CA1183125A - Compositions, concentrates, lubricant compositions and methods for improving fuel economy of internal combustion engines - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Fuel economy of internal combustion engines, especially gasoline engines, is improved by lubricating such engines with lubricant compositions comprising A. at least one tartrate of the formula

Description

Title: Comp~itions, Concentrates, Lubricant Compositions and Methods for Improv;ng~ Fuel Economy of Internal Combustion Engines BACK(3ROUND OF THE INVENTION
Thîs invention relates to compositions and methods for improving the operation of internal combustion engines, speeifically by reducing the amount of fuel consumed by such engines. More particularly, the invention 5 comprises lubricating compositions which may be used in such engines to decrease fuel consumption, and a method of using such lubricating compositions to accomplish this purpose.
Efforts to reduce the amount of fuel consumed by internal combustion engines such ~s automobile engines have increased in recent 10 years as a result of the petroleum shortage, the increas2d cost of petroleum products, and the desire for conservation of natural resources such as petroleum. It is recognized that a situation under which fuel consumption is minimized is desirable, both because of the conservation factor and because such a situation is economical for the user o~ the engine.
Many OI the proposed solultions to the ~uel consewation problem have been mechanical, as for example, adjusting the engine for a leaner burn or simply building smaller cars and smaller engines. Other efforts have related to developing lubricants that reduce the overall friction of the engine thereby reduci~ energy requirements. Some synthetie lubricants 20 have been developed and compounded for use in the automobile engine to reduce fuel consumption. A considerable amount of effort has been expended toward developing additives for use in mineral lubricating oils and greases to reduce the friction properties of the oils and greases.
Oil-soluble aliphatic polycarboxylic acids including those wherein 25 the aliphaffe group contains one or more hydroxyl groups have been suggested as additives for use in mineral lubricating oils and motor fuels to improve the perIormance OI the oils and motor fuels. U~S. Patents 2,370,299 and 2,37Q,300 describe compounded lubricants comprising lubricating oil containing organic esters which comprise an aliphatic alcohol of from 10 to 30 30 carbon atoms esterified with a hydroxy aliphatic acid having at least one hydroxyl group. The presence of the organic ester decreases the coefficient of friction between metal frictional surfaees at low rubbing speeds.

~3~ S

Lubricating oils and motor fllels ContAinirlg derivatives of tartaric acid with various amines and amino alcohols are described in U.S. Patents 23977,309; 2~865,723; 2,811,~29; 3,183,069 and 4~237,022~ In general, the rust inhibition and anti-oxidation properties of the lubricants and fuels are improved by these amino derivatives.
U.~. Patent 2,715,108 describes a lubricating oil useful particularly as a turbine oil which contains an additive amount o~ a mixture of an aliphatic polycarbcxylic acid or partial ester thereoI, and oil-soluble phenolic compound or its thio or seleno analogs, and an aromatic carboxylic acid. This mixture added to a turbine oil results in improved rust and corrosion inhibition and improved resistance to emulsification in the presence of water. Mineral oils containing a small amount of an ester of a trialkylammonium acid salt of a hydroxy aliphatic dicarboxylic acid and a primary, aliphatie, monohydric alcohol are described in U.S. Patent 2,585,877. In addition to the beneficial effects on rust inhibition, the additive improves the arlti-wear properties and cutting ef~iciencies of mineral oilsO Extreme pressure lubricants containing compounds obtained by reacting aliphatic hydroxy carboxylic acids and lower aliphatic polyhydric alcohols are described in U.S. Patent 2,755,250. Mineral transformer oils are described in U.S. Patent 2,397,332 which include a small amount of a tartaric di~acid ester of a eyclic alcohol. The extreme pressure properties of lubricants are reported to be improved in U.S. Patent 2,628,941 by incorporating into lubricatin~ compositiolls a reaction product obtained by reacting a polyacidic compound containing from 1 to 3 free carboxylic acid groups and at least one hydroxy group with an alkylene oxide, an alkylene sulfide or an alkylene imine.
SUMMARY OF TH~ INVENTION
In its broadest sense, the present invention provides a multi-component composition comprising A. at least one tartrate of the formula HO-CHCO R

HO-CHCo2 R
wherein each R is independen~ly a hydrocarbon-based group and the sum of carbon atoms in both the R groups is at least about 8; and B. àt least one oil soluble detergent and dispersant;

3~S

and the use of such compositions in lubricating oils for internal eombustion engines. Lubricating oils containing the compositions of the invention are effective in reducing the amount of fuel consumed by internal combustion engines. The invention also relates to a method of reducing the amount of S fuel consumed by an intern&l combustion engine. The lubricants also can contain other additives such as corrosion- and oxidation-inhibiting agents, pour point depressing agents, viscosity-improving components, color stabi lizers snd anti-îoam ~ents.
D~SCD PIION O- ~IID Pr~l8ERRFD EMBO131MENTS
As mentioned above, the multi-component compositions of the invention comprise, in the broadest sense, component A which is at least one tartrate and component B which is an oil-soluble detergent or dispersant, or mixtures thereof.
~a~
Component A of the compositions OI the invention is at least one tartrate of the formula H~}CHC02R
H~CHC02R
wherein each R is independently a hydrocarbon-based group, and the sum of the carbon atoms in both R groups is at least about 8.
One method of preparing the tartrates represented by the above formula involves esterification of tartaric acid with an alcohol or mixture of alcohols which are preferably monohydric alcohols.
The monohydric alcohols which can be employed to provide the tartrate compounds with the desired R groups are well known and can compriset for example, primary and secondary aliphatic aleohols. The preferred monohydric alcohols, however, are primary aliphatic alcc hols, especially 1iphatic hydrocarbon alcohols such as alkenols and alkanols of from about 4 to about 40 carbon atoms, and preferably from about 8 to about 40 carbon ~toms. Mixtures of alcohols can be utilized provided that the total number of carbon atoms in the two R groups is at least about 8.
More preferably, each R group is derived from a monohydric alcohol containing at least 8 carbon atomsO Accordingly, examples of the preferred monohydric alcohols from which the R group is derived include l-octanol, l-decanol, l-dodec~mol, l-tetradecanol, l-hexadecanol, l-octadecanol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, phytol, myricyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl aleohol and behenyl alcohol.
C)f course, commerci~l alcohols (mixtures) are contemplated herein9 and these commercial alcohols may comprise minor amount~s of 5 alcohols which9 although not specified herein, do not detract from the major purposes of this invention. Higher synthetic monohydric alcohols of the type formed by the Oxo process (e.g., 2-ethylhexyl), the aldol condensation, or by organoaluminum-catalyzed oligomerization of alpha-olefins (especially ethylene), followsd by oxidation~ also are useful.
,~ 10 Examples of some preferred monohydric alcohols and alcohol mixtures suitable for forming the tartrates useful in the compositions of the invention include commercially available "Alfol" ~alcohols marketed by Continental Oil Corporation. Alfol 810 is a mixture containing alcohols consisting essentially of straight chain, primary alcohols having from 8 to 10 carbon atoms. The Alfol 20+ alcohols are mixtures of C18-C28 primary alcohols having mostly, on an alcohol basis, C20 alcohols as determined by GLC (gas-liquid-chromatography). The Alfol 22~ alcohols are C18-C28 primary alcohols having mostly, on an alcohol basis, C22 alcohols. These Alfol alcohols can contain a fairly large percentage (up to 40% by weight) of paraffinic compounds which can be removed before the esterification rea¢ffon if desired.
Another example of a commercially available alcohol mixture is Adol 6~ which comprises about 75% by weight of a straight chain C2~
primary alcohol, about 15% of a C20 primary alcohol and about 8% of C18 and C2a,L alcohols. Adol 60 is marketed by Ashland Chemical.
A variety of mixtures of monohydric fatty alcohols derived from naturally occurring triglycerides and ranging in chain length of from C8 to G18 are available from Procter ~c Gamble Company. These mixtures contain various amounts of fatty alcohols containing mainly 12,14,16, or 18 carbon atoms. For example, CO-1214 is a fatty alcohol mixture containing 0.5% of Clo alcohol, 66.0% of C12 alcohol, 26.0% of C14 alcohol and 6.596 of C16 alcohol.
Another group of commercially available mixtures include the "Neodol" products available from Shell Chemical Co. For example, Neodol tr.l61~ Ma~ I<s 23 is a mixture of C12 and C13 alcohols; Neodol 2S is a mixture of C12 and C15 alcohols; and Neodol 45 is a mixture of C14 and C15 alcohols.
Fatty vicinal diols also are useful and these include those available from Ashland Oil under the general trade designation Adol 114L and 5 Adol 15û. The former is derived from a straight chain ~pha olefin fraction of Cll-C14, and the latter is derived from a C15-Cl~ fraction.
~ a~amples of preferred branched chain monohydric alcohols suit-able for formir~ the tartrates useful in the present invention include, for example, commercial tridecyl alcohol corresponding in large part substan-10 tially to the formula CH3CH2CH(CH3)CH(CH3)CH(CH3)CH(CH3)CH2CH2CH20H
prepared by the Oxo process and which is available from Exxon Corporation,hexadecyl alcohol prepared by the Oxo process, 12-methylpentadecyl alcohol, 6-methyldecyl alcohol, 8-ethyltetradecyl alcohol, 5,6-dipropyldecyl alcohol 15 as well as mixtures of these alcohols. Branched chain alcohols of from 12 to 14 carbon atoms with one or more methyl branches are the more preferred.
The tartrates represented by the above formula can be obtained by esterification of tartaric acid with one or more of the above described alcohols under conditions whi¢h are typical for effecting esterification.
20 Such conditions include, for example, a temperature of up to the reflux temperature of the mixture provided that the temperature is maintained at a level below the decomposition of the reaction mixture or any products thereof. Water normally is removed as the esterifi¢ation proceeds. These conditions option~lly may include the use of ~n excess amount of alcohol 25 over the stoichiometric requirements for complete esterification with the alcohols in order to facilitate the esterification reaction~
Generally, the esterification reaction is conducted in a substan-tially inert, normally liquid, organic solvent or diluent such as minerAl oil, toluene, benzene, xylene and the like. Esterification catalysts are included 3n in the mixtuPe, and these catalysts include toluene sulfonic acid, sulfuric acid, aluminum chloride, boron trifluorîde~triethylamine, methane sulfonic acid, hydrochlor;c acid, ammonium sulfate, phosphoric acid, sodium methox-ide, etc.
The followin~ examples illustrate the procedure for preparing the 35 tartrates useful RS component A in the compositions of the invention.
Unless otherwise indicated, all parts and percentages are by weight.

