US3272743A - Lubricants containing metal-free dispersants and metallic dispersants - Google Patents

Lubricants containing metal-free dispersants and metallic dispersants Download PDF

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US3272743A
US3272743A US38775764A US3272743A US 3272743 A US3272743 A US 3272743A US 38775764 A US38775764 A US 38775764A US 3272743 A US3272743 A US 3272743A
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George R Norman
Suer William M Le
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
    • C10M2215/082Amides containing hydroxyl groups; Alkoxylated derivatives
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086Imides
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • C10M2225/041Hydrocarbon polymers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/10Internal-combustion engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/10Internal-combustion engines
    • C10N2240/101Alcohol fuelled engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/10Internal-combustion engines
    • C10N2240/104Gasoline engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/10Internal-combustion engines
    • C10N2240/104Gasoline engines
    • C10N2240/106Rotary engines

Description

United States Patent 3,272,743 LUBRICANTS CONTAINING METAL-FREE DIS- PERSANTS AND METALLIC DISPERSANTS George R. Norman, Lyndhurst, and William M. Le Suer,

Cleveland, Ohio, assignors to The Lubrizol Corporation, Wickliffe, Ohio, a corporation of Ohio No Drawing. Filed Aug. 5, 1964, Ser. No. 387,757 12 Claims. (Cl. 252-32.5)

This application is a continuation-in-part of earlier application Ser. No. 77,842, filed December 23, 1960, now forfeited, which was a continuation-in-part of earlier filed application Ser. No. 808,903, filed April 24, 1959, now abandoned, which was in turn a continuation-in-part of earlier filed application Ser. No. 802,667, filed March 30, 1959, now US. 3,172,892.

This invention relates to a combination of chemical compositions which are especially useful in lubricants. It relates in particular to lubricating compositions containing this combination of compositions.

There are two principal environments which are served by automotive crankcase lubricants. Each of these environments poses a specific problem which must be solved if a lubricant is to be regarded as satisfactory. These problems are the result of the inevitable presence in the lubricant of varying proportions of foreign particles such as dirt, soot, water and decomposition products resulting from breakdown of the oil. Even if there were none of this latter contaminant present, the very nature of the design of the modern internal combustion engine is such that a significant amount of foreign matter will accumulate in the crankcase. Perhaps the most important of these contaminants is water because it seems to be responsible for the deposition of a mayonnaise-like sludge. It appears that if there were no Water present, the solid components of the mayonnaise-like sludget would circulate with the oil and be removed by the oil filter. It will be readily appreciated that the deposition of the sludge presents a serious problem with respect to the efficient operation of the engine and that it is desirable to prevent such deposition of sludge-like material.

The presence of water and the precursors of sludge in a lubricating oil is dependent largely upon the operating temperature of the oil. If the oil is operated at a high temperature the water of course will be eliminated by evaporation about as fast as it accumulates. In the absence of water, as stated above, the other foreign particles will be removed by the filter. At low oil temperatures, on the other hand, water will accumulate and so consequently will sludge. It is apparent that this particular environment provides a serious problem for crankcase lubricants.

In ordinary stop-ancl-go driving, as is the case with taxicabs, delivery trucks, police cruisers, etc., the crankcase lubricant will be alternately hot and cold, an ideal environment for the accumulation of water. In such cases the formation of sludge is a serious problem. This problem has been with the automotive industry for many years and its solution has been sought by the use of many different types of additives, but without notable success. Although many of such additives are very effective in combatting the detergency problems associated with motor oils at high temperatures, they have not been particularly effective in solving the problems associated with low temperature operation, or to put it better, those problems which are associated with crankcase lubricants in engines which are operated at alternating high and low temperatures.

The other principal problem which must be solved by a satisfactory lubricant is that posed by the operation of an engine at continuous high temperatures. This is the situ- 3,272,743 Patented Sept. 13, 1966 ation caused by high speed operation such as all-day driving at speeds of 50-70 mph. on a hot summer day. In such an environment there is no significant accumulation of water, but there is a strong tendency toward chemical degradation of the lubricating oil. This breakdown of the oil results in the formation of acidic materials which in themselves corrode the metal surfaces of the bearings, pistons, etc. Furthermore these acidic products decompose to form hard, carbonaceous deposits which accumulate in the piston ring grooves; still further these acidic products decompose to form also a varnish on the piston skirts and other metal surfaces.

Although, as indicated before, the problems of a crankcase lubricant under such conditions of high temperatures have been dealt with by the use of certain known additives these approaches to the problem have not been entirely satisfactory. Even with the most effective detergents some appreciable deterioration of the lubricating oil still occurs and thus poses a problem.

It is accordingly a principal object of this invention to provide a novel process for the preparation of products which are effective as dispersants in lubricant compositions.

It is another object of this invention to provide novel products which are effective dispersants in lubricant composition intended for use in engines operated at alternating high and low temperatures.

It is another object of this invention to provide novel products which are effective dispersants in lubricant compositions intended for use in engines operated at high speed and therefore at high temperatures.

It is another object of this invention to provide improved lubricant compositions.

These and other objects of the invention are achieved by a lubricating composition consisting essentially of a major proportion of a lubricating oil and (a) from about 0.1 to about 10 percent by weight of an oil-soluble acylated amine prepared by the process which comprises reacting maleic anhydride with a material selected from the class consisting of aliphatic olefin polymers having an average molecular weight with in the range of from about 700 to about 100,000 and chlorinated aliphatic hydrocarbons having an average molecular weight within the range of from about 700 to about 100,000, to form a substituted carboxylic anhydride wherein the substiutent group is an aliphatic hydrocarbon radical having at least about 50 aliphatic carbon atoms, mixing a carboxylic acid compound selected from the class consisting of (1) said substituted carboxylic anhydrides, and

(2) substituted carboxylic acids corresponding thereto, with at least about onehalf an equivalent amount of an alkylene polyamine, and heating the resulting mixture, at a temperature above about C. to effect acylation and remove the water formed thereby, and

(b) from about 0.05 to about 5.0 percent by weight as sulfate ash of an oil-soluble dispersant selected from the class consisting of alkaline earth metal petroleum sulfonates, alkaline earth metal alkyl-aromatic sulfonates, alkaline earth metal alkyl phenates and alkaline earth metal salts of phosphorus acids prepared from polymers of olefins having 2-30 carbon atoms, said polymer having a molecular weight of at least about 750.

It will be seen that the reaction by which component is prepared involves an amidation of a dicarboxylic acid (or anhydride thereof) with a polyamine, and can result in a simple acyclic diamide, a cyclic diamide, a polymeric amide or a combination of any of these types of products. It will be noted also that the amide groups may react further to form imide groups and it is believed that a substantial amount of imide formation takes place in the process. Furthermore there is reason to believe that in certain instances there is present in the product an appreciable proportion of amine carboxylic salt.

The size of the substituent of the succinic acid or anhydride is of major importance in the process because it allows the preparation of a product which satisfies the objects of the invention, i.e., one which is effective as a dispersant in the lubricants of this invention. It is critically important that this substituent be large, that it have at least about 50 carbon atoms in its structure. These substituent groups are substantially aliphatic hydrocarbon radicals, including both alkyl and alkenyl radicals. They are commonly derived from polyolefins such as polyethylene, polypropylene, polybutylene, etc., although they may be derived from any substantially aliphatic hydrocarbon.

The substituted succinic acids and anyhdrides which are contemplated as a reactant in the process are readily available from the reaction of maleic anhydride with a high molecular weight olefin or a chlorinated high molecular weight olefin. The product from such a reaction is the corresponding alkenyl succinic anhydride. The reaction involves merely heating the two reactants at a temperature of about 150200 C. The reactions in each case are illustrated by the following equations.

It will be appreciated that the reactions may not go precisely as indicated in the above equations, especially with respect to the particular carbon atom of the olefin or chloride reactant which ultimately becomes attached to the maleic acid or anhydride reactant, but other than this the equations are believed to be illustrative. Furthermore although the product of this reaction has been indicated as being an alkenyl succinic anhydride it is apparent that similar products can be prepared by this process in which the substituent is something other than an alkenyl group. For the purposes of this invention this substituent should, however, be a substantially aliphatic group and in most cases of course it will be an alkyl or alkenyl group. In some cases, it may well be desirable to employ a substituted succinic anhydride in which the substituent is derived for example from a copolymer of styrene and isobutylene, or of a substituted styrene and some other lower aliphatic olefin. In these latter cases the copolymer will be substantially aliphatic, that is, the composition of the copolymer will be predominantly aliphatic, i.e., more than about 80% of the monomeric units will be those of the aliphatic monomer.

