MXPA99004646A - Compositions of gr - Google Patents

Abstract

Improved fat compositions comprising a larger amount of a base, oil-based metal-thickened grease, selected from the group consisting of base fat thickened with simple metallic soap, complex fat and failed complex fat, at least one composition that contains sulfur and phosphorus, an overbased metal salt of an organic acid, a hydrocarbyl phosphite and a substituted carboxylic acid with an aliphatic or anhydride group thereof, where the aliphatic group contains at least 12 carbon atoms in sufficient quantities to raise the drip point of the base fat, as measured by ASTM D-2265 method at at least 15OC, the phosphorus and sulfur compound being described in detail here

Description

GREASE COMPOSITIONS FIELD OF THE INVENTION This invention relates to fat compositions. More particularly, it relates to base fats thickened with metallic soap having drip points, as measured by the ASTM method D-2265, augmented by the addition of certain components which are described in detail below.

BACKGROUND OF THE INVENTION The need of man to reduce friction dates back to ancient times. In times as far back as 1400 BC, ram fat and beef fat (suet) were used with the intention of reducing the friction of the axle of the carts. Until the mid-1800s, lubricants continued to be mostly mutton and beef fats, with some types of vegetable fats playing minor roles. In 1859, however, Colonel Drake drilled his first oil well. Since then, most lubricants, including grease, have been based on petroleum ("mineral" oil), although lubricants based on synthetic oils are used for special applications. In the Lubricating Grease Guide. C 1994, from the National Lubricating Grease Institute, Kansas City, Missouri, USA, fats are discussed in detail, which include various types of thickeners. These thickeners include fats thickened with simple metallic soap, with metallic soap-metal complex complex and thickened fats with no-jón product. Thickened fats with simple soap have been very effective. However, under certain conditions, the drip point, measured by the ASTM method D-2265, needs to be increased. One way to raise the drip point of base fats is to convert a simple metallic soap grease into complex fat by incorporating certain acids, typically carboxylic acids such as acetic acid, alpha-omega-dicarboxylic acids and certain aromatic acids. . This procedure necessarily consumes a lot of time, resulting in reduced production. However, complex fats provide properties that are very desirable and widely used. Many times the formation of the complex does not take place and the grease retains substantially the properties of the corresponding simple soap grease. These fats are cited here as failed complex fats. The reasons for failure to achieve complex formation are not well understood. Doner et al. in a series of US Patents, specifically US Patents: 5,084,194 5,068,045 4,961,868 4,828,734 4,828,732 4,781,850 4,780,227 4,743,386 4,655,948 4,600,517 4,582,617 indicate that a Increased thickening of base fats thickened with metallic salt using a wide variety of boron-containing compounds. Other additives contemplated for use with boron-containing compounds are phosphorus and sulfur-containing materials, in particular zinc dithiophosphates. The reaction products of 0.0-dihydrocarbyl phosphorodithioic acids with epoxides are described by Asseff in U.S. Pat. 3,341,633. These products are described as gear lubricant additives and as intermediates for preparing lubricant additives. The U.S. Patent No. 3,197,405 (LeSuer) discloses phosphorus and nitrogen containing compositions prepared by forming an acid intermediate by reaction of a hydroxy-substituted triester of a phosphorothioic acid with an inorganic phosphorus reagent and neutralizing a substantial portion of said acid intermediate with an amine . These compositions are described as lubricant additives. The U.S. Patent 4,410,435 (Naka et al.) Discloses a lithium complex grease containing a base oil, a fatty acid having 12-24 carbon atoms, a dicarboxylic acid having 4-12 carbon atoms and / or an ester of dicarboxylic acid and lithium hydroxide thickened with a phosphate ester and / or a phosphite ester. The U.S. Patent 5,256,321 (Todd) refers to improved fat compositions comprising a greater amount of an oil-based base fat thickened with simple metallic soap and smaller amounts of a phosphorus-sulfur-containing composition to raise the drip point of the fat base . The U.S. patent 5,236,320 (Todd et al.) Refers to improved fat compositions comprising a composition containing phosphorus and sulfur, an overbased metal salt of an organic acid and a hydrocarbyl phosphite. The U.S. patent 5,362,409 (iggins et al) refers to improved fat compositions selected from the group consisting of complex fats and failed complex fats comprising a composition containing phosphorus and sulfur, alone or together with an overbased metal salt of a organic acid and a hydrocarbyl phosphite. The U.S. Patent No. 5,472,626 discloses a lubricating grease composition comprising lithium calcium 12-hydroxy stearate. It has been found that the response of base greases to additives that improve the drip point frequently depends on the viscosity index of the oil used to prepare the fat, with low viscosity index oils and medium viscosity index oils being the least respond It has also been found that the responses of base greases to additives that improve the drip point frequently depend on the way of preparing the base fat, with the base fats being prepared with equipment open to the atmosphere with a lower response to the additives that improve the fat. drip point than fats prepared in closed systems. The present invention is directed to treat and solve this problem.

COMPENDIUM OF THE INVENTION This invention relates to base fats thickened with improved metallic soap, an improvement that is produced by the incorporation thereto of certain additives as compared to fats without additional additives. In one embodiment, this invention relates to improved fat compositions comprising a higher amount of base fat thickened with simple metal soap, based on oil and (A) of about 0.25% to about 10% by weight of a overbased metal salt of an organic acid; (B) from about 0.25% to about 5% by weight of a composition containing phosphorus and sulfur selected from the group which is then described in more detail, (C) from about 0.25% to about 5% by weight of a hydrocarbyl phosphite; (D) from about 0.025% to about 2% by weight of a carboxylic acid substituted with aliphatic group or an anhydride thereof, the aliphatic group containing at least about 12 carbon atoms, where the drip point of the base fat is increased in at least about 15 ° C as measured by the ASTM D-2265 method. In another embodiment, this invention relates to improved fat compositions where the base fat is a base fat of a complex or a failed complex. The greases of this invention are useful for lubrication, sealing and protection of mechanical components such as gears, shafts, bearings, shafts, hinges and the like. These mechanical components are found in automobiles, trucks, bicycles, steel mills, mine equipment, railroad equipment including rolling stock, aviation, ships, construction equipment and numerous other types of industrial and consumer machinery.

DETAILED DESCRIPTION OF THE INVENTION The heat resistance of fats is measured by various methods. One measure of heat resistance is the drip point. The fat typically does not have a sharp melting point but often softens to a point where it no longer functions as a thickened lubricant. The American Society for Testing Materials (American Society of materials testing) (1916 Race Street, Piladelfia, Pa.) Has established a testing procedure, D-2265 from ASTM, which provides a means to measure the fat drip point. In general, the drip point of a grease is the temperature at which the grease passes from a semi-solid state to a liquid state under the conditions of the test. The drip point is the temperature at which the first drop of material falls from the test capsule used in the apparatus used in ASTM procedure D-2265. For many applications, base greases thickened with simple metallic soap are completely satisfactory. However, for some applications, a higher thermal resistance manifested by a drip point than that possessed by fats thickened with simple metallic soap is desirable. All the fats of this invention are fats with metallic soap, that is, one of the thickener components is a metal salt of fatty acid. The simple metallic soaps are the substantially stoichiometrically neutral metal salts of fatty acids.

By substantially stoichiometrically neutral it is meant that the metal salt contains from about 90% to about 110% of the metal required to prepare the stoichiometrically neutral salt, preferably from about 95% to about 100%. Fats that only contain these metal salts as thickeners are fats thickened with simple metallic soap. The complex metallic soap fats provide increased dropping points. Complex thickeners involve the addition of a non-fatty acid component, for example, benzoic, lower aliphatic, dibasic organic acids, etc. to a fatty acid component. By lower aliphatic is meant -C-aliphatic ,. The formation of complex fat typically requires prolonged heating periods, often several times that required to prepare a fat thickened with simple metallic soap. From time to time attempts to form complex fats fail, resulting in a fat having substantially the same drip point as the corresponding fat thickened with simple metallic soap, or at least a drip point lower than desired. The failure is usually manifested by a significantly lower drip point (eg, many times 20-50 ° C or more) than that presented by the complex fat successfully performed. The preferred minimum drip point of the fats of this invention is 260 ° C. It is desirable to increase the drip point of the base greases thickened with simple metallic soap. It is also desirable to bring the failed complex fats to the levels of complex fats achieved, and it is often desirable to provide a means for further raising the dropping points of complex fat compositions. Accordingly, an object of this invention is to provide new fat compositions. Another object of this invention is to provide fat compositions that have valuable properties. Another object of this invention is to provide fat compositions having improved thermal stability (heat stability) as indicated by an increased drip point as measured by the ASTM D-2265 method. Another object is to provide a means for bringing failing complex base fats to the levels of complex fats. Yet another object is to provide a means for increasing the dropping point of complex fats to levels exceeding those of complex base fat. Other objects will become apparent to those skilled in the art upon reading the specification of this invention. The fat compositions of this invention have higher dropping points than the dropping points of the corresponding base greases. This benefit is obtained by incorporating, to the base fat of complex or failed complex, of certain compositions containing sulfur and phorus, organic acid overbased, a hydrocarbyl phote and a carboxylic acid substituted with aliphatic group or an anhydride thereof, where the aliphatic group contains at least about 12 carbon atoms, in amounts sufficient to raise the dropping point of the corresponding base fat measured by the ASTM method D-2265. The fats of this invention are prepared by thickening an oily base material. The fats of this invention are based on oil, that is, they comprise an oil that has been thickened with a metallic soap. Complex fats are formed by reaction of a reagent containing metal with two or more acids. One of the acids is a fatty acid or reagent derived therefrom and the other is an aromatic acid such as benzoic acid, an alpha-omega dicarboxylic acid such as azelaic acid, a lower carboxylic acid such as acetic acid and the like. Metallic soap is the salt of the fatty acid and the non-fatty acid is the complexing agent.