~e~
A mixture of 153 parts of DL tartaric acid hydrate, 400 parts of Procter & Gamble's CO-1214~ an alcohol mixture containing principally C12 and C14 aliphatic alcohols, one part of toluene sulfonic acid and 500 parts of 5 toluene is heated to the reflux temperature of the mi~cture. Nitrogen is blown below the surface of the liquid and water is rernoved as the temperature re~ches 1~0 C. A total of 35 parts of water are collected. The residue i5 filtered through a filter aid, and the filtrate is the desired product.
10 ~
A mixture of 95 parts of meso-tartaric acid, 226 parts of the alcohol mixture used in Example 1, and 0.5 part of toluene sulfonic acid is heated to reflux with nitrogen blowing. At a temperature of 160 C, 25 parts of water are eollected. The mixture is cooled to 145-155C and heated for lS an additional two hours. The reaction mixture is filtered through a filter aid~ and the filtrate is the desired product.
E~
A mixture of 800 parts of the alcohol mixture of Example 1 and 14 parts of water is heated to 50 C whereupon sulfuric acid (107 parts~ is added 20 dropwise over a pePiod of two hours and the temperature of the mixture reaches 60C. Potassium bitartrate t376 parts) is added over ten minutes using high speed stirring followed by heating to a temperature of about 94 C
for one hour. Xylene (500 ml.~ is added and the mixture is heated to reflux while collecting water. The temperature of the reaction mixture reaches 25 165C near the end of the esterification. 85 parts of water are collected.
The residue is stripped at 140C and 30 mm. Hg. This residue is filtered through a filter aid, and the filtrate is the desired product.
~e~
A mixture of 150 parts of tartaric acid, 288 parts of Alfol 8-10 (a 30 commercial mixture of C8 and C10 aliphatic alcohols~, 1.12 parts of para-toluene sulfonic acid and 400 parts of toluene is heated to reflux while collecting water in a sidearm trap. A total of 34 parts of water was collected. The mixture is stripped to 150C/25mm Hg. Calcium hydroxide (0.44 parts~ is added with stirring for ten minutes at 80 C, and the mixture 35 is filtered through a filter aid. The filtrate is the desired product.

~3~

A mixture of 7S parts of tartaric acid, 468 parts of Alfol 22+ S.P.
and 1 part of para-toluene sulfonic acid is prepared and 400 parts of toluene is added. The mixture is heated to reflux for a total of thirteen hours and a total of 16 parts of water is collectedO The residue is stripped at 120C/Z5 mm. llg. and filtered through a filter aid. The filtrate is the desired product having a saponification number of 96.3 (t!heory is 107).
~e~
A mixture of 199 parts of tartaric acid, 718 parts of commercial alcohol mixture available flom Procter & Gamble under the general desig-nation "(~01895F" containing about 2% C16 and 96% C1~3 fatty aleohols, and 1.1 part OI para~toluene sulfonic acid is prepared and 500 parts of toluene is added. This mixture is heated to reflux for a total heating time of about thirteen hours, and 47 parts of water is collected in a sidearm trap. The mixture is stripped at 135 C/25 mm. Hg. The residue is filtered through a filter aid, and the filtrate is the desired product having a saponification number of 171 (theory is 172) and a melting point of 80-81 C.
_7 A
A mixture of 150 parts o~ tartaric acid, 590 parts of Aldol 158 (a commercial diol mixture available from Ashland Chemicals)9 500 parts of toluene and 1.1 part of para-toluene sulfonic acid is heated to reflux while collecting 33 parts OI water in a sidearm trap. The reaction mixture is stripped to 100C/25 mm. Hg, and the residue is filtered through a filter aid. The filtrate is the desired product having a saponification number OI
1$8 (repeat 157; theory is 159).

A mixture of 150 parts of tartaric acid5 414 parts of Neodol 23 (a commercial mixture of C12 and C13 alcohols), 1 part of para-toluene sulfonic acid and 500 parts of toluene is prepared and heated to reflux. Water (36 parts) is collected in a sidearm trap. The mixture then is stripped at 135C/27 mm. Hg. and filtered through a filter aid. The filtrate is the desired product having a saponification number of 218 (theory is 212) and a melting point of 5S-56 C.
Example 9-A
A mixture of 150 parts of tartaric acid, 436 parts of Neodol 45 (a tr~lt ~.rl~ ' commercial mixture of C14 and C15 alcohols)~ 1 part of para-toluene sulfonic acid and 500 parts of toluene is heated to reflux. Water (35 parts) is collected in a sidearm trap. The reaction mixture then is stripped at 110 C/21 mm. Hg. and filtered through a filter aid. The filtrate is the S desired product having a saponification mlmber of 189 (theory is 204).
Example 10-A
A rnixture of 112.5 parts of tartaric acid, 480 parts of Adol 60 (a commercially available alcohol containing about 75% by weight of a straight chain C22 primary alkanolJ about 15% of a C20 alcohol and about 8% of a mixture of C18 and C24 alcohols), 400 parts of toluene and 1 part of para-toluene sulfonic acid is heated to reflux. Water (25.5 parts) is collected in A
sidearm trap. The mixture is stripped At 115C122 mm. Hg. and filtered through a filter aid. The filtrate is the desired product having a saponification number of 139 (theory is 149).
15 ~
A rnixture is prepared comprising 163 parts (2.2 moles) of n-butanol, 400 parts (2 moles) of the commercial mixture of alcohols OI
Example 1, 150 parts of tartaric acid (2 moles), 1 part of para-toluene sulfonic acid and 1000 parts of toluene. This mixture is heated to reflux 20 while collecting water (7B parts) in a sidearm trap. The mixture is stripped at 100C/17 mm. EIg. and filtered through a filter aid. The filtrate is the desired product having a saponification number of 260 (theory is 283).

A mixture of 1500 parts of tartaric acid, 4000 parts o the 2S commercial alcohol mixture of Example 17 2000 parts of toluene and 10 parts of para-toluene sulfonic acid is heated to reflux while removing 36û parts of water (theory is 360 parts). The reaction mixture is stripped at 105 C/23 mm. Hgo Calcium hydroxide ~4 parti) is added at 100C with stirring for fiIteen minutes. The reaction mixture is filtered through a filter aid, and 30 the filtrate is the desired product.

A mixture of 150 parts of tartaric acid, 484 parts of an alcohol mixture available from Procter & Gamble under the trade designation CO-~- 1418 (comprising 1-4% C12; 35-47% C14; 15-27% C16 and 30~ 40% Cl~ alcohols), 35 400 parts of toluene and 2 parts of para-toluene sulfonic acid is prepared and tr~J~ K

~3~

heRted to reflux while removing water through a sidearm trap. The mixture then is stripped to 122C at 16 mm. Hg. The residue is filtered while hot through a filter aid, and the filtrate is the desired produet.
ExamJ?le 14-A
A mixture of 102Q parts of potassium bitartrate and 200û parts of the alcohol mixture of Example 1 is prepared3 and 737 parts of hydrochloric aci* (37%) are added dropwise over a period of about twenty minutes. The mixture is heated while purging with nitrogen, and water is collected over a period o one hour of heating at about 105-115C. EIeating is continued to 140C over a period of seven hours while removing additional water. After cooling overnight9 the mixture is reheated to about 155 C and maintained at this temperature for about two hours while removing additional water~ The mixture then is filterecl at about 90 C through a filter aid, and the filtrate is the desired product.
E_~
To a mixture of 2000 parts of the alcohol mixture of Example 1 and 49 parts of water there is ~dded 383 parts OI sulfuric acid (969~) over a period of ~wenty minutes, followed by the addition of 1020 parts of potassium bitartrate over a period of ten minutes. This mixture is heated while purging with nitrogen, and water is removed beginning at about 120 C
and up to a temperature of about 155 C. After cooling overnight, the mixture is reheated to a temperature of about 155 165C while removing additional water. The total heating time at esterification temperature is seven hours. The mixture is filtered at about 90 C through a filter aid, and the filtrate is the desired product~

A mixture of 882 parts of maleic anhydride, 819 parts of water and 21.78 parts of anhydrolls sodium molybdate is prepared and warmed gently until the maleic anhydride dissolves. The mixture is heated to about 75 C
under a vacuum of about 20 inches of mercury to allow gentle reflux. While maintaining the vacuum at about 19-21 inches of mercury, 1525 parts of 30%
aqueous hydrogerl peroxide is added over a period of 3.75 hours at 73-78C
with external heating appliecl only as necessary to maintain this temperature range~ The yellow solution becomes orange-red indicating the absence of peroxide and the conversion of the maleic anhydride to tartari~ acid.

3~

A mixture of 2828 parts of ~he tartaric acid solution prepared above, 2994 parts of the alcohol mixture of Exarnple 1, and 41 parts of phosphoric acid (85%) is prepared and heated under a nitrogen flow to 165 C
over several hours while removing water by distillation. The mixture is held at 165 C for R total of twelYe hours9 anld after cooling to 50 C, 30 parts of calcium hydroxide is added ~t once. Vacuum is applied, and the mixture is heated to 145~ C at 20 mm. EIg. The reaction mixture is filtered through a filter aid, and the filtrate is the desired product.
COMPONENT 13 - THE DETER~5ENT OR DISPERSANT
The terms "detergent" and "di~;persant" as used in the lubricant art generally mean, respectively, a composition which is capable OI removing deposits from engine parts and a composition which is capable of retaining such deposits in suspension in the oil once they are removed. Eor the most part, detergents comprise basic metal salts or complexes of various organic compositions (normally acidic~ containing both a polar and a non-polar group, while dispersants comprise compositions also containi~ag a polar and a non-polar group but which are metal-free or, if they contain metal~ contain at most about 1.1 equivalents thereof per equivalent of acidic moieties. Both detergents and dispersants will be more fully characterized hereinafter, although their general nature is well known to the skilled lubricant chemist.
Detergents As noted above, most detergents are basic metal salts or com-plexes of a phenol, sulfonic acid, carboxylic acid or phosphorus acid. The metals are usually alkali metals or alkaline earth metals; that is~ they are members respectively of (:roup lA and Group IIA of the Periodic Table. For the purpose of the present invention, alkaline earth metal salts are preferred. The preferred alkaline earth metals are magnesium, calcium, strontium and b~rium, particularly calcium or barium and still more particularly calciurn.
The non-metalllc moiety of the salt or complex is ordinarily the anion of an organic acidic compound. Examples of such compounds are phenoLs, sulfonic acids, carboxylic acids and phosphorus acids.
The word "phenol", as used herein, denotes any hydroxyaromatic compound inclucling hydroxy compou~ds derived from fused-ring hydr~
35 carbons (e.g., naphthols and the like). Especially preferred in the 3~

