams of water is added to the reaction mixture and carbonation was continued at about 90°C. (reflux) for about four hours. The material becomes hazy with the addition of the water but clarifies after 2-3 hours of continued carbonation. The carbonated product is then stripped to 160*C at 20 torr and fil¬ tered. The filtrate is a concentrated oil solution (47.5% oil) of the desired basic magnesium salt, the salt being characterized by a metal ratio of about 10.

Example (B-l)-8

Following the general procedure of Example (B-l)-7 but adjusting the weight ratio of methanol to water in

the initial reaction mixture to 4:3 in lieu of the 2:1 ratio of Example (B-l)-7 another concentrated oil-solu¬ tion (57.5% oil) of a basic magnesium salt is produced. This ethanol-water ratio gives improved carbonation at the methanol reflux stage of carbonation and prevents thickening of the mixture during the 90"C carbonation stage.

Example (B-l)-9 A reaction mixture comprising 135 parts mineral oil, 330 parts xylene, 200 parts (0.235 equivalent) of a mineral oil solution of an alkylphenylsulfonic acid (average molecular weight - 425), 19 parts (0.068 equiva¬ lent) of the above-described mixture of tall oil acids, 60 parts (about 2.75 equivalents) of magnesium oxide, 83 parts methanol, and 62 parts water are carbonated at a rate of 15 parts of carbon dioxide per hour for about 2 hours at the methanol reflux temperature. The carbon dioxide inlet rate is then reduced to about 7 parts per hour and the methanol is removed by raising the tempera¬ ture to about 98"C over a 3 hour period. Then 47 parts of water are added and carbonation is continued for an additional 35. hours at a temperature of about 95"C. The carbonated mixture is then stripped by heating to a temperature of 140"-145 ^β C over a 2.5 hour period. This results in an oil solution of a basic magnesium salt characterized by a metal ratio of about 10.

Then, the carbonated mixture is cooled to about 60"-65*C and 208 parts xylene, 60 parts magnesium oxide, 83 parts methanol and 62 parts water are added thereto. Carbonation is resumed at a rate of 15 parts per hour for 2 hours at the methanol reflux temperature. The carbon dioxide addition rate is reduced to 7 parts per hour and the methanol is removed by raising the temperature to about 95*C over a 3 hour period. An additional 41.5 parts of water are added and carbonation is continued at 7 parts per hour at a temperature of about 90"-95'C for 3.5 hours. The carbonated mass is then heated to about

150°-160 ^β C over a 3.5-hour period and then further stripped by reducing the pressure to 20 torr at this temperature. The carbonated reaction product is then filtered. The filtrate is a concentrated oil-solution (31.6% oil) of the desired basic magnesium salt charac¬ terized by a metal ratio of 20.

Example (B-l)-10 To a solution of 790 parts (1 equivalent) of an alkylated benzenesulfonic acid and 71 parts of polybutenyl succinic anhydride (equivalent weight about 560) containing predominantly isobutene units in 176 parts of mineral oil is added 320 parts (8 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. The temperature of the mixture increases to 89"C (reflux) over 10 minutes due to exotherming. During this period, the mixture is blown with carbon dioxide at 4 cfh. (cubic feet/hr.). Carbonation is continued for about 30 minutes as the temperature gradually decreases to 74"C. The methanol and other volatile materials are stripped from the carbonated mixture by blowing nitrogen through it at 2 cfh. while the temperature is slowly increased to 150"C over 90 minutes. After stripping is completed, the remaining mixture is held at 155-165°C for about 30 minutes and filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 7.75. This solution contains 12.4% oil.

Example (B-l)-11 Following the procedure of Example (B-l)-10, a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 119 parts of the polybutenyl succinic anhydride in 442 parts of mineral oil is mixed with 800 parts (20 equivalents) of sodium hydroxide and 704 parts (22 equivalents) of methanol. The mixture is blown with carbon dioxide at 7 cfh. for 11 minutes as the temperature slowly increases to 95*C. The rate of carbon dioxide flow is reduced to 6 cfh. and the temperature decreases slowly to 88*C over about 40 minutes. The rate

of carbon dioxide flow is reduced to 5 cfh. for about 35 minutes and the temperature slowly decreases to 73 *C. The volatile materials are stripped by blowing nitrogen through the carbonated mixture at 2 cfh. for 105 minutes as the temperature is slowly increased to 160*C. After stripping is completed, the mixture is held at 160"C for an additional 45 minutes and then filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 19.75. This solution contains 18.7% oil.

Example (B-l)-12 Following the procedure of Example (B-l)-10 a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 86 parts of the polybutenyl succinic anhydride in 254 parts of mineral oil is mixed with 480 parts (12 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. The reaction mixture is blown with carbon dioxide at 6 cfh. for about 45 minutes. During this time the temperature increases to 95*C and then gradually decreases to 74"C. The volatile material is stripped by blowing with nitrogen gas at 2 cfh. for about one hour as the temperature is increased to 160"C. After stripping is complete the mixture is held at 160"C for 0.5 hour and then filtered to yield an oil solution of the desired sodium salt, having a metal ratio of 11.8. The oil content of this solution is 14.7%.

Example (B-l)-13 Following the procedure of Example (B-l)-10, a solution of 2800 parts (3.5 equivalents) of an alkylated benzenesulfonic acid and 302 parts of the polybutenyl succinic anhydride in 818 parts of mineral oil is mixed with 1680 parts (42 equivalents) of sodium hydroxide and 2240 parts (70 equivalents) of methanol. The mixture is blown with carbon dioxide for about 90 minutes at 10 cfh. During this period, the temperature increases to 96*C and then slowly drops to 76'C. The volatile materials are

stripped by blowing with nitrogen at 2 cfh. as the temperature is slowly increased from 76"C to 165 ^β C by external heating. Water is removed by vacuum stripping. Upon filtration, an oil solution of the desired basic sodium salt is obtained. It has a metal ratio of about 10.8 and the oil content is 13.6%.

Example (B-l)-14

Following the procedure of Example (B-l)-10 a solution of 780 parts (1.0 equivalent) of an alkylated benzenesulfonic acid and 103 parts of the polybutenyl succinic anhydride in 350 parts of mineral oil is mixed with 640 parts (16 equivalents of sodium hydroxide and 640 parts (20 equivalents) of methanol. This mixture is blown with carbon dioxide for about one hour at 6 cfh. During this period, the temperature increases to 95"C and then gradually decreases to 75"C. The volatile material is stripped by blowing with nitrogen. During stripping, the temperature initially drops to 70"C over 30 minutes and then slowly rises to 78"C over 15 minutes. The mixture is then heated to 155"C over 80 minutes. The stripped mixture is heated for an additional 30 minutes 15 155-160*C and filtered. The filtrate is an oil solu¬ tion of the desired basic sodium sulfonate, having a metal ratio of about 15.2. It has an oil content of 17.1%.

Example (B-l)-15

Following the procedure of Example (B-l)-10, a solution of 780 parts (1 equivalent) of an alkylated bnezenesulfonic acid and 119 parts of the polybutenyl succinic anhydride in 442 parts of mineral oil is mixed well with 800 parts (10 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. This mixture is blown with carbon dioxide for about 55 minutes at 8 cfh. During this period, the temperature of the mixture increases to 95*C and then slowly decreases to 67"C. The methanol and water are stripped by blowing with nitrogen at 2 cfh. for about 40 minutes while the temperature is

slowly increased to 160*C. After stripping, the tempera¬ ture of the mixture is maintained at 160-165 ' C tor about 30 minutes. The product is then filtered to give a solution of the corresponding sodium sulfonate having a metal ratio of about 16.8. This solution contains 18.7% oil.

Example (B-l)-16 Following the procedure of Example (B-l)-10, 836 parts (1 equivalent) of a sodium petroleum sulfonate (sodium "Petronate") in an oil solution containing 48 % oil and 63 parts of the polybutenyl succinic anhydride is heated to 60"C and treated with 280 parts (7.0 equiva¬ lents) of sodium hydroxide and 320 parts (10 equivalents) of methanol. The reaction mixture is blown with carbon dioxide at 4 cfh. for about 45 minutes. During this time, the temperature increases to 85*C and then slowly decreases to 74*C. The volatile material is stripped by blowing with nitrogen at 1 cfh. while the temperature is gradually increased to 160 ^β C. After stripping is com¬ pleted, the mixture is heated an additional 30 minutes at 160 ^• C, and then is filtered to yield the sodium salt in solution. The product has a metal ratio of 8.0 and an oil content of 22.2%.

Example (B-l)-17 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. Thereaf¬ ter, 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 materi¬ al is then heated to about 140*C for 6 to 7 hours at a reduced pressure of about 2-8 torr to remove substantial¬ ly all water. An additional 40 parts of mineral oil are

added to the reaction product and the resulting material is filtered. 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-l)-18 A solution of 3192 parts (12 equivalents) of a polyisobutene-substituted phenol, wherein the polyisobutene substituent has a molecular weight of about 175, in 2400 parts of mineral is heated to 70°C and 502 parts (12 equivalents) of solid sodium hydroxide is added. The material is blown with nitrogen at 162"C under vacuum to remove volatiles and is then cooled to 125 ^β C and 465 parts (12 equivalents of 40% aqueous formaldehyde is added. The mixture is heated to 146 ^β C under nitrogen, and volatiles are finally removed again under vacuum. Sulfur dichloride, 618 parts (6 equivalents) , is then added over 4 hours. Water, 1000 parts, is added at 70 ^β C and the mixture is heated to reflux for 1 hour. All volatiles are then removed under vacuum at 155"C and the residue is filtered at that temperature, with the addi¬ tion of a filter aid material. The filtrate is the desired product (59% solution in mineral oil) containing 3.56% phenolic hydroxyl and 3.46% sulfur.

Example (B-l)-19 A mixture of 319.2 parts (1.2 equivalents) of a tetrapropene-substituted phenol similar to that used in Example B-18, 240 parts of mineral oil and 45 parts (0.6 equivalent) of 40% aqueous formaldehyde solution is heated to 70"C, with stirring, and 100.5 parts (1.26 equivalents) of 50% aqueous sodium hydroxide is added over about 20 minutes, while the mixture is blown with nitrogen. Volatile materials are removed by stripping at 160*C, with nitrogen blowing and subsequently under vacuum. Sulfur dichloride, 61.8 parts (1.2 equivalents), is added below the surface of the liquid at 140 ^β -150 ^β C,

over 6 hours. The mixture is then heated at 145*C for one hour and volatile materials are removed by stripping under nitrogen at 160*C.

The intermediate thus obtained is filtered with the addition of a filter aid material, and 3600 parts (7.39 equivalents) thereof is combined with 1553 parts of mineral oil and 230 parts of the polyisobutenyl succinic anhydride of Example B-2. The mixture is heated to 67"C and there are added 142 parts of acetic acid, 1248 parts of methanol and 602 parts (16.27. equivalents) of calcium hydroxide. The mixture is digested for a few minutes and then blown with carbon dioxide at 60 ^β -65 ^β C. The carbon dioxide-blown material is stripped at 160°C to remove volatiles and finally filtered with the addition of a filter aid. The filtrate is the desired product contain¬ ing 1.68% sulfur and 16.83% calcium sulfate ash.

Example (B-l)-20

To a mixture of 3192 parts (12 equivalents) of tetrapropenyl-substituted phenol, 2400 parts of mineral oil and 465 parts (6 equivalents) of 40% aqueous formal¬ dehyde at 82'C, is added, over 45 minutes, 960 parts (12 equivalents) of 50% aqueous sodium hydroxide. Volatile materials are removed by stripping as in Example B-18, and to the residue is added 618 parts (12 equivalents) of sulfur dichloride over 3 hours. Toluene, 1000 parts, and 1000 parts of water are added and the mixture is heated under reflux for 2 hours. Volatile materials are then removed at 180'C by blowing with nitrogen and the intermediate is filtered.

To 1950 parts (4 equivalents) of the intermediate thus obtained is added 135 parts of the polyisobutenyl succinic anhydride of Example B-2. The mixture is heated to 51'C, and 78 parts of acetic acid and 431 parts of methanol are added, followed by 325 parts (8.8 equiva¬ lents) of calcium hydroxide. The mixture is blown with carbon dioxide and is finally stripped with nitrogen blowing at 158"C and filtered while hot, using a filter

aid. The filtrate is a 68% solution in mineral oil of the desired product and contains 2.63% sulfur and 22.99% calcium sulfate ash.

Example (B-l)-21

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 ^β 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 temperature of about 95 ^β C to 100"C for about 1-1/2 hours and subsequently stripped at a tempera¬ ture 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-l)-22

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 equivalent) 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 ^β -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 salts and is characterized by a sulfated ash content of 15.59% (sulfated ash) corresponding to 274% of the εtoichiometrically equivalent amount.

Example (B-1)-23 A substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have from 16 to 24 aliphatic carbon atoms is prepared by reacting approximately stoichiometric amounts of magnesi¬ um chloride with a substantially neutral potassium salt of said alkylated salicylic acid. A reaction mass comprising approximately 6580 parts by weight of a mineral oil solution containing about 6.50 equivalents of said substantially neutral magnesium salt of the alkylated salicylic acid and about 388 parts by weight of an oil mixture containing about 0.48 equivalent of an alkylated benzenesulfonic acid together with approximate¬ ly 285 parts by weight (14 equivalents) of a magnesium oxide and approximately 3252 parts by weight of xylene is added to a flask and heated to temperatures of about 55"C to 75*C. The reaction mass is then heated to about 82*C and approximately 780 parts by weight of water are added to the reaction which is subsequently heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 95*-100'C for about 1 hour and subsequently stripped at a temperature of about 170"C, under 50 torr and filtered. The filtrate compris¬ es the basic carboxylic magnesium salts and has a sulfated ash content of 15.7% (sulfated ash) correspond¬ ing to 276% of the stoichiometrically equivalent amount.

(B-2) Carboxylic Disoersant Composition

The composition of the present invention comprises (B-2) at least one carboxylic dispersant characterized by the presence within its molecular structure of (i) at least one polar group selected from acyl, acyloxy or hydrocarbylimidoyl groups, and (ii) at least one group in which a nitrogen or oxygen atom is attached directly to said group (i) , and said nitrogen or oxygen atom also is attached to a hydrocarbyl group. The structures of the polar group (i) , as defined by the International Union of P Puurree aanndd AApppplliieedd CChheemmiissttrryy,, aarree aass ffιollows (R represent- ing a hydrocarbon or similar group) :

Acyl: R ⁶ - 8

O Acyloxy: R 6 CI'

NR

Ii

Hydrocarbylimidoyl: R>

Group (ii) is preferably at least one group in which a nitrogen or oxygen atom is attached directly to said polar group, said nitrogen or oxygen atom also being attached to a hydrocarbon group or substituted hydrocar¬ bon group, especially an amino, alkylamino-, polyalkyleneamino-, hydroxy- or alkyleneoxy-substituted hydrocarbon group. With respect to group (ii) , the dispersants are conveniently classified as "nitrogen- bridged dispersants" and "oxygen-bridged dispersants" wherein the atom attached directly to polar group (i) is nitrogen or oxygen, respectively.

Generally, the carboxylic dispersants can be pre¬ pared by the reaction of a hydrocarbon-substituted succinic acid-producing compound (herein sometimes referred to as the "succinic acylating agent") with at least about one-half equivalent, per equivalent of acid-producing compound, of an organic hydroxy compound, or an amine containing at least one hydrogen attached to a nitrogen group, or a mixture of said hydroxy compound and amine. The carboxylic dispersants (B-2) obtained in this manner are usually complex mixtures whose precise composition is not readily identifiable. The nitrogen- containing carboxylic dispersants are sometimes referred to herein as "acylated amines". The compositions ob¬ tained by reaction of the acylating agent and alcohols are sometimes referred to herein as "carboxylic ester" dispersants. The carboxylic dispersants (B-2) are either oil-soluble, or they are soluble in the oil-containing lubricating and functional fluids of this invention.