A common procedure for preparing complex fat is the realization of two stages, first the normal (simple) soap is formed, then the complex is formed by reaction with a second acid. Alternatively, the complex fat can be formed by reacting a mixture of the acids with the metal reagent. As stated above, the acid reagents can be reactive derivatives of the acid, such as esters. The reaction is typically carried out in a portion of the oil base and the rest of the oil is added once the complex formation has been completed. This allows a faster cooling of the fat with which the subsequent work can be carried out, such as grinding, immediately after the fat has been formed. There is no absolute industrial pattern that defines the drip point of a complex fat. However, it is frequently accepted that the minimum drip points presented by complex fats are approximately 260 ° C. However, a more general definition of a complex fat is that which is prepared as described hereinbefore and which has a significantly higher drip point, typically at least 20 ° C higher than the corresponding fat. of simple metallic soap. As noted herein, the dropping point of a failed complex fat is usually the same as that of the corresponding simple metal soap fat. It can then be concluded that a metallic soap contributes to the thickening of both complex and failed fat. According to this, both the complex fat obtained and the failing complex fat are mentioned here as fats thickened with metallic soap, but they are distinguished from the simple metallic soap fats as defined herein. The fat compositions of this invention employ an oil of lubricating viscosity, which includes natural or synthetic lubricating oils and mixtures thereof. Natural oils include animal oils, vegetable oils, mineral oils, mineral oils with solvent or treated with acid, and oils derived from coal or shale. Synthetic lubricating oils include hydrocarbon oils, halo-substituted hydrocarbon oils, alkylene oxide polymers, esters of carboxylic acids and polyalcohols, esters of polycarboxylic acids and alcohols, esters of phosphorus-containing acids, polymeric tetrahydrofurans, oils of silicone base and mixtures of them. Specific examples of lubricating viscosity oils are those described in U.S. Pat. 4,326,972 and European Patent Publication 107,282, which are incorporated herein by reference for their descriptions relating to lubricating oils. A brief basic description of lubricating base oils is that of D.V. Brock "Lubricant base oils", Lubricant Engineering, volume 43, pages 184-185, March 1987. This article is incorporated herein by reference for description relating to lubricating oils. A description of oils of lubricating viscosity is that of U.S. Pat. No. 4,582,618 (Davis) (column 2, line 37 to column 3, line 63, inclusive), which is incorporated herein by reference for its description of lubricating viscosity oils. Another source of information regarding the oils used to prepare lubricating greases is the NLGI Lubricating Grease Guide. National Lubricating Grease Institute, Kansas City, Missouri (1987), pages 1.06-1.09, which is hereby expressly incorporated by reference. As noted hereinbefore, the viscosity index of the oil from which the fat is derived has an effect on the response to a number of known additive systems designed to improve the dropping points. In particular, oils of low viscosity index (LVI) and medium viscosity index (MVI), which are sometimes cited in the art as medium range viscosity index oils, do not respond to many additive systems intended for Increase drip points. MVI oils have viscosity indexes of about 50 to about 85, determined using the procedure outlined in D-2270 of the ASTM Standards. LVI oils have viscosity indexes less than 50 and oils with high viscosity indexes (HVI) have viscosity indexes greater than 85, typically from about 95 to 110. Oils having viscosity indexes greater than 110 are frequently cited as very high viscosity index (VHVI) oils and extra high viscosity index oils (XHVI). These commonly have viscosity indexes ranging from 120 to 140. The ASTM D-2270 method provides a means of calculating the viscosity index from the kinematic viscosity to 40 ° C and at 100 ° C. The portion of metallic soap of the fats of this invention is well known in the art. These metal soaps are present in a base oil, typically a lubricating viscosity oil, in amounts typically from about 1 to about 30% by weight, more frequently from about 1 to about 15% by weight, of the base fat composition. In many cases, the amount of metallic soap used to thicken the base oil constitutes from about 5% to about 25% by weight of base fat. In other cases, from about 2% to about 15% by weight of metallic soap is present in the base fat. The specific amount of metallic soap required depends frequently on the metallic soap used. The type and amount of metallic soap used is often dictated by the nature of the desired fat. The type and amount of metallic soap used is also dictated by the desired consistency, which is a measure of the degree to which the grease resists a deformation when a force is applied. The consistency is usually indicated by the ASTM Cone Penetration Test, ASTM D-217 or ASTM D-1403. The types and amounts of metal soap thickeners that are employed are well known to those skilled in the fat art. The aforementioned Lubricating Grease Guide. pages 1.09-1.11 and 1.14-1.15 provides a description of metallic soap thickeners and soap complexes. This text is incorporated herein, therefore, as a reference for its description of metallic soap grease thickeners. As indicated hereinbefore, the fat compositions of this invention are based on oil, including both natural and synthetic oils. The fats are made from these oils by incorporating a thickening agent thereto. Thickening agents useful in the fats of this invention are metal soaps. Metallic soap is understood to mean a substantially stoichiometrically neutral metal salt of fatty acid and additional aliphatic and / or aromatic acid which is not a fatty acid as defined herein. By substantially stoichiometrically neutral it is meant that the metal salt contains from about 90% to about 130% of the metal required to prepare the stoichiometrically neutral salt, preferably from about 95% to about 120%, more preferably 99% to 110%. Fatty acids are defined herein as carboxylic acids containing from about 8 to about 24, preferably from about 12 to about 18 carbon atoms. The fatty acids are usually monocarboxylic acids. Among the examples of useful fatty acids are capric, palmitic, stearic, oleic and others. Mixtures of acids are useful. Preferred carboxylic acids are linear, ie they are substantially free of hydrocarbon branching. Particularly useful acids are the hydroxy-substituted fatty acids such as hydroxy-stearic acid where one or more hydroxyl groups may be located in internal positions on the carbon chain, such as 12-hydroxy, 14-hydroxy-, etc. acids, stearic Although soaps are fatty acid salts, they do not need to be prepared directly from fatty acids and often are not prepared as such. The typical process for obtaining the fat involves the saponification of a fat which is often a glyceride or other ester such as methyl or ethyl ester of fatty acid, preferably methyl ester, whose saponification is generally carried out in situ in the base oil to make the fat. If the fat is prepared from acids or esters, the fat is usually prepared in a fat kettle or other reactor as described by K.G. Timm in "Grease Mixer Design", NLGI Spokesman, June, 1980. Other reactors of this type include contact mixers and continuous grease forming reactors. One method is the Texaco Continuous Fat Processing which is discussed by Green et al. in NLGI Spokesman, pages 368-373, January, 1969, and by itte et al., in NLGI Spokesman, pages 133-136 (July, 1980). The U.S. Patent 4,392,967 relates to a process for the continuous manufacture of lubricating grease. As noted herein, the response of base greases to additive systems that improve the drip point depends on the oil used to prepare the base fat and the method of preparation. Low viscosity index and medium viscosity index oils are generally resistant to these additive systems, regardless of the method of preparation of the base grease. On the other hand, the base fats derived from high viscosity index oils generally respond to drip point improvement additives systems of prior art when the fat is prepared in a closed system, such as a contact mixer. On the other hand, fats derived from high viscosity index oils do not generally respond to prior art drip point additive systems when prepared in an open system. It has been found that the additive systems that improve the dropping point of this invention provide an increased drip point of the base fat, regardless of the oil used to prepare the fat 0 of the method of fat formation. The mixture of base oil, fat, ester, fatty acid or non-fatty acid and metal-containing reagent reacts to form the soap in situ. As mentioned hereinbefore, the complexing acids or reactive derivatives thereof may be present during soap formation or may be incorporated afterwards. The additives used in the fat can be incorporated during the manufacture of the fat, but they are often added after the formation of the base fat. The metals of the metallic soap fats of this invention are typically alkali metals, alkaline earth metals and aluminum. For the purposes of cost and ease of processing, the metals are incorporated by reaction of the acid reagents with the basic metal-containing reagents such as oxides, hydroxides, carbonates and alkoxides (typically lower alkoxides, which contain 1 to 7 carbon atoms in the alkoxy group). The soap and complex salts can also be prepared from the metals themselves although many metals are either too reactive or insufficiently reactive with the fat, ester or fatty acid to allow convenient processing. As stated hereinbefore, complex fats are prepared from a mixture of acids, one of which is a fatty acid and the other is not fatty acid as defined herein. The non-fatty acid can be incorporated in any of the stages of thickener formation. The preferred metals are lithium, sodium, calcium, magnesium, barium and aluminum. Especially preferred are lithium, sodium and calcium; the most preferred in particular is lithium. You can use mixtures. The preferred fatty acids are those of tallow, soy, stearic, palmitic, oleic acid and their corresponding esters, among which are included glycerides (fats) for example butter oil. Particularly preferred are hydroxy-substituted fatty acids and the corresponding esters, including fats. The preferred one in particular is 12-hydroxystearic acid. Preferred non-fatty acids used in the formation of complex fats include aromatic, lower aliphatic and dibasic acids. Representative examples are benzoic acid, acetic acid and azelaic acid. These and other thickening agents are described in U.S. Patent Nos. 2,197,263; 2,564,561; and 2,999,066, and the Lubricating Grease Guide mentioned above, all incorporated herein by reference for their descriptions of relevant fat thickeners. Complex fats, for example, those containing metal salt-soap complexes such as acetates-metallic soap, dicarboxylates-metallic soap, etc. they are not fat thickened by simple metallic soap. For reasons that are not well understood, complex formation does not always take place. In this way, although it is expected that the process is carried out and is normally carried out in such a way that the enhanced thermal properties of a complex grease are achieved, there is sometimes only a slight increase in the drip point or none at all. These fats are described herein with the expression of "failed complex" fat. For the purposes of this invention, both the complex fats achieved as well as the failed complex fats as well as the base fats thickened by simple metal soap, are grouped within the class of "fats thickened with metallic soap". Failed complex fats and base fats thickened with simple metallic soap are cited as such, and complex fats achieved are cited as complex fats. The thickeners of all these types of fats are cited here as metallic soap thickeners. It is to be understood that the metallic soap thickener of the failed fat is not a simple metallic soap, but as is evident from its inability to form complex fat does not possess the same characteristics as the complex metal salt of the obtained complex fat. . The distinction is based on the high temperature properties of the resulting fat composition. As used here, the term "hydrocarbyl" or "hydrocarbyl group" refers to a group having a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon character within the context of this invention. According to this, the term "hydrocarbyl" includes hydrocarbon groups, as well as substantially hydrocarbon groups. The term "substantially hydrocarbon" describes groups, which comprise hydrocarbon-based groups, which contain non-hydrocarbon substituents or atoms other than carbon in a ring or chain that do not alter the predominantly hydrocarbon nature of the group. The hydrocarbyl groups may contain up to three, preferably up to two, more preferably up to a non-hydrocarbon substituent, or non-carbon heteroatom in a ring or chain, for every ten carbon atoms provided this is a non-carbon hydrocarbon or non-carbon heteroatom substituent. do not significantly alter the predominantly hydrocarbon character of the group. Those skilled in the art will appreciate the heteroatoms in question, which are such as oxygen, sulfur and nitrogen, or substituents including, for example, hydroxyl, halo (especially chlorine and fluorine), alkyloxy, alkyl. mercapto, alkyl sulfoxyl, etc. Examples of hydrocarbyl groups include, but are not limited to, the following: (1) hydrocarbon groups, ie, aliphatic (eg, alkyl or alkenyl), alicyclic (eg cycloalkyl, cycloalkenyl), aromatic groups (e.g., phenyl, naphthyl), aromatic-, aliphatic- and alicyclic-substituted aromatic groups and the like as well as cyclic groups wherein the ring is completed through another portion of the molecule (i.e., for example, any two of the indicated groups can together form an alicyclic radical); (2) substituted hydrocarbon groups, that is, those groups containing non-hydrocarbon substituents which, in the context of this invention, do not significantly alter the predominantly hydrocarbon character; those skilled in the art will be aware of such groups (eg, halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.) (3) heterogroups, ie, groups that although they have predominantly hydrocarbon character within the context of this invention, they contain atoms other than carbon present in a ring or chain formed on the other hand by carbon atoms. Any person skilled in the art will be aware of suitable heteroatoms, which include, for example, sulfur, oxygen, nitrogen. Groups such as, for example, pyridyl, furyl, thienyl, imidazolyl, etc. they are representative of cyclic groups that contain heteroatom. Typically, there will be no more than 2, preferably no more than one non-hydrocarbon substituent or non-carbon atom in one chain or ring for every ten carbon atoms in the hydrocarbyl group. Normally, however, the hydrocarbyl groups are purely hydrocarbon and do not substantially contain such non-hydrocarbon groups, substituents or hetero-atoms. Unless otherwise indicated, the hydrocarbon groups are substantially saturated. By "substantially saturated" is meant that the group contains no more than one unsaturated carbon-carbon bond, olefinic unsaturation, for every ten carbon bonds present. Frequently, they contain no more than one non-aromatic carbon-unsaturated bond per 50 carbon-carbon bonds present. Frequently, the hydrocarbyl groups are substantially free of carbon-carbon unsaturation. It is to be understood that, within the content of this invention, the aromatic unsaturation is not normally considered olefinic unsaturation. That is, the aromatic groups are not considered to have unsaturated carbon-carbon bonds. (A) The overbased metal salt of an organic acid Component (A) is an overbased metal salt of an organic acid. Overbased materials are characterized by containing excess metal over which it would have to be present according to the stoichiometry of the metal and the organic acid reagent. The amount of excess metal is commonly expressed as the metal ratio. The term "metal ratio" (abbreviated MR) is the ratio of the equivalents of the metal base to equivalents of the organic acid substrate. A neutral salt has a metal ratio of 1. Overbased materials have metal ratios greater than 1, typically from 1.1 to about 40 or more. Among the preferred metals are Group I and Group II metals (version of the Periodic Table of Chemical Abstracts Elements (CAS)). Sodium, magnesium and calcium are preferred first, calcium being especially preferred. In the present invention, preferred overbased materials have an MR of from about 1.1 to about 25, with an MR of from about 1.5 to about 20 being most preferred, and MR more preferably from 5 to 15. Generally, overbased materials useful in the present invention are prepared by treatment of a reaction mixture comprising an organic acid, a reaction medium comprising at least one solvent, a stoichiometric excess of a basic metal compound and a promoter with an acidic material, typically dioxide carbon. In some cases, particularly when the metal is magnesium, the acidic material can be replaced by water. Organic Acids The organic acids useful for forming the overbased salts of the present invention include carboxylic acid, sulfonic acid, phosphorus-containing acid, phenol or mixtures of two or more of them. Carboxylic acids The carboxylic acids useful in obtaining salts (A) can be aliphatic or aromatic acids, mono- or polycarboxylic or be compounds that produce acid. These carboxylic acids include carboxylic acids of lower molecular weights (eg, carboxylic acids having up to about 22 carbon atoms such as acids having about 4 to about 22 carbon atoms or tetrapropenyl-substituted succinic anhydride) as well as carboxylic acids of weight higher molecular Throughout this specification and the appended claims, any reference to carboxylic acids is to be understood as including acid-yielding derivatives thereof, such as anhydride, lower alkyl esters, acyl halides, lactones and mixtures thereof. the same, unless specifically stated otherwise. The carboxylic acids of the overbased metal salts employed in this invention are preferably oil-soluble and the number of carbon atoms present in the acid is important in contributing to the desired solubility. Normally, in order to provide the desired oil-solubility, the number of carbon atoms in the carboxylic acid should be at least about 8, more preferably about 12, more preferably at least about 18, and even more preferably up to about 30. Generally, these carboxylic acids do not contain more than about 400 carbon atoms per molecule, preferably no more than about 100, often not more than about 50. The monocarboxylic acids of lower molecular weights that are contemplated in obtaining the salts Overbased metals for use in this invention include saturated and unsaturated acids. Examples of these useful acids include dodecanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, tall oil, etc. Mixtures of two or more of these agents can also be used. An exhaustive discussion of these acids is found in the "Encyclopedia of Chemical Technology" of Kirk-Othmer 3rd edition, 1978, John Wiley & amp; amp;; Sons, New York, pages 814-871; These pages are incorporated here for reference. Examples of lower molecular weight polycarboxylic acids include dicarboxylic acids and derivatives such as sebacic acid, cetyl malonic acid, tetrapropenyl substituted succinic anhydride, etc. The lower alkyl esters of these acids can also be used. The monocarboxylic acids include isoaliphatic acids. These acids frequently contain a backbone having from about 14 to about 20 aliphatic carbon atoms, saturated, and at least one, but usually not more than four side acyclic lower alkyl groups. Specific examples of these aliphatic acids include 10-methyl-tetradecanoic acid, 3-ethylhexadecanoic acid, and 8-methyl-octadecanoic acid.

Isoaliphatic acids include mixtures of branched chain acids prepared by isomerization of commercial fatty acids (eg, oleic, linoleic or tall oil acids) of, for example, about 16 to about 20 carbon atoms. The mono- and polycarboxylic acids of higher molecular weights used in obtaining the salts (A) are well known in the art and are described in detail in, for example, the following US, British and Canadian patents: US Pat. .237; 3,172,892 3. 219,666 3,245,910; 3,271,310; 3,272,746; 3,278,550 3,306,907 3,312,619; 3,341,542; 3,367,943; 3,374,174 3,381,022 3,454,607; 3,470,098; 3,630,902; 3,755,169 3,912,764 and 4,368,133; British Patents 944,136 1,085,903 1,162,436; and 1,440,219; and Canadian Patent 956,397. These patents are incorporated herein by reference for their description of mono- and polycarboxylic acids of higher molecular weights and methods for their production. A group of useful carboxylic acids are those of the formula: X * 1 (C - X * 2H), R * - Ar '(XV) (X * 3H) ( wherein, in Formula XV, R * is an aliphatic hydrocarbyl group of preferably about 4 to about 400 carbon atoms, a is a number in the range of zero to about 4, Ar is an aromatic group, X * 1, X * 2 and X * 3 are, independently, sulfur and oxygen, b is a number in the range of 1 to about 4, c is a number in the range of 1 to about 4, usually 1 to 2, with the proviso that the sum of a, b and c does not exceed the number of valencies of Ar. Preferably, R * and a are such that there is a 22 Preferably, R * 5 and a are such that the acid molecules contain at least an average of about 12 aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule. Within the class of aromatic carboxylic acids (XIV) are salicylic acids substituted with hydrocarbon wherein each aliphatic hydrocarbon substituent contains an average of at least about 8 carbon atoms per substituent and 1 to 3 substituents per molecule. Particularly useful are salts prepared from these salicylic acids wherein the aliphatic hydrocarbon substituents are derived from polymerized olefins, in particular polymerized lower 1-mono-olefins such as polyethylene, polypropylene, polyisobutylene, ethylene / propylene copolymers and the like and having carbon media of about 30 to about 400 carbon atoms. The aromatic carboxylic acids corresponding to the above Formulas XV and XVI are well known and can be prepared following procedures known in the art. Carboxylic acids of the type represented by these formulas and processes for preparing their neutral and basic metal salts are well known and are described, for example, in U.S. Patents 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092; 3,410,798; and 3,595,791. Sulfonic Acids The sulfonic acids useful in obtaining salts (A) used in compositions of this invention include sulphonic and thiosulfonic acids. Substantially neutral salts of sulfonic acids are also useful for preparing the overbased metal salts (A). The sulfonic acids include mono- or polynuclear aromatic or cycloaliphatic compounds. The oil-soluble sulfonic acids can be represented in their major 23 part by the following formulas: R # 1a-T- (S03H) b (XVII) R # 2- (SO, H) to (XVIII) In Formulas XVII and XVIII, T is a cyclic core such as, for example, benzene, naphthalene, anthracene, diphenylene oxide, diphenylene sulfide, petroleum naphthenes, etc.