preparation of component B are phenols substituted with aliphatic or cycl~
aliphatic groups having at least about 6 carbon atoms and up to as many as 7000 carbon atoms. Examples of such groups are hexyl, cyclohexyl, heptyl, decyl, eicosyl, and groups derived from the polymerization of olefins such as 5 ethyleneg propylene, 1-butene, 2-butene, isobutene and the like. Groups derived from polymers of propylene and commercial mixtures of butenes (comprising predominantly isobutene) ar~e preferred, especially those having a number average molecular weight (as determined, for example, by gel permeation chromatography) of about 150-1750 (containing about 10-125 10 aliphatic carbon atoms). The substituent and the aryl nucleus of the phenol may eontain other groups such as hydroxy, nitro, nitroso and sulfo groups.
Introduetion of the aliphatic or cycloaliphatic substituent onto the phenol can be effected by mixing the hydrocarbon (or a halogenated clerivative thereof, or the like~ and the phenol at a temperature of about 50-15 200 C in the presen~e of a suitable cat~lyst, such as aluminum trichloride,boron trifluoride, zine chloride or the like~ The substituent can also be introduced by other alkylation processes known in the art lt is irrelevant which position on the phenolic ring is substituted; any single isomer, or a mixture of isomers, may be used. Polysubstituted materials such as dialkyl 20 and trialkyl phenols may also be present9 either alone or in admixture with monoalkyl phenols.
Additional suitable phenols are polyphenols containing sulfur or alkylene bridges, typieally prepared by reaction of a simple phenol with sulfur, a sulfur halide such as sulfur monochloride or dichloride, or a lower 25 aliphatic aldehyde (preferably formaldehyde). Polyphenols containing both sulfur and alkylene bridges are also suitable.
The equivalent weight of a phenol for the purpose of this invention is its molecular weight divided by the number of phenolic hydroxy groups therein. Thus, the equivalent weight of an alkylated phenol is equal to its 30 molecular weight and that of an alkylated resorcinol is half its molecular weight.
The phosphorus acids useful in the preparation of component B
may eontain pentavalent or trivalent phosphorus. The pentavalent phos-phorus acids, which are preferred, may be represented by the ~ormula Rl~X)a \
P(X) XH
R~
wherein each Rl is independently hydrogen or a hydrocarbon-based group, at least one thereof being hydrocarbon based; each ~ is independently oxygen or sulfur; and each a is independently Cl or 1. Thus, it will be appreciated 5 that the phosphorus acid may be an organophosphoric, phosphonic or phosphinic acid, or a thio analog of any of these.
The term "hydrocarbon-based" as used herein denotes a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context OI this 10 invention. ~uch groups include the following:
(1~ Hydrocarbon groups; that is, aliphatic (e.g., alkyl or alkenyl), alicyclic ~e.g., cycloPlkyl or cycloalkenyl), aromatic, aliphati~ and al!i-cyclic-substituted aromatic? aromatic-substituted aliphatic and alicyclic groups, and the like, as well as cyclic groups wherein the ring is completed 15 ~hrough another portion of the molecule (that is, any two indicated substituents may together form an alicyclic group).
(2~ Substituted hydrocarbon groups; that is, hydrocarbon based groups as defined above also containing non-hydrocarbon substituents which, in the context of this invention3 do not alter the predominantly hydrocarbon 20 ch~acter of the group. Those skilled in t~le ar~ will be aware of suitable substituents; examples include halo, nitro, hydroxy, alkoxy, alkylthio7 carbalkoxy and acyl groups.
(3) Hetero groups; that isg groups which, while predominantly hydrocarbon in character within the context of this invention, contain atoms 25 other than carbon present in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen~ oxygen and sul~r.
In general, no more than about three substitu0nts or hetero atoms, and preferably no more than one, will be present for each 10 carbon atoms in 30 the hydrocarbon-based group.
Included among the suitable phosphorus acids are those prepared by the treatment of an ole~in polymer (e~g., a polybutene having a molecular weight of about 1000) with a phosphorizing agent such as phosphorus 3~25 trichloride9 phosphorus heptasulfide~ phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphoro-thioic chloride.
The equivalent weight of a phosphorus acid is its molecular weight 5 divided by the number of hydroxy groups bonded to phosphorus therein.
Carboxylic acids suitable for use in the preparation of comporlent El include aliph~tic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids free from acetylenic unsaturation, including naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, ~lkyl- or alkenyl-10 substituted cyclohexanoic acids9 and alkyl- or alkenyl-substituted aromatic carboxylic acids (including salicylic acids). The aliphatic acids generally contain at least 8 and preferably at least 12 carbon atomsO The cycloaliphatic and aliphatic carboxylic aeic1s ean be saturated or un-saturated. Specific examples include 2-ethylhexanoic acid, linolenic acid, 15 propylene tetrame~substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid7 ricinoleic acid, undecylic acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalenecarboxylic acid, stearyl-octa-hydroindenecarboxylic acid, palmitic acid, acids formed by oxidation of 2n petrolatum or of hydrocarbon waxes9 and commercially available mixtures of two or more carboxylic acids such as tall oil acids, rosin acids, and the like.
The equivalent weight of any sueh acid is its molecular weight divided by the number of carboxy groups present therein.
The sulfonie acids useful in the preparation of detergents suitable 25 for use as component B include mahogany sulfonic acids, petrolatwn sulfonic acicls, mon~ and polywax-substituted naphthalene sulfonic acids, cetyl-chlorobenzene sulfonic acids~ cetylphenol sulfonic acids, cetylphenol di-sulfide sulfonic acids, cetoxycapryl benzene sulfonic acids, dicetyl thi-anthrene sulfonic acids, di-lauryl beta-naphthol sulfonic acids, dicapryl 30 nitr~naphthalene sulfonic acids9 paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, tetraisobutylene sulfonic acids, tetraamylene sulfonic acids, chloro-substi-tuted paraffin wax sulfonic acids, nitros~substituted parafIin wax sulfonic acids, petroleum naphthene sulfonic acids, cetylcyclopentyl sulfonic acids, 35 lauryl cyclohexyl sulfonic acids, mono- and polywax-substituted cyclohexyl sulfonic acids, postdodecylbenzene sulfonic acids, "dimer alkylate" sulfonic ~3~

acids, and -the likeO These sulfonic acids are well known in the art and require no further discussion herein.
For the purpose of this invention, the equivalent weight of a sulfonic acid or derivative thereof is its molecular weight divided by the num~er of sulfonic acid groups or sulfonic acid derivative groups present therein. Thus, for a monosulfonic acid the equivalent weight is equal -to the molecular weight.
The basic salts and complexes useful as component B are well known in the art and are disclosed in many United States patents of which the following are exemplary:

2,616,904 3,031~28~ 3,410,671 2,616,905 3,256,186 3,437,465 2,695,910 3,312,618 31629rlO9 2,723,234 3,342,733 3,746,643 2,777,~74 3,350,308 3,764,533 2,781,403 3,410,670 as well as in German published application 1,243,915. The salts and complexes useful in the present invention are those disclosed in said patents and application both generically and in the working examples, and include those disclosed merely as intermediates for conversion into more highly basic salts and complexes.
The commonly employed method for the preparation of these basic salts and complexes involves heating a solution of the organic acid compound in a substantially inert, normally liquid organic diluent such as mineral oil with a stoichiometric excess of a metal neutraliæiing agent such as the oxide, hydroxide, carbonate, bicarbonate or sulfide at a temperature above 50C and filtering the resulting mass. A "promoter" is often used in the neutralization step to ald the incorporation of a large excess of metal. Examples of compounds useful as promoters include phenolic compounds such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and condensation products of phenols with formaldehyde; alcohols such as methanol, 2-propanol r actyl alcohol, Cellosolve*, Carbitol*, ethylene glycol, stearyl alcohol and * trade marks

3~5 - 14a -cyclohexyl alcohol; and amines such as aniline, phenylene diamine, phenothiazine, phenyl-beta-naphthylamine and dodecylamine. It is also frequently preferred to further treat the basic compound prepared as .....

3~lY~5 described above w;th an acidic gas, especially carbon dioxide. This treatment may be intermittent and followed by successive treatments with the metal neutralizing agent, and often enables the incorporation of still larger amounts of basic metal in the complexO
S The preferred organic acidic s~ompounds for use in the preparation of the detePgent are the abov~described sulfonic and carboxylic acids, especially those having an equivalent weight of about 300 500. The sulfonic acids are most often used, and a particulQr preference is expre~ssed for alkylaromatic sulfonic acids and more particularly or alkylbenzene sulfonie acids.
The preferred detergents are the basic alkali or alkaline earth metal salts of carboxylic and sulfonic acids. Particul~ly useful as detergents are the oil soluble basic c~lcium sulfonates.
~?~
Oil dispersible dispersants are particularly useful as component B
in the present invention. As previously noted, these dispersants are generally metal-Iree or contain relatively small amounts of metal in comparison to the detergents described above. Their characterizing feature7 with respect to molecular structure, is the presence of an oil-solubilizing aliphatic hydrocarbon-based group containing at least about 40 aliphatic carbon atoms bonded directly to a polar group. The dispersant may contain more than one of either of such groups per molecule, as will be apparent from the description hereinafter.
M~ny dispersants of this type are known in the art and are described in various patents. Any of such dispersants are suitable for use in the compositions and methods OI this invention. The foLlowing are illustrative:
(1~ Reaction products of carboxylic acids ~or derivatives ther~
of~ containing at least about 44 and preferably at least about 54 aliphatic carbsn atoms with nitrogen-containing compounds having at least one ~NH
group such as amines, ureRs and hydrazines, with organic hydroxy compounds such as phenols and alcohols, and/or with reactive basic inorganic materials.
Examples o these products, referred to herein as "carboxylic dispersants", are described in British Patent 1,306,529 and in many U.S. patents including the following:

~3~

3,163,603 37351,552 3,S41,012 3~1~4,47~ 3,381,0~2 3,5~2,~78 3,215,707 3,399,141 3,542~B80 3,219,666 3,415,750 3,5679637 3,271,310 3,433,744 3,57~,101 3,272,746 3,4~4,17 0 3,576,743 3,281,357 3,448,04~ 3,630,~04 3,306,908 3,448,0~9 3,632,510 3,311,558 3,451,9~3 3,632,511 3,316,177 3,454,607 3,897,~28 3,3~0,281 3,467,668 3,725~441 3,341,542 3,501,405 Re 2~,433 3,3~6,493 3,~2~,179 (2) Reaction products of aliphati~ or alicyclic halides containing lS at least about 40 carbon atoms with amines, preferably polyalkylene polyamines. These may be characterized as "amine dispersants" and example~ reof ~re described, for example, in the following U.S. patents~
3,275,554 3,454,~55 3,438,757 3956~,804 (3) R~action products of alkyl phenols in which the alkyl group contains at lea~t about 40 carbon atoms with aliphatic aldehyde~ containing at most about 7 carbon atoms (especially ~ormaldehyde) and amines (especi~lly alkylene polyamines), which may be characterized as 'IManni~h dispersants". The materials des~ribed in the following U.S. patents are illustrativ~:
29459,112 35442,808 3~591,598 2,962,442 3,448,047 3,600,372 2,984,550 ~9454,497 3,634,S15 3~03~,003 3,459,661 3,649,229 3,1669516 3,461,172 3,697,574 3,23~,770 3,4~3,520 3,725,277 3,355,270 3,~39,633 3y725,480 39368,972 3,558,743 3,726,8~2 3,413,347 3,586,629 3,980,563 11 3~

(4) Polymers containing an oil-solubilizing group (e.g., a p~ndant alkyl group having at least about 8 carbon a~oms) and a polar groupO Illustrative are interpolymers of decyl methacrylate, vinyl decyl ether or a rela-tively high molecular weight olefin with aminoalkyl acrylates, aminoalkyl acrylamides or poly-(oxyalkylene)-substituted alkyl acrylates, as well as copolymers of styrene, alkyl maleates and maleic acid amides or imides. These may be characterized as "polymeric dispersants" and examples thereof are disclosed in the following U.S. patents:
3,329,658 3,6~6,730 3,449,?50 3,687,849 3,519,565 3,702,300