The soluble nitrogen-containing carboxylic disper¬ sants useful as component (B-2) in the compositions of the present invention are known in the art and have been described in many U.S. patents including

3,172,892 3,341,542 3,630,904 3,219,666 3,444,170 3,787,374 3,272,746 3,454,607 4,234,435 3,316,177 3,541,012 The carboxylic ester dispersants useful as (B-2) also have been described in the prior art. Examples of patents describing such dispersants include U.S. Patents 3,381,022; 3,522,179; 3,542,678; 3,957,855; and 4,034,038. Carboxylic dispersants prepared by reaction of acylating agents with alcohols and amines or amino alcohols are described in, for example, U.S. Patents, 3,576,743 and 3,632,511.

The above U.S. patents are expressly incorporated herein by reference for their teaching of the preparation of carboxylic dispersants useful as component (B-2)

In general, a convenient route for the preparation of the nitrogen-containing carboxylic dispersants (B-2) comprises the reaction of a hydrocarbon-substituted succinic acid-producing compound ("carboxylic acid acylating agent") with an amine containing at least one hydrogen attached to a nitrogen atom (i.e., H-N<) . The hydrocarbon-substituted succinic acid-producing compounds include the succinic acids, anhydrides, halides and esters. The number of carbon atoms in the hydrocarbon substituent on the succinic acid-producing compound may vary over a wide range provided that the nitrogen-con¬ taining composition (B-2) is soluble in the lubricating compositions of the present invention. Thus, the hydro¬ carbon substituent generally will contain an average of at least about 30 aliphatic carbon atoms and preferably will contain an average of at least about 50 aliphatic carbon atoms. In addition to the oil-solubility considerations, the lower limit on the average number of carbon atoms in the substituent also is based upon the effectiveness of such compounds in the lubricating oil compositions of the present invention. The hydrocarbyl substituent of the succinic compound may contain polar groups as indicated above, and, providing that the polar groups are not present in proportion sufficiently large to significantly alter the hydrocarbon character of the substituent.

The sources of the substantially hydrocarbon substituent include principally the high molecular weight substantially saturated petroleum fractions and substan¬ tially saturated olefin polymers, particularly polymers of mono-olefins having from 2 to 30 carbon atoms. The especially useful polymers are the polymers of 1-mono- olefins such as ethylene, propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-l-heptene,

3-cyclohexyl-l-butene, and 2-methyl-5-propyl-l-hexene. Polymers of medial olefins, i.e., olefins in which the olefinic linkage is not at the terminal position.

likewise are useful. They are illustrated by 2-butene, 2-pentene, and 4-octene.

Also useful are the interpolymers of the olefins such as those illustrated above with other interpolymerizable olefinic substances such as aromatic olefins, cyclic olefins, and polyolefins. Such interpolymers include, for example, those prepared by polymerizing isobutene with styrene; isobutene with butadiene; propene with isoprene, ethylene with piperylene; isobutene with chloroprene; isobutene with p-methyl styrene; 1-hexene with 1,3-hexadiene; 1-octene with 1-hexene; 1-heptene with 1-pentene; 3-methyl-l-butene with 1-octene; 3,3-dimethyl-l-pentene with 1-hexene; isobutene with styrene and piperylene; etc.

The relative proportions of the mono-olefins to the other monomers in the interpolymers influence the stabil¬ ity and oil-solubility of the final products derived from such interpolymers. Thus, for reasons of oil-solubility and stability the interpolymers contemplated for use in this invention should be substantially aliphatic and substantially saturated, i.e., they should contain at least about 80%, preferably at least about 95%, on a weight basis of units derived from the aliphatic monoolefins and no more than about 5% of olefinic linkag¬ es based on the total number of carbon-to-carbon covalent linkages. In most instances, the percentage of olefinic linkages should be less than about 2% of the total number of carbon-to-carbon covalent linkages.

Specific examples of such interpolymers include copolymer of 95% (by weight) of isobutene with 5% of styrene; terpolymer of 98% of isobutene with 1% of piperylene and 1% of chloroprene; terpolymer of 95% of isobutene with 2% of 1-butene and 3% of 1-hexene, terpolymer of 80% of isobutene with 20% of 1-pentene and 20% of 1-octene; copolymer of 800% of 1-hexene and 20% of 1-heptene; terpolymer of 90% of isobutene with 2% of

cyclohexene and 8% of propene; and copolymer of 80% of ethylene and 20% of propene.

Another source of the substantially hydrocarbon group comprises saturated aliphatic hydrocarbons such as highly refined high molecular weight white oils or synthetic alkanes such as are obtained by hydrogenation of high molecular weight olefin polymers illustrated above or high molecular weight olefin polymers illustrat¬ ed above or high molecular weight olefinic substances.

The use of olefin polymers having molecular weights (Mn) of about 700-10,000 is preferred. Higher molecular weight olefin polymers having molecular weights (Mn) from about 10,000 to about 100,000 or higher have been found to impart also viscosity index improving properties to the final products of this invention. The use of such higher molecular weight olefin polymers often is desir¬ able. Preferably the substituent is derived from a polyolefin characterized by an Mn value of about 700 to about 10,000, and an Mw/Mn value of 1.0 to about 4.0.

In . preparing the substituted succinic acylating agents of this invention, one or more of the above-de¬ scribed polyalkenes is reacted with one or more acidic reactants selected from the group consisting of aleic or fumaric reactants such as acids or anhydrides. Ordinari¬ ly the maleic or fumaric reactants will be maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more of these. The maleic reactants are usually pre¬ ferred over the fumaric reactants because the former are more readily available and are, in general, more readily reacted with the polyalkenes (or derivatives thereof) to prepare the substituted succinic acid-producing compounds useful in the present invention. The especially pre¬ ferred reactants are maleic acid, maleic anhydride, and mixtures of these. Due to availability and ease of reaction, maleic anhydride will usually be employed.

For convenience and brevity, the term "maleic reactant" is often used hereinafter. When used, it

should be understood that the term is generic to acidic reactants selected from maleic and fumaric reactants including a mixture of such reactants. Also, the term "succinic acylating agents" is used herein to represent the substituted succinic acid-producing compounds.

One procedure for preparing the substituted succinic acylating agents useful in this invention is illustrated, in part, in U.S. Patent 3,219,666 which is expressly incorporated herein by reference for its teachings in regard to preparing succinic acylating agents. This procedure is conveniently designated as the "two-step procedure". It involves first chlorinating the polyalkene until there is an average of at least about one chloro group for each molecular weight of polyalkene.

(For purposes of this invention, the molecular weight of the polyalkene is the weight corresponding to the Mn value.) Chlorination involves merely contacting the polyalkene with chlorine gas until the desired amount of chlorine is incorporated into the chlorinated polyalkene.

Chlorination is generally carried out at a temperature of about 75"C to about 125"C. If a diluent is used in the chlorination procedure, it should be one which is not itself readily subject to further chlorination. Poly- and perchlorinated and/or fluorinated alkanes and benzenes are examples of suitable diluents.

The second step in the two-step chlorination proce¬ dure, for purposes of this invention, is to react the chlorinated polyalkene with the maleic reactant at a temperature usually within the range of about 100*C to about 200*C. The mole ratio of chlorinated polyalkene to maleic reactant is usually about 1:1. (For purposes of this invention, a mole of chlorinated polyalkene is that weight of chlorinated polyalkene corresponding to the Mn value of the unchlorinated polyalkene.) However, a stoichiometric excess of maleic reactant can be used, for example, a mole ratio of 1:2. If an average of more than about one chloro group per molecule of polyalkene is

introduced during the chlorination step, then more than one mole of maleic reactant can react per molecule of chlorinated polyalkene. Because of such situations, it is better to describe the ratio of chlorinated polyalkene to maleic reactant in terms of equivalents. (An equiva¬ lent weight of chlorinated polyalkene, for purposes of this invention, is the weight corresponding to the Εh value divided by the average number of chloro groups per molecule of chlorinated polyalkene while the equivalent weight of a maleic reactant is its molecular weight.) Thus, the ratio of chlorinated polyalkene to maleic reactant will normally be such as to provide about one equivalent of maleic reactant for each mole of chlorinat¬ ed polyalkene up to about one equivalent of maleic reactant for each equivalent of chlorinated polyalkene with the understanding that it is normally desirable to provide an excess of maleic reactant; for example, an excess of about 5% to about 25% by weight. Unreacted excess maleic reactant may be stripped from the reaction product, usually under vacuum, or reacted during a further stage of the process as explained below.

The resulting polyalkene-substituted succinic acylating agent is, optionally, again chlorinated if the desired number of succinic groups are not present in the product. If there is present, at the time of this subsequent chlorination, any excess maleic reactant from the second step, the excess will react as additional chlorine is introduced during the subsequent chlorina¬ tion. Otherwise, additional maleic reactant is intro¬ duced during and/or subsequent to the additional chlori¬ nation step. This technique can be repeated until the total number of succinic groups per equivalent weight of substituent groups reaches the desired level.

Another procedure for preparing substituted succinic acid acylating agents useful in this invention utilizes a process described in U.S. Patent 3,912,764 and U.K. Patent 1,440,219, both of which are expressly

incorporated herein by reference fro their teachings in regard to that process. According to that process, the polyalkene and the maleic reactant are first reacted by heating them together in a "direct alkylation" procedure. When the direct alkylation step is completed, chlorine is introduced into the reaction mixture to promote reaction of the remaining unreacted maleic reactants. According to the patents, 0.3 to 2 or more moles of maleic anhydride are used in the reaction for each mole of olefin polymer; i.e., polyalkylene. The direct alkylation step is conducted at temperatures of 180-250"C. During the chlorine-introducing stage, a temperature of 160-225"C is employed. In utilizing this process to prepare the substituted succinic acylating agents of this invention, it would be necessary to use sufficient maleic reactant and chlorine to incorporate at least 1.3 succinic groups into the final product for each equivalent weight of polyalkene.

Another process for preparing the substituted succinic acylating agents of this invention is the so-called "one-step" process. This process is described in U.S. Patents 3,215,707 and 3,231,587. Both are expressly incorporated herein by reference for their teachings in regard to that process.

Basically, the one-step process involves preparing a mixture of the polyalkene and the maleic preparing a mixture of the polyalkene and the maleic reactant con¬ taining the necessary amounts of both to provide the desired substituted succinic acylating agents of this invention. This means that there must be at least one mole of maleic reactant for each mole of polyalkene in order that there can be at least one succinic group for each equivalent weight of substituent groups. Chlorine is then introduced into the mixture, usually by passing chlorine gas through the mixture with agitation, while maintaining a temperature of at least about 140*C.

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

Usually, where the polyalkene is sufficiently fluid at 140" and above, there is no need to utilize an addi¬ tional substantially inert, normally liquid sol¬ vent/diluent in the one-step process. However, as explained hereinbefore, if a solvent/diluent is employed, it is preferably one that resists chlorination. Again, the poly- and perchlorinated and/or -fluorinated alkanes, cycloalkanes, and benzenes can be used for this purpose.

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

The minimum temperature at which the reaction in the one-step process takes place at a reasonable rate is about 140"C. thus, the minimum temperature at which the process is normally carried out is in the neighborhood of 140"C. the preferred temperature range is usually between about 160-220*C. Higher temperatures such as 250*C or even higher may be used but usually with little advantage. In fact, temperatures in excess of 220*C are often disadvantageous with respect to preparing the particular acylated succinic compositions of this inven¬ tion because they tend to "crack" the polyalkenes (that

is, reduce their molecular weight by thermal degradation) and/or decompose the maleic reactant. For this reason, maximum temperatures of about 200-210*C are normally not exceeded. The upper limit of the useful temperature in the one-step process is determined primarily by the decomposition point of the components in the reaction mixture including the reactants and the desired products. The decomposition point is that temperature at which there is sufficient decomposition of any reactant or product such as to interfere with the production of the desired products.

In the one-step process, the molar ratio of maleic reactant to chlorine is such that there is at least about one mole of chlorine for each mole of maleic reactant to be incorporated into the product. Moreover, for practi¬ cal reasons, a slight excess, usually in the neighborhood of about 5% to about 30% by weight of chlorine, is utilized in order to offset any loss of chlorine from the reaction mixture. Larger amounts of excess chlorine may be used but do not appear to produce any beneficial results.

The molar ratio of polyalkene to maleic reactant preferably is such that there is at least about one mole of maleic reactant for each mole of polyalkene. This is necessary in order that there can be at least 1.0 succinic group per equivalent weight of substituent group in the product. Preferably, however, an excess of maleic reactant is used. Thus, ordinarily about 5% to about 25% excess of maleic reactant will be used relative to that amount necessary to provide the desired number of succinic groups in the product.

The amines which are reacted with the succinic acid-producing compounds to form the nitrogen-containing compositions (B-2) may be monoamines and polyamines. The monoamines and polyamines must be characterized by the presence within their structure of at least one H-H< group. Therefore, they have at least one primary (i.e..

H ₂ N-) or secondary amino (i.e., 1 H-N<) group. The amines can be aliphatic, cycloaliphatic, aromatic, or heterocyclic, including aliphatic-substituted cycloaliphatic, aliphatic-substituted aromatic, aliphatic-substituted heterocyclic, cycloaliphatic-sub- stituted aliphatic, cycloaliphatic substituted aromatic, cycloaliphatic-substituted heterocyclic, aromatic-substi¬ tuted aliphatic, aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic-substituted alicyclic, and heteroσycliσ-substituted aromatic amines and may be saturated or unsaturated. 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 inven¬ tion. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl mercapto, nitro, interrupting groups such as -0- and -S- (e.g., as in such groups as -CH ₂ CH -X-CH ₂ CH ₂ - where X is -o- or -S-) . In general, the amine of (B-2) may be characterized by the formula

R ⁷ R ⁸ NH

wherein R 7 and R8 are each independently hydrogen or hydrocarbon, amino-substituted hydrocarbon, hydroxy-sub- stituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl and acylimidoyl ggrrooiups provided that only one of R 7 and R8 may be hydro- gen,

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

Aliphatic monoamines include mono-aliphatic and di-aliphatic substituted amines wherein the aliphatic groups can be saturated or unsaturated and straight or

.branched chain. Thus, they are primary or secondary aliphatic amines. Such amines include, for example, mono- and di-alkyl-substituted amines, mono- and di- alkenyl-substituted amines, and amines having one N- alkenyl substituent and one N-alkyl substituent and the like. The total number of carbon atoms in these aliphatic monoamines will, as mentioned before, normally not exceed about 40 and usually not exceed about 20 carbon atoms. Specific examples of such monoamines include ethylamine, diethylamine, n-butylamine, di-n- butylamine, allylamine, isobutyla ine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleyl- amine, N-methyl-octylamine, dodecyla ine, octadecyl- amine, and the like. Examples of cycloaliphatic-substi- tuted aliphatic amines, aromatic-substituted aliphatic amines, and heterocyclic-substituted aliphatic amines, include 2-(cyclohexyl)-ethylamine, benzylamine, phenethylamine, 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 heterocyclic-substituted cycloaliphatic monoamines include propyl-substituted cyclohexylamines, phenyl-sub- stituted cyclopentylamines, and pyranyl-substituted cyclohexyla ine.