As mentioned earlier the size of this substituent group appears to determine the effectiveness of the product of the process of the invention as a dispersant in motor oils. Substituted succinic anhydrides and their derivatives have been known for some time and it has likewise been known that these compounds are useful in lubricants, but their utility heretofore has been predicated upon their rustpreventing properties, corrosion-inhibiting properties, viscosity-temperature characteristics, etc. The usefulness of compositions of this type as dispersants has never been realized and an important aspect of this invention resides in the discovery that by increasing the size of this particular substituents an entirely new property, i.e., dispersancy, can be incorporated into the composition.

The most commonly used sources of these substantially aliphatic hydrocarbon substituents are the polyolefins. These are illustrated by polyethylene, polypropylene, polyisobutylene, etc. A particularly preferred polyolefin for this use is polyisobutylene. Thus the condensation of a polyisobutylene having a molecular weight of 750 with maleic anhydride yields an alkenyl succinic anhydride which upon further reaction with an ethylene amine produces an especially effective lubricating oil dispersant. Polyisobutylenes of this particular molecular weight are quite economically available and the effectiveness of products prepared from this material makes this starting material particularly desirable for use in a process of this invention.

Other sources of such hydrocarbon substituents are the polymers of higher l-mono-olefins such as l-octene, 1- dodecene, and l-octadecene. These l-mono-olefins may contain as many as 30 carbon atoms. Interpolymers of these l-mono-olefins may also be used provided that the interpolymers are substantially aliphatic, and more particularly such interpolymers are preferred in which the composition thereof comprises at least on a molar basis, of l-mono-olefin units.

Interpolymers of such l-mono-olefins with isoprene, butadiene, piperylene, vinyl cyclohexene, chloroprene, vinyl chloride, styrene, vinyl acetate, chlorostyrene, and vinyl alkyl ethers are thus contemplated.

The molecular weight of the substantially aliphatic hydrocarbon substituent of component (a) may range from one having the minimum of about 50 carbon atoms or a molecular weight of about 700 up to one having a molecular Weight of 75,000 or 100,000 or even higher. It should be noted that the expression hydrocarbon substituent, as is used in the specification and claims, denotes a substituent which is hydrocarbon or substantially hydrocarbon in character. Thus, the substituent may contain polar groups provided, however, that such polar groups are not present in proportions sufficiently large to alter significantly the hydrocarbon character of the substituent. The polar groups which may be present are exemplified by chloro, bromo, ioto, keto, aldehydo, ether and nitro radicals. The maximum proportion of such polar groups in the substituent is approximately 10 percent based upon the weight of the hydrocarbon portion of the substituent.

The substituted succinic anhydride ordinarily is reacted directly with the alkylene amine although in some circumstances it may be desirable first to convert the anhydride to the acid before reaction with the amine. In other circumstances it may be desirable to prepare the substituted succinic acid by some other means and to use an acid prepared by such other means in the process. In any event either the acid or the anhydride may be used in the process of this invention.

The term alkylene amine is used in a generic sense to denote a class of polyamines conforming for the most part to the structure H N 0 Hz? HNH) H R in which x is an integer and R is a low molecular weight alkyl radical or hydrogen. Thus it includes for example ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, etc. These compounds are discussed in some detail under the heading, Ethylene Amines, in Encyclopedia of Chemical Technology, Kirk and Othmer, vol. 5, pages 898-905, Interscience Publishers, New York (1950). Such compounds are prepared most conveniently by the reaction of ethylene or propylene dichloride with ammonia. This process results in the production of somewhat complex mixtures of ethylene amines including cyclic condensation products such as piperazines and these mixtures find use in the process of this invention. On the other hand quite satisfactory products may be obtained also by the use of pure ethylene amines. An es pecially useful ethylene amine, for reasons of economy as well as effectiveness as a dispersant, is a mixture of ethylene amines prepared by the reaction of ethylene chloride and ammonia, having a composition which corresponds to that of a tetraethylene pentamine. This is available in the trade under the trade name 'Polyamine HI! Other polyamines quite suitable for the purposes of this invention, include alkylene polyamines such as 1,3- propylene diamine, 1,4-butylene diamine, propylene polyamines in which the amino groups are attached to the land 3 carbon atoms, butylene polyamines in which the amino groups are attached to the 1- and 4-carbon atoms, and the C-alkyl-substituted derivatives of these and other such alkylene polyamines. F or the most part, polyalkylene polyamines having up to about alkylene groups and up to about 10 carbon atoms in each alkylene group are useful.

It has been noted that at least one-half of a chemical equivalent amount of the alkylene amine per equivalent of substituted succinic anhydride must be used in the process to produce a satisfactory product with respect to dispersant properties and generally it is preferred to use these reactants in equivalent amounts. Amounts up to 2.0 chemical equivalents (per equivalent of substituted succinic anhydride) have been used with success, although there appears to be no advantage attendant upon the use of more than this amount. The chemical equivalency of the al kylene amine reaction is based upon the nitrogen content, i.e., one having four nitrogens per molecule has four equivalents per mole.

The reaction of the process involves a splitting out of water and the reaction conditions are such that this water is removed as it is formed. Presumably the first principal reaction that occurs, following salt formation, is the formation of a half amide HCO R C R -CHCOOH 0 'l- HzNR CHZCONHR CHiOO followed then by salt formation RCHCOOH RGHCOO'HaNR HgNR CHaOONHR CHzCONHR and involving finally dehydration of this salt to form the product The first two of these reactions appear to take place spontaneously (when a substituted succinic :anhydride is used) upon mixing, but the third requires heating. Temperatures within the range of about 80 C. to about 200 C. are satisfactory, and within this range it is preferred to use a reaction temperature of from about 100 C. to about 160 C. A useful method of carrying out this step is to add some toluene to the reaction mixture and to remove the water by azeotropic distillation. As indicated before there is also some imide-formation.

Component (a) is unique in that it acts as a dispersant in lubricant cempositions although it contains no metal within its molecular structure. Component (b) on the other hand may be any of several well-known dispersants all of which are metal salts. As indicated earlier these well-known dispersants are the alkaline earth metal sulfonates, the alkaline earth metal alkyl phenates and the alkaline earth metal salts of phosphorus acids prepared from polymers of olefins having 24 carbon atoms.

Of the alkaline earth metal salts contemplated for use in the lubricants of this invention the barium and calcium salts find widest applicability. The magnesium and strontium salts have been used somewhat, but on a much smaller scale than the barium and calcicm salts. All, however, are useful for the purposes of this invention and all are contemplated as being within the scope thereof.

The sulfonates include chiefly those sulfonates derived from petroleum. These are the mahogany sulfonates prepared by sulfonation of naphthenic stocks with concentrated sulfuric acid, oleum or sulfur trioxide, etc., as well as those derived from the chlor-osulfonation, with chlorine and sulfur dioxide, of substantially aliphatic petroleum fractions. These chlorosulfonated aliphatic fractions are saponified with sodium hydroxide and then converted to the alkaline earth metal salt by double decomposition with the metal chloride. A variety of such sulfonation processes are available and the oil soluble sulfonates derivable from any of these are suitable for use in this invention. The synthetic sulfonates prepared by sulfonation of alkylated aromatic hydrocarbons likewise are valuable for this purpose. A common sulfonate of this type is that prepared by the sulfonation of a dodecenyl benzene prepared from tetrapropylene and benzene.

The alkaline earth metal alkyl phenates include those derived from such simple alkyl phenols as heptylphenol, octylphenol, decyl henol, eto., and also condensation products prepared from such alkyl phenols and from 0.5 to 2.0 moles of formaldehyde or .acetaldehyde. The alkyl phenate may be derived also from alkyl phenol sultides such as for example the reaction product of 1 mole of sulfur monochloride with 2 moles of diisobutyl phenol.

The phosphorus acids from which component (b) may be derived include several types of acidic materials. They are prepared in most instances from polyisobutylene, although they may be prepared from any substantially aliphatic polymer Within the limits of the definition of component (b). Thus, the polymer may be a polyethylene, polypropylene, polyhexene, polyd-odecene, or a polymer of other l-mon-o-olefins having as many as 30 carbon atoms. It may likewise be an interpolymer in which the preponderant proportion of monomeric units is derived either from ethylene, propylene, isobutylene, or any other l-mono-olefin having up to 30 carbon atoms. Such interpolymers are illustrated by an interpolymer of 95 molar parts of isobutylene and 5 molar parts of styrene.