R '#? it is preferably an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, etc., a is at least 1, and R # 1a-T contains a total of at least about 15 carbon atoms. When R * 2 is an aliphatic group, this normally contains at least about 15 carbon atoms. When it is a substituted aliphatic cycloaliphatic group, the aliphatic groups normally contain a total of at least about 12 carbon atoms. R * 2 is preferably alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R # 1 and R # 2 are groups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including olefins of C2, C3, C4, C5, C6, etc. polymerized containing about 15 to 700 or more carbon atoms. The groups T, R # 1 and R # 2 in the above Formulas XVII and XVIII may also contain other inorganic or organic substituents in addition to those listed above such as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide , disulfide, etc. In Formula XVII, a and b are at least 1, and likewise in Formula XVIII, a is at least 1. Specific examples of oil-soluble sulfonic acids are mahogany sulphonic acids; sulphonic acids of refined heavy oil; sulfonic acids derived from lubricating oil fractions; sulfonic acids of petrolatum; sulphonic and polysulphonic acids mono- and polysubstituted with wax of, for example benzene, naphthalene, phenol, diphenyl ether, naphthalene disulfide, etc .; other 24 substituted sulfonic acids such as alkyl benzene sulfonic acids (where the alkyl group has at least 8 carbons), sulfonic acids of cetylphenol monosulfide, dilauryl beta naphthyl sulfonic acids and alkaryl sulfonic acids such as dodecyl benzene sulphonic acids of "bottoms". Alkyl-substituted benzene sulfonic acids wherein the alkyl group contains at least 8 carbon atoms including dodecyl benzene sulphonic acids of "bottoms" are particularly useful. The latter are acid derivatives of benzene which has been alkylated with propylene tetramers or isobutene trimers to introduce 1, 2, 3 or more branched chain C12 substituents onto the benzene ring. Dodecyl benzene funds, mainly mixtures of mono- and di-dodecyl benzenes, are available as a byproduct of the manufacture of household detergents. Similar products obtained from alkylation bottoms formed during the manufacture of linear alkyl sulfonates (LAS) to produce the sulfonates used in this invention are also useful. The production of sulfonates from by-products of the manufacture of detergents by reaction with, for example, S03, is well known to those skilled in the art. See, for example, the article "Sulfonates" in Kirk-Othmer's "Encyclopedia of Chemical Technology", second edition, Vol. 19, pages 291 et seq., Edited by John Wiley & Sons, New York (1969). Illustrative examples of these sulfonic acids include naphthalene sulphonic acids substituted with polybutene or polypropylene, sulphonic acids derived by treating polybutenes having a number average molecular weight (n) in the range of 700 to 5000, preferably 700 to 1200. , more preferably about 1500, with chlorosulfonic acids, sulfonic acids of paraffin waxes, polyethylene acids (n equal to about 900-2000, preferably about 900-25). 1500, more preferably 900-1200 or 1300) sulphonic, etc. Preferred sulfonic acids are mono-, di- and tri-alkylated benzene acids (including their hydrogenated forms) sulfonic acids. Also included are aliphatic sulfonic acids such as paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, polyisobuten sulfonic acids where the polyisobutene contains from 20 to 7000 or more carbon atoms, sulphonic acids of chlorine-substituted paraffin wax, etc .; cycloaliphatic sulfonic acids such as petrolnaphthen sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- or poly-substituted cyclohexylsulfonic acids with wax, etc. With respect to sulfonic acids or their salts described herein and in the appended claims, the term "petrolsulfonic acids" or "petrolsulfonates" is used to cover all sulfonic acids or salts thereof derived from petrolproducts . A useful group of petrolsulfonic acids are mahogany sulphonic acids (so called because of their reddish-brown color) obtained as a byproduct of the manufacture of white petroloils by a sulfuric acid process. The basic (overbased) salts of the synthetic sulfonic acids and petroldescribed above are useful in the practice of this invention. Phenols The phenols useful in obtaining the salts (A) used in the compositions of this invention can be represented by the formula R # 3 -Ar- (OH): (XIX) being, in Formula (XIX) R a hydrocarbyl group of 26 about 4 to about 400 carbon atoms; Ar is an aromatic group; a and b are, independently, numbers of at least 1, the sum of a and b being in the range of 2 up to the number of displaceable hydrogens in the aromatic nucleus or nuclei of Ar. Preferably, a and b are, independently, numbers in the range of 1 to about 4, more preferably 1 to about 2. R # 3 are preferably such that there is an average of at least about 8 aliphatic carbon atoms provided by the R # groups 3 for each phenol compound represented by Formula XIX. Although the term "phenol" is used herein, it is to be understood that this term is not intended to limit the aromatic group of phenol to benzene. Accordingly, it is to be understood that the aromatic group represented by "Ar" of Formula XIX, as well as where it appears in other formulas of this specification and appended claims, may be mononuclear such as phenyl, pyridyl or thienyl, or polynuclear. The polynuclear groups can be of the condensed type where an aromatic nucleus is condensed at two points to another nucleus such as is found in naphthol, anthranil, etc. The polynuclear groups can also be of the type of link where at least two nuclei (mononuclear or polynuclear) are linked together through bridging links. These bridging bonds can be selected from the group consisting of alkylene bonds, ether bonds, keto bonds, sulfide bonds, polysulfide bonds of 2 to about 6 sulfur atoms, etc. The number of aromatic, condensed, linked, or both, nuclei of Ar can play a role in determining the values of the integers a and b of Formula XIX. For example, when Ar contains a single aromatic nucleus, the sum of a and b is from 2 to 6. When Ar contains two aromatic nuclei, the sum of a and b is from 2 to 10. With a tri-nuclear Ar radical, the sum of a and b is from 2 to 15. The value of the sum of a and b is limited by the fact that you can not 27 surpass the total number of displaceable hydrogens in the aromatic nucleus or Ar nuclei. The R # 3 group of Formula XIX is a hydrocarbyl group that is directly linked to the aromatic group Ar. R # 3 preferably contains from about 6 to about 80 carbon atoms, preferably from about 6 to about 30 carbon atoms, more preferably from about 8 to about 25 carbon atoms and advantageously from about 8 to about 15 carbon atoms. Examples of R # 3 groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, 5-chlorohexyl, 4-ethoxypentyl, 3-cyclohexyloctyl, 2,3,5-trimethylheptyl and substituents derived from polymerized olefins such as polyethylenes. , polypropylenes, polyisobutylenes, ethylene-propylene copolymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers, propylene tetramer and tri (isobutene). Metal Compounds Metal compounds useful for the production of overbased metal salts of organic acids are generally basic metal compounds capable of forming salts with organic acids, and are frequently oxides, hydroxides, carbonates, alkoxides, etc. The preferred ones are metal compounds of Group I or Group II (CAS version of the Periodic Table of the Elements). The metals of Group I of the metal compound include alkali metals (sodium, potassium, lithium, etc.) as well as Group IB metals such as copper. Preferred Group I metals are sodium, potassium and copper, more preferred sodium or potassium and most preferred sodium. The Group II metals of the metal base include alkaline earth metals (magnesium, calcium, barium, etc.) as well as Group IIB metals such as zinc or cadmium. Preferably the Group II metals are magnesium, calcium or zinc, preferably magnesium or calcium, more preferably 28calcium. Acid materials An acidic material is often used, as defined below, to obtain the overbased salt. The acidic material can be a liquid such as formic acid, acetic acid, nitric acid, sulfuric acid, etc. Acetic acid is useful in particular. Acidic inorganic materials such as HCl, H3B03, S02, S03, C02, H2S, etc. may also be used, with carbon dioxide being preferred. A preferred combination of acidic materials is carbon dioxide and acetic acid. Promoter A promoter is a chemical used to facilitate the incorporation of metal into basic metal compositions. Among the chemicals useful as promoters are water, ammonium hydroxide, organic acids of up to about 8 carbon atoms, nitric acid, sulfuric acid, hydrochloric acid, metal complexing agents such as alkyl salicylaldoxime, and alkali metal hydroxides. such as lithium hydroxide, sodium hydroxide and potassium hydroxide, phenolic substances such as phenols and naphthols, amines such as aniline and dodecyl amine and mono- and polyhydric alcohols of up to about 30 carbon atoms. An exhaustive discussion of promoters is found in U.S. Patents 2,777,874; 2,695,910; 2,616,904; 3,384,586 and 3,492,231. These Patents are incorporated herein by reference for their description of promoters. Particularly useful are monohydric alcohols having up to about 10 carbon atoms, mixtures of methanol with higher monohydric alcohols and phenolic materials. Patents that specifically describe techniques for the production of basic salts of sulfonic acids, carboxylic acids and mixtures of two or more of them, described hereinbefore, include U.S. Patent Nos. 2,501,731; 29 2. 616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109. The descriptions of these patents are incorporated herein by being pertinent in this regard as well as by their description of specific suitable basic metal salts. As indicated here before, acidic material (for example C02, acetic acid, etc.) can be replaced by water. The resulting overbased salts are described as hydrated. Most often, these products are overbased magnesium compositions. The U.S. Patent 4,094,801 (Forsberg) and U.S. Patent 4,627,928 (Karn) describe such compositions and methods for their production. These patents are here expressly incorporated by their pertinent descriptions of overbased metallic salts hydrated from organic acids. A large number of overbased metal salts are available for use in the compositions of this invention. These overbased salts are well known to those skilled in the art. The following Examples are given to illustrate types of overbased materials. These examples are not to be understood as limitations on the scope of the claimed invention. Unless otherwise indicated, all parts are parts by weight and temperatures are in degrees Celsius. Example Al Carbon dioxide is blown into a mixture of 906 grams of an oil solution of an alkyl phenyl sulfonic acid (with an average molecular weight of 450, vapor phase osmometry), 564 grams of mineral oil, 600 grams of toluene, 98 , 7 grams of magnesium oxide and 120 grams of water, at a temperature of 78-85 ° C for 7 hours at a rate of approximately 3 cubic feet (0.027 m3) of carbon dioxide per hour. The reaction mixture is stirred constantly throughout the course of carbonation. After carbonation, the reaction mixture is stripped off at 165 ° C / 20 torr and the residue is filtered. The filtrate is an oily solution (34% oil) of the desired overbased magnesium sulphonate having a metal ratio of about 3. Example A-2 A mixture of 160 grams of mixing oil is mixed together, 111 grams of polyisobutenyl anhydride (number average molecular weight = 950) succinic, 52 grams of n-butyl alcohol, 11 grams of water, 1.98 grams of Peladow (a product of Dow Chemical identified by a content of 94- 97% CaCl2) and 90 grams of hydrated lime. Additional hydrated lime is added to neutralize the sulfonic acid subsequently added, the amount of said additional lime depending on the acid number of the sulfonic acid. An oily solution (1078 grams, 58% by weight oil) of a straight-chain dialkyl benzene sulfonic acid (molecular weight = 430) is added without the temperature of the reaction mixture exceeding 79 ° C. The temperature is adjusted to 60 ° C. The reaction product of heptyl phenol, lime and formaldehyde (64.5 grams) and 217 grams of methyl alcohol are added. Carbon dioxide is blown into the reaction mixture to a base index (phenolphthalein) of 20-30. Hydrated lime (112 grams) is added to the reaction mixture, and the mixture is blown with carbon dioxide to a base number (phenolphthalein) of 45-60, while maintaining the temperature of the reaction mixture at 46-52. ° C. The last stage of hydrated lime addition followed by carbon dioxide insufflation is repeated three more times with the exception that in the last repetition the reaction mixture is carbonated to a base index (phenolphthalein) of 45-55. The reaction mixture is dried for a moment at 93-104 ° C, dried in a boiler at 149-160 ° C, filtered and adjusted with oil to a level 31 of 12.0%. The product is an overbased calcium sulfonate having, according to the analysis, an acid number (bromophenol blue) of 300, a metal content of 12.0% by weight, a metal ratio of 12, an ash content of sulfate of 40.7% by weight, and a sulfur content of 1.5% by weight. The oil content is 53% by weight. Example A-3 A reaction mixture comprising 135 grams of mineral oil, 330 grams of xylene, 200 grams is carbonated with carbon dioxide at a rate of 15 grams per hour. (0.235 equivalents) of a mineral oil solution of an alkylphenylsulphonic acid (average molecular weight 425), 19 grams (0.068 equivalents) of tall oil, 60 grams (about 2.75 equivalents) of magnesium oxide, 83 grams of methanol, and 62 grams of water, for about two hours at reflux temperature of methanol. The rate of carbon dioxide input is then reduced to about 7 grams per hour, and the methanol is removed by raising the temperature to about 98 ° C over a period of three hours. Water (47 grams) is added and carbonation is continued for a further 3.5 hours at a temperature of about 95 ° C. The carbonated mixture is then stripped by heating at a temperature of 140-145 ° C over a period of 2.5 hours. This results in an oil solution of a basic magnesium salt characterized by a metal ratio of about 10. The carbonated mixture is cooled to about 60-65 ° C, 208 grams of xylene, 60 grams of magnesium oxide, 83 grams of methanol and 62 grams of water.

The carbonation is restarted at a rate of 15 grams per hour for two hours at the reflux temperature of methanol. The rate of addition of carbon dioxide to 7 grams per hour is reduced and methanol is removed by elevation of the gas. temperature at about 95 ° C over a period of three hours. 41.5 grams of more water are added and the carbonation is continued at 7 grams per hour at a temperature of about 90-95 ° C for 3.5 hours. The carbonated mass is then heated to about 150 ° -160 ° C over a period of 3.5 hours and then stripped off under reduced pressure of 20 mm (Hg) at this temperature. The carbonated reaction product is filtered, and the filtrate is an oil solution of the desired basic magnesium salt characterized by a metal ratio of about 20. Example A-4 A mixture of 835 grams of neutral 100 mineral oil is prepared, 118 grams of a substituted succinic anhydride polybutenyl (molecular weight = 950), 140 grams of a mixture of 65:35 molar ratio of isobutyl alcohol and amyl alcohol, 43.2 grams of an aqueous solution of calcium chloride 15% and 86.4 grams of lime. While maintaining the temperature below 80 ° C, 1000 grams of an 85% solution of a benzene sulfonic mono-alkyl primary acid, having a molecular weight of about 480, a neutralization acid number, is added to the mixture. of 110, and 15% by weight of an organic diluent. The mixture is dried at 150 ° C to about 0.7% water. The mixture is cooled to 46-52 ° C then adding 127 grams of the mixture of isobutyl alcohol-amyl alcohol described above, 277 grams of methanol and 87.6 grams of 31% solution of heptyphenol coupled with calcium formaldehyde having a ratio 0.8% metal and 2.2% calcium is added to the mixture. Three increments of 171 grams of lime are added separately and carbonated to a base neutralization index in the range of 50-60. A fourth lime increment of 171 grams is added and carbonated to a neutralization base index of 45-55 (phenolphthalein). 33 are used approximately 331 grams of carbon dioxide. The mixture is dried at 150 ° C to about 0.5% water. The reaction mixture is filtered and the filtrate is the desired product. The product contains, according to the analysis, 12% calcium and has a metal ratio of 11. The product contains 41% oil. Example A-5 A reactor is charged with 1122 grams (2 equivalents) of a polybutenyl-substituted succinic anhydride derived from a polybutene (Mn = 1000, 1: 1 ratio of polybutene to maleic acid), 105 grams (0.4 equivalents) of tetrapropenyl phenol, 1122 grams of xylene and 1000 grams of mineral oil 100 neutral. The mixture is stirred and heated to 80 ° C under nitrogen, and 580 grams of a 50% aqueous solution of sodium hydroxide are added to the vessel over 10 minutes. The mixture is heated from 80 ° C to 120 ° C for 1.3 hours. The reaction mixture is carbonated to a standard cubic foot (0.027 m3) per hour while water is removed by azeotropic reflux. The temperature rises to 150 ° C for 6 hours while collecting 300 grams of water. (1) The reaction mixture is cooled to about 80 ° C then 540 grams of 50% aqueous sodium hydroxide solution is added to the vessel. (2) The reaction mixture is heated at 140 ° C for 1.7 hours and water is removed under reflux conditions. (3) The reaction mixture is carbonated to a standard cubic foot (0.027 m3) per hour while water is separated for 5 hours. Steps (1) - (3) are repeated using 560 grams of an aqueous solution of sodium hydroxide. Steps (1) - (3) are repeated using 640 grams of an aqueous solution of sodium hydroxide. Steps (l) - (3) are repeated with another 640 grams of a 50% aqueous sodium hydroxide solution. The reaction mixture is then cooled and 1000 grams of neutral 100 mineral oil is added to the mixture of reaction. The reaction mixture is vacuum stripped at 115 ° C to approximately 30 millimeters of mercury.