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. Examples of aromatic monoamines include aniline.

di-(para-methylphenyl)amine, naphthylamine, N-N- butyl)-aniline, and the like. Examples of aliphatic-sub¬ stituted, cycloaliphatiσ-substituted, and heterocyclic- substituted aromatic monoamines are para-ethoxy-aniline, para-dodecylaniline, cyclohexyl-substituted naphthyl¬ amine, and thienyl-substituted aniline.

The polyamines from which (B-2) is derived include principally alkylene amines conforming for the most part to the formula

A-N-(alkylene-N) .-H A A wherein t is an integer preferably less than about 10, A is a hydrogen group or a substantially hydrocarbon group preferably having up to about 30 carbon atoms, and the alkylene group is preferably a lower alkylene group having less than about 8 carbon atoms. The alkylene amines include principally methylene amines, ethylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines. They are exemplified specifically by: ethylene diamine, triethylene tetramine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene) triamine. Higher homologues such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are useful.

The ethylene amines are especially useful. They are described in some detail under the heading "Ethylene Amines" in Encyclopedia of Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950) . Such compounds are prepared most conve¬ niently by the reaction of an alkylene chloride with ammonia. The reaction results in the production of somewhat complex mixtures of alkylene amines, including cyclic condensation products such as piperazines. These mixtures find use in the process of this invention. On

the other hand, quite satisfactory products may be obtained also by the use of pure alkylene amines. An especially useful alkylene amine for reasons of economy as well as effectiveness of the products derived there¬ from is a mixture of ethylene amines prepared by the reaction of ethylene chloride and ammonia and having a composition which corresponds to that of tetraethylene pentamine.

Hydroxyalkyl-substituted alkylene amines, i.e., alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are contem¬ plated for use herein. The hydroxyalkyl-substituted alkylene amines are preferably those in which the alkyl group is a lower alkyl group, i.e., having less than about 6 carbon atoms. Examples of such amines include N-(2-hydroxyethyl)ethylene diamine, N, N'-bis(2-hydroxy- ethyl)-ethylene diamine, 1 -(2-hydroxyethyl)piperazine, mono-hydroxypropyl)piperazine, di-hydroxypropyl- substituted tetraethylene pentamine, N-(3-hydroxypropyl)- tetramethylene diamine, and 2-heptadecy1-1-(2-hydroxy¬ ethyl)-imidazoline.

Higher homologues such as are obtained by condensa¬ tion of the above illustrated alkylene amines or hydroxy alkyl-substituted alkylene amines through amino radicals or through hydroxy radicals are likewise useful. It will be appreciated that condensation through amino radicals results in a high amine accompanied with removal of ammonia and that condensation through the hydroxy radi¬ cals results in products containing ether linkages accompanied with removal of water.

Heterocyclic mono- and polyamines can also be used in making the nitrogen-containing compositions (B-2) . As used herein, the terminology "heterocyclic mono- and polyamine(ε)" is intended to describe those heterocyclic amines containing at least one primary secondary amino group and at least one nitrogen as a heteroatom in the heterocyclic ring. However, as long as there is present

in the heterocyclic mono- and polyamines at least one primary or secondary amino group, the hetero-N atom in the ring can be a tertiary amino nitrogen; that is, one that does not have hydrogen attached directly to the ring nitrogen. Heterocyclic amines can be saturated or unsaturated and can contain various substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the total number of carbon atoms in the substituents will not exceed about 20. Heterocyclic amines can contain hetero atoms other than nitrogen, especially oxygen and sulfur. Obviously they can contain more than one nitrogen hetero atom. The 5- and 6-membered heterocyclic rings are preferred.

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

The nitrogen-containing composition (B-2) obtained by reaction of the succinic acid-producing compounds and the amines described above may be amine salts, amides, imides, i idazolines as well as mixtures thereof. To prepare the nitrogen-containing composition (B-2) , one or more of the succinic acid-producing compounds and one or more of the amines are heated, optionally in the presence of a normally liquid, substantially inert organic liquid solvent/diluent at an elevated temperature generally in the range of from about 80"C up to the decomposition point of the mixture or the product. Normally, tempera¬ tures in the range of about 100 ^β C up to about 300'C are utilized provided that 300*C does not exceed the decompo¬ sition point.

The succinic acid-producing compound and the amine are reacted in amounts sufficient to provide at least about one-half equivalent, per equivalent of acid-produc¬ ing compound, of the amine. Generally, the maximum amount of amine present will be about 2 moles of amine per equivalent of succinic acid-producing compound. For the purposes of this invention, an equivalent of the amine is that amount of the amine corresponding to the total weight of amine divided by the total number of nitrogen atoms present. Thus, octyl amine has an equiva¬ lent weight equal to its molecular weight; ethylene diamine has an equivalent weight equal to one-half its molecular weight; and aminoethyl piperazine has an equivalent weight equal to one-third its molecular weight. The number of equivalents of succinic acid-pro¬ ducing compound will vary with the number of succinic groups present therein, and generally, there are two equivalents of acylating reagent for each succinic group in the acylating reagents. Conventional techniques may be used to determine the number of carboxyl functions (e.g., acid number, saponification number) and, thus, the number of equivalents of acylating reagent available to react with amine. Additional details and examples of the

proσedures for preparing the nitrogen-containing composi¬ tions of the present invention by reaction of succinic acid-producing compounds and amines are included in, for example, U.S. Patents 3,172,892; 3,219,666; 3,272,746; and 4,234,435, the disclosures of which are hereby incorporated by reference.

Oxygen-bridged dispersants comprise the esters of the above-described carboxylic acids, as described (for example) in the aforementioned U.S. Patents 3,381,022 and 3,542,678. As such, they contain acyl or occasionally, acylimidoyl groups. (An oxygen-bridged dispersant containing an acyloxy group as the polar group would be a peroxide, which is unlikely to be stable under all conditions of use of the compositions of this invention.) These esters are preferably prepared by conventional methods, usually the reaction (frequently in the presence of an acidic catalyst) of the carboxylic acid-produσing compound with an aromatic compound such as a phenol or naphthol. The preferred hydroxy compounds are alcohols containing up to about 40 aliphatic carbon atoms. These may be monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, neopentyl alcohol, monomethyl ester of ethylene glycol and the like, or polyhydric alcohols including ethylene glycol, diethylene glycol, dipropylene glycol, tetramethylene glycol, pentaerythritol, tris-(hydroxymethyl)aminomethane (THAM) , glycerol and the like. Carbohydrates (e.g., sugars, starches, cellulose) are also suitable as are partially esterified derivatives of polyhydric alcohols having at least three hydroxy groups.

The reaction is usually effected at a temperature above about 100*C and typically at 150-300 ^* C. the esters may be neutral or acidic, or may contain unesterified hydroxy groups, according as the ratio or equivalents of acid-producing compound to hydroxy compound is equal to, greater than or less than 1:1.

As will be apparent, the oxygen-bridged dispersants are normally substantially neutral or acidic. They are among the preferred ester dispersants for the purposes of this invention.

It is possible to prepare mixed oxygen- and nitro¬ gen-bridged dispersants by reacting the acylating agent simultaneously or, preferably, sequentially with nitro¬ gen-containing and hydroxy reagents may be between about 10:1 and 1:10, on an equivalent weight basis. The methods of preparation of the mixed oxygen- and nitro¬ gen-bridged dispersants are generally the same as for the individual dispersants described, except that two sources of group (ii) are used. As previously noted, substan¬ tially neutral or acidic dispersants are preferred, and a typical method of producing mixed oxygen- and nitrogen- bridged dispersants of this type (which are especially preferred) is to react the acylating agent with the hydroxy reagent first and subsequently react the interme¬ diate thus obtained with a suitable nitrogen-containing reagent in an amount to afford a substantially neutral or acid product.

The following examples are illustrative of the process for preparing the carboxylic dispersant composi¬ tions useful in this invention:

Example (B-2)-l

A polyisobutenyl succinic anhydride is prepared by the reaction of a chlorinated polyisobutylene with maleic anhydride at 200*C. The polyisobutenyl group has an average molecular weight of 850 and the resulting alkenyl succinic anhydride is found to have an acid number of 113 (corresponding to an equivalent weight of 500) . To a mixture of 500 grams (lequivalent) of this polyisobutenyl succinic anhydride and 160 grams of toluene there is added at room temperature 35 grams (1 equivalent) of diethylene triamine. The addition is made portionwise throughout a period of 15 minutes, and an initial exothermic reaction caused the temperature to rise to

50"C. The mixture then is heated and a water-toluene azeotrope distilled from the mixture. When no more water distills, the mixture is heated to 150"C at reduced pressure to remove the toluene. The residue is diluted with 350 grams of mineral oil and this solution is found to have a nitrogen content of 1.6%.

Example (B-2)-2 The procedure of Example (B-2)-l is repeated using 31 grams (1 equivalent) of ethylene diamine as the amine reactant. The nitrogen content of the resulting product is 1.4%.

Example (B-2)-3 The procedure of Example (B-2)-l is repeated using 55.5 grams (1.5 equivalents) of an ethylene amine mixture having a composition corresponding to that of triethylene tetramine. The resulting product has a nitrogen content of 1.9%.

Example (B-2)-4 The procedure of Example (B-2)-l is repeated using 55.0 grams (1.5 equivalents) of triethylene tetramine as the amine reactant. The resulting product has a nitrogen content of 2.9%.

Example (B-2)-5 An acylated nitrogen composition is prepared accord¬ ing to the procedure of Example (B-2)-l except that the reaction mixture consists of 3800 grams of the polyisobutenyl succinic anhydride, 376 grams of a mixture of triethylene tetramine and diethylene triamine (75:25) weight ratio), and 2785 grams of mineral oil. The product is found to have a nitrogen content of 2%.

Example (B-2)-6 A mixture of 510 parts (0.28 mole) of polyisobutene (Mn=1845; Mw=5325) and 59 parts (0.59 mole) of maleic anhydride is heated to 110 ^* C. This mixture is heated to 190*C in 7 hours during which 43 parts (0.6 mole) of gaseous chlorine is added beneath the surface. At 190-192*C an additional 11 parts (0.16 mole) of chlorine

is added over 3.5 hours. The reaction mixture is stripped by heating at 190-193*C with nitrogen blowing for 10 hours. The residue is the desired polyisobutene- substituted succinic acylating agent having a saponification equivalent number of 87 as determined ASTM procedure D-94.

A mixture is prepared by the addition of 10.2 parts (0.25 equivalent) of a commercial mixture of ethylene polyamines having from about 3 to about 10 nitrogen atoms per molecule to 113 parts of mineral oil and 161 parts (0.25 equivalent) of the substituted succinic acylating agent at 130*C. The reaction mixture is heated to 150"C in 2 hours and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.

Example (B-2)-7 A mixture of 100 parts (0.495 mole) of polyisobutene (Mn=2020; Mw=6049) and 115 parts (1.17 moles) of maleic anhydride is heated to 100*C. This mixture is heated to 184*C 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 equiva¬ lent number of 87 as determined by ASTM procedure D-94.

A mixture is prepared by the addition of 57 parts (1.38 equivalents) of a commercial mixture of ethylene polyamine having from about 3 to 10 nitrogen atoms per molecule to 1067 parts of mineral oil and 893 parts (1.38 equivalents) of the substituted succinic acylating agent at 140-145"C. The reaction mixture is heated to 155"C in 3 hours and stripped by blowing with nitrogen. The reaction mixture if filtered to yield the filtrate as an oil solution of the desired product.

Example (B-2 ) -8

A four-necked, 500 ml. flask is charged with 201 grams tetraethylenepentamine (TEPA) , 151 grams of 40% aqueous Tris(hydroxymethyl)-aminomethane (THAM) and 3.5 grams of 85% H-PO. as catalyst. The mixture is heated to 120 ^β C over 1 hour. With N ₂ sweeping, the mixture is heated to 130°C over 1 hour and to 230 ^β C over 2 hours more. The mixture is held at 230-240 ^β C for 4 hours and at 241-250°C for 3 hours. The contents are cooled to 150 ^Q C and filtered. In a 12-liter flask are added 460 grams of the filtered contents and 2500 grams diluent oil. The mixture is heated to 105"C and 3360 grams of a poly(isobutene) (molecular weight 1000)-substituted succinic anhydride having a saponification number of 100 was added over 1.5 hours while slowly blowing with nitrogen. The mixture is heated to 160 ^β C and held for 5 hours. The mixture is filtered at 150 ^β C to give a product containing 2.31% nitrogen and no free amine.

(B-3) Diaryl amine

The diaryl amines having utility in this invention are N, N-diphenylamine; N-phenyl-N-naphthy1amine and N, N-dinaphthy1amine as well as any alkyl substituted derivative of the aryl group wherein the alkyl substituent contains from 1 to about 6 carbon atoms. The preferred diaryl amine is N, N-diphenylamine.

B-4 The Sulfurized Composition

Within the purview of this invention, two different sulfurized compositions are envisaged and have utility. The first sulfurized composition, (B-4a) is a sulfurized olefin prepared by reacting an olefin/sulfur halide complex by contacting the complex with a protic solvent in the presence of metal ions at a temperature in the range of 40 ^• C. to 120 ^β C. and thereby removing halogens from the sulfurized complex and providing a dehalogenated sulfurized olefin; and isolating the sulfurized olefin.

The preparation of (B-4a) generally involves react¬ ing an olefin with a sulfur halide to obtain an alkyl/sulfur halide complex, a sulfochlorination reac¬ tion. This complex is contacted with metal ions and a protic solvent. The metal ions are in the form of Na ₂ S/NaSH which is obtained as an effluent of process streams from hydrocarbons, additional Na_S and NaOH. The Na ₂ S/NaSH may also be in the form of a fresh solution, that is, not recycled. The protic solvent is water and an alcohol of 4 carbon atoms or less. Preferably, the alcohol is isopropyl alcohol. The reaction with the metal ions and protic solvent represents a sulfurization-dechlorination reaction. The metal ions are present in an aqueous solution. The metal ions solution is prepared by blending an aqueous a ₂ S solution with the Na_S/NaSH process streams. Water and aqueous NaOH are added as necessary to adjust the Na ₂ S and NaOH concentration to a range of 18-21% Na ₂ S and 2-5% NaOH. A sulfurized product is obtained which is substantially free of any halide, i.e. the product obtained has had enough of the halide removed so that it is useful as a lubricant additive.

A wide variety of olefinic substances may be charged to the initial sulfochlorination reaction including hydrocarbon olefins having a single double bond with terminal or internal double bonds and containing from about 2 to 50 or more, preferably 2 to 8 carbon atoms per molecule in either straight, branched chain or cyclic compounds, and these may be exemplified by ethylene, propylene, butene-1, cis and trans butene-2, isobutylene, diisobutylene, triisobutylene, pentenes, cyclopentene, cyclohexene, the octenes, decene-1, etc. In general, Co_—o,. olefins or mixtures thereof are desirable for preparing sulfurized products for use as extreme pressure additives as the combined sulfur content of the product decreases with increasing carbon content yet its

miscibility with oil is lower for propylene and ethylene derivatives.

Isobutylene is particularly preferred as the sole olefinic reactant, but it may be employed, desirably in major proportion, in mixtures containing one or more other olefins; moreover, the charge may contain substan¬ tial proportions of saturated aliphatic hydrocarbons as exemplified by methane, ethane, propane, butanes, pentanes, etc. Such alkanes are preferably present in minor proportion in most instances to avoid unnecessary dilution of the reaction, since they neither react nor remain in the products but are expelled in the off-gases or by subsequent distillation. However, mixed charges can substantially improve the economics of the present process since such streams are of lower value than a stream of relatively pure isobutylene.