In general those interpolymers are preferred in which at least on a molar basis of the interpolymer composition is derived from the aliphatic l-mono olefin. Such preferred interpolymers may include up to about 20%, on a molar basis, of units derived from isoprene, butadiene, piperylene, vinyl cyclohexene, chloroprene, vinyl chloride, styrene, vinyl acetate, chlorostyrene, or a vinyl alkyl ether. The proportion of l-mono-olefin units present in such interpolymers influences the oil solubility of the phosphorus acid salt derived from any particular interpolymer.

The molecular weight of this lower olefin polymer reactant to be employed in the preparation of component (b) may vary within a rather wide range. Thus, it may be as low as about 750 or, on the other hand, range upward to as high as 75,000 or, in some instances, even higher. The various types of phosphorus acids available from these polymers are prepared by reaction of the polymers with any of several well-known phosphorizing agents, followed by reaction with a reagent having an active hydrogen atom, usually water, and then neutralization with a basic, metal neutralizing compound such as barium oxide or lime.

Illustrative phospohrus acids include, for example, the reaction products of any of these polymers with phosphorus pentasulfide and sulfur, followed by steam treatment and then neutralization with a basic inorganic alkaline earth metal compound, such as barium oxide. Alternatively the neutralization step may be effected prior to the step of steam treatment. Another important type of phosphorus acid is that prepared from a polyolefin as defined in component (b) with phosphorus trichloride and sulfur followed by the neutralization and steam-treatment steps. Still another such phosphorus acid is that which can be prepared by the chlorination of the polyolefin followed by reaction with phosphorus trichloride and either steam or an alkyl phenol. This acid then, of course, can be neutralized with a basic metal compound. Another type of phosphorus acid is that which is prepared by the reaction of an aliphatic polyolefin with phosphorus and sulfur monochloride, followed by steam treatment and neutralization. Still another type of phosphorus acid can be prepared by reaction of a polymer of the type described before with a phosphorus sulfide, followed by steam treatment and neutralization with a basic inorganic alkaline earth metal compound.

A general definition of the phosphorus acid salts contemplated for use as component (b) includes those prepared by reaction of a polymer of a l-mono-olefin with a phosphorizing agent, followed by treatment of the resulting product with a hydrolyzing agent and neutralizing agent. The phosphorizing agents include phosphorus sulfides, phosphorus chlorides, thiophosphoryl chloride, phosphorus pentoxide, phosphorus, and combinations of these with sulfurizing agents such as sulfur, sulfur chloride, and sulfur monochloride. Illustrative combinations of these phosphorizing and sulfurizing agents include phosphorus pentasulfide and sulfur monochloride, phosphorus and sulfur monochloride, and phosphorus pentachloride and sulfur.

The structure of such phosphorus acids is not known and in fact it is commonly believed that an acid prepared in this fashion, viz., by reaction of a polyolefin with a phosphorizing agent followed by hydrolysis of the intermediate phosphorized product, is really a mixture, not only of two or more different acids, but a mixture perhaps of different types of acids. Thus, this mixture may contain acids having carbon-to-phosphorus bonds or acids having carbon-to-oxygen-to-phosphorus bonds, or carbonto-sulfur-to-phosphorus bonds. Inasmuch, however, as the structure of these phosphorus acids is not known, it is necessary to refer to them in terms of the process by which they can be prepared.

The basicity of any of these alkaline earth metal detergents can be varied considerably. Starting with the free acid, it may be neutralized to provide merely the normal valkaline earth metal salt which is useful, or it can be treated with an excess of the neutralizing alkaline earth metal compound to form a basic salt. This also, of course, is useful. Generally speaking, however, it is preferred to neutralize the acid with a considerable excess of basic inorganic alkaline earth metal compound and to carbonate the product so that that product contains a stoichiometrically excessive amount of metal with respect to the organic acidic anions present in the product.

Various promoters may be used to assist in the incorporation of such excessive metal and these include principally phenolic compounds and low molecular weight alcohols.

Yet another type of alkaline earth metal salt may be prepared. Using as a starting material the metal salt of any of the organic acids of component (b), such metal salt may be sulfonated with chlorosulfonic acid to yield an acidic metal salt. This acidic metal salt then may be neutralized with a basic inorganic alkaline earth metal compound to form either a normal or a basic alkaline earth metal salt. This process is described in more detail in copending application Ser. No. 658,737 and the details of the disclosure of this copending application are incorporated herein by reference. Thus a sodium mahogany sulfon'ate may be sulfonated with chlorosulfonic acid and then treated with a stoichiometric excess of barium oxide in the presence of methanol, carbonated and then filtered to yield an especially effective additive for use in the combination of this invention. Another very good additive for such use can be prepared by the reaction of polyisobutylene having a molecular weight of about 750 with phosphorus trichloride and sulfur, followed by treatment with steam, then neutralization with barium oxide to form the normal barium salt, followed by sulfonation with chlorosulfonic acid and neutralization with a stoichiometric excess of barium oxide in the presence of heptylphenol, carbonation "and filtration. Similarly the sulfonation of a neutralized chlorinated polyisobutylene (M.W.:850)-phosphorus trichloride-steam product is an excellent starting material for the preparation of satisfactory components in the combination of this invention.

The combination of additives of this invention have been found to be effective in many different types of lubricating oils. Oils derived from paraffinic and asphaltic crudes are benefitted thereby as well as all of the ordinarily available synthetic lubricants. These latter include the polyethers, polyesters, silicones, voltolized oils, etc.

Example 1.A polyisobutenyl succinic anhydride was prepared by the reaction of a chlorinated polyisobutylene with maleic anhydride at 200 C. The polyisobutenyl radical had an average molecular weight of 850 and the resulting alkenyl succinic anhydride was found to have an acid number of 113 (corresponding to an equivalent weight of 500). To a mixture of 500 grams (1 equivalent) of this polyisobutenyl succinic anhydride and 160 grams of toluene there was added at room temperature 35 grams (1 equivalent) of diethylene triamine. The addition was made portionwise throughout a period of 15 minutes, and an initial exothermic reaction caused the temperature to rise to 50 C. The mixture then was heated and a water-toluene azeotrope distilled from the mixture. When no more water would distill the mixture was heated to 150 C. at reduced pressure to remove the toluene. The residue was diluted with 350 grams of mineral oil and this solution was found to have a nitrogen content of 1.6%.

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

Example 3.-The procedure of Example 1 was repeated using 55.5 grams (1.5 equivalents) of an ethylene amine mixture having a composition corresponding to that of triethylene tetramine. The resulting product had a nitrogen content of 1.9%.

Example 4.The procedure of Example 1 was repeated using 55.0 grams (1.5 equivalents) of triethylene tetramine as the amine reactant. The resulting product had a nitrogen content of 2.5%.

Example 5.To a mixture of grams of toluene and 400 grams (0.78 equivalent) of a polyisobutenyl succinic anhydride (having an acid number of 109 and prepared from maleic anhydride and the chlorinated polyisobutylene of Example 1) there was added at room temperature 63.6 grams (1.55 equivalents) of an ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine and available from carbide and carbon under the trade name, Polyamine H. The mixture was heated to distill the water-toluene azeotrope and then to C. at reduced pressure to remove the remaining toluene. The residual polyamide had a nitrogen content of 4.7%.

Example 6.The procedure of Example 1 was repeated using 46 grams 1.5 equivalents) of ethylene diamine as the amine reactant. The product which resulted had a nitrogen content of 1.5%.

Example 7.A polyisobutenyl succinic anhydride having an acid number of 105 and an equivalent weight of 540 was prepared by the reaction of a chlorinated polyisobutylene (having an average molecular weight of 1,050

and a chlorine content of 4.3%) and maleic anhydride.

To a mixture of 300 parts by weight of the polyisobutenyl succinic anhydride and parts by weight of mineral oil there was added at 6595 C. an equivalent amount (25 part by weight) of Polyamine H (identified in Example 5). This mixture then was heated to 150 C. to distill all of the water formed in the reaction. Nitrogen was bubbled through the mixture at this temperature to insure removal of the last traces of water. The residue was diluted by 79 parts by weight of mineral oil and this oil solution found to have a nitrogen content of 1.6%.

Example 8.A mixture of 2,112 grams (3.9 equivalents) of the polyisobutenyl succinic anhydride of Example 7, 136 grams (3.9 equivalents) of diethylene tri- 9 amine, and 1060 grams of mineral oil was heated at 140-150 C. for one hour. Nitrogen was bubbled through the mixture at this temperature for four more hours to aid in the removal of water. The residue was diluted with 420 grams of mineral oil and this oil solution was found to have a nitrogen content of 1.3%.