(5) Products obtained by post-treating the carboxylic, amine, Mannich or polymeric dispersants with such reagents as sulfur, urea, thiourea, guanidine, carbon disulfide, aldehydes, ketones, carboxylic acids, h~drocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Products of these types are described in Canadian patent 1,064,479 and in the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,242 3,087,936 3,312,619 3,502,677 3,64g,229 3,200,107 3,366,56~ 3,513,093 3,649,659 3,216,936 3,367,943 3,533,9~5 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,536 3,280,234 3,455,831 3,591,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522 4~161,475 The carboxylic and Mannich dispersants are preferred.
Carboxylic dispersants may be most conveniently and accurately described in terms of the groups (B-l and s-2) present therein.
Group B 1 is usually an acyl, acyloxy or acylimidoyl yroup containing at least about 44 carbon atoms. The structures of these yroups, as defined by the International Union of Pure and ~L183~ AJSj Applied Chemistry, are as foLlows ~each R2 individually representing a hydrocarbon or similar group):
o Acyl: R2 -C-Acyloxy: R C-0-N~2 Acylimidoyl: R -C~
Group B-2 is preferably at least one group in which a nitrogen or oxygen atom is attached directly to sQid acyl, acyloxy or acylimidoyl radical, said nitrogen or oxygen atom also being attached to 2 hydrocarbon-based group. The carboxylic dispersants are conveniently classified as la "nitrogen-bridged dispersants" and "oxygen-bridged dispersants" wherein the atom attached directly to radical B 1 is nitrogen or oxygen respectively.
The nitrogen-bridged carboxylic dispersants, which will be de-scribed first, are those diselosed (for example) in the above-mentioned U.~.
Patents 3~219,666 and 3,~72,746 which also describe a large number oE
15 methods for their preparationO
The source of group B-l in the nitrogen bridged dispersants is an acylating agent comprising a earbo2cylic aci~producing compound containing a hydrocarbon or substituted hydrocarbon substituent which has at least about 40 and preferably at least about 50 carbon atoms. By "carboxylic 20 acid-producing compound" is meant an acid, anhydride, a~id halide, ester, amide, imide, amidine or the like; the acids and anhydrides are preferred.
The carboxylic acid producing compound is usually prepared by the reaction (more fully described hereinafter~ of a relatively low mole~ular weight carboxylic acid such as maleic acid, fumaric acid, maleic anhydride, 25 etc., or derivative thereof with a hydroearbon source containing at least about 4û and preferably at least about 5û carbon atoms. The hydrocarbon source i9 usually aliphatic and should be substantially saturated, i.e., at least about 95% of the total number of carbon-to-carbon covalent linkages should be saturated. It should also be substantially free from pendant groups 30 containing more than about six aliphatic carbon atoms. It rnay be a - l9 -substituted hydrocarbon source; by "substituted" is meant sources cont~ining substituents which do not alter significalltly their character or reactivity.
Examples are halide, hydroxy, ether, keto, carboxy, ester (especially lower carbalkoxy~, amide~ nitro, cyano, sulfoxy and sulfone radicals. The S substituents, if present, generally comprise no more than about 10% by weight of the hydrocarbon source.
The preferred hydrocarbon sources are those derived from substantially saturated petroleum fractions and olefin polymers, particularly polymers of monoolefins having from 2 to about 30 carbon atoms and more 10 particu~arly frorn 216 carbon a~oms. Thus, the hydrocarbon source may be derived from a polymer of ethylene, propene, l-butene, isobutene, l-octene, 3-cyclohexyl-1-butene, 2-butene, 3-pentene or the like. Also useful are interpolymers of olefins such as those illustrated above with other polymerizable olefinic substanees such as styrene, chloroprene, isoprene, p-15 methylstyrene, piperylene and dienes such as 1,3-hexadiene, isoprene, 1~4-hexadiene ~nd 1,4-cyclohexadiene. In general, these interpolymers should contain at least about 80%, preferably at least about 95%, on a weight basis OI units derived from the aliphatic monoolefins.
Another suitable hydrocarbon source comprises saturated aliphatic 20 hydrocarbolls such as highly refined high molecular weight white oiLs or synthetic alkanes.
In many instances, the hydrocarbon source should contain an activating polar group to facilitate its reaction with the low mdecular weight aeid-producing compound. The preferred activating groups are 25 halogen atoms, especially chlorine, but other suitable groups include sulfide, disulfide, nitro, mercaptan9 ketone and ~ldehyde group~.
As already pointed out, the hydrocarbon sources generally contain at least about 4a and prePerably at least about 50 carbon atoms. Among the olefin polymers those having a number average molecular weight above 30 about 600 ar~ useful and those between about 1300 and about 50ûO (as deter-mined by gel permeation chromatography) are preferred, although higher polyrners having moleclllar weights from absut 10,000 to about 100,000 or higher may sometimes be used. The ratio o~ weight average to number average molecular weight (Mw/Mn) may be about 1.5-6.0 ~d is usually L5-35 4Ø

2~;

A first preferred class of polymers comprises those of terminalolefins such as propylene, l-butene, isobutene and l-hexene. Especially preferred within this class are polybutenes comprlsing predominantly isobutene units. A second preferred class comprises terpolymers of 5 ethylene, a C3-8 alpha-monoolefin and a polyene selected from the group ~;, consisting of non-conjugated dienes (which are especially pref erred) and trienes. Illustrative of these terpolymer~ is "Ortholeum 2052" m~nufactured by E~ I. duPont de Nemours dc Company, which is a terpolymer containing about 48 mole percent ethylene groups, 48 mole percent propylene groups 10 and 4 mole percent 1,4-hexadiene groups and having an inherent viscosity of 1.35 (8.2 grams of polymer in lU0 rnl. of carbon tetrachloride at 30 C).
Any one of a number of known reactions may be employed for the preparation of the carboxylic acid producing compound. Thus, an alcohol o the desired molecular weight may be oxidized with potassium permanganate, 15 nitric acid or a similar oxidizing agent; a halogenated olefin polymer may bereaeted with a ketone; an ester of an active hydrogen-containing acid, such as acetoacetic acid, may be converted to its sodium derivative and the sodium derivative reacted with a halogenated high molecular weight hydrocarbon such as brominated wax or brominated polyisobutene; a high 20 molecular weight olefin may be ozonized; a methyl ketone of the desired molecular weight may be oxidized by means of the haloform reaction; an organometallic derivative of a halogenated hydrocarbon or olefin polymer may be converted to a nitrile, which is subsequently hydrolized; or an olefin polymer or its halogenated derivative may undergo a reaction with an 25 unsaturated carboxylic acid or derivative thereof such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid7 itaconis~ anhydride, citraconic acid, citraconic anhydride5 mesaconic acid, glutaconic acid, chlorQmaleic acid, aconitic acid, crotonic acid, methyl-crotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid, 2-pentene-30 1,3,5-tricarboxylic acid, and the like, or with a halogen~ubstituted car-boxylic acid or derivative thereof. This latter reaction is preferred, especially when the acid-producing compound is unsaturated and preferably when it is maleic acid or anhydride. The resulting product is then a hydrocarbon-substîtuted succinic acid or deriva~ive thereof. The reaction 35 leading to its formation involves merely heating the two reactants at a * ~r~ e~r~

3~ AJS

temperature from about 100 to about 20U C. The mole ratio of the polymer to the maleic acid or anhydri-3e may be equal to, greater than or less than 1, depending on the type of dispersant product desired. It is often preferred, however, to employ proportions such that the dispersant will 5 contain an average of at least 1.3 succinic rnoities per polymeric moiety;
such dispersants are termed "polysuccinated dispersants". Especially preferred are polysuccinated dispersants containing about 1.4-3.5 succinic groups and most desirably about 1.5-2.5 succinic groups per polymer group.
The substituted succirlic acid or anhydride thus obtained, may, if desired, be 10 converted to the corresponding acid halide by reaction with known halogenating agents sueh as phosphorus trichloride, phosphorus pentachloride or thionyl chloride.
The nitrogen-bridged carboxylic dispersants are prepared by reacting the acylating agent such as the substituted succinic acids or 15 anhydrides with at least one nitrogen compound preferably having the structure~NH wherein the two remaining valences of nitrogen are satisfied by hydrogen9 amino or organic radicals bonded to said nitrogen atom through direct carbon-t~nitrogen linkages. These eompounds include aliphatic, aromatic, heterocyclic and carbocyclic amines as well as substituted ureas, 20 thiorueas, hydrazines, guanidines, amidines, amides, thioamides, eyanamides and the like.
Arnong the amines useful in preparing the nitrogen-hridged dispersant are rnonoarnines. These monoamines can be secondary, i.e., those eontaining only one hydrogen atom bonded directly to an amino nitrogen 25 a~om. Preferably, however, they contain at least one primary amino group, i.e., a group wherein an amino nitrogen atom is directly bonded to two hydrogen atoms. The monoamines are generally substituted with Cl 30 hydrocarbon-based groups. Preferably these hydrocarbon-based groups are aliphatic in nature and free from acetylenic unsaturation and contain from 30 about 1 to about 10 carbon atoms. Saturated aliphatic hydrocarbon groups are particularly preferred.
Among the preferred monoamines are those' of the general formula HNR3R4, wherein R3 is an alkyl group of up to ten carbon atoms and R4 is hydrogen or an alkyl group of up to ten carbon atoms. C)ther 35 preferred monoarnines are arornatic monoamines of the general formula ~L83~

--2~--HNR5R6 wherein R5 is a phenyl, alkylated phenyl, naphthyl or alkylated naphthyl group of up to 10 carbon atoms and R6 Ig a hydro~en atom, an alkyl group of up to 10 carbon atoms, or a group similar to R5. Examples of suitable monoamines are ethylamine, diethylamine, n-butylamine, di-n-S butylamine~ allylamine, isobutylamine, cocoamine, stearylamine, lauryl-amine, methyl laurylamine, oleylamine, aniline, methylaniline, N-methyl-aniline, diphenylamine, benzylamine, tolylamine and methyl-2-cyclohexyl-amine.
Hydroxy amines are also included in the class of useful mono-10 amines. Such compounds are the hydroxyhydrocarbyl-substituted analogs of the afore-described monoamines. Preferred hydroxy monoamines have the formulas HNR7R8 and HNR9R10, wherein R7 is an alkyl or hydroxy-substituted alkyl group of up to 10 carbon atoms, R8 is hydrogen or a group simil~r to R7, R9 is a hydroxy-substituted phenyl, alkylated phenyl, naphthyl 15 or alkylated naphthyl group of up to 10 carbon atoms, and R10 is hydrogen or A group similar to R9, at least one of R7 and R8 and at least one of R9 and R10 being hydroxy-substituted.
Suitable hydroxy~substituted monoamines include ethanolamine, di-3-propanolamine, 4-hydroxybutylamine, diethanolamine, N-methyl-2-20 propylamine, 3-hydroxyaniline, N-hydroxyethylethylene diamine, N,N-di-(hydroxypropyl~propylene diamine and tris(hydroxymethyl)methylamine.
While in general, hydroxy amines containing only one hydroxy group will be employed as reactants, those containing more can also be used.
Heterocy~lic amines are also useful in making the nitrogen-25 bridged dispersant, provided they contain a primary or secondary aminegroupO The heterocyclic ring can also incorporate unsaturation and can be substituted with hydrocarbon groups such as alkyl~ alkenyl, aryl, alkaryl or aralkyl. In addition, lhe ring can also contain o~her hetero atoms such as oxygen, sulfur, or other ni$rogen atoms including those not having hydrogen 30 atoms bonded to them. Generally, these rings have from about 3 to about 10, preferably 5 or 6, ring members. Among such heterycydes are aziridines, azetidines, azolidines, pyridines, pyrroles, piperidines, imidazoles, indoles, piperazines,isoindoles, purines, morpholines, thiamorpholines, N-aminoalkyl morpholines, N-aminoalkyl thiamorpholines, azepines7 azocines, azonines, 35 azecines and tetrahydro-, dihydr~ and perhydro- derivatives of each of the ~3~