The residue is filtered through diatomaceous earth. The filtrate has a total base index of 361, 43.4% sulphated ash, 16.0% sodium, 39.4% oil, a specific gravity of 1.11 and the overbased metal salt has a metal ratio of about 13. Example A-6 The overbased salt obtained in Example A-5 is diluted with mineral oil to provide a composition containing 13.75 sodium, a total base number of about 320 and 45% oil. Example A-7 A reactor is charged with 700 grams of a 100 neutral mineral oil, 700 grams (1.25 equivalents) of the succinic anhydride of Example A-5 and 200 grams (2.5 equivalents) of a 50% aqueous solution. of sodium hydroxide. The reaction mixture is stirred and heated to 80 ° C adding then 66 grams (0.25 equivalents) of tetrapropenylphenol to the reaction vessel. The reaction mixture is heated from 80 ° C to 140 ° C for 2.5 hours while blowing nitrogen and 40 grams of water are separated. Carbon dioxide (28 grams, 1.25 equivalents) is added over 2.25 hours at a temperature of 140-165 ° C. Nitrogen is then blown into the reaction mixture at 2 cubic feet. (0.054 m3) per hour (scfh) and a total of 112 grams of water is separated. The reaction temperature is reduced to 115 ° C and the reaction mixture is filtered through diatomaceous earth. The filtrate has 4.06% sodium, a total base number of 89, a specific gravity of 0.948, 44.5% oil, and the overbased salt has a metal ratio of approximately 2. Example A-8 35 A reactor is charged with 281 grams (0.5 equivalents) of succinic anhydride of Example A-5, 281 grams of xylene, 26 grams of tetrapropenyl-substituted phenol and 250 grams of neutral mineral oil. The mixture is heated to 80 ° C and 272 grams (3.4 equivalents) of a sodium hydroxide solution are added to the reaction mixture. Nitrogen is blown into the mixture at 1 scfh (0.027 m3 per hour) and the reaction temperature is raised to 148 ° C. Carbon dioxide is then blown at 1 scfh (0.027 3 per hour) into the reaction mixture for 1 hour and 25 minutes while collecting 150 grams of water. The reaction mixture is cooled to 80 ° C then 272 grams (3.4 equivalents) of the above sodium hydroxide solution is added, and nitrogen is blown into the mixture at 1 scfh (0.027 m3 per hour). The reaction temperature is raised to 140 ° C by then insufflating carbon dioxide in the reaction mixture at 1 scfh (0.027 m3 per hour) for 1 hour and 25 minutes while collecting 150 grams of water. The reaction temperature is reduced to 100 ° C, and 272 grams (3.4 equivalents) of the above sodium hydroxide solution are added while blowing nitrogen into the mixture at 1 scfh (0.027 m3 per hour). The reaction temperature is raised to 148 ° C, and carbon dioxide is blown into the reaction mixture at 1 scfh (0.027 m3 per hour) for 1 hour and 40 minutes while collecting 160 grams of water. The reaction mixture is cooled to 90 ° C and 250 grams of neutral 100 mineral oil is added to the reaction mixture. The reaction mixture is vacuum stripped at 70 ° C and the residue is filtered through diatomaceous earth. The filtrate contains 50.0% sodium sulphate ash, according to ASTM D-874, total base index of 408, specific gravity of 1.18, 37.1% oil, and the salt has a metal ratio of approximately 15.8. Example A-9 36 A solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid (57% by weight of 100 neutral mineral oil and unreacted alkylated benzene) and 119 parts (0.2 equivalent) of the polybutenyl succinic anhydride in 442 parts of oil is mixed. mineral with 800 parts (20 equivalents) of sodium hydroxide and 704 parts (22 equivalents) of methanol. Carbon dioxide is blown into the mixture at 7 cubic feet (0.189 m3) per hour for 11 minutes as the temperature slowly increases to 97 ° C. The velocity of the carbon dioxide stream is reduced to 6 cubic feet (0.162 m3) per hour and the temperature decreases slowly to 88 ° C over approximately 40 minutes. The velocity of the carbon dioxide stream is reduced to 5 cubic feet (0.135 m3) per hour for approximately 35 minutes and the temperature slowly decreases to 73 ° C. Volatile materials are entrained by blowing nitrogen stream through the carbonated mixture to 2 cubic feet (0.054 m3) per hour for 105 minutes while slowly raising the temperature to 160 ° C. Once the entrainment is complete, the mixture is maintained at 160 ° C for an additional 45 minutes and then filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 19.75. Example A-10 A mixture of 135 parts of magnesium oxide and 600 parts of an alkylbenzenesulfonic acid having an equivalent weight of about 385 and containing about 24% of unsulfonated alkylbenzene is prepared. During the mixing an exothermic reaction takes place which raises the temperature to 57 ° C. The mixture is stirred for half an hour and then 50 parts of water are added. Upon heating to 95 ° C for 1 hour, the desired magnesium oxide-sulfonate complex is obtained as a firm gel containing 9.07% magnesium. 37 Example A-11 A mixture comprising about 506 parts by weight of a solution in mineral oil containing about 0.5 equivalents of a substantially neutral magnesium salt of an alkylated salicylic acid where the alkyl groups have an average is added to a flask. from about 16 to 24 aliphatic carbon atoms and about 30 parts by weight of an oil mixture containing about 0.037 equivalents of an alkylated benzene sulphonic acid together with about 22 parts by weight (about 1.0 equivalents) of a magnesium oxide and about 250 parts by weight of xylene and heated to temperatures of about 60 ° C to 70 ° C. The reaction is then heated to about 85 ° C and about 60 parts by weight of water are added to the reaction mass which is then heated to reflux temperature. The reaction mass is maintained at the reflux temperature of about 95 ° C-100 ° C for about an hour and a half and then stripped to about 155 ° C, 44 mm Hg, and filtered. The filtrate comprises the basic carboxylic salts of magnesium and is characterized by a sulfated ash content of 15.59% (sulphated ash) corresponding to 274% of the stoichiometric equivalent amount. Example A-12 A reaction mixture comprising about 1575 parts by weight of an oil solution containing about 1.5 equivalents of an alkylated 4-hydroxy-1,3-benzenedicarboxylic acid where the alkyl group has one is added to a flask. average of at least about 16 aliphatic carbon atoms and an oil mixture containing about 0.5 equivalents of a tall oil fatty acid together with 120 parts by weight (6.0 equivalents) of a magnesium oxide and about 700 parts by weight weight of a solvent 38 organic material containing xylene and heated to temperatures ranging from approximately 70 to 75 ° C. The reaction is then heated to about 85 ° C and about 200 parts by weight of water are added to the reaction which is then heated to reflux temperature. The reaction mass is maintained at the reflux temperature of about 95 ° -100 ° C for about 3 hours and then stripped at a temperature of about 155 ° C., vacuum, and filtered. The filtrate comprises the basic carboxylic magnesium salts. Example A-13 A reaction mixture is added to a reactor comprising about 500 parts by weight of an oil solution containing about 0.5 equivalents of an alkylated 1-hydroxy-2-naphthoic acid where the alkyl group has an average of at least about 16 aliphatic carbon atoms and an oily mixture containing 0.25 equivalents of a petroleum sulphonic acid together with about 30 parts by weight (1.5 equivalents) of a magnesium oxide and about 250 parts by weight of a hydrocarbon solvent and heated to temperatures ranging from approximately 60 ° C to 75 ° C. The reaction mass is then heated to about 85 ° C and about 30 parts by weight of water are added to the mass which is then heated to the reflux temperature. The reaction mass is maintained at the reflux temperature of about 95 ° -100 ° C for about 2 hours and then stripped at a temperature of about 150 ° C and filtered. The filtrate comprises the basic carboxylic salts of magnesium metal. Example A-14 An overbased calcium salicylate is prepared by reaction in the presence of a diluent mineral oil, an acid salicylic substituted with C13_18 alkyl with lime and carbonated in the presence of a suitable promoter such as methanol which leads to an overbased calcium salicylate having a metal ratio of about 2.5. The oil content is approximately 38% by weight.