Example 9.To a solution of 1,000 lgrams (1.87 equivalents) of the polyisobutenyl succinic anhydride of Example 7, in 500 grams of mineral oil there was. added at 85-95 C. 70 grams (1.87 equivalents) of tetraethylene pentamine. The mixture then was heated at 150-165 C. for four hours, blowing with nitrogen to aid in the removal of water. The residue was diluted with 200 grams of mineral oil and the oil solution found to have a nitrogen content of 1.4%.

Example 10.A polypropenyl succinic anhydride was prepared by the reaction of a chlorinated polypropylene (having a molecular weight of about 900 and a chlorine content of 4%) and maleic anhydride at 200 C. The product had an acid number of 75. To a mixture of 390 grams (0.52 equivalent). of this polypropenyl succinic anhydride, 500 grams of toluene, and 170 grams of mineral oil there was added portionwise 22 grams (0.52 equivalent) of Polyamine H. The reaction mixture was heated at reflux temperature for three hours and water removed from an azeotrope with toluene. The toluene then was removed by heating to 150 C./20 millimeters. The residue was found to contain 1.3% of nitrogen.

Example 11.A substituted succinic anhydride was prepared by reacting maleic anhydride with a chlorinated copolymer of isobutylene and styrene. The copolymer consisted of 94 parts by weight of isobutylene units and 6 parts by weight of styrene units, had an average moleoular weight of 1,200, and was chlorinated to a chlorine content of 2.8% by weight. The resulting substituted succinic anhydride had an acid number of 40. To 710 grams (0.51 squivalent) of this substituted succinic anhydride and 500 grams of toluene there was added portionwise 22 grams (0.51 equivalent) of Polyamine H. The mixture was heated at reflux temperature for three hours to remove by azetropic distillation all of the water formed in the reaction, and then at 150 C./20 millimeters to remove the toluene. The residue contained 1.1% by weight of nitrogen.

Example 12.A substituted succinic anhydride was prepared by reacting maleic anhydride with a chlorinated copolymer of isobutylene and isoprene. The copolymer consisted of 99 parts of isobutylene units and 1% by weight of isoprene units. The molecular weight of the copolymer was 28,000 and the chlorine alkenyl succinic anhydride had an acid number of 54. A stirred mixture of 228 grams (0.22 equivalent) of an oil solution of this alkenyl succinic anhydride, 58 grams of additional mineral oil, 500 grams of toluene and 9.3 grams (0.22 equivalent) of Polyamine H was heated at 110- 120 C. for three hours, water being removed from an azeotrope with toluene. When all of the water had thus been removed the toluene was distilled by heating to 150 C./20 millimeters. The residue was found to have a nitrogen content of 1.1%.

Example 13.A polyisobutenyl succinic anhydride was prepared by the reaction of a chlorinated polyisobutylene with maleic anhydride. The chlorinated polyisobutylene had a chlorine content of 2% and an average molecular weight of 1 1,000. The polyisobutenyl succinic anhydride had an acid number of 48. A mixture of 410 grams (0.35 equivalent) of this anhydride, 15 grams (0.35 equivalent) of Polyamine H and 500 grams of toluene was heated at reflux temperature for four hours to remove water from an azetrope with toluene. The toluene then was removed by heating to 150 C./20 millimeters. The nitrogen content of the residue was 1.3%.

Example 14.The procedure for Example 5 was repeated except that 0.94 equivalent of Polyamine H was used instead of 1.55 equivalents. The nitrogen content of the product was 3%.

Example 15.A polyisobutenyl-substituted succinic acid was prepared by hydrolysis of the corresponding anhydride (prepared in turn by the condensation of a chlorinated polyisobutylene and maleic anhydride). To 1152 grams (1.5 equivalents) of a 70% mineral oil solution of this polyisobutenyl succinic acid having an acid number of 62 there was added at room temperature 59.5 grams (1.5 equivalents) of Polyamine H. This mixture was heated at 150167 C. for 7 hours during which time a total of 19.5 grams of water was distilled from the mixture. The residue was diluted with 174 grams of mineral oil and then filtered at 150 C. The filtrate had a nitrogen content of 1.6%.

Example 16.-A mixture of 1056 grams (2.0 equivalents) of the polyisobutenyl succinic anhydride of the preceding example (in which the polyisobutenyl group has a molecular weight of 850), 89 grams (2.0 equivalents) of dis-(1,2-propylene) triamine (having a nitro gen content of 31.3%), 370 grams of mineral oil and grams of toluene was heated at reflux temperature (180- 190 C.) for 5 hours. A total of 18 grams of water was collected from the water-toluene azeotrope. The residue was heated to C./20 mm. to remove any last traces of water which might have remained. The nitrogen analysis of this residuewas 1.9%.

Example 17.A polyisobutylene having an average molecular weight of 50,000 was chlorinated to a chlorine content of 10% by weight. This chlorinated polyisobutylene was reacted with maleic anhydride to produce the corresponding polyisobutenyl succinic anhydride having an acid number of 24. To 6,000 grams (2.5 equivalents) of this anhydride there was added portionwise at 70-105 C. 108 grams (2.55 equivalents) of Polyamine H over a period of 45 minutes. The resulting mixture was heated for four hours at -180 C. while nitrogen was bubbled throughout to remove water. When all ofthe water had been removed the product was filtered and the filtrate found to have a nitrogen content of 0.6%.

Example 18.-A mixture of 1,000 grams (1.89 equivalents) of a polyisobutenyl succinic anhydride in which the polyisobutenyl group has an average molecular weight of 850, 60 grams (1.45 equivalents) of an ethylene amine mixture having a nitrogen content of 33.9%, 15 grams (0.44 equivalent) of diethylene triamine, and 161 grams of toluene was heated at 12174 C. (reflux temperature) for 9 hours. A total of 17 ml. of water was removed from the toluene-water azeotrope. The residual product was found to have a nitrogen analysis of 1.4%.

Example 19.-

(a) A mixture of 2,500 parts (3.0 equivalents) of polyisobutylene having an average molecular weight of 840 and 84 parts (as a catalyst) of a 40% oil solution of a barium dialkyl phosphorodithioate (in which the alkyl radicals are 50% octyl, 12% cyclohexyl and 38% hexyl) was heated to 245 F. To this mixture there was added 133 parts (4.0 equivalents) of sulfur and the mixture heated to 310 P. Then 458 parts (3.3 equivalents) of phosphorus trichloride was introduced beneath the surface of the reaction mixture over a period of 4 hours. The temperautre was maintained at 310320 F. throughout and after an additonal 30 minutes of heating at this temperature and the reaction mixture was heated at reduced pressure to remove any volatile components. The residue was blown with steam for four hours at 320 3 30 F., then dried with nitrogen to a water content of less than 0.25%. The acidic product had a neutralization number of 68.

(b) To a mixture of 2,090 parts of mineral oil and 250 parts of water at 180 F. there was added 70 parts (0.9 equivalent) of barium oxide and then 1,900 parts (2.3 equivalents) of the .above acid. The latter was added throughout a period of 1.5 hours and during this time and throughout an additional 1.5 hours there was added 1,337 parts (17.4 equivalents) more of barium oxide. The addition of barium oxide caused the temperature to rise to 270 F. and when all of the barium oxide has been added 443 parts (2.3 equivalents) of heptyl phenol was added. This mixture was dehydrated by heating at 300 F. for two hours and blowing with nitrogen. Thereupon carbon dioxide was blown through the solution for 5 hours at 280 F. The thus carbonated mixture was diluted with 1,200 parts of mineral oil and filtered through a siliceous filter aid. The filtrate showed the presence of 26.0% barium as sulfate ash.

Example 20.-An acid was prepared by the process of Example 19(a) using a polyisobutylene having an average molecular weight of 41,000. This acid (300 parts, 0.12 equivalent) was added over a 1.3 hour period to a mixture of 120 parts of mineral oil, 15 parts of water, and 5 parts (0.06 equivalent) of barium oxide. Throughout this period and an additional 1.3 hours 77 parts (1.0 equivalent) of barium oxide was added to the mixture. Then the mixture was heated to 240 F. and 38 parts (0.2 equivalent) of heptyl phenol was added throughout a period of 30 minutes. The temperature was increased to 300 F., nitrogen bubbled through for an hour, and then carbon dioxide for hours. Forty parts of a siliceous filter aid was added and the mixture filtered. The filtrate showed a barium content of 14.5% as sulfate ash.

Example 21.An acid was prepared by the process of Example 19(a) except that the polyisobutylene had an average molecular weight of 44,000. To a mixture of 392 parts of mineral oil, parts of water and 22 parts (0.3 equivalent) of barium oxide there was added at 180 F. over a period of 2.7 hours, 292 parts (0.23 equivalent) of this acid. After heating for an additional 90 minutes, 7 parts more (0.1 equivalent) of barium oxide was added. This mixture then was heated to 300 F., blown with nitrogen for 30 minutes and filtered through a siliceous filter aid. The filtrate had a barium content of 2.5% as sulfate ash.