above. Preferred heterocyclic amines are the saturated ones with 5- and 6-membered rings, especially the piperidines, piperazines and morpholines described above.
Polyamines are preferred for preparing the nitrogen-bridged 5 dispersant. Among the polyamines are alkylene polyamines (and mixtures thereof) including those having the formula A ~ N~RIl- N~jH
A A
wherein n is an integer between about 1 and about 10, preferably between 2 and 8; each A is independently hydrogen or a hydrocarbon or hydroxy-10 substituted hydrocarbon group having up to about 30 atoms; and Rll is adivalent hydrocarborl group having from about 1 to about 18 carbons.
Preferably A is an sliphatic group of up to about 10 carbon atoms which may be substituted with one or two hydroxy groups, and Rll is a lower alkylene group having 1-10, preferably 2-6 carbon atoms. Rspecially preferred are the 15 alkylene polyamines wherein each A is hydrogen. Such alkylene polyamines include methylene polyamines, ethylene polyaminesS butylene polyamines, propylene polyamines, pentylene polyamines3 hexylene polyamines and heptylene polyamines. The higher homologs of such ~mines and related aminoalkyl-substituted piperaæines are also included. Specific examples of 20 such polyamines include ethylene diamine, triethylene tetramine, tris(2-aminoethyl)amine, prowlene diamine, trimethylene diamine9 hexamethylene diamine9 decamethylene diamine, octamethylene diamine, di(hepta-methylene)triamine, tripropylene tetramine, tetraethylene pentamine9 tri-methylene diamine, pentaethylene hexamirle, di(trimethylene) triamine, 2-25 heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis-(2-aminoethyl)imidazoline, 1-(2-aminopropyl)-piperazine, 1,4-bis(2-aminoethyl)piperazine ~nd 2-methyl-1-(2-aminobutyl~piperazine. Higher homologs, obtained by condensing two or more o~ the abov~illustrated alkylene amines, are also useful, as are the .~ polyoxyalkylene polyamines (e.g., "Jeffamines" available from Jefferson 30 Chemical Co.).
The ethylene polyamines, examples of which are mentioned abo~e, are especially us~eful for reasons of cost and effectiveness. Such polyamines are described in detail under the heading "I)iamines and Higher Amines" in E~irk-Othmer, ~lopedia o~ ~,, Second Edition, Vol. 7, -~r~J~ ma~

33~

pp. 22-39. They are prepared most conveniently by the reaction of an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia. These reactions result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines. Bec~use of their availabllity, these mixtures are parti~ularly useful in preparing the nitrogen-bridged dispersant. Satisfsctory products can also be obtained by the use of pure alkylene polyamines.
Hydroxy polyamines, e.g., alkylene polyamines having one or more hydroxyallcyl substituents on the nitrogen atoms, are also useful in preparing the nitrogen-bridged dispersant. Preferred hydroxyalkyl-substituted alkyl-ene polyamines are those in which the hydroxyalkyl group has less than about 10 carbon atoms. Examples of such hydroxyalkyl-substitllted polyamines include N-(2-hydroxyethyl)ethylene diamine, N,N'-bis(2-hydroxyethyl)-ethylene diamine, 1~(2-hydroxyethyl~p;perazine, monohydroxypropyl-substi-tuted diethylene triamine, dihydroxypropyltetraethylene pentamine and N-(3-hydroxybutyl)tetramethylene diamine. Higher homologs obtained by condensation of the above-illustrated hydroxyalkyl~ubstituted alkylene amines through amino groups or through hydroxy groups are likewise useful.
The dispersant can also be prepared from hydrazine or an organo-substituted hydrazine of the general formula /N-N \

wherein each R12 is independently hydrogen or a Cl 30 hydrocarbon radical, at least one R radical being hydrogen. Pre~erably, the others are Cl 10 aliphatic groups. More preferably at least two R radicals are hydroges~, and most preferably at least two such groups bonded to the same nitrogen atom are hydrogen and the remaining ones are alkyl groups of up to 10 carbon atoms. Examples of suitable substituted hydrazines are m ethyl-hydrazine, N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenyl-hydra7ine, N-phenyl-N'-ethylhydrazine, N-(p-tolyl)-N'-(n-butyl)hydrazine, N-(p-nitrophenyl}N-methylhydrazine9 N,N'-di~chlorophenyl)hydrazine and N-phenyl-N' cyclohexylhydrazine.

~3 ,~

For the forma~ion of the nitrogen-bridged dispersant, the hydro-earbon-substituted succinic anhydride or acid, or other carboxylic acid-producing compound, and the alkylene polyamine or other nitrogen-containing reagent are heated to a temperature above about 80 C, preferably from about 100 tc about ~250C. The product thus obtained has predominantly amide, imide and/or amidine linkages (containing acyl or acylamidoyl groups). The process may in some instances be carried out at a temperature below 80C to produce a product having predominantly salt linkages (containing acyloxy groups)~ The use of a diluent such as mineral lD oil, benzene, toluene, naphtha or the like is often desirable to facilitate control of the reaction temperature.
The relative proportions of the carboxylic acid-producing com pound and the alkylene polyamine or the like are such that at least about one-half the stoichiometrically equivalent amount of polyamine is used for each eguivalent of carboxylic acid-producing compound. In this regard it will be noted that the equivalent weight of the alkylene polyamine is based upon the number of amine radicals therein, and the equivalent weight OI the earboxylic acid-producing compound is based on the number of acidic or potentially acidic radicals. (Thus, the equivalent weight of a hydrocarbon-substituted succinic acid or anhydride is one-half its molecular weight.) Although a minimum of on~half equivalent of polyamine per equivalent of acylating agent should be used, there does not appear to be an upper limit for the amount of polyamine. If an excess is used, it merely remains in the product unreacted without any apparellt adverse effects. Ordinarily, about 1-2 equiv~ents of polyamine are used per equivalent of acylating agent.
In an alternative method for producing the nitrogen-bridged dispersant, the alkylene polyamine is first reacted with a low moleculai weight, unsaturated or halogen-substituted carboxylic acid or derivative thereof lsuch as maleic anhydride or one OI the others previously mentioned) and tSle resulting intermediate is subsequently reacted with the hydrocarbon source as previously described.
Oxygen-bridged carboxylic dispersants comprise the esters of the abov~described carboxylic acids9 as described (for example) in the afore-mentioned U.S. Patents 3,381,022 and 3,5427678. As such, they contain acyl 35 or, occasionally, acylimidoyl groups as group B-l. (An oxygen-bridged dispersant containing an acyloxy group as group B-l 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 5 catalyst~ of the cnrboxylic acid-producing compound with a monohydric or polyhydric hydrocarbon-based alcohol or with an aromatic hydroxy compound such as a phenol or naphthol. The hyd]roxy compounds are usually alcohols containing up to about 4a aliphatic carbon atoms. These may be monohydric alcohols such as methanol, ethanol, the propanols, butanols, pentanols, 10 isooctanol, dodecanol, cyclohexanol, neopentyl alcohol, monomethyl ether of ethylene glycol as well as the so called fatty alcohols such as lauryl myristyl, cetyl, stearyl and behenyl alcohols and their mixtures, or polyhydric alcohols includil~ ethylene glycol, diethylene glycol, dipropylene glycol, tetramethylene glycol, pentaerythritol, glycerol and the like. ~atty 15 alcohols containing minor arnolmts of unsaturated (e.g., no more than about two earbon-t~carbon unsaturated bonds per molecule) also are usefuL
These are exemplified by palmitoleyl (C~6H30O), oleyl (C18H36O) and eicosenyl (C2oH4oO3 alcohols-A further class of useful hydroxy compounds comprises the 20 polyoxyalkylene compounds of the type commonly sold as deml]lsifiers.These include the "Ethomeens~ "~thoduomeens'i, "Pluronics", "Tergitols", "Tetronics", "Dow Polyglycols", etc. Carbohydrates (e.g~, sugars, starches9 cellulose) are also suitable as are partially esterified derivatives of polyhydric alcohols having at least three hydroxy radicalsO Aliphatic polyols 25 containing up to 10 carbon atoms and at least 3 hydroxy groups, especially those with up to 6 carbon atoms and 3-6 hydroxy groups, are preferred.
The esterification reaction is usually effected at a temperature above about 100C and typically from about 150 to about 3û0C. The esters may be neutral or acidic; or may contain unesterified hydroxy groups, 30 according as the ratio of equivalents of acid-producing compound to hydroxy compound is equal to, greater than or less than 1:1.
It is possible to prqpare mixed oxygen- and nitrogen-bridged dispersants by reacting the acylating agent simultaneously or, preferably, sequentially with nitrogen-containing and hydroxy reagents such as those 35 described above. The relative amounts of the nitrogen-containing and tra le ~n~r Ks 3 ~

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 nitrogen-bridged dispersants are generally the same as for the individual dispersants described, except that two sources of group B-2 are used. Mixtures of S independently prepared dispersants are slso suitable. Mixed dispersants of these types are frequently preferred for the purposes of this invention.
Illustrative reactive metal compounds which may be reacted with the carboxylic acids described above to produce dispersants include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentyloxide, sodium 10 oxide, sodium hydroxide, sodium carbonate, sodium methoxide, sodium propoxide, potassium oxide, potassiwn hydroxide, potassium carbonate, potassium methoxide, magnesium oxide, magnesium hydroxide, magnesium carbonate, ma~nesium methoxide, magnesium propoxide, magnesium salt of ethylene glycol monomethyl ether, calcium oxide, calcium hydroxide, 15 calcium carbonate, calcium methoxide, calcium propoxide~ calcium pentyl-oxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc propoxide, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethoxide, barium oxide, barium hydroxide, barium carbonate, barium ethoxide, barium pentyloxide, aluminum oxide, aluminum 20 isopropoxide, cupric acetate~ lead oxide, lead hydroxide, lead carbonate, tino~ide, tin butoxide, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentyloxide, nickel oxide, nickel hydroxide~ nickel chloride, nickel carbonate and chromium (II~ acetate.
Typical carboxylic dispersants suitable for use as component B are ~5 listed in Table I. "Reagent B-l" and "Reagent B-2" are, respectively, the sources of groups B-l and B-2 as previously defined.