(B) The compositions containing phosphorus and sulfur The phosphorus and sulfur-containing compositions employed in the fat compositions of the present invention include acids, salts and other derivatives, and other phosphorus and sulfur-containing compounds, including compounds of thiophosphite. Useful compositions containing phosphorus and sulfur include (B-1) a compound represented by the formula wherein each X17 X2, X3 and X4 is, independently, oxygen or sulfur provided that at least one is sulfur, each a and b is, independently 0 or 1; and where each Rx, R2 and R3 is, independently, hydrogen, hydrocarbyl, a group of the formula wherein each R4 and R5 is independently hydrogen or hydrocarbyl provided that at least one of R4 and R5 is hydrocarbyl, R6 is an alkylene or alkylidene group, each a and b is, independently, 0 or 1, and each X5, X6, X7 and X8 is, independently, oxygen or sulfur; or a group of the formula R60H, wherein R6 is an alkylene or alkylidene group; (B-2) an amine or an ammonium salt of (A-1) when at least R 3 is hydrogen; (B-3) is a compound represented by the formula R7 (XQ 9) "a (I II) H where each R7, R8 and R9 is, independently, hydrogen or a hydrocarbyl group provided that at least one is hydrocarbyl, each X9, X10 and X?: L is independently oxygen or sulfur provided that at least one is sulfur, and each a and b is independently 0 or 1; and (B-4) mixtures of two or more of (B-1) to (B-3). In a preferred embodiment, a and b are each of them. In one embodiment, the composition containing sulfur and phosphorus is the compound (B-1). Preferably, a and b are, each of them, 1. In one embodiment and R2 are, each independently, hydrocarbyl groups containing from 1 to about 30 carbon atoms and R3 is H or a hydrocarbyl group containing from 1 to about 30 carbon atoms. In a particular embodiment, each of between and R17 R2 and R3 is, independently, an alkyl group containing from 1 to about 18 carbon atoms or an aryl group containing from about 6 to about 18 carbon atoms, and more in particular each of R1 t R2 and R3 is , independently, a butyl, hexyl, heptyl, octyl, oleyl or cresyl group. In another particular embodiment, R3 is H. When R3 is H, it is preferred that each Rx and R2 is independently an alkyl group containing from 1 to about 18 carbon atoms or an aryl group containing from about 6 to about 18. carbon atoms, and more in particular each of Rx and R2 is independently a butyl, hexyl, heptyl, octyl, oleyl or cresyl group. In a preferred embodiment, each R, R2 and R3 is independently hydrogen or Preferably R3 is hydrogen and each Rx and R2 is independently hydrogen or X6R5 As mentioned here before, at least one of X? r X2, X3 and X4 must be sulfur while the remaining groups can be oxygen or sulfur. In a preferred embodiment, one of Xx, X2 and X3 is sulfur and the remainder is oxygen. When Rl f R2 or R3 is a group of the formula sR5 42 it is preferred that X5 and X6 are oxygen and that X7 and X8 are sulfur, or one of X5, X6, X7 and X8 is sulfur and the remainder is oxygen. In these cases, preferably each X3 and X4 is oxygen and more preferably X2 is oxygen. In a further embodiment each Rx and R2 is independently hydrocarbyl having from 1 to about 30 carbon atoms and R3 is R60H where R6 is an alkylene or alkylidene group containing from 2 to about 28 carbon atoms. In this case, one of Xl t X2, X3 and X4 is sulfur and the rest oxygen. In a preferred embodiment, X3 and X4 are sulfur and Xx and X2 are oxygen. The case where R6 is alkylene is also preferred. In another embodiment, the phosphorus and sulfur-containing composition is the ammonium or amine salt (B-2). Preferably, a and b are each 1. When any of Rx, R2 or R3 is H, the compound of Formula I is an acid. The salts (B-2) can be considered derived from that acid. When (B-2) is the ammonium salt, the salt is considered to be derived from ammonia (NH3) or ammonia-conducting compounds such as NH4OH. The specialists will be aware of other compounds that produce ammonia. When (B-2) is an amine salt, the salt can be considered derived from amines. The amines can be primary, secondary or tertiary, or mixtures of them. The hydrocarbyl groups of the amines can be aliphatic, cycloaliphatic or aromatic. Preferably, the hydrocarbyl groups are aliphatic, more preferably alkyl or alkenyl, more preferably alkyl. When the amine is an alkylamine, it is preferred that the alkyl group contains from 1 to about 24 carbon atoms. In a preferred embodiment, the amines are primary hydrocarbyl amines containing about 43 2 to about 30, more preferably from about 4 to about 20, carbon atoms in the hydrocarbyl group. The hydrocarbyl group can be saturated or unsaturated. Representative examples of primary saturated amines are alkylamines such as methyl amine, n-butyl amine, n-hexyl amine; those known as primary fatty aliphatic amines, for example those commercially known as primary amines "Armeen" (products of Akzo-Nobel Chemicals, Chicago, Illinois). Typical fatty amines include amines such as n-octylamine, n-dodecylamine, n-tetradecylamine, n-octadecylamine (stearyl amine), octadecenylamine (oleyl amine), etc. Mixed fatty amines such as Armeen-C, Armeen-0, Armeen-OD, Armeen-T, Armeen-HT, Armeen S and Armeen SD from Akzo-Nobel are also suitable, which are all fatty amines of varying purity. In another preferred embodiment, the amine salts of this invention are those derived from primary aliphatic-tertiary amines having from about 4 to about 30, preferably about 6 to about 24, more preferably about 8 to about 24, carbon in the aliphatic group. Normally the primary amines of tertiary aliphatic are monoamines, preferably alkyl amines represented by the formula CH, 11 R. C_ NH, CH, where R * 7 is a hydrocarbyl group contai from 1 to about 30 carbon atoms. These amines are represented by tert-butyl amine, 1-methyl-1-amino-cyclohexane, tert-octyl primary amine, tert-tetradecyl primary amine, tert-hexadecyl amine primary, tert-octadecyl amine primary, tert-octacosanyl amine primary. Mixtures of tere-alkyl amines 44 are also useful. primary for the purposes of the invention. Representative examples of mixtures of amines of this type include "Primene 81R" which is a mixture of primary tere-alkyl amines of C1] L-C14 and "Primene JMT" which is a similar mixture of primary tere-alkyl amines of C18-C22 (both from Rohm and Haas Company). The primary tere-alkyl amines and methods for their preparation are known to one skilled in the art. The primary tere-alkyl amines useful for the purposes of this invention and methods for their preparation are described in U.S. Patent 2,945,749, which is incorporated herein by reference for its guidelines in this regard. Also useful are primary amines in which the hydrocarbyl group comprises olefinic unsaturation. Accordingly, the hydrocarbyl groups may contain one or more olefinic unsaturations depending on the length of the chain, usually no more than one double bond per 10 carbon atoms. Representative amines include dodecenylamine, oleylamine and linolethylamine. These unsaturated amines can be found under the trade name of Armeen. Secondary amines include dialkylamines having two of the above hydrocarbyl groups, preferably alkyl or alkenyl groups described for the primary amines including commercial secondary fatty amines such as Armeen 2C and Armeen HT, and also mixed dialkylamines where, for example, a The alkyl group is a fatty group and the other alkyl group can be a lower alkyl group (1-7 carbon atoms) such as ethyl, butyl, etc., or the other hydrocarbyl group can be an alkyl group bearing other non-substituted substituents. reactants or polar (CN, alkyl, carbalkoxy, amide, ether, thioether, halo, sulfoxide, sulfone) so as not to destroy the essentially hydrocarbon character of the group. Tertiary amines such as trialkyl or trialkenyl amines and those contai a mixture of alkyl and alkenyl amines. The alkyl and alkenyl groups are substantially as described above for primary and secondary amines. Other useful primary amines are the primary amines ether R "OR'NH2 where R 1 is a divalent alkylene group having 2 to 6 carbon atoms and R" is a hydrocarbyl group of about 5 to about 150 carbon atoms. These primary amines are usually prepared by the reaction of an alcohol R "OH, where R "is as defined hereinbefore, with an unsaturated nitrile Typically, and for efficiency and economy, the alcohol is a linear or branched aliphatic alcohol in which R" has up to about 50 carbon atoms, preferably up to 26 carbon atoms and more preferably from 6 to 20 carbon atoms. The nitrile reagent can have from 2 to 6 carbon atoms, with acrylonitrile being most preferred. Ether amines can be found commercially under the name of SURFAM marketed by Mars Chemical Company, Atlanta, Georgia. Typical of these amines are those having a molecular weight of about 150 to about 400. The preferred amines are represented by those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A (linear C16), SURFAM P17B (tridecyloxypropylamine). The chain lengths (ie, C14, etc.) of the SURFAMs described above and which are used afterwards are approximate and include the oxygen linkage of ether. For example, an SURFAM amine of C14 will have the following general formula C10H21OC3H6NH2 The amines used to form the amine salts can be hydroxyamines. In one embodiment, these hydroxyamines can be represented by the formula alkoxylated in which a is 1"Ethoduomeen T / 13" and "T / 20" which are condensation products of ethylene oxide with N-tallow trimethylene diamine are included. containing 3 and 10 moles of ethylene oxide per mole of diamine, respectively. The fatty diamines include mono- or dialkyl ethylene diamines, symmetric or asymmetric, propane diamines (1.2 or 1.3) and polyamine analogs of the foregoing. Suitable fatty polyamines such as those sold under the name Duomeen are the commercial diamines described in Product Data Bulletin No. 7-10R of Armak Chemical Co., Chicago, Illinois. In another embodiment, the secondary amines can be cyclic amines such as piperidine, piperazine, morpholine, etc. In another embodiment, the composition containing sulfur and phosphorus is (B-3). Preferably a and b are each of them. In one embodiment, each R7, R8 and R9 is independently hydrogen or a hydrocarbyl group having from about 1 to about 18 carbon atoms, and a and b are each 1. Preferably, each R7, R8 and R9 is independently hydrogen or an alkyl or aryl group selected from the group consisting of propyl, butyl, pentyl, hexyl, heptyl, oleyl, cresyl, or phenyl, provided that at least one is the aforementioned alkyl or aryl group. In a preferred embodiment at least two of X9, X10 and X?: L are sulfur. In another embodiment, the sulfur- and phosphorus-containing composition can be (B-4) a mixture of two or more of the compounds represented by (B-1) a (B-3). In another embodiment (B-1) it is a thiophosphoric acid. The di-organo-thiophosphoric acid materials used in this invention can be prepared by well-known methods. The O, O-di-organo dithiophosphoric acids can be prepared, for example, by reaction of hydroxyl organic compounds with phosphorus pentasulfide. Among the compounds 48 hydroxyl organics include alcohols, such as alkanols, alkanediols, cycloalkanols, alkyl- and cycloalkyl-substituted aliphatic alcohols, ether alcohols, ester alcohols, and mixtures of alcohols; phenolic compounds, such as phenol, cresol, xylene, alkyl-substituted phenols, cycloalkyl-substituted phenols, phenyl-substituted phenols, alkoxy phenol, phenoxy phenol, naphthol, alkyl-substituted naphthols, etc. The non-benzenoid organic hydroxy compounds are generally the most useful in the preparation of the 0.0-di-organo dithiophosphoric acids. A complete discussion of the preparation of these compounds is in Journal of the American Chemical Society, volume 67, (1945), page 1662. S, S-di-organo tetrathiophosphoric acids can be prepared by the same method described above, except in that mercaptans are used instead of the organic hydroxy compounds. O, S-di-organo trithiophosphoric acids can be prepared in the same manner used in the preparation of the dithiophosphoric acids described above, except that a mixture of mercaptans and organic hydroxyl compounds is reacted with phosphorus pentasulfide. The compound (B-1) containing phosphorus and sulfur includes thiophosphoric acids, including, but not limited to, dithiophosphoric acids as well as monothiophosphoric, thiophosphinic or thiophosphonic acids. The use of the term thiophosphoric, thiophosphonic or thiophosphinic acid means that both the mono-thio-derivatives and the di-thio-derivatives of these acids are encompassed. Useful phosphorus-containing acids are described below. In one embodiment, when a and b are 1, and one of X, X2, X3 or X4 is sulfur and the remainder is oxygen, the phosphorus-containing composition is characterized as monothiophosphoric acid or onothiophosphate. Monothiophosphoric acids can be characterized by 49 one or more of the following formulas R1 © P (0) SH R20- R1 ^ P (S) OH R'O / RX < X * P (0) OH R20- where R1 and R2 are defined as before, preferably each R1 and R2 is independently a hydrocarbyl group. The monothiophosphates can be prepared by reaction of a sulfur source such as sulfur, hydrocarbyl sulfides and polysulfides and the like and a dihydrocarbyl phosphite. The sulfur source is preferably elemental sulfur. The preparation of monothiophosphates is described in U.S. Patent 4,755,311 and PCT Publication WO 87/07638 which is incorporated by reference for its description of monothiophosphates, sulfur source for preparing monothiophosphates and the process for producing monothiophosphates. The monothiophosphates can be formed in the lubricant mixture by the addition of a dihydrocarbyl phosphite to a lubricant composition containing a sulfur source. The phosphite can react with the sulfur source under mixing conditions (ie temperatures of about 30 ° C to about 100 ° C or higher) for 50 form monothiophosphate. It is also possible to form the monothiophosphate under the conditions found in the operating equipment. In Formula I, when a and b are 1, X ± and X2 are oxygen; and X3 and X4 are sulfur, and R3 is H, the phosphorus-containing composition is characterized as dithiophosphoric or phosphorodithioic acid. Dithiophosphoric acid can be characterized by the formula S R, 0 P SH I OR, where Rx and R2 are such as defined above. Preferably Rx and R2 are hydrocarbyl groups. Dihydrocarbyl phosphorodithioic acids can be prepared by reaction of alcohols with P205 normally between a temperature of about 50 ° C to about 150 ° C. The preparation of dithiophosphoric acids and their salts is well known to those skilled in the art. In another embodiment, the phosphorus-containing composition is represented by Formula (I) wherein each Xx and X2 is oxygen, each X3 and X4 is sulfur, R3 is hydrogen and each Rx and R2 is independently hydrogen or where the various R, a, b and groups X are as defined above. Preferably both R? as R2 are the group of Formula II; or Rx is hydrogen and R2 is the group of Formula II. Preferably, when each R "and Rc is independently hydrocarbyl, these are as described for R1 or R2. Preferably, X5 and X6 are oxygen, and X7 and X8 are sulfur. Preferably R6 is an arylene group, or an alkylene or alkylidene group having from 1 to about 12, more preferably from about 2 to about 6, more preferably about 3 carbon atoms. Rs is, preferably ethylene, propylene or butylene, more preferably a propylene group. The group represented by Formula II is derived from a compound which is the reaction product of a dithiophosphoric acid with an epoxide or a glycol. The dithiophosphoric acids are those described above. The epoxide is usually an aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, styrene oxide, etc. The propylene oxide is preferred. The glycols can be aliphatic glycols having from 1 to about 12, preferably about 2 to about 6, more preferably 2 or 3 carbon atoms, or aromatic glycols. The aliphatic glycols include ethylene glycol, propylene glycol, triethylene glycol, and the like. Aromatic glycols include hydroquinone, catechin, resorcin and the like. The reaction product of the dithiophosphoric acid and the glycol or epoxide is then reacted with an inorganic phosphorus reagent such as a phosphorus pentoxide, phosphorus trioxide, phosphorus tetraoxide, phosphorus acid, phosphorus halides and the like. The above reaction is known in the art and is described in U.S. Patent 3,197,405 issued to LeSuer. This patent is incorporated herein by reference for its description of dithiophosphoric acids, glycols, epoxides, inorganic phosphorus, reagents and reaction methods of the foregoing. The salts of the previous product 52 they are also described in LeSuer (US Pat. No. 3,197,405) which is incorporated herein by reference for their descriptions in this regard. These salts are included within the group of compounds (B-2). Within the compounds identified as (B-1) the compounds of the Formula are also included S a RxO P- -SR6OH (XI) OR, where each of the groups is as defined here before. Preferably Rx and R2 are each alkyl, which more preferably contain 1 to about 30 carbons, even more preferably 1 to about 18 carbons. R6 is alkylene or alkylidene containing from 2 to about 28 carbons, preferably alkylene containing from 2 to about 18 carbons, more preferably from 2 to about 6 carbons, and even more preferably 2 to 4 carbons. The compounds of Formula (XI) can be prepared by reacting 0.0-dihydrocarbyl dithiophosphates with a glycol or epoxide as discussed hereinbefore. These compounds and methods for preparing them are described in U.S. Patent 3,197,405 (LeSuer) and U.S. Patent 3,341,633 (Asseff), which are hereby expressly incorporated by reference for their relevant descriptions contained therein. Triesters may be prepared by reaction of the corresponding phosphorus and sulfur containing acid with, for example, an olefin. In U.S. Patent 2,802,856 (Norman et al), a detailed discussion of triesters and methods of preparing them is given; the patent is incorporated herein by reference to the relevant discussions in this regard. The compounds (B-3) include thiophosphites and hydrogen thiophosphites. These are readily prepared by methods known in the art which include the reaction of mercaptans with phosphorus halides, alcohols with thiophosphorus halides and the like. Preferred are the compounds wherein a and b are each 1 in Formula III and wherein R and R 8 are hydrocarbyl, preferably alkyl having from about 1 to about 24 carbons, more preferably from 1 to about 18 carbons, more preferably 4 to about 12 carbons, and aryl having from 6 to about 18 carbons, preferably 6 to about 12 carbons, more preferably 6 to about 10 carbons. When the compound (B-3) has the Formula IV, it is preferred that R7 and R8 are as defined hereinbefore, and R9 is hydrocarbyl or hydrogen. In a preferred embodiment, R9 is H which gives a tautomeric form of Formula III. Alternatively, in another preferred embodiment R9 is hydrocarbyl, preferably alkyl or aryl as defined for R7 and R8 hereinbefore. Preferably said phosphorus and sulfur-containing composition is selected from the group consisting of (B-1) a compound represented by the formula O ll R? O_ P, OR3 (VI) I OR2 where each Rx, R ^ and R3 is independently hydrogen, hydrocarbyl or S ft R40 - P - SR6- (VII) OR5 provided that at least one between Rl r R2 and R3 is 54 S II R40"P SR, (VII) 0RC wherein each R4 and R5 is independently hydrogen or hydrocarbyl, provided that at least one of R4 and Rs is hydrocarbyl, and where R6 is an alkylene or alkylidene group; (B-2) an ammonium or amine salt of (B-1) provided that at least R 3 is hydrogen; (B-3) a compound represented by the formula S li R70, P_ ORa (VIII) H 0 II R70. P- SRQ (IX) H SRQ R7S SRH (X) wherein each R7 and R8 and R9 is independently hydrogen or a hydrocarbyl group provided that at least one is hydrocarbyl; And (B-4) mixtures of two or more between (B-l) to B-3). In an especially preferred embodiment, the composition containing phosphorus and sulfur is (B-1), wherein at least one of R and R 2 is hydrogen or S II R40 - P SR6- (vile) I 0RC 56 about 5: 1, and neutralization at a temperature of about 0 ° C to 200 ° C, to at least about 50% of the acid mixture, with an amine selected from the group consisting of a hydrocarbyl and a hydroxy-substituted hydrocarbyl amine having from about 4 to about 30 carbon atoms. Preferably the amine is a primary tere-alkyl amine, which more preferably contains from about 10 to about 16 carbon atoms in the tertiary alkyl group. The following examples illustrate types of sulfur and phosphorus containing compounds useful in the fat compositions of this invention. These examples are only intended to be illustrative and not limiting of the scope of the invention. Unless stated otherwise, all parts are parts by weight and temperatures are in degrees Celsius. EXAMPLE Bl 0.0'-Di- (2-ethylhexyl) dithiophosphoric acid (354 grams) having an acid number of 154 is introduced into a 1320 ml capacity stainless steel "shaker" autoclave with controlled heating mantle. thermostatically Propylene is admitted until the pressure reaches 170 pounds per square inch (0.01195 kg / mm2) at room temperature, and then the autoclave is closed and shaken for 4 hours at 50 ° C-100 ° C, during which time the pressure reaches a maximum of 550 pounds per square inch (3.85 kg / mm2). The pressure decreases as the reaction progresses. The autoclave is cooled to room temperature, the propylene is allowed to leave in excess and the content is removed. The product (358 grams), a dark liquid having an acid number of 13.4 is substantially 0.0'-di- (2-ethylhexyl) -S-isopropyl dithiophosphate. Example B-2 Ammonia is insufflated in 364 parts (1 equivalent) of the dithiophosphoric acid of Example B-1 until a substantially neutral product is obtained. Example B-3 To 1780 grams (5 moles) of 0.0 '-di- (2-ethylhexyl) phosphorodithioic acid, stirred at room temperature, 319 grams (5.5 moles) of propylene oxide are added in portions. The reaction that occurs is quite exothermic and the temperature rises to 83 ° C in 15 minutes. The temperature is maintained at 90-91 ° C for three hours, after which another 29 grams (0.5 moles) of propylene oxide is added. The mixture is maintained at 90 ° C for another hour, followed by stripping at a final temperature of 90 ° C and 28 mm Hg pressure. The dark yellow liquid residue shows the following analysis: S, 15.4%; P, 7.4%. Using substantially the same procedure of Example 3 the following is reacted: Eg Phosphorodithioic acid Epoxide B-4 0,0 '-di- (4-methyl-2-pentyl) Epichlorohydrin B-5 0,0' -di- (isopropyl) Propylene oxide B-6 0,0 '-di- (2-ethylhexyl) styrene oxide Example B-7 Phosphorus pentoxide (64 grams, 0.45 moles) is added, 58 ° C over a 45 minute period, at 0.0 '-di (4-methyl-2-pentyl) hydroxypropyl phosphorodithioate (514 grams, 1.35 moles, prepared by di (4-) acid treatment methyl-2-pentyl) -phosphorus-dithioic acid with 1.3 moles of propylene oxide at 25 ° C). The mixture is heated at 75 ° C for 2.5 hours, mixed with filtering material (diatomaceous earth) and filtered at 70 ° C. It is found that the filtrate has, by analysis, a phosphorus content of 11.8%, a sulfur content of 15.2% and an acid number of 87 (bromophenol blue indicator).