Example 22.

(a) Polyisobutylene having an average molecular weight of 1,000 was chlorinated to a chlorine content of 4.3%.

(b) To 900 parts (1.0 equivalent) of this chlorinated polyisobutylene at 230370 F. there was added portionwise over a period of 15 hours 150 parts (1.1 equivalent) of phosphorus trichloride. After an additional 2 hours of heating at 390 F. the mixture was freed of volatile components by heating at reduced pressure for an additional 1.5 hours and then blowing with nitrogen for 2 hours. Steam at 320330 F. was blown through the mixture for 4 hours at which point successive samples showed no change in neutralization number.

To a mixture of 495 parts of mineral oil, 100 parts (0.5 equivalent) of heptyl phenol, 38 parts of water and 62 parts (0.8 equivalent) of barium oxide at 180200 F. there was added over a period of 3 hours 400 parts (0.2 equivalent) of the above acid. An additional 257 parts (3.3 equivalents) of barium oxide was added to the -mixture whereupon carbon dioxide was bubbled through for 3 hours at 270280 F. The mixture was diluted with 281 parts of mineral oil and then filtered through a siliceous filter aid. The filtrate had a barium content of 25.0% as sulfate ash.

Example 23.-

(a) To 783 parts (0.87 equivalent) of the chlorinated polyisobutylene of Exam le 22(a) there was added at 210 F. 125 parts (0.9 equivalent) of phosphorus trichloride. Heptyl phenol (205 parts, 1.0 equivalent) then was added portionwise over .a period of 2 hours. The temperature was maintained at about 180 F. for an additional 3 hours and then increased to 375 F. and held there for another 2 hours. Nitrogen was blown through the mixture for 30 minutes and then steam at 350380 F. until the neutralization number leveled off at about 50.

(b) To a mixture of 700 parts of mineral oil, 18 parts of water and 27 parts (0.35 equivalent) of barium oxide at 180 F. there was added 171 parts (0.15 equivalent) of the above acid. Eleven parts (0.06 equivalent) of heptyl phenol was added and the mixture heated for an additional hour at 190 P. Then 113 parts (1.47 equivalents) more of barium oxide was added. After another hour of heating, carbon dioxide was blown through the mixture for 6 hours and then nitrogen for 30 minutes. The mixture was diluted with 118 parts of mineral oil and filtered through a siliceous filter aid. The filtrate showed a barium content of 26.5% as sulfate ash.

Example 24.The process of Example 23 was repeated except that 1.5 moles of phosphorus trichloride and 0.3 mole of heptyl phenol was used in the preparation of the acid of (a). Also the temperature of steam blowing was reduced to 310 F. The product had a barium content of 26.5% as sulfate ash.

Example 25.To .a mixture of 6,640 grams (13.3 equivalents) of barium petroleum sulfonate, 873 grams (4.5 equivalents) of heptyl phenol and 2,200 grams of water in 8,500 grams of mineral oil there was added at 180-300 F. 4,000 grams (52.2 equivalents) of barium oxide. The stirred reaction mixture then was heated to 300 F. to remove the water and carbon dioxide was blown through the mixture at this temperature until it was neutral. The product was diluted with 4,169 grams of mineral oil and filtered through a siliceous filter aid. The filtrate was further diluted until the barium content was 25% as sulfate ash.

Example 26.To a mixture of 6,245 grams (12.5 equivalents) of barium petroleum sulfonate, 1,460 grams (7.5 equivalents) of heptyl phenol, and 2,100 grams of water in 8,045 grams of mineral oil there was added at 180 F. 7,400 grams (96.5 equivalents) of barium oxide. The addition of barium oxide caused the temperature to rise to 290 F. which temperature was maintained until all of the water had been distilled away. The mixture then was blown with carbon dioxide until it was substantially neutral. 5,695 grams of mineral oil was added and the mixture filtered through a siliceous filter aid. The filtrate was diluted further with mineral oil to a barium content of 30.5% as sulfate ash.

Example 27.The barium salt of a phosphorusand sulfur-containing acid was prepared by reaction of polyisobutylene (M.W.:850) with phosphorus pentasulfide and sulfur followed by treatment with steam and neutralization with barium oxide. To 5,850 grams (6.8 equivalents) of this barium salt there was added portionwise at 120- 160 F. over a period of 2 hours 419 grams (3.6 equivalents) of chlorosulfonic acid. The mixture then was blown with nitrogen to remove gaseous materials.

To the resulting sulfonic acid and 858 grams (4.4 equivalents) of heptyl phenol there was added a slurry of 400 grams (5.2 equivalents) of barium oxide and 71 grams of water in 3,300 grams of mineral oil. After this mixture had been agitated at 150-220 F. for 30 minutes an additional 1,931 grams (25.2 equivalents) of barium oxide was added. Enough water was introduced, either as steam or liquid water to hydrate all of the barium oxide. At a temperature of 270 F. carbon dioxide was bubbled through the mixture until it was substantially neutral. The mixture then was filtered through a siliceous filter aid to yield a filtrate which was further diluted with mineral oil to a barium content of 25.0% as sulfate ash.

Example 28.To a mixture of 1,000 parts (1.0 equivalent) of sodium petroleum sulfonate, a solution of 69.5 parts weight (1.2 equivalents) of 96% calcium chloride in 84 parts of water there was added at 200 F. over a 2-hour period 72 parts (1.7 equivalents) of 85% calcium hydroxide. This mixture was heated for an additional 2 hours at 200 F. and then cooled to F. while adding parts of methanol. Carbon dioxide was bubbled through the mixture at this temperature until it was substantially neutral and then the temperature was raised to 300 F. to remove the methanol and water. The mixture was filtered through a siliceous filter aid to yield a clear filtrate as the product. It had a calcium content of 16.4% as sulfate ash.

Example 29.A slurry of 1,854 gr-arns (9.0 equivalents) of diisobutyl phenol, 370 grams (10.0 equivalents) of calcium hydroxide, 450 grams of water and 4,800 grams of oil was prepared and heated to 75 C. T this slurry there was added 90 ml. of ammonium hydroxide and 405 grams (13.5 equivalents) of paraformaldehyde. This mixture was stirred to reflux temperature for 1 hour and then dried by heating to 150 C. The mixture was filtered through a siliceous filter aid to yield a filtrate having a calcium content of 7.0% as sulf-a-te ash.

Example 30.A mix-ture of 1,000 grams (1.05 equivalents) of polyisobutylene, 37 grams (1. 2 equivalents) of yellow phosphorus, 157 grams (1.2 equivalents) of sulfur monochloride and 1,000 grams of mineral oil was heated at 160 C. for 6 hours in an atmosphere of nitgrogen. The reaction mixture then was blown with steam at this same temperature for 2 hours. To this steam treated mixture there was added 198 grams (2.6 equivalents) of barium oxide and 187 grams of water. The resulting mixture was heated at 150 C. for an hour and then filtered through a siliceous filter aid. This filtrate was heated at 150 C. with 393 grams (5.1 equivalents) of barium oxide and 168 grams (0. 8 8 equivalent) of heptyl phenol, then carbonated with carbon dioxide until it was neutral. Filtration yielded a clear product having a barium content of 21.7.

\Example 31 .--To a solution of 47 parts of polyisobutylene having an average molecular Weight of 60,000, in 76 parts of mineral oil, heated at 200 F., there was added 2.8 parts of phosphorous pentasulfide. This mixture was heated at 500 F. for two hours, then cooled to 300 F. Steam was blown through the mixture at this temperature (for 6 hours) until the acid number of the mixture increased no further.

To 40 par-ts of this acid, having an acid number of 12.0, there was added 3.3 parts of barium oxide and the slurry was heated to 265 F. The neutralized mixture was diluted with 79 parts of mineral oil and then filtered. The filtrate was found to have a sulfate ash content of 1.7%.

Example 32.An alkenyl succinic anhydride was prepared by chlorination of a polyisobu-tylene having an average molecular weight of 900, followed by reaction of this chlorinated product with maleic anhydride. To 265 parts of this polyisobutenyl succinic anhydride there was added 8 parts of heptyl phenol, 1,527 pants of mineral oil and 55 parts of water. This mixture was heated to 70 C. whereupon 460 parts of barium oxide was added. The temperature was increased to 150 C. and carbon dioxide blown through the mixture until it was slightly acidic. The carbonated mixture was filtered to yield a filtrate having a sulfate ash content of 23.3%.