~1~83~5 C .~ .~ .o .~
3 ~ a ~ ~ c ~ 3 .~ ~ ~ U~
E~
.
.0 ~ ~ d~ O
3 ~ o o o *. :~c a~
¢¦ q c E a E ~ 1 E

V ~ c 2 ~ E : ~ ;~ , E

C~ Z

o ~ ~ tq 0 ~ 3 U F~l 3 ~ ~_ ~ 3 a~ ~ .~, D ~ Q 3 m ~ ~
~ ~ X 7 E o 7 ~ ~ x ~ 7 ~ ~ ~ .~ F~ D ~ 'g,D ~ p,.D ~ a~
7 m m ~
~ , ~ c ~

3~ ~

~ I ~o .~ .~
C
C
~ ~
a~

~ E 3 3 ~

o Z C~
'~ ~ ~ o ~ ~ ~ o a~

~i ~J = ~I~c~ o ~ E

S ~ ~ _ ~ ~ S ~

c ~ ra e ~D o X C ~ ~ e~ ~; X ~ ~ '~.
.~0 Q~
O ~
E E E E = E o ~ o c~ 3 E

0 '~ 0 ~ C~ V7 ~ ~o ~ 3 5; ~ .Q 3 a~
a~ q m a: m CO ~ o ~

~ ~3 C .~

oC _ o C~ ", o ,,, ~i3 ~ ~ X 00 ~ Q ~ ~ O
~ m O O O O
a~

3 ~ c ~;
~ ~ e o~

n~
m a~ m ~I l ~ ~ N

3~

.~ .~
d .~ X
o ~
C~ ~ c) ~ ~ , ~

U~
o ~ ~ ol ~ o ~ ' ~o m E c E E o 1 a~
e~

~1 In the preparation of carboxylie dispersants such as those described in Examples lB-24B, reagent B-1 is normally prepared by reacting approximately equimolar amounts of the hydrocarbon source and the low molecular weight carboxylic acid or derivative thereof. It is also within the 5 scope of the invention, however, to u~se as component B a nitrogen- or oxygen-bridged, or mixed nitrogen- and oxygen-bri~ged, dispersant prepared by initially reacting substantially more than one mole of acid or acid derivative with one mole OI hydrocarbon source. In the preferred dispersants of this type, as in those previously described herein, the hydrocarbon source 0 i5 an olefin polymer such as polybutene and the carboxylic acid derivative is maleic anhydride. Dispersants of this type usually contain up to about 3.5 and most often from about 1.5 to about 2.5 succinic groups for each ~roup derived from the hydrocarbon source.
The method of preparation of dispersants of this type is basically 15 the same as for the carboxylic dispersants already described. Reagent B-1, in particular, may be prepared by a one step procedure in which the hydrocarbon source i5 reacted with maleic anhydride; by a tw~step procedure in which the hydrocarhon source is chlorinated and the chlorinated intermediate is reacted with maleic anhydride; or by various combinations of 20 the two procedures.
The following examples illustrate typical methods for the prepara-tion of suitable dispersants of this type~
Exam~_5-B
A mixture of 1000 parts (0.495 mole) of a polybutene comprising 25 principally isobutene units and having a number average molecular weight of 2020 and a weight average molecular weight of 6049 and 115 parts (1.17 moles) of maleic anhydride is heated to 184 C over 6 hours as 85 parts (1.2 moles) of 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 30 is stripped by blowing with nitrogen at 186-190C for 26 hours to yield a polybutene substituted succinic anhydride having a saponification number o 87 as determined by ASTM Procedure D94.
To 893 parts (1.38 equivalents) of this substituted succinic anhydride is added lOG7 parts of mineral oil and 57 parts (1.38 equivalents) of 35 a commercial ethylene polyamine mixture containing from about 3 to about 33~

10 nitrogen atoms per molecule. The mixture is heated to 140-155 C for 3 hours and is then stripped by blowing with nitrogen. The stripped liquid is filtered and the filtrate is the desired dispersant (approximately 50%
solution in oil).
Example 26-B
A mixture of 334 parts (0.52 equivalent) of the polybutenyl succinic anhydride of Example 25-B, 548 parts of mineral oil, 30 parts (0.88 equivalent) of pentaerythritol and 8.6 parts (0.0057 equivalent) of Polyglycol 112-2 demulsifier from Dow Chemical Company is heated at 150-21()C for 1() about 11 hours. The mixture is cooled to 190 C and 8.5 parts (0.2 equivalent) of the ethylene polyamine mixture of Example 25-B is added. The mixture is stripped by blowin~ with nitrogen for 3 hours at 205C and is filtered to yield the desired dispersant as an approximately 40% solution in oil.
Example 27-B
A substituted succinic anhydride is prepared by the procedure o Example 26-B, using a similar polybutene with a Mn of 1457 and a Mw of 5808. A mixture of 550û parts OI this anhydride, 3000 parts of mineral oil and 236 parts of the ethylene polyamine mixture of Example 26-B is heated at 155-165C for 2 hours, stripped by blowing with nitrogen at 165C for 1 20 hour, and filtered to yield an oil solution of the desired dispersant.
Example 28-B
.
A product is prepared by the procedure of Example 26-B from 1 equivalent of the substituted succinic anhydride of Example 25-B, 1-8 equivalents OI pentaerythritol, 0.2 equivalent of the ethylene polyamine 25 mixture of Example 26-B, and mineral oil in an amount to afford a 30%
solution of the product in oil.
~e~
A product is prepared by the procedure of Example 25-B using a substituted succinic anhydride prepared by the reaction of 98 parts of maleic 3n anhydride with 5670 parts of a 10% solution of "Ortholeum 2052l' in mineral oil.
Oil~soluble metal salts of substituted succinic acid acylated aliphatic polyamines also are useful as detergents in the compositions of the invention. These are exemplified by the alkali, alkaline earth, lead, 35 cadmium, zinc, nickel and cobalt salts of hydrocarbon-substituted succinic 31 ~

-3~--acid acylated alkylene polyamines. The prineipal sources of the hydrocarbon substituent incluAe the higll molecular weight petroleum fraction and olefin polymers as described above, and the substituent should be substantially saturated, that is, at least about 95% of the total number of carbon-to-5 carbon covalent linkages are saturated linkages.
The si7e of the hydrocarbon substituent of the succinic compoundappears to determine the effectiveness of the additive as a dispersant. It is important, therefore, that the substituent be large, that is, that it have at least about 50 aliphatic carbon atoms. The molecular weight of the 10 hydrocarbon substituent should be within the range of from 70Q to about 100,000. The most common sources of the substantially aliphatic hydro-carbon substituents are the polyolefins such as polyethylene, polypropylene, polybutene, etc. A particularly preferred polyolefin is polyisobutene having a molecular weight of about 1000.
The basic metal reactant can be an alkali metal, alk~line earth metal, lead, cadmium and zinc oxides, hydroxides, - carbonates and lower alcoholates and a combination of all of an alkali metal hydroxide and an inorganic metal salt selected from the group consisting of alkaline earth metal, lead, cadmium, zinc, nickel and eobalt halides and nitrates.
20 Illustrative examples of the basic metal compounds include sodium oxide, sodium methylate9 potassium hydroxide, potassium carbonate, lithium hydroxide, calcium hydroxide, calcium carbonate, calcium chloride, barium oxide, barium fluoride, magnesium ethylate, magnesium bromide, magnesium phenoxide, zinc hydroxide, ~ine nitrate trihydrate, cadmium oxide, lead 25 oxide, lead chloride, nickel hydroxide, nickel carbonate, cobalt hydroxide, cobaltous bromide, etc.
The amines which are useful in the preparation of these detergents inelude alkaline polyamines and hydroxyalkyl-substituted alkaline polyamines of the types described above with respect to the carboxylate 30 disper~ants.
These metal salts of substituted succinic acid acylated aliphatic polyamines can be prepared by either (1) first preparing the acylated amine of the hydrocarbon-substituted succinic compound and then reacting the acylated amine with the basic metal compound, or (2) first preparing the 35 mono-metal salt of the hydrocarbon-substituted succinic compound and then 3~ ~

reactlng said mono-metal salt wlth an alkaline polyamine or hydroxyalkyl-substituted alkallne polyamine. In the first method, it is preEerred -that the succinic compound be the succinic anhydride and that trace amounts of water, that is, up to about 2.5% by weight, be present when the basic metal compound is an oxide. In the second method, it is preferred that the succinic compound be the succinic acid. In all cases, it is preferred that nitrogen or some inert gas be bubbled through the reaction mixtures to remove any water formed as a result of the acylation reaction.
The oil-soluble metal salts of subs-tituted succinic acid acylated aliphatic polyamines and processes for their preparation are described in detail in U.S. Patent Re 26,433. The following examples illustrate the preparation o:E the oil-soluble metal salts of substituted succinic acid acylated aliphatic polyamines.
~ 30-B
A polyisobutenyl succinlc anhydride is prepared by the reaction of a chlorinated polyisobutylene (having an average chlorine content of 4.3 weight percent and an average of 70 carbon atoms) with maleic anhydride at about 200C. The resulting polyisobutenyl succinic anhydride has an acid number of 103. To a mixture of 3,264 grams (6 equivalents) of this polyisobutenyl succinic anhydride, 2,420 grams of mineral oil and 75 grams of water, there is added at 80 to 100C, 122.1 grams (3 equivalents) of zinc oxide. The addition is made portionwise over a period of 30 minutesO The mixture is maintained at a temperature of 90-100C for a period of 3 hours. Thereupon, the mixture is heated to 150C and maintained at this temperature until it is essentially dry. The mixture is cooled to 100C and there is added 245 grams (6 equivalents) of an ethylene polyamine mixture having an average compositi.on corxesponding to that of tetraethylene pentamine and an equivalent weight of 40.8. The addition is made portionwise over a period of 30 minutes whereupon the mixture is heated to a temperature of 150-160C and maintained at this temperature for 5 hours. Throughout the 5-hour period, nitrogen is bubbled through the mixture to remove water formed as a result of acylation. The residue is filtered. The resulting filtra-te has a zinc content of 1.63% and a nitrogen content of 1.39%.

~3~

To a mixture of 3,750 grams (6 equivalents) of a polyisobutenyl suceinic anhydride (having an acid number of 89.8 and prepared, as in Example 30-B~ from maleic anhydride and chlorinated polyisobutylene having an average chlorine content of 4.3 weight percent and an average of 81 carbon atoms), 2,632 grams of mineral oil and 75 grams of water, th~re is added, at 80-100C, 60 grams (3 equivalents) of magnesium oxide. The addition is m~de portionwise over a lO~minute period. The mixture is maintained ~t a temperature of 100-105C for 3 hours. During the first part of this 3-hour period, 50 grams of water is adcled. Thereupon, 113 grams ~3 equivalents) of an amine mixture such as described in Example 30-B tbut with an equivalent weight of 3~.8) is aclded portionwise over a period of 30 minutes while the temperature of the mixture is maintained at 98-100C.
The mixture is heated at 210-215 C and maintained at this temperature for 4 hours. Throughout the 4-hour period, nitrogen is bubbled through the mixture to remove water resulting from acylation. The residue is filtered.
The filtrate has a magnesium content of 0.S5%, based on sulfate ash, and a nitrogen content of 0.64%.

To a mixture of 1,028 grams (2 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 109 and prepared, as in Example 30~B, from maleic anhydride and a chlorinated polyisooutylene having an average chlorine content of 4.3 weight percent and an average of 65 carbon atoms), 707 grams of mineral oil and 1,5()0 grams of benzene, ~here is added at 60 C, 41 grams (1 equivalent) of an amine mixture such as described in Example 30-B (but with an equivalent weight of 41). The addition is made portionwise over a 3û-minute period. The mixture is maintained at a temperature of 85-90C for 7 hours. Throughout this 7-hour period, nitrogen is bubbled through the mixture to remove water resulting from acylation. To 1,034 grams of the above mixture and 52 grams of water, there is added 80-90C, 52 grams (0.67 equivalent) of barium oxide. The addition is made portionwise over a 30-minute period. The mixture is maintained at a temperature of 80-90 C for 2 hours~
Thereupon, the rnixture is heated to 150 C and stripped of the last traces of water. The residue is filtered. The filtrate has a barium content of 3.9%
and a nitrogen content of 0~76%.