Example B-8 A mixture of 667 grams (4.7 moles) of phosphorus pentoxide and the hydroxypropyl 0.0 '-diisopropyl phosphorodithioate prepared by reaction of 3514 grams of diisopropyl phosphorodithioic acid with 986 grams of propylene oxide at 50 ° C is heated at 85 ° C for 3 hours and filtered. The filtrate has, by analysis, a phosphorus content of 15.3%, a sulfur content of 19.6% and an acid number of 126 (bromophenol blue indicator). Example B-9 To 217 grams (0.5 equivalents) of the acid filtrate of Example B-6 are added, at 25 ° -60 ° C over a period of 20 minutes, 66 grams (0.35 equivalents) of a commercial primary tertiary-aliphatic amine (Primene 81-R, Rohm &Haas Co.) having an average molecular weight of 191 in which the aliphatic radical is a mixture of tertiary alkyl radicals containing 11 to 14 carbon atoms . The partially neutralized product has, according to the analysis, a phosphorus content of 10.2%, a nitrogen content of 1.5% and an acid number of 26.3. Example B-10 A portion of the filtrate from Example B-7 (1752 grams) is neutralized by treatment with a stoichiometrically equivalent amount (764 grams) of the primary aliphatic amine of Example 8 at 25 ° -82 ° C. The neutralized product has, according to the analysis, a phosphorus content of 9.95%, a nitrogen content of 2.72%, and a sulfur content of 12.6%. Example B-ll Phosphorus pentoxide (208 grams, 1.41 moles), between 50 ° C and 60 ° C, is added at 0.0 '-di-isobutylphosphorus hydroxypropyl dithioate (prepared by reaction of 280 grams of oxide of propylene with 1184 grams of O, O '-diisobutyl-phosphorodithioic acid at 30 ° C - 60 ° C). The reaction mixture is heated to 80 ° C and maintained at that temperature for 2 hours. To the acidic reaction mixture is added a stoichiometrically equivalent amount (384 grams) of the commercial primary aliphatic amine of Example 8 at 30 ° C-60 ° C. The product is filtered. The filtrate has, according to analysis, a phosphorus content of 9.31%, a sulfur content of 11.37%, a nitrogen content of 2.50% and a base index of 6.9 (blue indicator of bromophenol Example B-12 To 400 parts of 0.0 '-di- (isooctyl) phosphorodithioic acid are added 308 parts of oleylamine (Armeen O-Armak). Example B-13 Dichloride butyl phosphonic (175 parts, 1 mole) is reacted with a mixture of 146 parts, 1 mole, 1-octanotiol and 74 parts, 1 mole, of 1-butanol.

(C) Hydrocarbyl Phosphites The compositions of the present invention may include (C) a hydrocarbyl phosphite. The phosphite can be represented by the following formulas: Or I! R10O_ P H (XI II) 0RX1 OR, R10O P 0R12 (XIV) wherein each R group is, independently, hydrogen or a hydrocarbyl group provided that at least one of R10 and RX1 is hydrocarbyl. In a particularly embodiment 60 preferred, the phosphite has the formula (XIII) and Rxo and R1X are, each independently, hydrocarbyl. Within the limits just noted, it is preferred that each R10, RX1 and R12 is independently a hydrogen or a hydrocarbyl group having from 1 to about 30, more preferably from 1 to about 18, and more preferably from about 1 to about 8 carbon atoms. Each group R10, R1X and R12 can be, independently alkyl, alkenyl or aryl. When the group is aryl, it contains at least 6 carbon atoms; preferably 6 to about 18 carbon atoms. Examples of alkyl or alkenyl groups are propyl, butyl, hexyl, heptyl, octyl, oleyl, linoleyl, stearyl, etc. Examples of aryl groups are phenyl, naphthyl, heptylphenyl, etc. Preferably, each of these groups is, independently propyl, butyl, pentyl, hexyl, heptyl, oleyl or phenyl, more preferably butyl, octyl or phenyl and more preferably butyl. The groups R10, R11 and R12 may also comprise a mixture of hydrocarbyl groups derived from commercial mixed alcohols. Examples of monohydric alcohols and alcohol blends include "Alfol" alcohols which are commercial and sold by Continental Oil Corporation. Alfol 810 is a mixture containing alcohols consisting essentially of straight chain primary alcohols having 8 to 10 carbon atoms. Alfol 812 is a mixture comprising mainly C12 fatty alcohols. Alfol 1218 is a mixture of synthetic, primary, linear chain alcohols having 12 to 18 carbon atoms. The Alfol 20+ alcohols are mixtures of 18-28 primary alcohols which are mostly alcohol-based, C20 alcohols as determined by GLC (gas-liquid chromatography). Another group of alcohol blends commercially available available includes "Neodol" products from Shell Chemical Company. For example, Neodol 23 is a mixture of C 12 and C 13 alcohols; Neodol 25 is a mixture of C12 and C1S alcohols; and Neodol 45 is a mixture of linear alcohols of C14 and C1S. Neodol 91 is a mixture of alcohols of C9, C10 and C1X. Another example of a commercially available alcohol mixture is Adol 60 comprising about 75% by weight of C22 straight chain primary alcohol, about 15% of a C20 primary alcohol and about 8% of C18 and C24 alcohols. Adol 320 comprises predominantly oleyl alcohol. Adol alcohols are marketed by Ashland Chemical. There are a variety of mixtures of monohydric fatty alcohols that are derived from triglycerides that are found in nature and whose chain length varies from C8 to C18 and are from Procter & 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 mixture of fatty alcohols containing 0.5% C10 alcohol, 66.0% C12 alcohol, 26.0% C14 alcohol and 6.5% C16 alcohol. The phosphites and their preparation are known and many phosphites are commercial. Particularly useful phosphites are dibutyl hydrogen phosphite, trioleyl phosphite and triphenyl phosphite. Preferred phosphite esters are generally dialkyl hydrogen diaphragms.

In commerce there is a certain number of dialkyl hydrogen phosphites, such as lower dialkyl hydrogen phosphites, which are preferred. The lower dialkyl hydrogen phosphites include dimethyl, diethyl, dipropyl, dibutyl, dipentyl and dihexyl hydrogen phosphites. Mixed alkyl hydrogen phosphites are also useful in the present invention. Examples of mixed alkyl hydrogen phosphites include ethyl hydrogen phosphites, butyl; propyl, pentyl; and of 62 methyl, pentyl. Preferred hydrocarbyl (C) phosphites useful in the compositions of the present invention can be prepared by techniques well known in the art, and many are commercially available. In a preparation method, a dialkyl phosphite of lower molecular weight (eg, dimethyl) is reacted with alcohols comprising a straight chain alcohol, a branched chain alcohol or mixtures thereof. As noted above, each of the two types of alcohols may themselves consist of mixtures. Accordingly, the straight chain alcohol may consist of a mixture of straight chain alcohols and the branched chain alcohols may comprise a mixture of branched chain alcohols. Higher molecular weight alcohols replace the methyl groups (analogous to classical transesterification) with methanol formation which is stripped from the reaction mixture. In another embodiment, the branched chain hydrocarbyl group can be introduced into a dialkyl phosphite by reaction of low molecular weight dialkyl phosphite such as dimethyl phosphite with a more sterically hindered branched chain alcohol such as neopentyl alcohol (2). , 2-dimethyl-1-propanol). In this reaction, one of the methyl groups is replaced by a neopentyl group, and, apparently due to the size of the neopentyl group, the second methyl group is not displaced by the neopentyl alcohol. Another neo alcohol which has utility in this invention is 2,2,4-trimethyl-1-pentanol. In another embodiment, aliphatic-aromatic mixed phosphites and aliphatic phosphites can be prepared by reaction of an aromatic phosphite such as triphenyl phosphite, with aliphatic alcohols to replace one or more of the aromatic groups with aliphatic groups. Thus, for example, triphenyl phosphite can be reacted with butyl alcohol to prepare butyl phosphites. Hydrogen 64 can be prepared 135 ° C while purging with nitrogen. The mixture is heated slowly to 145 ° C and maintained at this temperature for 6 hours after which a total of 183.4 parts of distillate is recovered. The residue is subjected to vacuum stripping at 145 ° C (10 mm Hg) and 146.3 parts of additional distillate are collected. The residue is filtered through filtering material and the filtrate is the desired product containing 9.3% phosphorus (theory, 9.45%). Example C-3 A mixture of 518 parts (7 moles) of n-butanol, 911.4 parts (7 moles) of 2-ethylhexanol, and 777.7 parts (7 moles) of dimethyl phosphite is prepared and heated to 120 ° C while blowing nitrogen. After about 7 hours, 322.4 parts of distillate are collected, and the material is then stripped by vacuum stripping (50 mm Hg at 140 ° C) whereby 198.1 additional parts of distillate are recovered. The residue is filtered through filtering material, and the filtrate is the desired product containing 12.9% phosphorus (theoretical, 12.3%). Example C-4 A mixture of 193 parts (2.2 moles) of 2,2-dimethyl-1-propanol and 242 parts (2.2 moles) of dimethyl phosphite is prepared and heated to about 120 ° C while insufflates nitrogen. The distillate is separated and collected, and the residue is subjected to vacuum stripping. The residue is filtered and the filtrate is the desired product containing 14.2% phosphorus.