In the preceding examples all parts are by Weight.

The dispersant qualities of the combination of the additives prepared by the processes of the above-illustrated examples are most striking when they are used in mineral oil lubricants. These products are miscible in such lubricants in all proportions, and normally the acylated amine product is employed in a concentration ranging from 0.1 to about 10.0% by weight of the lubricant composition Whereas the alkaline earth metalcontaining dispersant is employed in a concentration within the range of from about 0.05 to about 5.0% by weight as sulfate ash of the lubricant composition. The optimum concentration of each additive depends largely upon the nature of the particular base mineral oil stock and types of service to which the lubricants are to be subjected. In the case of the acylated amine additive this optimum concentration is within the narrower range of from about 0.5% to about 3%. For the alkaline earth metal-containing dispersant this narrower optimum range is from about 0.05 to about 2% by weight as sulfate ash.

14 As indicated earlier, the combination of additives of this invention may be used with advantage in synthetic lubricants also.

The lubricating compositions of this invention are effective for use in the crankcases of the internal combustion engines employed either under conditions of continuous high speed and high temperatures as Well as under conditions of stop-and-go driving, idling, low speed, etc.

The efficacy of these lubricant compositions under conditions of high speed, high temperature operation is shown by the results of engine tests carried out in accordance with US. Army Ordnance tentative specification AXS-155 1. This test is known as the Caterpillar CRC-L1 engine test and the particular test to which the lubricants of this invention were subjected is a modification of that test, the modification consisting of the use of a fuel having a sulfur content of 1% (significantly higher than that of the specified fuel). The results of such tests carried out on lubricants of this invention as well as lubricants containing only one of the two types of dispersants are shown as follows.

Lubricant Time Ring (hr-s.)

Filling, percent;

Piston Cleanliness Additives 0.9% of a product prepared as in Example 7 except that the polyisobutenyl radical contains an average of 61 carbons.

1.250% of the product of Example 1.4% of a product prepared as in Example 7 except that the polyisobutenyl radical contains an average of 61 carbons.

oi the product of Example 0.66% of a product prepared as in Example 7 except that toluene was used as the solvent.

0.579% of the product of Example 1.5% of a product prepared as in Example 7 except that toluene was used as the solvent.

0.559% of the product of Example 0.71% of the product of Example of the product of Example 0.81% of the product prepared as in Example 7 except that the polyisobutenyl radical contains an average of 61 carbons.

of the product of Example 1.02% of a product prepared as in Example 7 excect that the polyisobutcnyl radical contains an average of 61 carbons.

0.22% of the product of Example 1.2% of a product prepared as in Example 7 except that the polyisobutenyl radical contains an average of 61 carbons.

of the product of Example 0.524% of the product of Example 1.02% of a product prepared as in 93. 0

Example 7 except that the polyisobutenyl radical contains an average of 61 carbons.

of the product of Example 0.531% of the product of Example 1.02% of the product prepared as in Example 7 except that the polyisobutenyl radical contains an average of 61 carbons.

of the product of Example 0.636% of the product of Example 1.02% of the product prepared as in Example 7 except that the polyisobutenyl radical contains an average of 61 carbons. of the product of Example 0.57% of the product of Example 1.01233 of the product of Example of the product of Example in the engine (on a scale of 100-0, 100 being indicative Lubri Time 13mg pistm of no deposits and being indicative of extremely heavy cant Additives (hrs.) Filling, l anhdeposits). The results are summarized in Table III.

percent ncss i0 0.5 2% ofthe product ofExarnplo 480 7 05. 5 5 32?" Additives gf fg sludge 0.57% of a product prepared as Flumg Deposit in Example 25 except that the barium sul mate 25 0.97 of a product prepared as 2 77. 9 07. 0 ture of 90 parts of banum in Exarnple 7 except that the troleurn sulfonate and 10 parts polyisobutenyl radical com olbariuni alkaryl sulfonatc. 10 tains'an avem O of 61 cap 20 0.62% of a product preparidtlas 120 3. 4 90.1 bons g in Example 25 except 111 ie bariurfn sg/lftnate wasta ilnix- 'g fi ggg product of Ex ture o 90 ariuln pe ro eum sulfonate zfiid lg% barium g product of EX alkary su ona e. 21 0.5 2% ofthe product of Example 120 1 00. 5 26 g g fggggf ggiggfifgl 5 0.222% of the product of Example 323 5 gg gsg g g bons. 0.177 of the barium salt of a Car Dh sphorus-andsulfur-con- 'iz qg gf product of EX" E g g f l g 27 0.68% 01 the product prepared 1 77. 3 95. 7

o u y e as in Example 7 except that (M.W..85O)w1th phosphorus the polyisobumnyl radical penmsulfide and contains an average of 61 lowed by treatment with carbons steam. 22 0.30% ofthe product ofExample 120 11 84.5 3 Product Of 2 M 0 0.19% of the barium salt of a 28 gg i gfiggg gigggfifi 1 7 7 3 l W m the polyisobutenyl radical tiunmg acid. prepared by contains an average of 61 tit/1H of pol)y1soli1ut3l leneh carbzms .W.:85O wit piosp orus Dentasulfide and sulfur 101- g; :5 zg grgguct prepared as by treatment mm 9 0.82% of a product prepared as 6 72. 3 89. 3 2s 1.3 5% ofthe product olExamplc 480 7 94.5 ig fitz igg fl Example 30 25. of the product of Example 30 1.34% of the product prepared 1 72. 3 88. 24 1.25% olthc product ofExamplc 240 2 98.5 gfi gf fi z g gg fi gg 0.3% of the product of Example an average of 61 32. 0.44% of the product of Example 25.

31 .1 0.82% ofsthe product of Ex- 2 75.1 93.0 0 am e Each of the above lubr cants contained in addition t 0.25% of the product of Ex? the specified dispersant additives 0.075% (as phosphorus) ample 2 of a zinc dialkyl phosphorodithioate and 3 parts per m1l- 32 -gi gig ifig g ggz g g gi 5 lion of a dimethyl silicone foam inhibitor. The lubricat- 4O triethylcne tctramine was ing oil was an SAE 30 mineral oil. The test results were 5 the evaluated according to two numerical standards: 0.2% of the product of Ex- (I) The piston cleanliness rating should be greater 33 3 g i product of 3 M 2 92 5 than 90. am e 5.

(II) The number obtained by subtracting the top ring 'i rh ig zgi product of Exgroove filling value from the piston cleanliness rating pro- 34 0.82% lofsthe product of Ex- 7 50. 3 85.9 vides an overall indication of the efficacy of the test lubrigajg l'jmduct prepared as cant, in Example 28 except that The piston cleanliness rating is based upon a scale of E 1 i ijfgfigfi }gggfig 1-100, 100 representing a perfectly clean piston. 35 i; t p t f x- 1 7 -4 92.

Further illustration of the usefulness of the combinafif d t fE tion of additives of this invention was gained from a modi- 0 3e 1. 5 ftl 1: 3. s. fied version 1 of the CRCEX3 Engine Test. This test 2 product of 3 7 0 8 0 is recognized in the field as an important test by which 0-(glfim'7umgf3the p t of lubricants can be evaluated for use under light-duty serv- 0 07% f m ca1ciumpetm. ice conditions. In this particular test the lubricant is used 1mm sulfonatcin the crankcase of a 1954 6-cylinder Chevrolet Powerglide engine for 144 hours under recurring cycling condi- What is Claimed trons, each cycle consisting of: 1. A lubricating composition consisting essentially of 2 hours at an engine speed of 500:25 ripim. under zero amajor proportion of alubricating oil and load at an oil sump temperature of 100-125 F.; air- (a) from about 0.1 to about 10 percent by weight of fuel ratio of 10:1; an oil-soluble acylated amine prepared by the proc- 2 hours at an engine speed of 2500:25 rpm. under a ess which comprises mixing one equivalent of a subload of 40 brake-horsepower at an oil sump temperastituted succinic compound selected from the class ture of 240-250 F.; air-fuel ratio of 16:1. consisting of substituted succinic acids having the After completion of the test, the engine is dismantled Structuralformula and various parts of the engine are examined for engine RCHCOOH deposits. The lubricant dispersant addition agent is then (311.0001; rated according to (1) the extent of piston ring-filling, (2) the amount of sludge formed in the engine (on a scale and substituted succinic anhydrides having the strucof 80-0, 80 being indicative of no sludge and 0 being tural formula indicative of extremely heavy sludge), and (3) the total amount of engine deposits, i.e., sludge and varnish, formed 0 1 Ordinarily this test lasts for 96 hours. oHa/co in which structural formulas R is a radical selected from the class consisting of large aliphatic hydrocarbon radicals having at least about 50 carbon atoms with at least about one-half an equivalent amount of an alkylene polyamine, and heating the resulting mixture, at a temperature above about 80 C. to eifect acylation and remove the water formed thereby, and

(b) from about 0.05 to about 5.0 percent by Weight as sulfate ash of an oil-soluble dispersant selected from the class consisting of alkaline earth metal petroleum sulfonates, alkaline earth metal alkylaromatic sulfonates, alkaline earth metal alkyl phenates and alkaline earth metal salts of phosphorus acids prepared from polymers of olefins having 2-30 carbon atoms said polymer having a molecular Weight of at least about 750.