Rxample 33-B
To a mixture of 4,200 grams (6 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 80 and prepared, as in Example 30-B, from m~leic anhydride and chlorinated polyisobutylene having an 5 average chlorine content of 4.3 weight percent and an average of 92 carbon atoms) and 2,930 grams of mineral oil, there i9 added at 80C, 390 grarns of 1-(2-hydroxyethyl)piperazine. The addition is made portionwise over a 30-minute period and the resulting mixture is maintained at a temperature of 180-205C for 5 hours. Throughout tlhe 5-hour period, nitrogen is bubbled 10 through the mixture to remove wal:er resulting from acylation. To the above mixture, combined with 35 grams of water, there is added nt 30C, 159 grams (3 equi-ralents) of sodium carbonate. The addition is made portionwise over a 45-minute period. The temperature is maintained at 70-80C for 3 hours whereupon the mixture is heated to 150C and stripped of the last 15 traces of water. The residue is filtered. The filtrate has a sodium content of 0.88 percent and a nitrogen content of 1.1 percent.
Example 34-B
To a mixture of 1,245 grams (2 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 90 and prepared, as in Example 20 30-B3 from maleic anhydride and chlorinated polyisobutylene having an average chlorine content OI 4.3 weight percent and an average OI 81 carbon atoms), 871 grams of mineral oil and 25 grams of water, there is added at 80~ C, 56 grams (1 equivalent) of potassium hydroxide. The addition is made porffonwise over a 30-minute period, after whieh the mixture is held at 85-25 95C for 1 hour, then dried by heating at 135S'-140C for 1 hour. Thereupon, 104.2 grams (I equivalent) of barium chloride is added portionwise over a pelqod of 30 minutes, with the temperature at 80-90 C. The mixture then is heated at 130-140 C for 9 hours, and filtered. To the filtrate there is added 41 grams (1 equivalent) of an amine mixture such as described in 30 Example 30-B (but with an equivalent weight of 413. The addition is made portionwise over a 30-mimJte period, with the temperature at 110-140C.
The mixture then is heated at 160-165C for 4 hours, throughout which period nitrogen is bubbled into the mixture to remove wa~er resulting from acylation. The residue is filtered. The filtrate has a barium content of 2.7%
35 and a nitrogen content OI 0.61%.

~3~

Also preferred for use as component B, as an alternative to the carboxylic dispersAnts hereinabo7re described, are the Manrlich dispersants.
These are, as previously noted, reaction products of certain alky] phenols with aldehydes (usually lower aliphatic aldehydes and especially formalde-5 hyde) and amino compounds. The StrUCtllre of the alkyl substituent on thephenol is subject to the same preferene~es as to source, structure, molecular weight and the lilce expressed hereinabove with respect to the carboxylic dispersant. The amino compounds ar~e the snme as those described with reference to nitrogen-bridged carboxylic dispersants and are subject to the 10 same preferellces.
Suitable Mannich dispersants for use as component B are illus-trated in the workin~ examples of the aforementioned U.S0 Patent 3,980,569 /~ Ca.q~ an p~ 06~J~ ~q and ~e ~. The following examples also are illustrative.
~
A mixture of 3~40 parts (2 equivalents) of a polybutenyl phenol in which the polybutene substituent comprises principally isobutene units and has a molecular weight of abcut 160û, 1250 parts of textile spirits and 2000 parts of isopropyl alcohol is stirred as 352 parts (2.2 equivalents) of 50%
aqueous sodium hydroxide is added, followed by 480 parts (6 equiv~lents~ of 389S aqueous formaldehyde solution. The mixture is stirred for 2 hours, ~llowed ~o stand for 2 days and then stirred again for 17 hours. Acetic acid, 150 parts (2.5 equivalents~, is added and the mixture is stripped of volatile materials under vacuunn. The remaining water is removed by adding benzene and distilling azeotropicaily; during the distillation, 1000 parts of mineral oil is added in two portions. The distillation residue is filtered.
To 430 parts (0.115 equivalent) of the filtrate is added with stirring, at 90C, 14.1 parts (0.345 equivalent) of the polyethylene amine mixture containing about 3 to 7 amino groups per rnolecule. The mixture is heated at 90-120~C for 2 hours and then at 150-160C for 4 hours, with nitrogen blowing to rsmove volatiles. The resulting solution is filtered to yield the desired Mannich dispersant (52% solution in mineral oil) which contains 1.03% nitrogen~

A mi~.~ture of 564 parts (0.25 equivalent) of polybutenyl phenol in which the polybutene substituent comprises principally isobutene units and .2~

has a rnolecular weight of about 2020, 400 parts of mineral oil and 16.5 parts of isobutyl alcohol is heated to 65C, with stirring, and 2.15 parts ~0.025 equivalent) of 50% aqueous sodium hydroxide solution is added, ïollowed by 16.5 parts (0.5 equivalent) of paraformaldehyde. The mixture is stirred at 80 88C for 6 hours and then 5 parts (00025 equivalent) of 18.5% aqueous hydro~hloric acid is added slowly~ with continued stirring, ~ollowed by 36 parts (0.875 equivalent) of a polyethylene amine mixture containing about 3 to 7 amino groups per molecule~ at 88C. Mixing is continu~d at 88-91C
for 30 minutes. The mixture is then heated to about lS8C with nitrogen blowing to remove volatiles.
Sul~ur, 16 parts (0.5 mole), and 25 parts of a filter aid material are added slowly at 150C, with stirring, after which the mixture is blown with nitrogen at 150-155 C for 3 hours. The mixture is then cooled to 132 C and filtered to yield the desired sulfurized Mannich product as a 6D% solution in mineral oil; it contains about 0.63% sulfur.
In general, the compositions of this invention comprise about 0.2-3.0 parts by weight of component A per part of component B. These proportions are of active chemicals; that is, they disregard any diluent such as mineral oil. The preferred proportions are about 0.3-1.0 part of component A per part OI component B.
Specific examples of the multi-component compositions of the invention comprising mixtures of components A and B are as follows:
TABLE II

25Composition Exame~ ~ ~ Weight Ratio A l-A 3-B 1:2 B 12-A 26-B 0.3:1 C 12-A2-B:4-B 0.3:0.5:0.5 D 13-A 30-B 0.4-1 30 E 6-A3-B:32-B 0.3:0.4:0.4 F 8-A 3B-B 1:1 As previously indicated, the compositions of this invention are also useful as additives for lubricants. They are particularly useful for lubricating machinery which operates at relatively high temperatures, and 3~"S

are effective over a wide range of concentrations. Moreover, they frequently result in a decrease in the amount of oxidation inhibiting additives (examples of which are listed hereinafter) which rnust be incorporated in the lubricant and in a decrease in fuel consumption.
The compositions c~n be employed in a variety of lubricants based on diverse oils of lubricatin~ viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal com-bustion engines, including automobile ~d truclc engines, tw~cycle engines7 aviation piston engines, marine and railroad diesel engines, and the like.
They can ~lso be used in gas engines, stationary power engines and turbines and the like. Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions can also benefit from the ineorporation therein lS of the compositions of the present invention.
Natural oils include snimal oils and vegetable oils (e.g., castor oil, lard oil) as well as mineral lubricating oil such as liquid petroleum oils and solvent-refined or acid-refined mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating vis-eosity derived from coal or shale are also useful base oils. Synthetic lubri-cating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, poly-propylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes), poly(l-octenes, poly(l decenes)l etcO and mixtuPeS thereof), alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes9 dinonylbenzenes, di~2-ethylhexyl)benzenes, etc.3; polyphenyls (e.g., biphenyls, terphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof, etc.
Alkylene o~ide polymers and interpolymers and derivatives there-of where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another elass of kr;own synthetic lubricating oils. These are exemplified by the oils prepared through polymeriæation of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average mo]ecular weight of lUOQ, diphenyl ether of polyethylene glycol ~ !33~'~S

having a molecular weight of 500-1000, diethyl ether of polypropylene glycol hRving a molecular weight of 1000-1500, etc) or rnono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C13Oxo acid diester of tetraethylene glycol.
Another suitable elass of synthetic lubricating oils comprises the esters of dlcarboxylic acids (e~g., phthalic acid, succinic acid, rnaleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl ~lcohol9 2-ethylhexyl alcohol, ethylene glycol, etc.).
Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl~
sebELcate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diis~
decyl azelate, dioctyl phthalate, didecyl phthalate~ dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of seba~ic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.
Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols flnd polyol athers such as trimethylol propane, pentaery~hritol, dipentaerythritol, etc.
Silicorl-based oils such as the polyalkyl-, polyaryl-polyalkoxy-, or polyarylo2~y-siloxane oils and siliG~te oils comprise another useful ~lass of synthetic lubri~ants ~e.g., tetraethyl silicate~ tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-tetraethyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(methyl~
siloxanes, poly(methylphenyl)-siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.gO, tricresyl phosphate trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils, either natural or synthetic (as well as mixtllres of two or more of any of these) of the type disclosed hereinabove can be used in the lubricant eompositions of the present invention. Unrefined oils are those obtained directly from a natur~l or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operatiorls, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an 3i~

unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those of skill in the art such as sol-rent extraction, second~ry distillation, acid or base 5 extraction, filtration9 percolation, el c. Rerefined oils are obtained by proeesses similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown 10 products.
Generally, the lubricants oP this invention will cont~in an amount of the composition of the invention which is e~fective to reduce fuel consumption of engines lubricated with the lubricants OI the invention.
Normally this amount will be in the range of from about Ooû5% to about 10%
15 although amounts of 0.1 to 5% per lOa parts of the total finished lubricant weight are preIerred.
The compositions of the present invention can contain, in addition to components A and B, other additives that are normally used in lubrieants.
Such additi~es include, for example, auxiliary detergents oî the ash-forming 20 and of the ashless type, viscosity index improving agents7 pour-point depre~sants, anti-foam agents, extreme pressure agents7 rust inhibiting agents, oxidation and corrosion inhibiting agents.
l[he ash-producing detergents are exemplified by oil-soluble neutrP1 and basic salts of alkali or alkaline earth metals with sulfonic acids, 25 carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-t~phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene h~ving a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide9 phosphorus trichloride and sulfur, 30 white phosphorus and a sulIur halide7 or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.
The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid 35 radical. The commonly employed methods for preparing the basic salts .