(D) Acid or carboxylic anhydride substituted with aliphatic group Component (D) is a carboxylic acid substituted with aliphatic group or an anhydride thereof wherein the aliphatic group contains at least about 12 carbon atoms, and up to about 500 carbon atoms, preferably from about 30 to about 300 carbon atoms and frequently from about 30 to about 150 carbon atoms, and often from about 30 to about 100 carbon atoms. In one embodiment, the component (D) is an anhydride or succinic acid substituted with aliphatic group containing from about 12 to about 500 carbon atoms in the aliphatic substituent, preferably from about 30 to about 400 carbon atoms, and frequently from about 50 to about 200 carbon atoms. Patents describing useful aliphatic carboxylic acids or anhydrides or methods for their preparation include, among many others, U.S. Patent Nos. 3,215,707 (Rense); 3,219,666 (Norman et al.), 3,231,587 (Rense); 3,912,764 (Palmer); 4,110,349 (Cohen): and 4,234,435 (Meinhardt et al.); 5,696,060 (Baker et al); 5,696,067 (Adams et al.); and United Kingdom Patent 1,440,219. As indicated in the aforementioned patents, which are incorporated herein by reference by their description of compounds useful as component (D) of this invention, carboxylic acids (or various derivatives thereof) are usually derived from the reaction of a compound which contains carboxylic acid with a polyalkene or halogenated derivative thereof or a suitable olefin. The carboxylic acid-containing compounds useful as reagents for forming component (D) include α, β-unsaturated materials such as acrylic and methacrylic acids, maleic acid, esters of these acids, compounds of the formula R3C (0) (R4) nC (0) OR5 (IV) and reactive sources thereof such as compounds of formula 66 R30 II R3 (R4) n - C (0) 0R5 (V) R90 where each of R3, R5 and each R9 is, independently, H or a hydrocarbyl group, R4 is a divalent hydrocarbylene group, and n is 0 or 1. The polyalkenes from which the carboxylic acids derive (D) are homopolymers and interpolymers of polymerizable olefinic monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms. Interpolymers are those in which two or more olefin monomers are interpolymerized according to well-known conventional procedures to form polyalkenes having units within their structure derived from each of said monomers of two or more olefins. According to this, the term "interpolymer (s)", as used herein, includes copolymers, tetrapolymer terpolymers and the like. As will be understood by one skilled in the art, the polyalkenes from which the substituent groups derive are conventionally referred to frequently as "polyolefin (s)". The olefin monomers from which the polyalkenes are derived are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups (ie >; C = C < ); that is, they are monoolefin monomers such as ethylene, propylene, butene-1, isobutene, and octene-1 or polyolefin monomers such as butadiene-1,3 and isoprene. These olefin monomers are usually polymerizable terminal olefins; that is, olefins that are characterized by the presence of the group > C = CH2 in its structure. However, polymerizable internal olefinic monomers (which are sometimes referred to in the literature) can also be used to form polyalkenes. central defines) which are characterized by the presence in their structure of the group -C-C = C-C- When internal olefin monomers are used, they will normally be used with terminal olefins to produce polyalkenes which are interpolymers. For the purposes of this invention, when a particular polymerized olefin monomer can be classified as both terminal olefin and internal olefin, it will be considered a terminal olefin. Accordingly, 1,3-pentadiene (ie, piperylene) is considered a terminal olefin for the purposes of this invention. Preferred useful materials as component (D) include succinic acids substituted with polyolefin, succinic anhydrides, ester acids, lactones or lactone acids. Component (D) is generally used in the fat composition of this invention in amounts ranging from about 0.025% to about 2%, often up to about 1% by weight, of the fat composition, preferably about 0, 04% to about 0.25% by weight. Non-limiting examples of compounds useful as component (B) include the following: EXAMPLE Dl A mixture of 6400 parts (4 moles) of a polybutene comprising predominantly isobutene units and having an isobutene unit is heated at 225-240 ° C for 4 hours. molecular weight of about 1600 and 408 parts (4.16 moles) of maleic anhydride. It is then cooled to 170 ° C and an additional 102 parts (1.04 mole) of maleic anhydride are added, followed by 70 parts (0.99 mole) of chlorine; the latter is added over 3 hours at 170-215 ° C. The mixture is heated for 3 68 additional hours at 215 ° C and then purged by vacuum stripping at 220 ° C and filtered through diatomaceous earth. The product is the desired polybutenyl-substituted succinic anhydride having a saponification number of 61.8. Example D-2 A monocarboxylic acid is prepared by chlorination of a polyisobutene having a molecular weight of 750 to a product with a chlorine content of 3.6% by weight, the product being converted into the corresponding nitrile by reaction with an equivalent amount of potassium cyanide in the presence of a catalytic amount of cuprous cyanide and hydrolyzing the resulting nitrile by treatment with 50% excess of dilute aqueous sulfuric acid at the reflux temperature. Example D-3 A high molecular weight monocarboxylic acid is prepared by telomerization of ethylene with carbon tetrachloride to give a telomer having an average of 35 ethylene radicals per molecule and hydrolyzing the telomer to the corresponding acid according to the procedure described in British Patent No. 581,899. Example D-4 A polybutenyl succinic anhydride is prepared by reaction of a chlorinated polybutylene with maleic anhydride at 200 ° C. The polybutenyl radical has an average molecular weight of 805 and contains mainly isobutene units. It is found that the resulting alkenyl succinic anhydride has an acid number of 113 (corresponding to an equivalent weight of 500). Example D-5 A lactone acid is prepared by reaction of 2 equivalents of a substituted succinic anhydride with polyolefin (Mn about 900) with 1.02 equivalents of water at a temperature of about 90 ° C in the presence of 69 a catalytic amount of concentrated sulfuric acid. After completion of the reaction, the catalyst is neutralized with sulfuric acid with sodium carbonate and the reaction mixture is filtered. Example D-6 An ester acid is prepared by reaction of 2 equivalents of an alkyl-substituted succinic anhydride having an average of about 35 carbon atoms in the alkyl group with 1 mole of ethanol. Example D-7 A reactor is charged with 1000 parts of polybutene having a molecular weight determined by vapor phase osmometry of about 950 and consisting mainly of isobutene units, followed by the addition of 108 parts of maleic anhydride. The mixture is heated to 110 ° C followed by the addition, under the surface, of 100 parts of Cl2 over 6.5 hours at a temperature that varies between 110 and 188 ° C. The exothermic reaction is controlled so that it does not exceed 188 ° C. Nitrogen is blown into the batch and then stored. Example D-8 The procedure of Example D-7 is repeated using 1000 parts of polybutene having a molecular weight determined by vapor phase osmometry of about 1650 and consisting mainly of isobutene units and 106 parts of maleic anhydride. Cl2 is added starting at 130 ° C and continuing to be added at an almost continuous rate so that a maximum temperature of 188 ° C is reached near the end of the chlorination. Nitrogen is blown into the residue and collected. Example D-9 A reactor is charged with 3000 parts of a polyisobutene having a number average molecular weight of about 1000 and containing about 80 mole% terminal vinylidene groups and 6 parts acid 70 70% aqueous methanesulfonic acid. The materials are heated to 160 ° C under N2 followed by the addition of 577.2 parts of 50% aqueous glyoxylic acid over 4 hours while maintaining at 155-160 ° C. Water is collected and collected in a Dean-Stark trap. The reaction is maintained at 160 ° C for 5 hours, cooled to 140 ° C and filtered. The filtrate has a total acid number (Method D-974 of ASTM) = 34.7 and saponification index (Method D-74 of ASTM) = 53.2. The l ^ (by gel permeation chromatography (GPC)) = 1476 and the, (GPC) = 3067; the unreacted polyisobutene (by thin-layer chromatography-flame ionization detector (TLC-FID) is equal to 8.6% The minimum amounts of each component used in the fat compositions also depend to some extent on the specific nature of the component, but generally at least about 0.25% of each of the components (A), (B) and (C) and at least about 0.025% by weight of the component (D) must be present. component (A) vary from about 0.25% to about 10% by weight, preferably from about 0.5% to about 5%, more preferably from about 1% to about 2%. With respect to component (B), the amounts useful for the purposes of this invention range from about 0.25% to about 5% by weight, preferably from about 0.5% to about 3%, more preferably from about 0.5% to about 1% by weight. Component (C) is generally present in amounts ranging from about 0.25% to about 5%, preferably from about 0.5% to about 3%, more preferably from about 0.75% to about 2% in weight, more frequently up to about 1% by weight. Component (D) is used in amounts ranging from about 0.025% to about 2.5%, preferably 71 from about 0.04% and up to about 1%. As mentioned above, component (B) is used together with components (A), (C) and (D) in minor amounts effective to increase the drip point of the base grease or complex fat or failed complex. The preferred minimum amounts of sulfur and phosphorus-containing compound that are employed depend to some extent on the additive. When the additive containing sulfur and phosphorus is (B-1) it is preferred to use at least about 0.75% by weight. The same is true when the additive is (B-2) but the preferred minimum amount of (B-3) is about 0.25% by weight. The preferred minimum amounts of sulfur and phosphorus-containing compounds employed individually depend to some extent on the additive. When the additive containing sulfur and phosphorus is (B-1) it is preferred to employ at least about 0.75% by weight. The same is true when the additive is (B-2), but the preferred minimum amount of (B-3) is about 0.25% by weight. It is generally not necessary to use more than about 5% by weight of sulfur and phosphorus-containing compound since no additional benefit is obtained and, frequently, deterioration in behavior is observed with respect to the drip point and other fat characteristics prior to this level of treatment. More frequent is not to use more than about 5%, often not more than about 2% of the sulfur and phosphorus-containing compound. Many times 1% by weight is sufficient. It is generally not necessary to employ more than a total of about 20% by weight of the components since no additional benefit is obtained and, frequently, a deterioration in performance is observed with respect to the drip point and other previous fat characteristics. at this level of treatment. More frequent is not to use more than a total of approximately 10%, often not more than 72 approximately 5%. L% -3% by weight is often sufficient to provide an increase in the drip point. In a particularly preferred embodiment, the components are used in relative amounts ranging from about 1 part of (A) to about 0.5-1.5 parts of each (B) and (C) to about 0.05 to about 0.1 part (D) ). According to this, it is preferred to use a minimum amount of additives that corresponds to achieving the desired elevation of the drip point. The components (A), (B), (C) and (D) can be present during the formation of fat, that is, during the formation of the thickener, or can be added after the base fat has been prepared. Normally, the components are added to the preformed base grease as they can be adversely affected during the preparation of metal soap and complex thickeners. Other additives can be added to the base grease to improve the behavior of the base grease as a lubricant. These other additives include corrosion inhibitors, antioxidants, extreme pressure additives and others which are useful for improving the specific performance characteristics of a base fat, which are known and will be readily appreciated by those skilled in the art. Many times these other additives have an adverse effect on the drip point of the fat. The use of components (A) - (D) with these other additives frequently compensates for this effect.

The following examples illustrate the fat compositions of this invention or are comparative examples indicating the benefits obtained using this invention. It is to be understood that these examples are only illustrative and not limitative of the invention in any way. The dropping points are determined using the ASTM method D-2265. All quantities, unless stated otherwise, are based on the product without oil and are by weight. 73 are used products of the examples of this invention as prepared including a possible diluent. Temperatures, unless stated otherwise, are in degrees Celsius. Example A A base fat thickened with simple lithium 12-hydroxystearate is prepared in a Stratco contact mixer by mixing 9.75 parts of 12-hydroxy stearic acid (Cenwax A, Union Camp) in 70 parts of mineral oil (850 SUS @ 40 ° C, Texaco HVI) at 77 ° C until the acid dissolves, then adding 2.15 parts of LiOH-H20 (MMC). The contact mixer is closed and the pressure is increased to 80 pounds per square inch (0.056 kg / mm2). The materials are heated to 204 ° C, the temperature is maintained for 0.2 hours, then the pressure in the mixer is eliminated. The temperature is reduced to 177 ° C, the materials are passed to a finishing boiler, an additional 14.9 parts of oil are added and the materials thoroughly mixed until uniform. The drip point is 203 ° C. Example B The procedure of Example A is repeated, replacing the oil with a mineral oil having a viscosity index of approximately 59 (Shell MVI, 800 SUS @ 40 ° C). The drip point is 206 ° C. Example C The procedure of Example A is repeated except that the fat is prepared in an open boiler, and the water of reaction is removed during heating. The drip point is 207 ° C. Examples D-F A concentrate of additives is prepared by mixing, at moderately elevated temperature, dibutyl hydrogen phosphite, the overbased calcium salicylate of Example A-14 and the phosphorus-sulfur-containing composition of the compound.

Example B-10 in a weight ratio of 0.9: 1.7: 0.6. No adjustment is made for the oil content of the overbased calcium salicylate. The fat compositions are prepared by mixing in 96.8 parts of the indicated base fat of Examples A-C, 3.2 parts of the additive concentrate described above.

Example Base grease Drip point (° C) D A 321 E B 218 F C 210 Examples G-I A concentrate of additives is prepared by mixing, at moderately elevated temperature, dibutyl hydrogen phosphite, the overbased calcium salicylate of Example A-14, the phosphorus and sulfur-containing composition of Example B-10, and the succinic anhydride of the Example B-7 in a weight ratio of 0.9: 1.62: 0.6: 0.08. No adjustment is made regarding the oil content of the overbased calcium salicylate.

The fat compositions are prepared by mixing in 96.8 parts of the indicated base fat of Examples A-C, 3.2 parts of the additive concentrate described above.

Example Base grease Drip point (° C) G A 314 H B 300 I C 300 From the previous examples it is deduced that the effect of additive systems that improve the drip point depends largely on the viscosity index of the base oil used in the preparation of the base fat. In addition, the effect depends on the method of preparation of the base fat. The combination of 75 The additives described here dramatically reduce this dependence, which gives the grease manufacturer a wide margin of selection. Although the invention has been described in connection with its preferred embodiments, those skilled in the art will understand that modifications may be made thereto upon reading this specification. Therefore, it is to be understood that the invention described herein attempts to cover such modifications when they come within the scope of the appended claims.

Claims (4)