The other reactant in the preparation of (B-4a) is the sulfurizing agent. This agent may be selected from compounds such as sulfur monochloride (S ₂ C1 ₂ ) ; sulfur dichloride; and S_C1 ₂ as well as the corresponding but more expensive sulfur bromides. The sulfurizing agent may be employed in an amount which will provide the desired quantity of sulfur. The amount of sulfurization desired will vary depending on the end use of the product and can be determined by one of ordinary skill in the art. The molar ratio of olefin to sulfur halide will vary depending on the amount of sulfurization desired in the end product and the amount of olefinic unsaturation. The molar ratio of sulfur halide to olefin could vary from 1: (1-20) . When the olefin to be sulfurized contains a single double bond, one mole of the olefin can be reacted with 0.5 moles or less of ^S ₂ ^C1 2 (sulfur monochloride) . The olefin is generally added in excess with respect to the amount of the sulfur being added so that all of the sulfur halide will be reacted and any unreacted olefin can remain as unreacted diluent oil or can be removed and recycled.

An olefin or mixture of olefins and a sulfur halide or mixture of sulfur halides are sufficiently reacted to form an olefin/sulfur halide complex.

After the εulfurization-dechlorination reaction, the reaction mixture is allowed to stand and separate into an aqueous layer and another liquid layer containing the desired organic sulfide product. The product iε usually dried by heating at moderately elevated temperatures under subatmospheric pressure, and its clarity may often be improved by filtering the dried product through a bed of bauxite, clay or diatomaceous earth particleε.

The following example iε provided εo as to provide those of ordinary skill in the art with a complete dis- cloεure and deεcription of how to make the (B-4a) .

EXAMPLE (B-4a)-l

Added to a three-liter, four-necked flask are 1100 grams (8.15 moles) of sulfur monochloride. While stir¬ ring at room temperature 952 grams (17 moles) of iεobutylene are added below the surface. The reaction is exothermic and the addition rate of isobutylene controls the reaction temperature. The temperature is allowed to reach a maximum of 50*C and obtained is a sulfochlorination reaction product.

A blend of 1800 grams of 18% Na ₂ S solution is obtained from process streams. To this blend is added 238 grams 50% aqueous NaOH, 525 grams water and 415 grams isopropyl alcohol to prepare a reagent for use in the sulfurization-dechlorination reaction. To this reagent is added 1000 grams of the εulfo-chlorination reaction product in about 1.5 hours. One hour after the addition is completed, the contents are permitted to settle and the liquid layer is drawn off and discarded. The organic layer is stripped to 120*C and 100 mm Hg to remove any volatiles. Analyses: % sulfur 43.5, % chlorine 0.2.

Table I outlines other olefins and sulfur chlorides that can be utilized in preparing (B-4a) . The procedure iε essentially the same as in Example (B-4a)-l. In all

the examples, the metal ion reagent is prepared according to Example (B-4a)-l.

Table I

The second sulfurized composition (B-4b) is an oil-soluble sulfur-containing material which comprises the reaction product of sulfur and a Diels-Alder adduct. The Dielε-Alder adductε are a well-known, art-recognized claεε of compounds prepared by the diene syntheεiε or Diels=Alder reaction. A summary of the prior art relating to this class of compounds is found in the Rusεian monograph, Dienowi Sintes. Izdatelεtwo Akademii Nauk SSSR, 1963 by A.S. Oniεchenko. (Translated into the English language by L. Mandel as A.S. Onischenko, Diene Syntheεis. N.Y., Daniel Davey and Co., Inc., 1964) This

monograph and referenceε cited therein are incorporated by reference into the preεent εpecification.

Baεically, the diene εynthesis (Dielε-Alder reac¬ tion) involves the reaction of at least one conjugated diene, >C=C-C=C<, with at least one ethylenically or acetylenically unsaturated compound, >C=C<, these latter compounds being known as dienophiles. The reaction can be represented as follows: Reaction 1:

\ / C

\ /

C

/ \

Reaction 2:

\ /

C

/ \

\ / C

/ \

The products, A and B are commonly referred to as Dielε-Alder adductε. It iε these adducts which are used as starting materials for the preparation of (B-4a) .

Representative examples of such 1,3-dienes include aliphatic conjugated diolefins or dieneε of the formula

wherein R 9 through R14 are each independently εelected from the group consisting of halogen, alkyl, halo, alkoxy, alkenyl, alkenyloxy, carboxy, cyano, amino, alkylamino, dialkylamino, phenyl, and phenyl-εubεtituted with 1 to 3 substituents corresponding to R 9 through R14 with the proviso that a pair of R's on adjacent carbons do not form an additional double bond in the diene.

Preferably not more than three of the R variables are other than hydrogen and at least one is hydrogen. ;

Normally the total carbon content of the diene will not exceed 20. In one preferred aspect of the invention, adducts are used where R 11 and R12 are both hydrogen and at least one of the remaining R variables iε alεo hydrogen. Preferably, the carbon content of theεe R variableε when other than hydrogen iε 7 or leεε. In this most preferred class, those dienes where R 9, R10, R13, and R 14 are hydrogen, chloro, or lower alkyl are especially useful. Specific examples of the R variableε include the following groupε: methyl, ethyl, phenyl, H00C-, N≥C-, CH ₃ 0-, CH ₃ COO-, CH ₃ CH ₂ 0-, CH ₃ C(0)-, HC(O)-, Cl, Br, tert-butyl, CF ₃ , tolyl, etc. Piperylene, iεoprene, methylisoprene, chloroprene, and 1,3-butadiene are among the preferred dienes for use in preparing the Diels-Alder adducts.

In addition to these linear 1,3-conjugated dienes, cyclic dienes are also useful as reactants in the forma¬ tion of the Diels-Alder adducts. Examples of these cyclic dienes are the cyclopentadienes, fulvenes, 1,3-cyclohexadienes, 1,3-cycloheptadienes,

1,3,5-cycloheptatrienes, cyclooctatetraene, and 1,3,5-cyclonoatrienes. Various substituted derivatives of these compoundε enter into the diene synthesis.

The dienophiles suitable for reacting with the above dienes to form the adductε uεed aε reactants can be represented by the formula

wherein the K variables are the εame aε the R variableε in Formula above with the proviso that a pair of K'ε may from an additional carbon-to-carbon bond, i.e., , but do not neceεsarily do so.

A preferred class of dienophiles are those wherein at leaεt one of the K variableε iε εelected from the claεs of electron-accepting groups such as formyl, cyano, nitro, carboxy, carbohydrocarbyloxy, hydrocarbylcarbonyl, hydrocarbylεulfonyl, carbamyl, acylcarbanyl, N-acyl-N- hydrocarbylcarbamyl, N-hydrocarbylcarbamyl, and N, N-dihydrocarbylcarbamyl. Those K variables which are not electron-accepting groups are hydrogen, hydrocarbyl, or substituted-hydrocarbyl groups. Usually the hydrocarbyl ad substituted hydrocarbyl groups will not-contain more than 10 atoms each.

The hydrocarbyl groupε preεent aε N-hydrocarbyl εubεtituentε are preferably alkyl of 1 to 30 carbonε and especially 1 to 10 carbons. Representative of this claεε of dienophiles are the following: nitroalkenes, e.g., 1-nitrobutene-l, 1-nitropentene-l, 3-methyl-l-nitro- butene-1, 1-nitroheptene-l, 1-nitrooctene-l, 4-ethoxy-l- -nitrobutene-1; alpha, beta-ethylenically unεaturated aliphatic carboxylic acid eεterε, e.g., alkylacrylateε and alpha-methyl alkylacrylateε (i.e., alkyl metha- crylateε) εuch aε butylacrylate and butylmethacrylate, decyl acrylate and decylmethacrylate, di-(n-butyl)- maleate, di-(t-butyl-maleate) ; acrylonitrile, methacrylonitrile, beta-nitroεtyrene, methylvinyl-εulfone, acrolein, acrylic acid; alpha.

beta-ethylenically unsaturated aliphatic carboxylic acid amideε, e.g., acrylamide, N, N-dibutylacrylamide, ethacrylamide, N-dodecylmetha- crylamide, N-pentylcrotonamide; crotonaldehyde, crotonic acid, beta, beta-dimethyldivinylketone, methyl-vinyl-ketone, N-vinyl pyrrolidone, alkenyl halideε, and the like.

One preferred class of dienophiles are those wherein at least one, but not more than two of K variables iε -C(0)0-R° where R° is the residue of a saturated aliphatic alcohol of up to about 40 carbon atoms; e.g., for example at leaεt one K iε carbohydrocarbyloxy εuch as carboethoxy, carbobutoxy, etc., the aliphatic alcohol from which -R is derived can be a mono or polyhydric alcohol such as alkyleneglycols, alkanols, a inoalkanols, alkoxy-substituted alkanols, ethanol, ethoxy ethanol, propanol, beta-diethylaminoethanol, dodecyl alcohol, diethylene glycol, tripropylene glycol, tetrabutylene glycol, hexanol, octanol, isooσtyl alcohol, and the like. In this eεpecially preferred claεs of dienophiles, not more than two K variables will be -C(0)-0-R° groups and the remaining K variables will be hydrogen or lower alkyl, e.g., methyl, ethyl, propyl, isopropyl, and the like.

Specific examples of dienophiles of the type diε- cussed above are those wherein at least one of the K variables is one of the following groupε: hydrogen, methyl, ethyl, phenyl, H00C-, HC(0)-, CH ₂ =CH-, HC=C, CH ₃ C(0))-, C1CH ₂ -, HOCH ₂ -, alpha-pyridyl, -N0 ₂ , Cl, Br, propyl, iεo-butyl, etc.

In addition to the ethylenically unεaturated dienophiles, there are many useful acetylenically unsatu¬ rated dienophiles εuch aε propiolaldehyde, methyle- thynylketone, propylethynylketone, propenylethynylketone, propiolic acid, propiolic acid nitrile, ethylopropiolate, tetrolic acid, propargylaldehyde, acetylenedicarboxylic acid, the dimethyl eεter of acetylenedicarboxylic acid, dibenzoylacetylene, and the like.

Cyclic dienophiles include cyclopentenedione, coumarin, 3-cyanocourmarin, dimethyl maleic anhydride, 3, 6-endomethylene-cyclohexenedicarboxylic acid, etc. With the exception of the unsaturated dicarboxylic anhydrides derived from linear dicarboxylic acids (e.g., maleic anhydride, methylmaleic anhydride, chloromaleic anhydride) , this clasε of cyclic dienophileε are limited in commercial uεefulneεε due to their limited availabili¬ ty and other economic conεiderations.

The reaction products of these dienes and dienophiles correspond to the general formulae

(XIII)

wherein R 9 through R14 and K1 through K4 are as defined hereinbefore. If the dienophile moiety entering into the reaction is acetylenic rather than ethylenic, two of the K variableε, one from each carbon, form another carbon- to-carbon double bond. Where the diene and/or the

dienophile is itself cyclic, the adduct obviously will be bicyclic, tricyclic, fuεed, etc. , aε exemplified below:

Reaction 3:

Reaction 4:

Normally, the adductε involve the reaction of equimolar amountε of diene and dienophile. However, if the dienophile haε more than one ethylenic linkage, it iε possible for additional diene to react if present in the reaction mixture.

The adducts and procesεes of preparing the adducts are further exemplified by the following examples. Unlesε otherwiεe indicated in theεe exampleε and in other parts of this specification, as well as in the appended claimε, all partε and percentageε are by weight.

EXAMPLE A A mixture comprising 400 parts of toluene and 66.7 parts of aluminum chloride is charged to a two-liter flask fitted with a stirrer, nitrogen inlet tube, and a solid carbon dioxide-cooled reflux condenser. A second mixture comprising 640 parts (5 moles) of butyl acrylate and 240.8 parts of toluene is added to the A1C13 slurry while maintaining the temperature within the range of 37-58'C over a 0.25-hour period. Thereafter, 313 parts (5.8 moles) of butadiene is added to the εlurry over a 2.75-hour period while maintaining the temperature of the reaction mass at 50-61*C by means of external cooling. The reaction masε is blown with nitrogen for about 0.33 hour and then transferred to a four-liter separatory funnel and washed with a solution of 150 parts of concen¬ trated hydrochloric acid in 1100 parts of water. There¬ after, the product is subjected to two additional water washings using 1000 partε of water for each waεh. The washed reaction product iε subsequently distilled to remove unreacted butyl acrylate and toluene. The residue of this first diεtillation step is subjected to further distillation at a presεure of 9-10 millimeterε of mercury whereupon 785 parts of the desired product is collected over the temperature of 105-115*C.

EXAMPLE B The adduct of iεoprene and acrylonitrile iε prepared by mixing 136 parts of isoprene, 106 partε of acrylonitrile, and 0.5 partε of hydroquinone (polymeriza¬ tion inhibitor) in a rocking autoclave and thereafter heating for 16 hourε at a temperature within the range of 130-140*C. The autoclave iε vented and the contents decanted thereby producing 240 parts of a light yellow liquid. This liquid is stripped at a temperature of 90*C and a pressure of 10 millimeters of mercury thereby yielding the desired liquid product as the residue.

EXAMPLE C Uεing the procedure of Example B, 136 partε of

iεoprene, 172 partε of methyl acrylate, and 0.9 part of hydroquinone are converted to the iεoprenemethyl acrylate adduct.

EXAMPLE D Following the procedure of Example B, 104 parts of liquified butadiene, 166 partε of methyl acrylate, and 1 part of hydroquinone are charged to the rocking autoclave and heated to 130-135* for 14 hours. The product is subsequently decanted and stripped yielding 237 parts of the adduct.

EXAMPLE E The adduct of isoprene and methyl methacrylate iε prepared by reacting 745 parts of isoprene with 1095 partε of methyl methacrylate in the preεence of 5.4 parts of hydroquinone in the rocking autoclave following the procedure of Example B above. 1490 partε of the adduct is recovered.

EXAMPLE F The adduct of butadiene and dibutyl maleate (810 partε) iε prepared by reacting 915 partε of dibutyl maleate, 216 parts of liquified butadiene, and 3.4 parts of hydroquinone in the rocking autoclave according to the technique of Example B.

EXAMPLE G A reaction mixture comprising 378 parts of butadiene, 778 parts of N-vinylpyrrolidone, and 3.5 parts of hydroquinone is added to a rocking autoclave previous¬ ly chilled to -35*C. The autoclave iε then heated to a temperature of 130-140*C for about 15 hourε. After venting, decanting, and stripping the reaction mass, 75 parts of the desired adduct are obtained.

EXAMPLE H Following the technique of Example B, 270 parts of liquified butadiene, 1060 parts of isodecyl acrylate, and 4 partε of hydroquinone are reacted in the rocking autoclave at a temperature of 130-140*C for about 11

hourε. After decanting the εtripping, 1136 partε of the adduct are recovered.

EXAMPLE I Following the same general procedure of Example A, 132 parts (2 moles) of cyclopentadiene, 256 parts (2 moles) of butyl acrylate, and 12.8 partε of aluminum chloride are reacted to produce the deεired adduct. The butyl acrylate and the aluminum chloride are firεt added to a two-liter flask fitted with stirrer and reflux condenser. While heating reaction masε to a temperature within the range of 59-52*C, the cyclopentadiene is added to the flask over a 0.5-hour period. Thereafter the reaction maεε iε heated for about 7.5 hourε at a tempera¬ ture of 95-100*C. The product iε waεhed with a solution containing 400 parts of water and 100 partε of concen¬ trated hydrochloric acid and the aqueouε layer is dis¬ carded. Thereafter, 1500 parts of benzene are added to the reaction mass and the benzene solution is washed with 300 parts of water and the aqueouε phaεe removed. The benzene iε removed by diεtillation and the reεidue εtripped at 0.2 partε of mercury to recover the adduct as a distillate.