3~ t3 -~3-involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50 C and filtering the resulting mass. The use of a "promoter" in the neutralization step to aid the incorporation o~ a large excess of mletal likewise is known. ExalTIples of compounds useful as the promoter include phenolic substances such as phenoll naphthol, ~Ikylphenol, thiophenol, sulfurized alkylphenol, and con-dens~tion products of formaldehyde with a phenolic subst~nce; ~lcohols such AS methanol, 2-propanol, octyl alcoholr cellosolve, carbitol, ethylene glycol~
stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, and dodecyl-amineO A particularly effective method for preparing the basic salts comprises mixing an acid with an excess oi a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonatir~ the mixture at an elevated temperature such as 60-20û C.
Auxiliary ashless detergents and dispersants are so called despite the fact that~ depending on its constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Many types are known in the art and are disclosed in patents induding those listed hereinabove with respect to component B. Also useful as auxiliary dispersants al e interpolymers OI oil-solubilizing monomers such as decyl methacrylate, vinyl deeyl ether and high molecular weight olefins with monomers containing polar substi~uents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene~substituted acrylates. These may be characterized as "poly-,~ meric dispersants" arld examples thereof are disclosed in the following U.S.
k~ patents ~_:
3,329,658 3,666,730 3,449~2S0 3,687,849 3,519,565 3,702,300 Extreme pressure agents and corrosion- and oxidation inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorînated wax; organic sldfides and polysulfides such as benzyl disulfide, bis~chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized Islethyl ester of ~33~h~5 -4~l-oleic acid, sul:t`urized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally dihydro-carbon and trihydrocarbon phosphite~ such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite9 tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phos-phite, oleyl 4-pentylphenyl phosphite, polypropylene ~molecular weight 500)-substitu~ed phenyl phosphite, diisobutyl~substituted phenyl phosphite; methl thiocarbamates, such as zinc dioctyldithiocarbamate, and barium h~ptyl-0 phenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithio~te, zinc dioctylphosphorodithioate, barium ~i-(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropylalcohol and n-hexyl alcohol.
The compositions of this invention also can contain at least one viscosity improving component; that is~ at least one component capable of substantiRlly improving the viscosity properties thereof. For the purposes oP
this invention, a substance is considered to substantially improve the viscosity properties of a composition if its incorporation in the composition in operative amounts causes an increase in its viscosity index (as determined by ASTM procedure D2270) of at least 6 unitsO
A number of types OI viscosity improvers are known in the art, and many of these are described in Ranney, ~iv~ (Noyes Data Corporation, 1973)7 pp. 93-119. Illustrative viscosity improvers include various olefin polymers such as polybutene (especially containing predomi-nantly isobutene units); ethylen~propylene copolymers; copolymers of ethylene and other low molecular weight olefin.q (especially alpha-olefins);
terpolym ers of ethylene, propylene and various dienes (especially non-conjugated dienes); polybutadiene; hydrogenated styrene-butadiene co polymers; alkylated polystyrenes; polymers of alkyl methacrylates; alkylene polyethers; and polyesters prepared from polyols, short-chain dicarboxylic acids and monobasic carboxylic acid terminators (useful predominantly in lubricants in which the lubrieating oil is a synthetic ester).
It is also within the scope of this invention to use as component B

- ~5 ~ 3~2S

a composition which improves viscosity properties as well as serving as a dispersant or detergent. When component B also improves viscosity propertiesl it may be possible to decrease the amount of auxiliary viscosity improver used or to eliminate it entirely~
The present invention contemplates two materials as being particularly useful as combination viscosity improvers and detergents or dispersants. The first comprises the dispersants containing more than one succinic moiety per molecule, particularly those prepared from a hydrocarbon source having a number average molecular weight (Mn~ of at least about 1300 and usually about 1300-5000 as determined by gel permeation chromatography. Examples 25~-29B hereinabove illu,strate suitable dispersants of this type which also have viscosity improving properties.
The second type of preferred viscosity improver having dispersant or detergent properties comprises interpolymers being substantially free of titratable acidity and containing carboxylic ester groups in which part of the alcohol moieties have at least 8 aliphatic carbon atoms and another part have no more than 7 aliphatic carbon atoms, and also containing carbonyl-polyamino groups in which the polyamino group is derived from a compound having one primary or secondary amino group. These polymers are described in U.S. Patent 3,702,300. Preferred are interpolymers prepared by first copolymerizing styrene with maleic anhydride and subsequently esterifying a portion of the carboxylic acid groups with a mixture of primary alcohols having the numbers of carbon atoms noted above, and neutralizing the remaining carboxylic acid groups with a suitable amine. The working examples of U.S. Patent 30 3,702,300 illustrate specific suitable polymers.
A further component in -the phosphorus acid salt compositions of this invention can be at least one compound of the formula P-SM

~.

3~
- 45a -wherein each of R13 and Rl is independently a hydrocarbon-based group having from about 3 -to about 20 carbon atoms and M is a Group I metal, a Group II metal, aluminum, -tin, iron, cobalt, lead, arsenic, molybdenum, ....

,~' -46~

manganese, nickel, or a mixture of any of said metals. These phosphorus acid salts~ when present9 provide load c~rryir4~ and oxidation inhibiting properties to the lubricant.
Each of R13 and R14 is preferably an alkyl group, although it may 5 be an aryl or substituted aryl group (e.g., phenyl, tolyl, chlorophenyl).
Suitable alkyl groups include propylJ butyl, octyl, decyl, hexadecyl, octa decyl, eicosyl and mixtures thereof. Most often, each of R13 and R14 is an allcyl group containing from about 6 to about 20 and preferably from about 6 to about 10 c~rbon atoms. Branched groups (e.g., isooctyl, 2 ethylhexyl) are 10 especially pref erred.
The metal ~M) of the phosphorus acid salt is preferably 2inc or molybdenum and especially zinc. As previously noted, it is within the scope of the invention to use salts of more than one metal or to use a mixed salt of two or more metals (e.g., zinc and arsenic, zinc and nickel, molybdenum and 15 manganese).
The compositions OI this invention can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive ~oncentrate. These concentrates 20 usually contain about 20~90% by weight of the composition of this inven$ion and may contain, in addition, one or more other additives known in the art or described hereinabove.
Illustrative concentrates of this invention are listed in Table III
and illustrative lubricants of this invention are listed in Table IVo All 25 amounts except ~hose for the products of Examples are exclusive of diluents such as mineral oil.

I o I I I o I I I o~

I I I o o I ~ ~ I I I o ~c ) ¢ ~ ¢ I 1 ~1~1 1 1 1 1 1 V O r~
o ~
E ~ ~, v ~D
~ ~ ~ p o,~
'` ~ ¢ ¢ ~ .g C

.~ , ' ~ U~ E ~ E E :~ ~ o, r ._ o ~o ~ ~ o o ~a o ~ Y,~ ~
~
~t 7 3~

~ 1~1~ 11111 1111111 a ~ ~ I ~,, I I I I I I I I I I I I I

3 ~ o I c~ I

~ ~ ~4 ~ o _, ~ I o I I I o o :~ E~

E~ .= ~ n c ~ I o I I to U~ X I ~ I I I O I o C g.
E ~ 3 ~ c = E 3 ~ ~ ~ , s ~ E E = E o. ~ E ~ ;, ~ ~ E
& ~ S 0 e ~ ~ 4 ;~
C ~ o o o O ~ ~ ~ 3 v ~ c~ c~ .~ '' ,, ~ E ~ , o o .N Y ~
,, " e S ~ ~ 3 0 33~

The fuel consumption of internE~l combustion engines is reduced when the engines are lubricated with the compositions OI this invention.
This can be shuwn by the Pinto Friction Horsepower Test, in which a ~ord Pinto engine is driven by a dynamometer at constant temperature while 5 engine r.p.m. and torque are measured by a digital tachometer and a precision dial manometer, respectively. Friction horsepower, as calculated from these values9 is roughly proportional to fuel consumed and thus decreases with improved fuel economy.

Claims (24)

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

1. A multi-component composition comprising (A) at least one tartrate of the formula:

wherein each R is independently a hydrocarbon-based group and the sum of carbon atoms in both R groups is at least about 8; and (B) at least one oil-soluble detergent or dispersant.

2. The composition of claim 1 wherein each R group is of about 8-20 carbon atoms.

3. The composition of claim 1 wherein at least one R group contains an uninterrupted chain of at least about eight -CH2- units.

4. The composition according to claim 1 wherein the detergent is a basic alkali or alkaline earth metal salt or complex of a phenol, sulfonic acid, carboxylic acid or phosphorus acid.

5. The composition according to claim 4 wherein the detergent is a basic alkali or alkaline earth metal salt.

6. The composition according to claim 5 wherein the detergent is a basic calcium sulfonate.

7. The composition according to claim 1 wherein the dispersant is characterized by the presence of an oil-solubilizing group containing at least about 40 aliphatie carbon atoms bonded directly to Q polar group.

8. The composition according to claim 7 wherein the dispersant is a carboxylic dispersant, a Mannich dispersant, an amine dispersant, a polymeric dispersant, or a post-treatment product of any of the foregoing.

9. The composition according to claim 8 wherein the dispersant is a carboxylic dispersant characterized by the presence within its molecular structure of an acyl, acyloxy or acylimidoyl group containing at least about 44 carbon atoms and a group in which a nitrogen or oxygen atom is attached directly to said acyl, acyloxy or acylimidoyl group, said nitrogen or oxygen atom also being attached to a hydrocarbon-based group.

10. The composition according to claim 9 wherein the dispersant is prepared by reaction of a substantially saturated hydrocarbon-substituted or halohydrocarbon-substituted succinic acid compound with at least one alcohol or an alkylene polyamine.

11. The composition of claim 10 wherein the substantially saturated hydrocarbon-substituted succinic acid compound is prepared by reaction of more than one mole of maleic anhydride with one mole of an olefin polymer.

12. The composition of claim 11 wherein the substituted succinic acid contains an average of 1.3 to 3.5 succinic acid groups for each olefin polymer derived group.

13. The composition according to claim 10 wherein the hydro-carbon substituent on the succinic acid-producing compound contains at least about 50 aliphatic carbon atoms and the dispersant is prepared by the reaction of said succinic acid-producing compound with at least one alcohol.

14. The composition according to claim 13 wherein the alcohol is pentaerythritol.

15. The composition according to claim 10 wherein the substitu-ent on the succinic acid-producing compound contains at least about 50 alipilatic carbon atoms and the dispersant is prepared by the reaction of said succinic acid-producing compound with at least one alkylene polyamine.

16. The composition according to claim 15 wherein the alkylene polyamine is an ethylene polyamine.

17. The composition according to claim 8 wherein the dispersant is a Mannich dispersant comprising the reaction product of an alkyl phenol in which the alkyl group contains at least about 40 carbon atoms with an aliphatic aldehyde containing at least about 7 carbon atoms and an amine.

18. The composition according to claim 17 wherein the aldehyde is formaldehyde and the amine is an alkylene polyamine.

19. The composition according to claim 18 wherein the amine is an ethylene polyamine.

20. The composition of claim 1 wherein both a detergent and a dispersant are present.

21. The composition of claim 20 wherein the detergent is a basic alkali or alkaline earth metal sulfonate and the dispersant is prepared by reaction of ~ hydrocarbon substituted succinic acid-producing compound with at least one alcohol or an alkylene polyamine.

22. An additive concentrate comprising from 10 to 80 parts of an inert liquid solvent or diluent and from 20 to 90 parts of the composition of claim 1, 2 or 3.

23. A lubricant comprising a major proportion of oil and a minor proportion of the composition of claim 1, 2 or 3.

24. A method of reducing fuel consumption in an internal combustion engine which comprises lubricating said engine during operation with a lubricant comprising a composition according to claim 1, 2 or 3.