1. 76 Claims 1. An improved fat composition comprising a higher amount of a base fat thickened with simple metal soap, based on oil and (A) of about 0.25% to about 10% by weight of an overbased metal salt of an organic acid; (B) from about 0.25% to about 5% by weight of a composition containing phosphorus and sulfur selected from the group (B-1) a compound represented by the formula R? (X?). P 3 3 (i) (X2 2) 'bbRi.2 where each Xx, X2, X3 and X4 is, independently, oxygen or sulfur provided that at least one is sulfur; each a and b is, independently 0 or 1; and wherein each R1 # R2 and R3 is, independently, hydrogen, hydrocarbyl, a group of the formula X = IL R4 (XS), X7R6 (H) (ß6) bbR5. wherein each R4 and R5 is independently hydrogen or hydrocarbyl provided that at least one of R4 and R5 is hydrocarbyl, R6 is an alkylene or alkylidene group, each a and b is, independently, 0 or 1, and each Xs, X6, X7 and X8 is , independently, oxygen or sulfur; or a group of the formula R60H, wherein R6 is an alkylene or alkyllidene group; (B-2) an amine or ammonium salt of (B-1) when at least R 3 is hydrogen; (B-3) -. is a compound represented by the formula 77 X, R7 (X9 9) '(X, 0) bR. (III) H O wherein each R7, R8 and R9 is independently hydrogen or a hydrocarbyl group provided that at least one is hydrocarbyl, and each X9, X10 and XX1 is oxygen or sulfur provided that at least one is sulfur, and (B-4) mixtures of two or more from (Bl) to (B-3). (C) from about 0.25% to about 5% by weight of a hydrocarbyl phosphite, and (D) from about 0.025% to about 2% by weight of a carboxylic acid group substituted with aliphatic group or anhydride thereof, where the aliphatic group contains at least about 12 carbon atoms, where the dropping point of the base fat is increased by at least about 15 ° C as measured by the ASTM D-2265 method.
2. 2. The grease composition according to claim 1, wherein the metal of the metallic soap is alkali metal, alkaline earth metal or aluminum.
3. 3. The grease composition according to claim 2, wherein the metal of the metallic soap is an alkali metal.
4. 4. The grease composition according to claim 3, wherein the alkali metal is lithium. 78 5. The grease composition according to claim 2, wherein the metal of the metallic soap is an alkaline earth metal. 6. The fat composition according to claim 5, wherein the alkaline earth metal is barium, calcium or magnesium. 7. The fat composition according to claim 1, wherein the metallic soap is a C8 to C24 mono-carboxylate. 8. The fat composition according to claim 7, wherein the monocarboxylate is hydroxy-substituted. 9. The grease composition according to claim 1, wherein the overbased metal salt (A) is an alkali metal salt, an alkaline earth metal salt or a zinc salt. 10. The fat composition according to claim 1 wherein the overbased metal salt (A) is selected from the group consisting of carboxylates, phenates and sulfonates. 11. The fat composition according to claim 1, wherein the composition containing phosphorus and sulfur is (B-1) and a and b are, each, 1. 12. The fat composition according to claim 11, wherein one of Xx, X2 and X3 is sulfur and the remainder is oxygen. 13. The fat composition according to claim 11, wherein each Rx, R2 and R3 is, independently, hydrogen or x6Rs 79 14. The fat composition according to claim 12, wherein R3 is hydrogen and each Rx and R2 is independently hydrogen or > a8 R4 Xs X7R6- (V) x6Rs 15. The fat composition according to claim 1, wherein the phosphorus and sulfur-containing composition is the ammonium or amine salt (B-2) and a and b are, each, 1. 16. The fat composition according to claim 1, wherein the composition containing phosphorus and sulfur is the compound (B-3). 17. The fat composition according to claim 1, wherein the phosphorus and sulfur-containing composition is (B-1) having the formula S II RJLO. P SR60H (XI) OR, where each of R? and R2 is alkyl containing from 1 to about 18 carbon atoms and R6 is alkylene containing from 2 to about 18 carbon atoms. 18. The fat composition according to claim 1, wherein each hydrocarbyl group of the phosphite (C) independently contains from 1 to about 30 carbon atoms. 80 19. The fat composition according to claim 18 wherein the phosphite is a hydrocarbyl hydrogen phosphite. 20. The fat composition according to claim 1, wherein (D) is a succinic acid or anhydride substituted with polyolefin, or an ester acid or lactone acid thereof. 21. The fat composition according to claim 20 wherein the polyolefin substituent is a polypropylene group, a polybutene group or a mixture thereof. 22. The grease composition according to claim 1, wherein the base grease thickened with simple metallic soap has been prepared in an open fat kettle. 23. The grease composition according to claim 1 wherein the base grease thickened with simple metallic soap has been prepared in a continuous grease processor. 24. The grease composition according to claim 1, wherein the base grease thickened with simple metallic soap has been prepared in a contact mixer. 25. The grease composition according to claim 24 wherein the base grease is a base grease thickened with simple metal soap based on medium viscosity index oil. 26. The grease composition according to claim 1 wherein the base grease is a base grease thickened with simple metal soap based on medium viscosity index oil. 27. The fat composition according to claim 1 wherein the drip point has an increase of at least 81 approximately 50 ° C. 28. An improved fat composition comprising a larger amount of a base grease thickened with simple metal soap, based on oil, which has been prepared in an open fat kettle, (A) from about 0.25% to about 10% by weight of an overbased metal salt of an organic acid, (B) from about 0.25% to about 5% by weight of at least one composition containing sulfur and phosphorus selected from the group consisting of (B-1) a compound represented by the formula where each Rx, R2 and R3 is iinnddeepp < endinently hydrogen, hydrocarbyl or S 1) R40-_ p SR6- (VII) OR ^ provided that at least one between R? r R2 and R3 be R40 P - SRC (VII) OR, wherein each R4 and R5 is independently hydrogen or hydrocarbyl, provided that at least one of R4 and R5 is hydrocarbyl, and wherein Rs is an alkylene or alkylidene group; (B-2) an ammonium or amine salt of (B-1) provided that at least R 3 is hydrogen; 82 (B-3) a compound represented by at least one of the following formulas: S (i R70 P_ 0RP (VIII) H O II R.S- P- SRH (XI) H SRQ R7S SRQ (X) wherein each of R7 and R8 and R9 is independently hydrogen or a hydrocarbyl group provided that at least one is hydrocarbyl; (B-4) mixtures of two or more of (B-1) - (B-3). (C) from about 0.25% to about 5% by weight of a hydrocarbyl phosphite; and (D) from about 0.025 to about 2% by weight of a carboxylic acid substituted with aliphatic group or an anhydride thereof, wherein the aliphatic group contains at least about 12 carbon atoms, where the drop point of the base fat is increased by at least about 50 ° C as measured by the ASTM D-2265 method. 29. The fat composition according to claim 28 wherein the organic acid of (A) is selected from the group consisting of carboxylic acids, sulfonic acids and phenols. 30. The grease composition according to claim 28 83 wherein the metal salt is (A-1) a carboxylate containing at least about 8 carbon atoms. 31. The fat composition according to claim 28 wherein the metal salt is (A-2) an alkylbenzene sulfonate containing one or two alkyl substituents. 32. The fat composition according to claim 31 wherein (A-2) has at least one alkyl substituent containing at least about 12 carbon atoms. 33. The fat composition according to claim 28 wherein the metal salt is (A-3) a phenate substituted with alkyl or alkenyl, wherein the alkyl or alkenyl substituent contains at least about 8 carbon atoms. 34. The fat composition according to claim 28 wherein the overbased alkaline earth metal salt (A) is selected from the group consisting of calcium, magnesium or barium salts. 35. The grease composition according to claim 28, wherein the metal of the metallic soap is an alkali metal, an alkaline earth metal or aluminum. 36. The grease composition according to claim 35, wherein the metallic metal soap is an alkali metal selected from the group consisting of sodium or lithium or an alkaline earth metal selected from the group consisting of barium, calcium or magnesium. 37. The fat composition according to claim 28 wherein the metallic soap is a hydroxy-substituted monocarboxylate of C8 to C24. 84 38. The grease composition according to claim 37, wherein the metallic soap is lithium 12-hydroxy stearate. 39. The fat composition according to claim 28, wherein the composition containing phosphorus and sulfur is (B-1) where at least one of R x and R 2 is hydrogen or S II R40- P- SRC (vile) 0RC provided that at least R3 is hydrogen, where each R4 and R5 is independently an alkyl group having from about 2 to about 12 carbon atoms and R, is an alkylene group having from about 2 to about 6 carbon atoms. 40. The fat composition according to claim 28, wherein the phosphorus-sulfur-containing composition is the amine salt (B-2) and derives from an alkyl amine having from about 1 to about 24 carbon atoms. 41. The fat composition according to claim 40, wherein the alkylamine is a primary tere-alkyl amine containing from about 10 to about 16 carbon atoms. 42. The fat composition according to claim 28, wherein the phosphorus-sulfur-containing composition is the compound (B-3), wherein each R is independently a propyl, butyl, pentyl or oleyl group. 43. The fat composition according to claim 28 wherein the phosphite (C) is a hydrogen phosphite substituted with dialiphatic group, each aliphatic group containing 86 then at a temperature of about 0 ° C to 200 ° C, to at least about 50% of the acid mixture, with an amine selected from the group consisting of a hydrocarbyl amine and a hydroxy hydrocarbyl amine having from about 4 to about 30 carbon atoms; and (C) at least one dihydrocarbyl hydrogen phosphite of the formula O II R10O. P - H (XIII) I ORÍ wherein each R10 and R1X is independently a hydrocarbyl group containing from 1 to about 50 carbon atoms, and (D) a substituted carboxylic acid with an aliphatic group or an anhydride thereof, wherein the aliphatic group contains at least about 12 carbon atoms. carbon, and wherein (A) is present in amounts ranging from about 0.25% to about 10% by weight, and (B) and (C) are present, each independently, in amounts ranging from about 0.25. % to about 5% by weight, and (D) is present in amounts ranging from about 0.025 to about 2% by weight, and (D) is present in amounts ranging from about 0.025 to about 2% by weight, where the The drip point of the base grease is increased by at least 50 ° C as measured by the ASTM D-2265 method. 47. The fat composition according to claim 46 wherein the overbased metal carboxylate (A) is an alkyl- or alkenyl-substituted salicylate wherein the substituent contains from about 12 to about 50 carbon atoms. 87 48. The grease composition according to claim 46 wherein the epoxide contains from 2 to about 18 carbon atoms where each R 10 and R n_ is an alkyl group containing from 1 to about 18 carbon atoms. 49. The fat composition of claim 45 wherein (A) is an overbased calcium alkyl salicylate having a metal ratio of 3 to about 20, (B) is a composition prepared by reaction of a phosphorodithioic acid wherein each R 4 and R 5 is , independently, an aliphatic group having from 3 to about 12 carbon atoms or an aromatic group containing from 6 to about 12 carbon atoms, with an epoxide having from 2 to about 4 carbon atoms, subsequent reaction of about 2 5 to about 3.5 moles of the phosphorodithioic acid-epoxide reaction product with about 1 mole of phosphorus pentoxide, neutralization of at least about 50% of the acid mixture with an alkylamine containing from about 8 to about 16 carbon atoms; and wherein (C) is a dialkyl phosphite wherein each of R10 and R1X, independently, contains from about 3 to about 8 carbon atoms, and (D) is a polyisobutylene-substituted succinic anhydride containing from about 30 to about 100 carbon atoms in the polyisobutylene substituent. 50. The fat composition according to claim 49, wherein the alkyl amine is a primary tere-alkyl amine. 51. The fat composition according to claim 46 comprising from about 0.5% to about 5% by weight of (A), from about 0.25-3% by weight of (B), from 0.25-3% by weight weight of (C), and from about 0.04% to about 0.25% by weight of (D). 88 52. An improved fat composition comprising a greater amount of a base, oil-based metallic soap thickened base, selected from the group consisting of complex fat and failed complex fat, and (A) of about 0.25% a about 10% by weight of an overbased metal salt of an organic acid; (B) from about 0.25% to about 5% by weight of a phosphorus and sulfur-containing composition selected from the group consisting of (B-1) a compound represented by the formula ?4 where each X17 X2, X3 and X4 is, independently, oxygen or sulfur provided that at least one is sulfur; each ß, and b is, independently 0 or 1; and wherein each RX, R2 and R3 is, independently, hydrogen, hydrocarbyl, a group of the formula where each R, R-. is independently hydrogen or hydrocarbyl provided that at least one of R4 and R is hydrocarbyl, R6 is an alkylene or alkylidene group, each a and b is independently 0 or 1, and each X5, X6, X7 and X8 is independently oxygen or sulfur; or a group of the formula R6OH, wherein R6 is an alkylene or alkylidene group; (B-2) an amine or ammonium salt of (B-1) when at least R 3 is hydrogen; (B-3) is a compound represented by the formula 90 (B-1) a compound represented by the formula Ra (X?). P X3R3 i (I) (X2) pR2 where each XX, X2, X3 and X4 is, independently, oxygen or sulfur provided that at least one is sulfur; each = and b is, independently 0 to 1; and where each R1 f R2 and R3 is, independently, hydrogen, hydrocarbyl, a group of the formula wherein each R * and R5 is independently hydrogen or hydrocarbyl provided that at least one of R4 and R5 is hydrocarbyl, R6 is an alkylene or alkylidene group, each a and b is independently 0 or 1, and each X5, X6, X7 and X8 is, independently, oxygen or sulfur; or a group of the formula -R6OH, wherein R6 is an alkylene or alkylidene group; (B-2) an amine or ammonium salt of (B-1) when at least R 3 is hydrogen; (B-3) a compound represented by the formula R7 (Xg 9) 'to P (X? O) bR? (III) 1 H where each R7, R8 and R9 is, independently, hydrogen or a hydrocarbyl group provided that at least one is hydrocarbyl, and each X9, X10 and X1X is oxygen or sulfur provided that at least one is sulfur, and (B-4) mixtures of two or more of (B-1) to (B-3). (C) from about 0.25% to about 5% by weight of a hydrocarbyl phosphite, and (D) from about 0.025% to about 2% by weight of a carboxylic acid group substituted with aliphatic group or anhydride thereof, where the aliphatic group contains at least about 12 carbon atoms. 54. A method of increasing the drip point of a base fat thickened with simple metal soap, based on oil, by at least 15 ° as measured by ASTM process D-2265, said method comprising incorporation into the base grease from (A) from about 0.25% to about 10% by weight of an overbased metal salt of an organic acid; (B) from about 0.25% to about 5% by weight of a phosphorus and sulfur-containing composition selected from the group consisting of (B-1) a compound represented by the formula X4 n R? (X?); where each X1 t X2, X3 and X4 is, independently, oxygen or sulfur provided that at least one is sulfur; each a and b is independently 0 to 1; and wherein each R17 R2 and R3 is, independently, hydrogen, hydrocarbyl, a group of the formula R4 (Xs) a - P - X7R6- (II) 1 (ß) b ^ -5 92 wherein each R4 and R5 is independently hydrogen or hydrocarbyl provided that at least one of R4 and R5 is hydrocarbyl, R6 is an alkylene or alkylidene group, each a and b is, independently, 0 or 1, and each X5, X6, X7 and X8 is , independently, oxygen or sulfur; or a group of the formula -R6OH, where Rs is an alkylene or alkylidene group; (B-2) amine or ammonium salt of (B-1) when at least R 3 is hydrogen; (B-3) a compound represented by the formula OR wherein each R7, R8 and R9 is, independently, hydrogen or a hydrocarbyl group provided that at least one is hydrocarbyl, and each X9, X10 and XX1 is oxygen or sulfur provided that at least one is sulfur, and (B-4) mixtures of two or more from (Bl) to (B-3). (C) from about 0.25% to about 5% by weight of a hydrocarbyl phosphite, and (D) from about 0.025% to about 2% by weight of an aliphatic carboxylic acid or anhydride thereof, wherein the aliphatic group contains at least about 12 carbon atoms. 55. The method according to claim 54 wherein the dropping point is increased by at least 50 ° C. 93 56. The method according to claim 54 wherein the base fat is prepared in an open boiler. 57. The method according to claim 54 wherein the base grease is prepared in a continuous processor. 58. The method according to claim 54 wherein the base fat is prepared in a contact mixer. 59. The method according to claim 54 wherein the base grease is a base grease thickened with simple metallic soap, based on oil of medium viscosity index. 60. A method of increasing the drip point of a base fat thickened with oil-based metallic soap selected from the group consisting of complex fat and failing complex fat at at least about 15 ° C as measured by ASTM procedure D-2265, said method comprising incorporating to the base fat of (A) from about 0.25% to about 10% by weight of an overbased metal salt of an organic acid; (B) from about 0.25% to about 5% by weight of a phosphorus and sulfur-containing composition selected from the group consisting of (B-1) a compound represented by the formula , 4 R? (?). P X3R3 i (D (X2) b ^ 2 where each X17 X2, X3 and X4 is, independently, oxygen or sulfur provided that at least one is sulfur; every a. and b is, independently 0 or 1; and where each R1 # R, and R3 is, independently, hydrogen, hydrocarbyl, a group of the formula Xc R * (XS). p X7RS (ID (XJ bR5 wherein each R4 and R5 is independently hydrogen or hydrocarbyl provided that at least one of R4 and Rs is hydrocarbyl, R6 is an alkylene or alkylidene group, each a and b is independently 0 or 1, and each X5, X6, X7 and X8 is , independently, oxygen or sulfur; or a group of the formula -R6OH, wherein R6 is an alkylene or alkylidene group; (B-2) an amine or ammonium salt of (B-1) when at least R 3 is hydrogen; (B-3) a compound represented by the formula X 1. 1 II R7 (X9) P (X1.00) I b bRl 8, t (III) H R7Xg wherein each R7, R8 and R9 is, independently, hydrogen or a hydrocarbyl group provided that at least one is hydrocarbyl, and each X9, X10 and Xxx is oxygen or sulfur provided that at least one is sulfur, and (B-4) mixtures of two or more from (Bl) to (B-3). (C) from about 0.25% to about 5% by weight of a hydrocarbyl phosphite; and (D) from about 0.025% to about 2% by weight of aliphatic carboxylic acid or anhydride thereof, wherein the aliphatic group contains at least about 12 carbon atoms. 61. A method for increasing the drip point of a base grease thickened with metal soap, based on oil, having a drip point of less than 260 ° C, to at least 260 ° C, the drip points being measured by the D method -2265 of ASTM, said method comprising incorporating to the base fat of (A) from about 0.25% to about 10% by weight of an overbased metal salt of an organic acid; (B) from about 0.25% to about 5% by weight of a phosphorus and sulfur-containing composition selected from the group consisting of (B-1) a compound represented by the formula Ra (X?) ß ~ Y ~ X3R3 (!) (X2) b ^ 2 where each Xx, X2, X3 and X4 is, independently, oxygen or sulfur provided that at least one is sulfur; every 3, and b is, independently 0 to 1; and where each Rx, R2 and R3 is, independently, hydrogen, hydrocarbyl, a group of the formula x I »8 R? X5), P X7R6- (II) (x * -66) 'bbRlx-5 wherein each R4 and Rs is independently hydrogen or hydrocarbyl provided that at least one of R4 and R5 is hydrocarbyl, R6 is an alkylene or alkylidene group, each a and b is, independently, 0 or 1, and each X5, X6, X7 and X8 is , independently, oxygen or sulfur; or a group of the formula 96 -R6OH, wherein R6 is an alkylene or alkylidene group; (B-2) amine or ammonium salt of (B-1) when at least R 3 is hydrogen; (B-3) a compound represented by the formula X u * R, (X9) P - (X? 1o0) 'b bRi -? 8 (I I I) i H o wherein each R7, R8 and R9 is, independently, hydrogen or a hydrocarbyl group provided that at least one is hydrocarbyl, and each X9, Xxo and Xxx is oxygen or sulfur provided that at least one is sulfur, and (B-4) mixtures of two or more from (Bl) to (B-3) thereof. (C) from about 0.25% to about 5% by weight of a hydrocarbyl phosphite; and (D) from about 0.025% to about 2 by weight of aliphatic carboxylic acid or anhydride thereof, wherein the aliphatic group contains the less about 12 carbon atoms.