2. The lubricating composition of claim 1 characterized further in that the oil-soluble acylated amine of (a) is prepared by the process which comprises mixing one equivalent of a substituted succinic anhydride having the structural formula in which structural formula R is a large aliphatic hydrocarbon radical having at least about 50 carbon atoms, with at least about one-half an equivalent amount of an ethylene polyamine having from 2 to about 6 amino groups, and heating the resulting mixture at a temperature above about 80 C. to effect acylation and remove the Water formed thereby.

3. The lubricating composition of claim 1 characterized further in that the acylated amine of (a) is prepared by the process which comprises mixing one equivalent of a substituted succinic anhydride having the structural formula R-CH-GO \O 011266 in which structural formula R is a large aliphatic hydrocarbon radical having about 60 carbon atoms, with about one equivalent amount of an ethylene amine having from 2 to about 6 amino groups, and heating the resulting mixmm at a temperature above about 80 C. to effect acylation and remove the water formed thereby.

4. The lubricating composition of claim 1 characterized further in that the oil-soluble dispersant of (b) is a carbonated basic barium petroleum sulfonate.

5. The lubricating composition of claim 1 characterized further in that the oil-soluble dispersant of (b) is a carbonated basic barium salt of a phosphorus acid prepared from a polymer of an olefin having 23() carbon atoms.

6. The lubricating composition of claim 1 characterized further in that the oil-soluble dispersant of (b) is a carbonated basic barium salt of a phosphorus acid prepared from a polymer of isobutylene.

7. The lubricating composition of claim 1 characterized further in that the oil-soluble dispersant of (b) is a carbonated basic barium salt of a phosphorus acid prepared by the steam-treatment of a chlorinated polyisobutylenephosphorus trichloride reaction product.

8. The lubricating composition of claim 1 characterized further in that the oil-soluble dispersant of (b) is a car- :bonated basic barium salt of a phosphorus acid prepared by the steam-treatment of a polyisobutylene-phosphorus sulfide reaction product.

18 9. A lubricating composition consisting essentially of a major proportion of a mineral lubricating oil and (a) from about 0.1 to about 5.0 percent by weight of an oil-soluble acylated amine prepared by the process which comprises mixing one equivalent of a substituted succinic anhydride having the structural formula ROHC o /C O OH2C o in which structural formula R is a large aliphatic hydrocarbon radical having at least about 50 carbon atoms, with about one equivalent amount of an ethylene polyamine, and heating the resulting mixture at a temperature above about 80 C. to eifect acylation and remove the water formed thereby, and

(b) from about 0.05 to about 10.0 percent by Weight as sulfate ash of a barium salt of a phosphorus acid prepared from an isobutylene polymer having a molecular weight of about 1000.

10. The lubricating composition of claim 9 characterized further in that the oil-soluble dispersant of (b) is a carbonated basic barium salt of a phosphorus acid prepared by the steam-treatment of a polyisobutylene-phosphorus pentasulfide-sulfur reaction product.

11. A lubricating composition consisting essentially of a major proportion of a mineral lubricating oil and (a) from about 0.1 to about 5 percent by Weight of an oil-soluble acylated amine prepared by the process which comprises mixing one equivalent of a substituted succinic acid or anhydride in which the substituent is a large hydrocarbon radical having at least about 50 aliphatic carbon atoms with about one-half an equivalent amount of an ethylene polyamine having from about 2 to about 6 amino groups and heating the resulting mixture at a temperature above about 80 C. to effect acylation, and

(b) from about 0.5 to about 10 percent by Weight of sulfate ash of a barium salt of a phosphorus acid prepared by the reaction of an olefin polymer having a molecular weight from about 750 to about 75,000 with phosphorus sulfide.

12. The lubricating composition of claim 11 characterized further in that the large hydrocarbon substituent of the substituted succinic acid or anhydride of (a) is a polyisobutene group having a molecular weight of from about 750 to about 11,000 and the oil soluble dispersant of (b) is a barium salt of a phosphorus acid prepared by the steam treatment of a polyisobutene-phosphorus pentasulfide reaction product.

References Cited by the Examiner UNITED STATES PATENTS 2,915,517 12/1959 Le Suer 252-327 X 3,001,981 9/1961 Le Suer 252-32.7 X 3,018,247 l/l962 Anderson et al. 25251.5 X 3,172,892 3/1965 Le Suer et al 25251.5 X 3,219,666 11/1965 Norman et al 252-515 X 3,232,883 2/1966 Le Suer 25232.5

FOREIGN PATENTS 541,926 6/1957 Canada. 570,814 2/1959 Canada.

DANIEL E. WYMAN, Primary Examiner.

P. P. GARVIN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 272 743 September 13 1966 George R. Norman et al It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1 line 36 for "sludget" read sludge column 2, line 26, for "position" read positions line 47, for "substiutent" read substituent line 67, for

"component is read component (a) is column 3 line 5 for "carboxylic" read carboxylate line 49, for "cases, it" read cases, however, it line 70, for "substituents" read substituent column 5, line 70, for "calcicm" read calcium column 6, line 60, for "phospohrus" read phosphorus column 9, line 37, for "squivalent" read equivalent line 41, for "azetropic" read azeotropic line 48, for "parts of" read parts by weight of column 10, 1 ine 20, for "dis-(1,2-propylene)" read di-(l, Z-propylene line 34, for 2.5" read 2.55 line 47, for "l2-l74 C." read ll2-l74 C. line 62, for "temperautre" read temperature lines 63 and 64, for "temperature and the" read H temperature the column 14, line 49, for "excect" read except line 67, for "0.56%" read 0.57% column 15, line 16, for "0.27%" read 0.25% column 16, line 28, for "as Example read as in Example line 30, for "88." read 88.5 line 49, for "92." read 92.6