EXAMPLE J Following the technique of Example B, the adduct of butadiene and ally chloride is prepared using two moles of each reactant.

EXAMPLE K One-hundred thirty-nine parts (1 mole) of the adduct of butadiene and methyl acrylate is tranεeεterified with 158 partε (1 mole) of decyl alcohol. The reactantε are added to a reaction flask and 3 partε of sodium methoxide are added. Thereafter, the reaction mixture is heated at a temperature of 190-200'C for a period of 7 hours. The reaction masε is washed with a 10% sodium hydroxide solution and then 250 parts of naphtha is added. The naphtha solution is waεhed with water. At the completion of the washing, 150 partε of toluene are added and the

reaction maεε is stripped at 150"C under preεεure of 28 partε of mercury. A dark-brown fluid product (225 parts) is recovered. Thiε product is fractionated under reduced presεure reεulting in the recovery of 178 partε of the product boiling in the range of 130-133*C at a preεεure of 0.45 to 0.6 partε of mercury.

EXAMPLE L

The general procedure of Example A iε repeated except that only 270 parts (5 moles) of butadiene is included in the reaction mixture.

The sulfurized compositions (B-4b) are readily prepared by heating a mixture of sulfur and at least one of the Diels-Alder adducts of the types discuεεed hereinabove at a temperature within the range of from about 100*C to just below the decomposition temperature of the Diels-Alder adducts. Temperatures within the range of about 100* to about 200*C will normally be uεed. This reaction results in a mixture of products, some of which have been identified. In the compounds of know structure, the sulfur reactε with the εubεtituted unεatu¬ rated cycloaliphatiσ reactantε at a double bond in the nucleuε of the unsaturated reactant.

The molar ratio of sulfur to Diels-Alder adduct used in the preparation of the εulfur-containing composition is from about 1:2 up to about 4:1. Generally, the molar ratio of sulfur to Diels-Alder adduct will be from about 1:1 to about 4:1 and preferably about 2:1 to about 4:1 based on the presence of one ethylenically unsaturated bond in the cycloaliphatic nucleus. If there additional unsaturated bonds in the cycloaliphatic nucleus, the ratio of sulfur may be increased.

The reaction can be conducted in the presence of suitable inert organic solvents εuch as mineral oils, alkanes of 7 to 18 carbons, etc., although no solvent is generally necessary. After completion of the reaction, the reaction masε can be filtered and/or subjected to other conventional purification techniques. There is no need to separate the various sulfur-containing products as they can be employed in the form of a reaction mixture comprising the compoundε of known and unknown εtructure.

As hydrogen sulfide is an undesirable contaminant, it iε advantageous to employ standard procedures for aεεiεting in the removal of the H2S from the productε. Blowing with steam, alcohols, air, or nitrogen gas assists in the removal of H2S aε doeε heating at reduced preεεures with or without the blowing.

When the Diels-Alder adduct is of the type repre- εented by Formula XIII (A) or (B) , the εulfur-containing products of known structure correspond to the following generic formulae:

(XVI)

wherein R' and R" are the same as R9 through R14 above and K' and K" are the εame as K 1 through K4 above. Y is a divalent sulfur group. The variables q and q" are zero or a poεitive whole number of 1 to 6 while v and v' are zero or poεitive whole number of 1 to 4, at least one of R', R", K', and K" in each compound being other than hydrogen or a saturated aliphatic hydrocarbon group. Generally not more than five of the R and K variables on each ring are other than hydrogen. Preferably, at least one K variable in each compound will be an electron accepting group of the type diεcussed supra. The pre¬ ferred class of substituents discussed hereinbefore with regard to the various "K" and "R" variables on the intermediates for making the Diels-Alder adducts and the adducts themselveε obviouεly applieε to the final prod- uctε prepared from the intermediates.

An espeσially preferred class of (B-4b) within the ambit of Formulae XIV-XVI is the therein at least one of the K variables is an electron accepting group from the claεs consisting of

wherein W" is oxygen or divalent sulfur, and R 15 is hydrogen, halo, alkyl of 1 to 30 carbons, alkenyl of 1 to

30 carbons, hydroxy, alkoxy, of 1 to 30 carbons, alkenoxy of 1 to 30 carbons, amino, alkylamino and dialkylamine wherein the alkyl groups contain from 1 to 30 carbons and preferably 1 to 10 carbonε. Preferably, W" iε oxygen. When R 15 iε halo, chloro iε preferred. Particularly useful are those compounds wherein the R'ε are hydrogen or lower alkyl and one K variable is carboalkoxy of up to

31 carbon atoms, the remaining K groups being hydrogen, lower alkyl, or another electron accepting group. Within this latter group, those wherein the carboalkoxy group is

carbo-n-butoxy produce excellent results as lubricant additives.

It is εometimes advantageous to incorporate materi¬ als useful as sulfurization catalystε in the reaction mixture. Theεe materials may be acidic, basic or neu¬ tral. Useful neutral and acidic materials, include acidified clays such as "Super Filtrol", p- tolueneεulfonic acid, dialkylphoεphorodithioic acidε, phoεphoruε εulfideε such aε phosphorus pentasulfide and phosphites such as triaryl phosphites (e.g., triphenyl phosphite) .

The basic materials may be inorganic oxides and salts such as sodium hydroxide, calcium oxide and sodium sulfide. The most deεirable baεic catalyεts, however, are nitrogen baseε including ammonia and amineε. The amineε include primary, εecondary and tertiary hydrocarbyl amines wherein the hydrocarbyl radicals are alkyl, aryl, aralkyl, alkaryl or the like and contain about 1-20 carbon atoms. Suitable amines include aniline, benzylamine, dibenzylamine, dodecylamine, naphthylamine, tallow amines, N-ethyldipropylamine, N-phenylbenzylamine, N,N-diethylbutylamine, m-toluidine and 2,3-xylidine. Also useful are heterocyclic amines such as pyrrolidine, N-methylpyrrolidine, piperidine, pyridine and quinoline.

The preferred basic catalysts include ammonia and primary, εecondary, or tertiary alkylamineε having about 1-8 carbon atomε in the alkyl radicals. Representative amines of this type are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, di-n-butylamine, tri-n-butylamine, tri-εec-hexylamine and tri-n-octylamine. Mixtureε of theεe amineε can be uεed, as well as mixtures of ammonia and amineε.

When a catalyεt is used, the amount is generally about 0.05-2.0% of the weight of the adduct.

The following exampleε illustrate the preparation of (B-4b) .

EXAMPLE (B-4b) -l

To 255 parts (1.65 moles) of the isoprene methacrylate adduct of Example C heated to a temperature of 110-120*C, there are added 53 parts (1.65 moles) of εulfur flowerε over a 45-minute period. The heating iε continued for 4.5 hours at a temperature in the range of 130-160*C. After cooling to room temperature, the reaction mixture is filtered through a medium sintered glasε funnel. The filtrate consists of 301 parts of the desired (B-4b) .

EXAMPLE (B-4b)-2

A reaction mixture comprising 1175 parts (6 moles) of the Diels-Alder adduct of butyl acrylate and isoprene and 192 parts (6 moles) of sulfur flowers is heated for 0.5 hour at 108-110*C and then to 155-165*C for 6 hours while bubbling nitrogen gas through the reaction mixture at 0.25 to 0.5 standard cubic feet per hour. At the end of the heating period, the reaction mixture is allowed to cool and filtered at room temperature. Thereafter, the product is permitted to stand for 24 hours and refiltered. The filtrate is the desired (B-4b) .

EXAMPLE (B-4b)-3

Sulfur (4.5 moles) and the adduct of iεoprene-methyl methacrylate (4.5 moles are mixed at room temperature and heated for one hour at 100*C while blowing nitrogen through the reaction masε at 0.25-0.5 εtandard cubic feet per hour. Subsequently the reaction mixture is raised to a temperature of 150-155*C for 6 hours while maintaining the nitrogen blowing. After heating, the reaction masε iε permitted to εtand for εeveral hours while cooling to room temperature and is thereafter filtered. The fil¬ trate consists of 842 parts of the desired (B-4b) .

EXAMPLE (B-4b)-4

A one-liter flask fitted with a stirrer, reflux, condenser, and nitrogen inlet line is charged with 256 parts (1 mole) of the adduct of butadiene and iεodecyl acrylate, and 51 grams (1.6 moles) of sulfur flowers and

then heated for 12 hourε at a temperature, εtand for 21 hours, and filtered at room temperature to produce the desired (B-4b) as the filtrate.

EXAMPLE (B-4b)-5 A mixture of 1703 parts (9.4 moles) of a butyl acrylate-butadiene adduct prepared as in Example L, 280 parts (8.8 moles) of sulfur and 17 parts of triphenyl phosphite is prepared in a reaction vessel and heated gradually over 2 hours to a temperature of about 185*C while stirring and sweeping with nitrogen. The reaction is exothermic near 160-170*C, and the mixture is main¬ tained at about 185°C for 3 hours. The mixture is cooled to 90 ^" C over a period of 2 hours and filtered using a filter aid. The filtrate is the desired (B-4b) contain¬ ing 14.0% sulfur.

EXAMPLE (B-4b)-6 The procedure of Example (B-4b)-5 iε repeated except that the triphenyl phoεphite iε omitted from the reaction mixture.

EXAMPLE (B-4b)-7 The procedure of Example (B-4b)-5 iε repeated except that the triphenyl phoεphite iε replaced by 2.0 partε of triamyl amine aε εulfurization catalyεt.

EXAMPLE (B-4b)-8 A mixture of 547 partε of a butyl acrylatebutadiene adduct prepared as in Example L and 5.5 parts of triphenyl phosphite iε prepared in a reaction veεεel and heated with εtirring to a temperature of about 50*C whereupon 94 partε of εulfur are added over a period of 30 minuteε. The mixture is heated to 150*C in 3 hours while εweeping with nitrogen. The mixture then iε heated to about 185*C in approximately one hour. The reaction iε exothermic and the temperature iε maintained at about 185"C by using a cold water jacket for a period of about 5 hourε. At thiε time, the contents of the reaction vessel are cooled to 85*C and 33 parts of mineral oil are added. The mixture is filtered at this temperature, and

the filtrate is the desired (B-4b) wherein the sulfur to adduct ratio is 0.98/1.

EXAMPLE (B-4b)-9 The general procedure of Example (B-4b)-8 with the exception that the triphenyl phosphite is not included in the reaction mixture.

EXAMPLE (B-4b)-10 A mixture of 500 parts (2.7 moleε) of a butyl acrylate-butadiene adduct prepared as in Example L and 109 parts (3.43 moles) of sulfur is prepared and heated to 180*C and maintained at a temperature of about 180 -190 ^" C for about 6.5 hourε. The mixture iε cooled while εweeping with a nitrogen gaε to remove hydrogen εulfide odor. The reaction mixture is filtered and the filtrate is the desired (B-4b) containing 15.8% sulfur.

EXAMPLE (B-4b)-ll A mixture of 728 partε (4.0 moleε) of a butyl acrylate-butadiene adduct prepared aε in Example L, 218 partε (6.8 moleε) of εulfur, and 7 partε of triphenyl phoεphite is prepared and heated with stirring to a temperature of about 181*C over a period of 1.3 hours. The mixture is maintained under a nitrogen purge at a temperature of 181-187"C for 3 hours. After allowing the material to cool to about 85°C over a period of 1.4 hours, the mixture- is filtered using a filter aid, and the filtrate is the desired (B-4b) containing 23.1% sulfur.

EXAMPLE (B-4b)-12 A mixture of 910 parts (5 moleε) of a butyl acrylate-butadiene adduct prepared aε in Example L, 208 partε (6.5 moleε) of εulfur and 9 partε of triphenyl phoεphite iε prepared and heated with stirring and nitrogen εweeping to a temperature of about 140*C over 1.3 hours. The heating iε continued to raise the temper¬ ature to 187*C over 1.5 hours, and the material is held at 183-187 ^* C for 3.2 hours. After cooling the mixture to

89*C, the mixture iε filtered with a filter aid, and the filtrate iε the deεired (B-4b) containing 18.2% sulfur.

EXAMPLE (B-4b)-13 A mixture of 910 parts (5 moles) of a butyl acrylate-butadiene adduct prepared as in Example L, 128 parts (4 moles) of sulfur and 9 parts of triphenyl phosphite is prepared and heated with stirring while sweeping with nitrogen to a temperature of 142 ^* C over a period of about one hour. The heating is continued to raise the temperature to 185-186*C over about 2 hours and the mixture is maintained at 185-187*C for 3.2 hours. After allowing the reaction mixture to cool to 96*C, the mixture is filtered with filter aid, and the filtrate is the desired (B-4b) containing 12.0% εulfur.

EXAMPLE (B-4b)-14 The general procedure of Example (B-4b)-13 is repeated except that the mixture contain 259 parts (8.09 moleε) of εulfur. The (B-4b) obtained in thiε manner containε 21.7% εulfur.

It haε been found that, if the (B-4b) iε treated with an aqueouε εolution of εodium εulfide containing from 5% to about 75% by weight Na2S, the treated product may exhibit less of a tendency to darken freshly polished copper metal.

Treatment involves the mixing together (B-4b) and the sodium sulfide solution for a period of time suffi¬ cient for any unreacted sulfur to be scavenged, usually a period of a few minutes to εeveral hourε depending on the amount of unreacted εulfur, the quantity and the concen¬ tration of the εodium εulfide εolution. The temperature iε not critical but normally will be in the range of about 20*C to about 100*C. After the treatment, the resulting aqueouε phaεe iε separated from the organic phase by conventional techniques, i.e., decantation, etc. Other alkali metal sulfideε, M2Sx where M iε an alkali metal and x is 1, 2, or 3 may be used to scavenge unreacted sulfur but those where x is greater than 1 are

not nearly as effective. Sodium sulfide solutions are preferred for reasons of economy and effectivenes . Thiε procedure iε described in more detail in U.S. Patent 3,498,915.

It haε alεo been determined that treatment of (B-4b) with εolid, insoluble acidic materials εuch aε acidified clayε or acidic reεinε and thereafter filtering the εulfurized reaction mass improves the product with respect to its color and solubility characteristics. Such treatment compriseε thoroughly mixing the reaction mixture with from about 0.1% to about 10% by weight of the εolid acidic material at a temperature of about 25-150*C and εubsequently filtering the product.

In order to remove the last traces of impurities from the (B-4b) reaction mixture, particularly when the adduct employed was prepared using a Lewis acid catalyεt, (e.g., A1C13) it is sometimes desirable to add an organic inert solvent to the liquid reaction product and, after thorough mixing, to refilter the material. Subsequently the solvent iε εtripped from the (B-4b) . Suitable εolventε include εolventε of the type mentioned hereinabove such as benzene, toluene, the higher alkanes, etc. A particularly useful class of solvents are the textile spiritε.

In addition, other conventional purification tech- niqueε can be advantageouεly employed in purifying εulfurized productε used in this invention. For example, commercial filter aids can be added to the materials prior to filtration to increase the efficiency of the filtration. Filtering through diatomaceous earth iε particularly uεeful where the uεe contemplated requires the removal of subεtantially all εolid materialε. However, εuch expedients are well known to those skilled in the art and require no elaborate discussion herein. B-5 The Metal Passivator

Function aε a metal passivator are tolytriazole or an oil-soluble derivative of a dimercaptothiadiazole.

The dimercaptothiadiazoles which can be utilized in the present invention starting materials for the prepara¬ tion of oil-soluble derivatives containing the dimercaptothiadiazole nucleus have the following struc¬ tural formulae and names: 2,5-dimercapto-l,3,4-thiadiazole

3,5-dimercapto-l,2,4-thiadiazole

S - N I II HS-σ C-SH

^N^

3,4-dimercapto-l,2,5-thiadiazole

HS-C C-SH

II II

N N

4,5-dimercapto-l,2 ,3-thiadiazole

N C SH

11 II

N C SH

\ / S

Of theεe the most readily available, and the one pre¬ ferred for the purpose of this invention, is 2,5-dimercapto-l,3,4-thiadiazole. Thiε compound will sometimes be referred to hereinafter as DMTD. However, it is to be understood that any of the other dimercaptothiadiazoles may be substituted for all or a portion of the DMTD.

DMTD is conveniently prepared by the reaction of one mole of hydrazine, or a hydrazine salt, with two moles of carbon diεulfide in an alkaline medium, followed by acidification.

Derivativeε of DMTD have been described in the art, and any such compounds can be included in the composi¬ tions of the present invention. The preparation of some derivatives of DMTD is described in E.K. Fields "Industrial and Engineering Chemistry", 4 »., P« 1361-4 (September 1957) . For the preparation of the oil-soluble derivatives of DMTD, it iε poεεible to utilize already prepared DMTD or to prepare the DMTD in εitu and εubεe- quently adding the material to be reacted with DMTD.

U.S. Patentε 2,719,125; 2,719,126; and 3,087,937 deεcribe the preparation of variouε 2,5-bis-(hydrocarbon dithio)-l,3,4-thiadiazoles. The hydrocarbon group may be aliphatic or aromatic, including cyclic, alicyclic, aralkyl,aryl and alkaryl. Such compoεitionε are effec¬ tive corroεion-inhibitorε for εilver, εilver alloyε and similar metalε. Such polysulfides which can be repre¬ sented by the following general formula

N N

H II R-fSJ^S-C ^C-S-(S)^-R'

(XVII)

wherein R and R' may be the same or different hydrocarbon

4c it groups, and x and y be integers from 0 to about 8, and it it the sum of x and y being at least 1. A process for preparing εuch derivativeε iε deεcribed in U.S. Patent 2,191,125 aε comprising the reaction of DMTD with a suitable sulfenyl chloride or by reacting the dimercapto diathiazole with chlorine and reacting the resulting diεulfenyl chloride with a primary or tertiary mercaptan. Suitable sulfenyl chlorides useful in the first procedure

can be obtained by chlorinating a mercaptan (RSH or R'SH) with chlorine in carbon tetrachloride. In a εecond procedure, DMTD is chlorinated to form the desired bissulfenyl chloride which is then reacted with at least one mercaptan (RSH and/or R'SH). The disclosures of U.S. Patents 2,719,125; 2,719,126; and 3,087,937 are hereby incorporated by reference for their deεcription of derivativeε of DMTD useful in the compositions of the invention.

U.S. Patent 3,087,932 describeε a one-step procesε for preparing 2,5-bis (hydrocarbyldithio)-l, 3-4- thiadiazole. The procedure involves the reaction of either DMTD or its alkali metal or ammonium εalt and a mercaptan in the preεence of hydrogen peroxide and a εolvent. Oil-εoluble or oil-diεpersible reaction products of DMTD can be prepared also by the reaction of the DMTD with a mercaptan and formic acid. Compositions prepared in this manner are described in U.S. Patent 2,749,311. Any mercaptan can be employed in the reaction although aliphatic and aromatic mono- or poly-mercaptan containing from 1 to 30 carbon atomε are preferred. The disclosures of U.S. Patents 3,087,932 and ,2,749,311 are hereby incorporated by reference for their description of DMTD derivatives which can be utilized aε a metal paεsivator.

Carboxylic esters of DMTD having the general formula

(XVIII)

wherein R and R' are hydrocarbon groups such as aliphatic, aryl and alkaryl groups containing from about 2 to about 30 or more carbon atoms are described in U.S. Patent 2,760,933. These esterε are prepared by reacting

DMTD with an organic acid halide (chloride) and a molar ratio of 1:2 at a temperature of from about 25 to about 130*C. Suitable solvents εuch as benzene or dioxane can be utilized to facilitate the reaction. The reaction product is washed with dilute aqueous alkali to remove hydrogen chloride and any unreacted carboxylic acid. The disclosure of U.S. Patent 2,760,933 is hereby incorporat¬ ed by reference for its deεcription of various DMTD derivatives which can be utilized in the compositionε of the preεent invention.

Condensation products of alpha-halogenated aliphatic monocarboxylic acids having at least 10 carbon atoms with DMTD are described in U.S. Patent 2,836,564. These condensation productε generally are characterized by the following formula

(XIX)

wherein R iε an alkyl group of at leaεt 10 carbon atomε. Exampleε of alpha-halogenated aliphatic fatty acids which can be used include alpha-bromo-lauric acid, alpha- chloro-lauric acid, alpha-chloro-stearic acid, etc. The disclosure of U.S. Patent 2,836,564 is hereby incorporat¬ ed by reference for its disclosure of derivativeε of DMTD which can be utilized in the compositions of the present invention.

Oil-soluble reaction products of unsaturated cyclic hydrocarbons and unsaturated ketoneε are deεcribed in U.S. Patents 2,764,547 and 2,799,652, respectively, and a disclosure of these referenceε alεo are hereby incorpo¬ rated by reference for their deεcription of materialε which are useful as metal passivators in the compositions of the present invention. Examples of unsaturated cyclic

hydrocarbonε deεcribed in the '547 patent include styrene, alpha-methyl styrene, pinene, dipentene, cyclopentadiene, etc. The unsaturated ketones deεcribed in U.S. Patent 2,799,652 include aliphatic, aromatic or heterocyclic unεaturated ketones containing from about 4 to 40 carbon atoms and from 1 to 6 double bonds. Exam¬ ples include mesityl oxide, phorone, isophorone, benzal acetopbenone, furfural acetone, difurfuryl acetone, etc.

U.S. Patent 2,765,289 describes productε obtained by reacting DMTD with an aldehyde and a diaryl amine in molar proportions of from about 1:1:1 to about 1:4:4. The resulting products are suggeεted aε having the general formula

N N

II II R-N-CH(R")-S-σ C-S-CH(R")-NR'_

S

(XX) wherein R and R' are the εame or different aromatic groups, and R" is hydrogen, and alkyl group, or an aromatic group. The aldehydes uεeful in the preparation of εuch products as repreεented by Formula X include aliphatic or aromatic aldehydeε containing from 1 to 24 carbon atomε, and εpecific examples of such aldehydes include formaldehyde, acetaldehyde, benzaldehyde, 2-ethylehexyl aldehyde, etc. The disclosure of thiε patent also is hereby incorporated by reference for its identification of various materials which can be utilized in the compositionε of thiε invention aε metal paεεivatorε.

Metal passivators in the compoεitionε of the preεent invention alεo may be amine εaltε of DMTD εuch as those having the following formula

(XXI)

in which Y is hydrogen or the amino group

in whiσh R is an aliphatiσ, aromatiσ or heteroσyσliσ group, and R 1 and R2 are i.ndependently ali.phatic, aromat¬ ic or heterocyclic groups containing from about 6 to about 60 carbon atoms. The amine used in the preparation of the amine salts can be aliphatic or aromatiσ mono- or polyamines, and the amines may be primary, seσondary or tertiary amines. Specific examples of suitable amines include hexylamine, dibutylamine, dodecylamine, ethylenediamine, propylenediamine, tetraethylenepentamine, and mixtures thereof. The discloεure of U.S. Patent 2,910,439 iε hereby incorporat¬ ed by reference for its listing of suitable amine saltε.

Dithioσarbamate derivatives of DMTD are described in U.S. Patents 2,690,999 and 2,719,827. Such compositions can be repreεented by the following formulae

N N II II

R ₂ N-C(S)-S-C. C-S-C(S)-NR ₂

(XXII) and

(XXIII)

wherein the R groupε are εtraight-chain or branch-chain saturated or unsaturated hydrocarbon groups selected from the group consisting of alkyl, aralkyl and alkaryl groups. The disclosures of these two patents also are hereby incorporated by reference for the identification of various thiadiazyl dithiocarbamates which are useful aε metal paεεivatorε in the compositions of the present invention.

U.S. Patent 2,850,453 describes productε which are obtained by reacting DMTD, an aldehyde and an alcohol or an aromatic hydroxy compound in a molar ratio of from 1:2:1 to 1:6:5. The aldehyde employed can be an aliphatic aldehyde containing from 1 to 20 carbon atomε or an aromatic or heterocyclic aldehyde containing from about 5 to about 30 carbon atomε. Exampleε of εuitable aldehydeε include formaldehyde, acetaldehyde, benzaldehyde. The reaction can be conducted in the preεence or abεence of εuitable εolventε by (a) mixing all of the reactantε together and heating, (b) by firεt reacting an aldehyde with the alcohol or the aromatic 2 hydroxy compound, and then reacting the resultant inter¬ mediate with the thiadiazole, or (c) by reacting the aldehyde with thiadiazole first and the resulting inter¬ mediate with the hydroxy compound. The discioεure of U.S. Patent 2,850,453 is hereby incorporated by reference for its metal pasεivatorε in the compoεitionε of the present invention.

U.S. Patent 2,703,784 describes products obtained by reacting DMTD with an aldehyde and a mercaptan. The aldehydes are similar to those disclosed in U.S. Patent 2,850,453, and the mercaptans may be aliphatic or

aromatic mono- or poly-mercaptans containing from about 1 to 30 carbon atoms. Examples of suitable mercaptans include ethyl .mercaptan, butyl mercaptan, octyl mercaptan, thiophenol, etc. The disclosure of this patent also is incorporated by reference.

The preparation of: 2-hydrocarbyldithio-5-mercapto-l,3,4-thiadiazoles having the formula

(XXIV)

wherein R' iε a hydrocarbyl substituent is described in U.S. Patent 3,663,561. The compositionε are prepared by the oxidative coupling of equimolecular portionε of a hydrocarbyl mercaptan and DMTD or itε alkali metal mercaptide. The compositions are reported to be excel¬ lent sulfur scavengerε and are uεeful in preventing copper corroεion by aσtive εulfur. The mono-merσaptanε uεed in the preparation of the compounds are represented by the formula

R'SH

wherein R' is a hydrocarbyl group containing from 1 to about 280 carbon atoms. A peroxy compound, hypohalide or air, or mixtureε thereof can be utilized to promote the oxidative coupling. Specific exampleε of the mono- mercaptan include methyl mercaptan, isopropyl mercaptan, hexyl mercaptan, decyl mercaptan, and long chain alkyl mercaptans, for example mercaptans derived from propene polymers and isobutylene polymers especially polyisobutylenes, having 3 to about 70 propene or isobutylene units per molecule. The disclosure of U.S. Patent 3,663,561 is hereby incorporated by reference for

its identification of DMTD derivative which are useful as metal pasεivators in the compositions of this invention.

Another material useful as metal passivatorε in the compositions of the present invention iε obtained by reacting a thiadiazole, preferably DMTD with an oil-εolu- ble diεperεant, preferably a εubstantially neutral or acidic carboxylic dispersant in a diluent by heating the mixture above about 100*C. This procedure, and the derivatives produced thereby are described in U.S. Patent 4,136,043, the disclosure of which is hereby incorporated by reference. The oil-soluble disperεantε which are utilized in the reaction with the thiadiazoles are often identified as "ashless dispersantε". Various types of suitable ashless dispersants useful in the reaction are deεcribed in '043 patent.

Another material uεeful aε metal paεεivatorε in the compoεitionε of the the invention iε obtained by reacting a thiadiazole, preferably DMTD, with a peroxide, prefera¬ bly hydrogen peroxide. The reεulting nitrogen- and sulfur-containing composition is then reacted with a polyεulfide, merσaptan or amino compound (especially oil-εoluble, nitrogen-containing diεpersants) . Thiε procedure and the derivatives produced thereby are described in U.S. Patent 4,246,126, the diεclosure of which is incorporated herein by reference.

U.S. Patent 4,140,643 deεcribeε nitrogen and εul- fur-containing compoεitionε which are oil-εoluble and which are prepared by reacting a carboxylic acid or anhydride containing up to about 10 carbon atomε and having at leaεt one olefinic bond with compoεitionε of the type described in U.S. Patent 4,136,043. The pre¬ ferred carboxylic acid or anhydride is maleic anhydride. The disclosures of U.S. Patents 4,136,043 and 4,140,643 are hereby incorporated by reference for their discio- sureε of materials useful as metal pasεivatorε in the compositions of the present invention.

U.S. Patent 4,097,387 describes DMTD derivatives prepared by reacting a sulfur halide with an olefin to form an intermediate which is then reacted with an alkali metal salt of DMTD. More recently, U.S. Patent 4,487,706 describes a DMTD derivative prepared by reacting an olefin, sulfur dichloride and DMTD in a one-step reac¬ tion. The olefins generally contain from about 6 to 30 carbon atoms. The diεclosures of U.S. Patentε 4,097,387 and 4,487,706 are hereby incorporated by referenσe for their descriptions of oil-soluble DMTD derivatives which are useful aε metal passivators in the compoεitionε of this invention.

(C) The Vicositv Modifying Additive

This invention also contemplates utilizing (C) viscoεity modifying compositions of two different types.

The firεt viεcoεity modifying compoεitionε, (C-l) , contemplateε the proviεion of a nitrogen-containing eεter of a carboxy-containing interpolymer, said interpolymer having a reduced specific viεcoεity of from about 0.05 to about 2, εaid eεter being substantially free of tiltratable acidity and being characterized by the presence within its polymeric structure of at least one of each of three pendant polar groups: (A) a relatively high molecular weight carboxylic ester group having at leaεt 8 aliphatic carbon atomε in the eεter radical, (B) a relatively low molecular weight carboxylic eεter group having no more than 7 aliphatic carbon atomε in the ester radical, and (C) a carbonyl-polyamino group derived from a polyamino compound having one primary or secondary amino group, wherein the molar ratio of (A) : (B) : (C) is

(60-90): (10-30) : (2-15)

An essential element of the viscoεity modifying additive iε that the eεter iε a mixed eεter, i.e., one in which there is the combined presence of both a high molecular weight ester group and a low molecular weight ester group, particularly in the ratio as stated above.

Such combined presence is critical to the viscoεity propertieε of the mixed eεter, both from the εtandpoint of itε viεcoεity modifying characteristics and from the εtandpoint of its thickening effect upon lubricating compositions in which it is used as an additive.

In reference to the size of the eεter groupε, it is pointed out that an ester radical is represented by the formula

-C(O) (OR)

and that the number of carbon atoms in an ester radical is this the combined total of the carbon atoms of the carbonyl group and the carbon atomε of the eεter group i.e., the (OR) group.

Another eεεential element of (C-l) iε the preεence of a polyamino group derived from a particular polyamino compound, i.e., one in which there iε one primary or secondary amino group and at least one mono-functional amino group. Such polyamino group, when preεent in the nitrogen-containing eεterε of (C-l) in the proportion εtated above enhances the disperεability of εuch eεters 2in lubricant compositions and additive concentrates fro lubricant compositionε.

Still another essential element of (C-l) is the extent of esterification in relation to the extent of neutralization of the uneεterified carboxy groupε of the carboxy-containing interpolymer through the converεion thereof to polyamino-containing groupε. For convenience, the relative proportionε of the high molecular weight ester group to the low molecular weight ester group and to the polyamino group are expreεεed in termε of molar ratios of (60-90) : (10-30) : (2-15) , respectively. The preferred ratio is (70-80) : (15-25) :5. It should be noted that the linkage described aε the carbonyl-polyamino group may be imide, amide, or amidine and inasmuch as any such linkage is contemplated within the present inven¬ tion, the term "carbonyl polyamino" is thought to be a

convenient, generic expreεεion uεeful for the purpose of defining the inventive concept. In particularly advantageous embodiment of the invention such linkage is imide or predominantly imide.