Signed and sealed this 8th day of October 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. A LUBRICATING COMPOSITION CONSISTING ESSENTIALLY OF A MAJOR PROPORTION OF A LUBRICATING OIL AND (A) FROM ABOUT 0.1 TO ABOUT 10 PERCENT BY WEIGHT OF AN OIL-SOLUBLE ACYLATED AMINE PREPARED BY THE PROCESS WHICH COMPRISES MIXING ONE EQUIVALENT OF A SUBSTITUTED SUCCINIC COMPOUND SELECTED FROM THE CLASS CONSISTING OF SUBSTITUTED SUCCINIC ACIDS HAVING THE STRUCTURAL FORMULA
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US3340190A (en) * 1965-06-01 1967-09-05 Standard Oil Co Railway diesel oil
US3368971A (en) * 1965-11-22 1968-02-13 Ethyl Corp Lubricating oil compositions
US3385790A (en) * 1965-04-27 1968-05-28 Monsanto Co Antioxidant compositions
US3401117A (en) * 1966-11-03 1968-09-10 Phillips Petroleum Co Reaction products of metal petroleum sulfonate, maleic anhydride and an amine as lubricant additives
US3445386A (en) * 1967-01-13 1969-05-20 Mobil Oil Corp Detergent compositions
US3496105A (en) * 1967-07-12 1970-02-17 Lubrizol Corp Anion exchange process and composition
US3793201A (en) * 1970-12-28 1974-02-19 Lubrizol Corp Stabilized basic magnesium sulfonate compositions
US4144181A (en) * 1977-04-29 1979-03-13 Exxon Research & Engineering Co. Polymeric additives for fuels and lubricants
EP0034397A1 (en) * 1980-01-03 1981-08-26 Exxon Research And Engineering Company Method for deconditioning an engine used in fuel economy tests
US4420407A (en) * 1981-10-22 1983-12-13 Texaco Inc. Method of lubricating upper cylinder of marine diesel engine
US4820432A (en) * 1987-07-24 1989-04-11 Exxon Chemical Patents Inc. Lactone-modified, Mannich base dispersant additives useful in oleaginous compositions
US4863624A (en) * 1987-09-09 1989-09-05 Exxon Chemical Patents Inc. Dispersant additives mixtures for oleaginous compositions
US4866141A (en) * 1986-10-07 1989-09-12 Exxon Chemical Patents Inc. Lactone modified, esterfied or aminated additives useful in oleaginous compositions and compositions containing same
US4866139A (en) * 1986-10-07 1989-09-12 Exxon Chemical Patents Inc. Lactone modified, esterified dispersant additives useful in oleaginous compositions
US4866140A (en) * 1986-10-07 1989-09-12 Exxon Chemical Patents Inc. Lactone modified adducts or reactants and oleaginous compositions containing same
US4906394A (en) * 1986-10-07 1990-03-06 Exxon Chemical Patents Inc. Lactone modified mono-or dicarboxylic acid based adduct dispersant compositions
US4938880A (en) * 1987-05-26 1990-07-03 Exxon Chemical Patents Inc. Process for preparing stable oleaginous compositions
US4943382A (en) * 1988-04-06 1990-07-24 Exxon Chemical Patents Inc. Lactone modified dispersant additives useful in oleaginous compositions
US4954276A (en) * 1986-10-07 1990-09-04 Exxon Chemical Patents Inc. Lactone modified adducts or reactants and oleaginous compositions containing same
US4954277A (en) * 1986-10-07 1990-09-04 Exxon Chemical Patents Inc. Lactone modified, esterified or aminated additives useful in oleaginous compositions and compositions containing same
US4963275A (en) * 1986-10-07 1990-10-16 Exxon Chemical Patents Inc. Dispersant additives derived from lactone modified amido-amine adducts
US4971711A (en) * 1987-07-24 1990-11-20 Exxon Chemical Patents, Inc. Lactone-modified, mannich base dispersant additives useful in oleaginous compositions
US5032320A (en) * 1986-10-07 1991-07-16 Exxon Chemical Patents Inc. Lactone modified mono- or dicarboxylic acid based adduct dispersant compositions
EP0462319A1 (en) * 1990-06-20 1991-12-27 The Lubrizol Corporation (an Ohio corporation) Lubricants, lubricant additives, and methods for lubricating sump-lubricated fuel-injected alcohol-powered internal combustion engines
US5756428A (en) * 1986-10-16 1998-05-26 Exxon Chemical Patents Inc. High functionality low molecular weight oil soluble dispersant additives useful in oleaginous composition
US6051537A (en) * 1985-07-11 2000-04-18 Exxon Chemical Patents Inc Dispersant additive mixtures for oleaginous compositions
US6127321A (en) * 1985-07-11 2000-10-03 Exxon Chemical Patents Inc Oil soluble dispersant additives useful in oleaginous compositions

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US2915517A (en) * 1957-05-08 1959-12-01 Lubrizol Corp Oil-soluble metal sulfonates and process for the preparation thereof
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US3172892A (en) * 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
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CA541926A (en) * 1957-06-04 The Lubrizol Corporation Lubricants
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US2915517A (en) * 1957-05-08 1959-12-01 Lubrizol Corp Oil-soluble metal sulfonates and process for the preparation thereof
US3172892A (en) * 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
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US3001981A (en) * 1959-11-30 1961-09-26 Lubrizol Corp Oil-soluble metal sulfonates and process for the preparation thereof
US3018247A (en) * 1960-03-15 1962-01-23 California Research Corp Lubricating oil compositions containing metal dithiophosphate-nu-dialkylaminoalkyl alkenyl succinimide blends
US3232883A (en) * 1961-12-28 1966-02-01 Lubrizol Corp Basic mixtures of metal salts and lubricants containing them

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385790A (en) * 1965-04-27 1968-05-28 Monsanto Co Antioxidant compositions
US3340190A (en) * 1965-06-01 1967-09-05 Standard Oil Co Railway diesel oil
US3368971A (en) * 1965-11-22 1968-02-13 Ethyl Corp Lubricating oil compositions
US3401117A (en) * 1966-11-03 1968-09-10 Phillips Petroleum Co Reaction products of metal petroleum sulfonate, maleic anhydride and an amine as lubricant additives
US3445386A (en) * 1967-01-13 1969-05-20 Mobil Oil Corp Detergent compositions
US3496105A (en) * 1967-07-12 1970-02-17 Lubrizol Corp Anion exchange process and composition
US3793201A (en) * 1970-12-28 1974-02-19 Lubrizol Corp Stabilized basic magnesium sulfonate compositions
US4144181A (en) * 1977-04-29 1979-03-13 Exxon Research & Engineering Co. Polymeric additives for fuels and lubricants
EP0034397A1 (en) * 1980-01-03 1981-08-26 Exxon Research And Engineering Company Method for deconditioning an engine used in fuel economy tests
EP0034397B1 (en) * 1980-01-03 1983-07-06 Exxon Research And Engineering Company Method for deconditioning an engine used in fuel economy tests
US4420407A (en) * 1981-10-22 1983-12-13 Texaco Inc. Method of lubricating upper cylinder of marine diesel engine
US6127321A (en) * 1985-07-11 2000-10-03 Exxon Chemical Patents Inc Oil soluble dispersant additives useful in oleaginous compositions
US6051537A (en) * 1985-07-11 2000-04-18 Exxon Chemical Patents Inc Dispersant additive mixtures for oleaginous compositions
US6355074B1 (en) 1985-07-11 2002-03-12 Exxon Chemical Patents Inc Oil soluble dispersant additives useful in oleaginous compositions
US4954277A (en) * 1986-10-07 1990-09-04 Exxon Chemical Patents Inc. Lactone modified, esterified or aminated additives useful in oleaginous compositions and compositions containing same
US4866140A (en) * 1986-10-07 1989-09-12 Exxon Chemical Patents Inc. Lactone modified adducts or reactants and oleaginous compositions containing same
US4866141A (en) * 1986-10-07 1989-09-12 Exxon Chemical Patents Inc. Lactone modified, esterfied or aminated additives useful in oleaginous compositions and compositions containing same
US5032320A (en) * 1986-10-07 1991-07-16 Exxon Chemical Patents Inc. Lactone modified mono- or dicarboxylic acid based adduct dispersant compositions
US4963275A (en) * 1986-10-07 1990-10-16 Exxon Chemical Patents Inc. Dispersant additives derived from lactone modified amido-amine adducts
US4954276A (en) * 1986-10-07 1990-09-04 Exxon Chemical Patents Inc. Lactone modified adducts or reactants and oleaginous compositions containing same
US4866139A (en) * 1986-10-07 1989-09-12 Exxon Chemical Patents Inc. Lactone modified, esterified dispersant additives useful in oleaginous compositions
US4906394A (en) * 1986-10-07 1990-03-06 Exxon Chemical Patents Inc. Lactone modified mono-or dicarboxylic acid based adduct dispersant compositions
US5756428A (en) * 1986-10-16 1998-05-26 Exxon Chemical Patents Inc. High functionality low molecular weight oil soluble dispersant additives useful in oleaginous composition
US5788722A (en) * 1986-10-16 1998-08-04 Exxon Chemical Patents Inc High functionality low molecular weight oil soluble dispersant additives useful in oleaginous compositions
US5451333A (en) * 1987-05-26 1995-09-19 Exxon Chemical Patents Inc. Haze resistant dispersant-detergent compositions
US5312554A (en) * 1987-05-26 1994-05-17 Exxon Chemical Patents Inc. Process for preparing stable oleaginous compositions
US4938880A (en) * 1987-05-26 1990-07-03 Exxon Chemical Patents Inc. Process for preparing stable oleaginous compositions
US4971711A (en) * 1987-07-24 1990-11-20 Exxon Chemical Patents, Inc. Lactone-modified, mannich base dispersant additives useful in oleaginous compositions
US4820432A (en) * 1987-07-24 1989-04-11 Exxon Chemical Patents Inc. Lactone-modified, Mannich base dispersant additives useful in oleaginous compositions
US4863624A (en) * 1987-09-09 1989-09-05 Exxon Chemical Patents Inc. Dispersant additives mixtures for oleaginous compositions
US4943382A (en) * 1988-04-06 1990-07-24 Exxon Chemical Patents Inc. Lactone modified dispersant additives useful in oleaginous compositions
EP0462319A1 (en) * 1990-06-20 1991-12-27 The Lubrizol Corporation (an Ohio corporation) Lubricants, lubricant additives, and methods for lubricating sump-lubricated fuel-injected alcohol-powered internal combustion engines
US5422022A (en) * 1990-06-20 1995-06-06 The Lubrizol Corporation Lubricants, lubricant additives, and methods for lubricating sump-lubricated fuel-injected alcohol-powered internal combustion engines

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