Still another important element of (C-l) is the molecular weight of the carboxy-containing interpolymer. For convenience, the molecular weight is expresεed in terms of the "reduced specific viscoεity" of the interpolymer which iε a widely reσognized meanε of expressing the molecular size of a polymeric substance. As used herein, the reduced specific viscosity (abbreviated as RSV) is the value obtained in accordance with the formula

RSV = Relative Viscosity - 1 Concentration

wherein the relative viscoεity iε determined by meaεur- ing, by meanε of a dilution viεcometer, the viεcoεity of a εolution of one gram of the interpolymer in 10 ml. of acetone and the viεcoεity of acetone at 30*± 0.02'C. For purpoεe of computation by the above formula, the concentration iε adjuεted to 0.4 gram of the interpolymer per 100 ml. of acetone. A more detailed diεcuεsion of the reduced specific viscosity, also known as the specific viscoεity, aε well aε itε relationεhip to the average molecular weight of an interpolymer, appearε in Paul J. Flory, Principles of Polymer Chemistry. (1953 Edition) pages 308 et seq.

While interpolymers having reduced specific viεcosi- ty of from about 0.05 to about 2 are contemplated in (C-l) , the preferred interpolymers are those having a reduced specific viscosity of from about 0.3 to about 1. In most instances, interpolymers having a reduced specific viscoεity of from about 0.5 to about 1 are particularly preferred.

From the standpoint of utility, as well aε for commercial and economical reaεonε, nitrogen-containing esters in which the high molecular weight ester group has from 8 to 24 aliphatic carbon atomε, the low molecular weight eεter group haε from 3 to 5 carbon atomε, and the carbonyl polyamino group iε derived from a primary— aminoalkyl-εubεtituted tertiary amine, particularly heterocyclic amineε, are preferred. Specific examples of the high molecular weight carboxylic ester group, i.e., the (OR) group of the ester radical (i.e., -(0)(OR)) include heptyloxy, isooctyloxy, decyloxy, dodecyloxy, tridecyloxy, tetradeσyloxy, pentadeσyloxy, octadecyloxy, eicoεyloxy, tricoεyloxy, tetracoεyloxy, etc. Specific exampleε of low molecular weight groupε include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, sec- butyloxy, iεo-butyloxy, n-pentyloxy, neo-pentyloxy, n-hexyloxy, cyclohexyloxy, xyxlopentyloxy, 2-methyl- butyl-1-oxy, 2,3-dimethyl-butyl-l-oxy, etc. In most instanceε, alkoxy groupε of suitable size compriεe the preferred high and low molecular weight eεter groupε. Polar substituentε may be preεent in εuch eεter groupε. Exampleε of polar εubstituents are chloro, bromo, ether, nitro, etc.

Exampleε of the carbonyl polyamino group include thoεe derived from polyamino compounds having one primary or secondary amino group and at least one mono-functional amino group εuch aε tertiary-amino or heterocyclic amino group. Such compoundε may thuε be tertiary-amino εubεti- tuted primary or εecondary amineε or other substituted primary or secondary amineε in which the substituent is derived from pyrroles, pyrrolidones, caprolactamε, oxazolidones, oxazoles, thiazoleε, pyrazoles, pyrazolines, imidazoles, imidazolineε, thiazineε, oxazines, diazines, oxycarbamyl, thiocarbamyl, uracilε, hydantoins, thiohydantoins, guanidines, ureas, εulfona ides, phosphoramides, phenolthiaznes, a idines, etc. Examples of such polyamino compounds include

dimethylamino-ethylamine, dibutylamino-ethylamine, 3-dimethylamino-l-propylamine, 4-methylethylamino-l- butylamine, pyridyl-ethylamine, N-morpholino-ethylamine, tetrahydropyridyl-ethylamine, bis-(dimethylamino)propyl- amine, bis-(diethylamino)ethylamine, N,N-dimethyl-p- phenylene diamine, piperidyl-ethylamine, 1-aminoethyl pyrazole, l-(methylamino)pyrazoline, l-methyl-4-amino- octyl pyrazole, 1-aminobutyl imidazole, 4-aminoethyl thiazole, 2-aminoethyl pyridine, ortho-amino-ethyl-N,N- dimethylbenzeneεulfamide, N-aminoethyl phenothiazine, N-aminoethylacetamidine, l-aminophenyl-2-aminoethyl pyridine, N-methyl-N-aminoethyl-s-ethyl-dithiocarbamate, etc. Preferred polyamino compoundε include the N-aminoalkyl-εubstituted morpholines such as aminopropyl morpholine. For the moεt part, the polyamino compounds are those which contain only one primary-amino or secondary-amino group and, preferably at leaεt one tertiary-amino group. The tertiary amino group iε preferably a heteroσyσliσ amino group. In εome instances polyamino compounds may contain up to about 6 amino groups although, in most instances, they contain one primary amino group and either one or two tertiary amino groups. The polyamino compounds may be aromatic or aliphatic amines and are preferably heterocycliσ amines such as amino-alkyl-substituted morpholines, piperazines, pyridines, benzopyrroles, quinolineε, pyrroleε, etc. They are uεually amines having from 4 to about 30 carbon atoms, preferably from 4 to about 12 carbon atoms. Polar substituents may likewise be present in the polyamines.

The carboxy-containing interpolymers include princi¬ pally interpolymers of alpha, beta-unsaturated acids or anhydrides such as maleic anhydride or itaconic anhydride with olefins (aromatic or aliphatic) such as ethylene, propylene, styrene, or isobutene. The styrene-maleic anhydride interpolymers are especially useful. They are obtained by polymerizing equal molar amounts of styrene and maleic anhydride, with or without one or more

additional interpolymerizable comonomers. In lieu of styrene, and aliphatic olefin may be used, such as ethylene, propylene or isobutene. In lieu of maleic anhydride, acrylic acid or methacrylic acid or ester thereof may be used. Such interpolymers are know in the art and need not be described in detail here. Where an interpolymerizable comonomer is contemplated, it should be present in a relatively minor proportion, i.e., less that about 0.3 mole, usually less than about 0.15 mole, per mole of either the olefin (e.g. styrene) or the alpha, beta-unsaturated acid or anhydride (e.g. maleic anhydride) . Various methods of interpolymerizing styrene and maleic anhydride are known in the art and need not be discusεed in detail here. For purpose of illustration, the interpolymerizable comonomers include the vinyl monomers such as vinyl acetate, acrylonitrile, methylacrylate, methylmethacrylate, acrylic acid, vinyl methyl either, vinyl ethyl ether, vinyl . chloride, iεobutene or the like.

The nitrogen-containing eεters of (C-l) are most conveniently prepared by first esterifying the carboxy-containing interpolymer with a relatively high molecular weight alcohol and a relatively low molecular weight alcohol to convert at least about 50% and no more than about 98% of the carboxy radicals of the interpolymer to ester radicals and then neutralizing the remaining carboxy radicals with a polyamino compound such as described above. To incorporate the appropriate amounts of the the two alcohol groups into the interpolymer, the ratio of the high molecular weight alcohol to the low molecular weight alcohol used in the proceεε should be within the range of from about 2:1 to about 9:1 on a molar basis. In most instances the ratio is from about 2.5:1 to about 5:1. More than one high molecular weight alcohol or low molecular weight alcohol may be used in the process; so also may be used commercial alcohol mixtures such as the so-called

Oxoalcoholε which comprise, for example mixtures of alcohols having from 8 to about 24 carbon atoms. A particularly useful claεs of alcohols are the commercial alcohols or alσohol mixtures comprising decylalcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol and octadecyl alcohol. Other alcohols useful in the process are illustrated by those which, upon eεterification, yield the eεter groups exemplified above.

The extent of esterification, as indicated previous¬ ly, may range from about 50% to about 98% conversion of the carboxy radicals of the interpolymer to ester radi¬ cals. In a preferred embodiment, the degree of esterification rangeε from about 75% to about 95%.

The esterification can be acσomplished εimply be heating the carboxy-containing interpolymer and the alcohol or alcoholε under conditions typical for effect¬ ing esterification. Such conditions usually include, for example, a temperature of at least about 80*C, preferably from about 150°C to about 350*C, provided that the temperature be below the decomposition point of the reaction mixture, and the removal of water of esterification as the reaction proceeds. Such conditions may optionally include the use of an excess of the alcohol reactant so as to facilitate esterification, the use of a εolvent or diluent εuch as mineral oil, toluene, benzene, xylene or the like and a esterification catalyst such as toluene sulfonic acid, sulfuric acid, aluminum chloride, boron trifluoride=triethylamine, hydrochloric acid, ammonium sulfate, phosphoric acid, sodium methoxide or the like. These conditions and variations there of are well know in the art.

A particularly desirable method of effecting esterification involves first reaσting the carboxy- containing interpolymer with the relatively high molecular weight alcohol and then reacting the partially esterified interpolymer with the relatively low molecular

weight alcohol. A variation of thiε technique involveε initiating the eεterification with the relatively high molecular weight alcohol and before εuch eεterification is complete, the relatively low molecular weight alcohol is introduced into the reaction masε εo aε to achieve a mixed esterification. In either event it has been discovered that a two-step eεterification process whereby the carboxy-containing interpolymer is first esterified with the relatively high molecular weight alcohol εo aε to convert from about 50% to about 75% of the carboxy radicalε to eεter radicalε and then with the relatively low molecular weight alcohol to achieve the finally deεired degree of eεterification reεultε in productε which have unuεually beneficial viscosity properties.

The esterified interpolymer is then treated with a polyamino compound in an amount εo aε to neutralize substantially all of the unesterified carboxy radicalε of the interpolymer. The neutralization iε preferably carried out at a temperature of at leaεt about 80*C, often from about 120*C to about 300*C, provided that the temperature doeε not exceed the decomposition point of the reaction masε. In most instances the neutralization temperature is between about 150*C and 250*C. a slight excess of the stoichiometric amount of the polyamino compound is often desirable, εo aε to inεure substantial completion of neutralization, i.e., no more than about 2% of the carboxy radicals initially preεent in the interpolymer remained unneutralized.

The following examples are illustrative of the preparation of (C-l) of the preεent invention. Unleεε otherwiεe indicated all partε and percentageε are by weight.

EXAMPLE (C-l)-l

A εtyrene-maleic interpolymer iε obtained by prepar ing a solution of styrene (16.3 parts by weight) and maleic anhydride (12.9 parts) in a benzene-toulene solution (270 parts; weight ratio of benzene:toluene

being 66.5:33.5) and contacting the solution at 86*C. in nitrogen atmosphere for 8 hours with a catalyst εolution prepared by diεsolving 70% benzoyl peroxide (0.42 part) in a similar benzene-toulene mixture (2.7 partε). The reεulting product is a thick slurry of the interpolymer in the solvent mixture. To the slurry there is added mineral oil (141 parts) while the solvent mixture is being distilled off at 150*C. and then at 150*C./200 mm. Hg. To 209 parts of the stripped mineral oil- interpolymer slurry (the interpolymer having a reduced εpecific viscosity of 0.72) there are added toluene (25.2 parts), n-butyl alcohol (4.8 parts), a commercial alcohol consisting essentially of primary alcoholε having from 12 to 18 carbon atoms of primary alcohols having from 12 to 18 carbon atoms (56.6 parts) and a commercial alcohol consisting of primary alcohols having from 8 to 10 carbon atoms (10 partε) and to the reεulting mixture there iε added 96% sulfuric acid (2.3 parts). The mixture is then heated at 150°-160*C. for 20 hours whereupon water iε diεtilled off. An additional amount of εulfuric acid (0.18 part) together with an additional amount of n-butyl alcohol (3 parts) is added and the esterification is continued until 95% of the carboxy radicals of the polymer haε been eεterified. To the eεterified interpolymer, there iε then added aminopropyl morpholine (3.71 partε; 10% in exceεs of the stoichiometric amount required to neutralize the remaining free carboxy radi¬ cals) and the resulting mixture iε heated to 150° -160*C./10 mm. Hg to diεtill off toluene and any other volatile componentε. The εtripped product iε mixed with an additional amount of mineral oil (12 parts) filtered. The filtrate is a mineral oil εolution of the nitrogen- containing mixed ester having a nitrogen content of 0.16-0.17%.

EXAMPLE (C-l)-2

The procedure of Example (C-l)-l is followed except

that the esterification is carried out in two stepε, the firεt step being the esterification of the εtyrene-maleiσ interpolymer with the commercial alcoholε having from 8 to 18 carbon atomε and the εecond εtep being the further esterification of the interpolymer with n-butyl alcohol.

EXAMPLE (C-l)-3 The procedure of Example (C-l)-l is followed except that the esterification is carried out by first esterifying the εtyrene-maleic interpolymer with the commercial alcohol having from 8 to 18 carbon atomε until 70% of the carboxyl radicalε of the interpolymer have been converted to ester radicals and thereupon continuing the esterification with any yet-unreacted commercial alcohols and n-butyl alcohol until 95% of the carboyle radicalε of the interpolymer have been converted to eεter radicalε.

EXAMPLE (C-l)-4 The procedure of Example (C-l)-l iε followed except that the interpolymer iε prepared by polymerizing a εolution conεiεting of εtyrene (416 partε) , maleic anhydride (392 parts) , benzene (2153 parts) and toluene (5025 partε) in the preεence of benzoyl peroxide (1.2 partε) at 65*-106*C. (The resulting interpolymer has a reduced specific viscoεity of 0.45)

EXAMPLE (C-l)-5 The procedure of Example (C-l)-l is followed except that the styrene-maleic anhydride iε obtained by polymer¬ izing a mixture of εtyrene (416 partε) , maleic anhydride (392 partε) , benzene (6101 partε) and toluene (2310 partε) in the preεence of benzoyl peroxide (1.2 partε) at 78*-92*C. (The resulting interpolymer has a reduced specific viscoεity of 0.91)

EXAMPLE (C-l)-6

The procedure of Example (C-l)-l iε followed except that the εtyrene-maleic anhydride is prepared by the following procedure: Maleic anhydride (392 partε) is disεolved in benzene (6870 parts) . To this mixture there

iε added εtyrene (416 partε) at 76"C. whereupon benzoyl peroxide (1.2 partε) is added. The polymerization mixture is maintained at 80-82*C. for about 5 hours. (The resulting interpolymer haε a reduced εpecifiσ viεcoεity of 1.24.)

EXAMPLE (C-l)-7

The procedure of Example (C-l)-l is followed except that acetone (1340 parts) is used in place of benzene as the polymerization εolvent and that azobiε- iεobutyronitrile (0.3 part) iε uεed in place of benzoyl peroxide aε a polymerization catalyst.

EXAMPLE (C-l)-8

An interpolymer (0.86 carboxyl equivalent) of styrene and maleic anhydride (prepared from an equal molar mixture of styrene and maleic anhydride and having a reduced specific viscoεity of 0.67-0.68) is mixed with mineral oil to form a slurry, and then esterified with a commercial alcohol mixture (0.77 mole; comprising primary alcohols having from 8 to 18 carbon atoms) at 150-160* C. in the presence of a catalytic amount of sulfuric acid until about 70% of the carboxyl radicals are converted to ester radicals. The partially esterified interpolymer is then further esterified with a n-butyl alcohol (0.31 mole) until 95% of the carboxyl radiσals of the interpolymer are converted to the mixed eεter radicalε. The eεterified interpolymer is then treated with aminopropyl morpholine (slight excess of the stoichiometriσ amount to neutralize the free carboxyl radicals of the interpolymer) at 150-160* C. until the resulting product is subεtantially neutral (acid number of 1 to phenolphthalein indicator) . the reεulting product iε mixed with mineral oil εo aε to form an oil solution containing 34% of the polymeric product.

The second viscosity modifying composition (C-2) is similar to (C-l) in all respects except that the carboxy containing interpolymer has a reduced εpecific viεcoεity of from about 0.05 to about 1 and being characterized by

the presence within its polymeric structure of at least one of each of the following groups which are derived from the carboxy groups of said interpolymer:

(A') a carboxylic ester group, said carboxylic ester group having at least eight aliphatic carbon atoms in the ester radical, and

(B ⁷ ) a carbonyl-polyamino group derived from a polyamino compound having one primary or secondary amino group and at least one mono- functional amino group, wherein the molar ration of carboxy groups of said interpolymer esterified to provide (A') to carboxy groups of said interpolymer neutralized to provide (B ⁷ ) is in the range of about 85:15 to about 99:1.

The (A ⁷ ) of (C-2) iε the εame aε the (A) of (C-l) and the (B ⁷ ) of (C-2) iε the εame aε the (C) of (C-l).

The following exampleε are illuεtrative of the preparation of (C-2) of the preεent invention. Unleεs otherwise indicated all partε and percentageε are by weight.

EXAMPLE (C-2)-l A εtyrene-maleic interpolymer iε obtained by prepar ing a εolution of εtyrene (536 partε) and maleic anhydride (505 partε) in toluene (7585 partε) and con¬ tacting the εolution at a temperature of 99-101*C and an abεolute preεεure of 480-535 mm. Hg. with a catalyεt εolution prepared by diεεolving benzoyl peroxide (2.13 partε) in toluene 51.6 partε). The catalyεt εolution iε added over a period of 1.5 hourε with the temperature maintained at 99-101*C. Mineral oil 2496 partε iε added to the mixture. The mixture iε maintained at 99-101*C and 480-535 mm Hg. for 4 hourε. The reεulting product iε a εlurry of the interpolymer in the εolvent mixture. The reεulting interpolymer haε a reduced εpecific viεcoεity of 0.42.

EXAMPLE (C-2 ) -2

A toluene slurry (2507 parts), having 11.06% solids and 88.94% volatiles, of the maleic anhydride/styrene interpolymer of Example (C-2)-l, Neodol 45 (632 partε), a product of Shell Chemical Company identified as a mixture of C14 and C15 linear primary alcohols, mineral oil (750 partε), and Ethyl Antioxidant 733 (4.2 partε), a product of Ethyl identified as an isomeric mixture of butyl phenols, are charged to a vessel. The mixture iε heated with medium agitation under nitrogen purge at 0.5 εtan- dard cubic feet per hour until the temperature reacheε 115*C. 70 % methane εulfonic acid catalyεt in water (10.53 parts) is added dropwise over a period of 20 minutes. Nitrogen purge is increased to 1.0 standard cubic feet per hour and temperature is raised by removal of toluene-water distillate. The mixture is maintained at a temperature of 150"C for five hours under a nitrogen purge of 0.1-0.2 standard cubic feet per hour. Addition¬ al methane sulfonic acid solution (15.80 parts) is added to the mixture over period of 15 minutes. The mixture is maintained at 150*C for 3.5 hours. The degree of esterification iε 95.08%. Amino propylmorpholine (35.2 parts) is added to the mixture dropwise over a period of 20 minuteε. The mixture iε maintained at 150"C for an additional 30 minutes then cooled with stirring. The mixture is εtripped from 50*C to 141*C at a preεεure of 102 mm.Hg. then permitted to cool. At a temperature of 100'C, mineral oil (617 partε) is added. Cooling is continued to 60*C. At 60*C, diatomaceous earth (36 partε) iε added and the mixture iε heated to 100*C. The mixture is maintained at 100-105 ^* C for one hour with stirring and then filtered to yield the desired product.

EXAMPLE (C-2)-3

The procedure of Example (C-2)-2 iε repeated with the exception that both Neodol 45 (315.4 partε) and Alfol 1218 (312.5 partε), a product of Continental Oil Company identified aε a mixture of εynthetic primary εtraight

chain alcohols having 12 to 18 carbon atoms, are initial¬ ly charged, rather than the 631 parts of Neodol 45 which were included in the initial charge in Example 2.

EXAMPLE (C-2)-4 A toluene slurry (1125 partε), having 13.46% εolidε and 86.54% volatileε, of the maleic anhydride/εtyrene interpolymer of Example (C-2)-l, mineral oil (250 partε) and Neodol 45 (344 partε) are charged to a veεεel. The mixture iε heated with medium agitation under nitrogen εweep of 0.5 εtandard cubic feet per hour until the temperature reaches 110*C. Paratoluene sulfonic acid (8.55 parts) in water 9 parts) is added dropwise over a period of 24 minutes. The temperature of the mixture iε increaεed to 152"C by removing toluene-water diεtillate. The temperature is maintained at 152-156*C under nitrogen sweep of 0.5 standard cubic feet per hour until the net acid number indicateε that esterification is at leaεt 95% complete. Aminopropylmorpholine (15.65 partε) iε added dropwiεe over a period of 10 minuteε. The temperature of the mixture iε maintained at 155*C for 1 hour and then cooled under a nitrogen εweep. Ethyl Antioxidant 733 (1.48 partε) iε added to the mixture. The mixture iε εtripped at 143"C and 99 mm.Hg. preεεure. The mixture iε cooled under nitrogen sweep. Mineral oil is added to provide a total 63% dilution. Ethyl Antioxidant 733 (1.79 parts) is added and the mixture is εtirred for 30 minuteε. The mixture iε heated 60*C while εtirring with a nitrogen εweep of 0.5 standard cubic feet per hour. Diatomaceous earth (18 parts) iε added to the mixture. The mixture iε heated to 90*C. The temperature of the mixture is maintained at 90-100*C for 1 hour and then filtered through a pad of diatomaceous earth (18 partε) in a heated funnel to yield the deεired product.

EXAMPLE (C-2)-5 The procedure of Example (C-2)-4 iε repeated with the exception that both Neodol 45 (172 partε) and Alfol 1218 (169 parts) are provided in the initial charge.

rather than the 344 parts of Neodol 45 provided in Example 4.

EXAMPLE (C-2)6 The product of Example (C-2)-1 (101 partε, Neodol 91 (56 parts(, a product of Shell Chemical Company identi¬ fied as a mixture of C9, CIO, and Cll alcohols, TA-1618 (92 parts) , a product of Procter & Gamble identified as a mixture of C16 and C18 alcohols, Neodol 25 (62 partε), a product Shell Chemical Company identified as a mixture of C12, C13, C14, and C15 alcohols, and toluene (437 parts) are charged to a vessel. The veεεel iε εtirred and the contents are heated. Methane sulfonic acid (5 parts) is added to the mixture. The mixture is heated under reflux conditions for 30 hours. Aminopropyl morpholine (12.91 parts) is added to the mixture. The mixture is heated under reflux conditions for an additional 4 hours. Diatomaceous earth (30 parts) and a neutral paraffinic oil (302 parts) are added to the mixture whiσh is then εtripped. The residue is filtered to yield 497.4 parts of an orange-brown visσous liquid.

EXAMPLE (C-2)-7 The produσt of Example (C-2)-l (202 pairtε) , Neodol 91 (112 parts) , TA 1618 (184 parts) , Neodol 25 (124 parts and toluene (875 parts) are charged to a vessel. The mixture is heated and stirred. Methane sulfonic acid (10 parts) is added to the mixture which is then heated under reflux conditions for 31 hours. Aminopropyl morpholine (27.91 partε) iε added to the mixture which is then heated under reflux conditions for an additional 5 hours. Diatomaceous earth (60 parts) is added to the mixture which is then stripped, 600 parts o polymer remaining in the vessel. A neutral paraffinic oil (600 parts) is added to the mixture which is then homogenized. The mixture is filtered through a heated funnel to yield 1063 parts of a clear orange-brown viεcouε liquid.

EXAMPLE (C-2)-8 The product of Example (C-2)-l (101 partε), Alfol

810 (50 parts) , a product of Continental Oil Company identified aε a mixture of C8 and CIO alcoholε, TA-1618 (92 partε) , Neodol 25 (62 parts) and toluene (437 parts) are charged to a vessel. The mixture is heated and stirred. Methane sulfonic acid (5 parts) is added to the mixture which is heated under reflux conditionε for 30 hourε. Aminopropyl morpholine (15.6 partε) iε added to the mixture which is then heated under reflux conditions for an additional 5 hourε. The mixture iε εtripped to yield 304 parts of a yellow-orange viscouε liquid. Diatomaceouε earth (30 parts) and a neutral paraffinic oil (304 parts) are added to the mixture which is then homogenized. The mixture is filtered through a heated funnel to yield 511 partε of a clear amber viεcouε liquid.

EXAMPLE (C-2)-9 A toluene εlurry (799 partε) of a maleiσ anhydride/εtyrene interpolymer (17.82% polymer) iε σharged to a vessel. The reduced εpecifiσ viεσoεity of the interpolymer iε 0.69. The veεεel iε purged with nitrogen while εtirring the contentε for 15 minuteε. Alfol 1218 (153 partε) , Neodol 45 (156 partε) and 93% εulfuric acid (5 partε) are added to the mixture. Toluene (125 parts) is then added to the mixture. The mixture is heated at 150-156"C for 18 hourε. Aminopropyl morpholine (1.3 partε) iε added to the mixture which iε then heated for an additional 1 hour at 150*C. The mixture iε cooled to 80*C. Ethyl Antioxidant 733 (1.84 partε) iε added to the mixture. The mixture iε εtripped at 143*C and 100 mm.Hg. Mineral oil (302 partε) and Ethyl Antioxidant 733 (2.5 partε) iε added to the mixture while the mixture iε εtirred. Diatomaceouε earth (25 parts) is added to the mixture. The temperature of the mixture iε maintained at 70*C for 45 minuteε and then heated to 110*C. Diatomaceouε earth (25 parts) is added to the mixture. The mixture is filtered through diatomaceouε earth to yield the deεired product.

EXAMPLE (C-2)-10 A toluene and mineral oil εlurry (699 partε) con taining 17.28% εolids of a maleic anhydride/styrene interpolymer (reduced specifiσ viεcoεity of 0.69), Neodol 45 (139 parts) , Alfol 1218 (138 parts) , Ethyl Antioxidant 733 (2.9 parts) and toluene (50 parts) are charged to a vesεel. The mixture iε heated under a nitrogen purge at 0.5 εtandard cubiσ feet per hour. 70% methane sulfoniσ acid (3.9 parts) iε added dropwise over a period of 9 minutes. The mixture is heated under reflux conditions for 35 minutes. Toluene (51 parts) is added to the mixture which is then heated for an additional 3 hours 15 minutes under reflux conditions. 70% methane sulfoniσ aσid (3 parts) is added dropwise over a period of 3 minutes. The mixture is heated under reflux conditions for 3 hourε 15 minuteε. 70% methane εulfonic aσid (3.9 parts) is added dropwise over a period of 12 minuteε. The mixture iε heated at 150-152*C for 3 hourε 45 min¬ uteε. Aminopropyl morpholine (14.3 parts) is added to the mixture dropwise over a period of 15 minutes. The mixture is maintained at a temperature of 149-150*C for an additional 30 minutes. The mixture iε stripped at 140*C and 100 mm.Hg. The mixture is cooled to 50°C. Mineral oil (338 parts) and diatomaceous earth (19 parts) are added to the mixture. The temperature of the mixture iε maintained at 100-105*C for 1.5 hourε and then fil¬ tered through additional diatomaσeous earth (18 parts) to yield the desired produσt.

D. A Svnthetiσ Ester Base Oil

Components (A) , (B) and (C) may further comprise compoment (D) a synthetic ester base oil. The εynthetic eεter base oil comprises the reaction of a monocarboxylic acid of the formula

R ¹⁶ — COOH

or a dicarboxylic aσid of the formula

R ¹⁷ —CHCOOH

CH ₂ COOH

with an alσohol of the formula

R ¹⁸ (OH).

wherein R is a hydroσarbyl group σontaining from about 5 to about 12 σarbon atoms, R 17 iε hydrogen or a hydroσarbyl group containing from about 4 to about 50 carbon atomε, R 18 iε a hydrocarbyl group containing from

1 to about 18 σarbon atomε, m is an integer of from 0 to about 6 and n is an integer of from 1 to about 6.

Useful monoσarboxyliσ aσids are the iεomeriσ σarboxyliσ aσidε of pentanoiσ, hexanoiσ, oσtanoiσ, nonanoiσ, deσanoiσ, undeσanoiσ and dodeσanoiσ aσids. When R 17 is hydrogen, useful diσarboxyliσ aσidε are εuσσiniσ aσid, maleiσ aσid, azelaiσ aσid, suberic aσid, sebaσiσ acid, fumaric aσid and adipiσ aσid. When R 17 iε a hydroσarbyl group σontaining from 4 to about 50 σarbon atomε, the uεeful dicarboxylic acids are alkyl sucσiniσ acids and alkenyl succinic acids. Alcoholε that may be employed are methyl alσohol, ethyl alσohol, butyl alσo¬ hol, the iεomeriσ pentyl alσoholε, the isomeriσ hexyl alσohols, dodeσyl alσohol, 2-ethylhexyl alσohol, ethylene glyσol, diethylene glyσol, propylene glycol, neopentyl glycol, pentaerythritol, dipentaerythritol, etc. Specific examples of these esters include dibutyl adipate,

di(2-ethyhexyl) sebaσate, di-n-hexyl fumarate, dioσtyl εebaσate, diiεooσtyl azelate, diiεodeσyl azelate, dioσtylphthalate, dideσyl phthalate, dieiσosyl sebaσate, the 2-ethylhexyl diester of linoleiσ aσid dimer, the σomplex eεter formed by reaσting one mole of εebaσiσ aσid with two moles tetraethylene glyσol and two moles of 2-ethylhexanoiσ aσid, the ester formed by reaσting one mole of adipiσ aσid with 2 moles of a 9 σarbon alσohol derived from the oxo proσess of a 1-butene dimer and the like.

The σompositions of the present invention σomprising σomponents (A) , (B) and (C) or (A) , (B) , (C) and (D) are useful as a multipurpose power transmission fluid. The following states the ranges of σomponents (A) , (B) , (C) and (D) in parts by weight

Compoment

(A) (B) (C) (D)

It iε underεtood that other σomponentε besides (A) , (B) , (C) and (D) may be present within this multipurpose power transmission fluid.

Component (B) σomprises (B-l), (B-2) , (B-3) , (B-4) and (B-5) . The following stateε the ranges of those sub σomponents as a funσtion of the range of (B) .

The following Table II outlineε exampleε εo aε to provide those of ordinary skill in the art with a complete disclosure and description on how to make the functional fluid of this invention and are not intended to limit the scope of what the inventor regards aε hiε invention. All partε are by weight.

TABLE II

Example Number

Ingredients

Rapseed oil

Synthetic fluid di 2-ethylhexyl alcohol/azelaic acid (2/1)m 1-butene dimer oxoalcohol/adipic acid (2/1)m

Foam inhibitor

Example (C-2)-2

Example (C-D-1

Example <B-1)-5

Propylenetetramer phenol/S C1 (4:3)m

Calcium overbased salicylate

Example (B-2)-7

Example (B-2)-8

Example 4b)-5

M,M-di henylamine

Oleamide-linoleomide mixture

Example (B-4a)-1

DMTD/formeldehyde/heptylphenol