EP0551466A1 - Verbesserte schmiermittelzusammensetzungen und zusaetse verwendbar dafuer - Google Patents

Verbesserte schmiermittelzusammensetzungen und zusaetse verwendbar dafuer

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Publication number
EP0551466A1
EP0551466A1 EP92915925A EP92915925A EP0551466A1 EP 0551466 A1 EP0551466 A1 EP 0551466A1 EP 92915925 A EP92915925 A EP 92915925A EP 92915925 A EP92915925 A EP 92915925A EP 0551466 A1 EP0551466 A1 EP 0551466A1
Authority
EP
European Patent Office
Prior art keywords
composition
metal
group
acid
compoεition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92915925A
Other languages
English (en)
French (fr)
Other versions
EP0551466B1 (de
Inventor
Timothy Cooper
James Noel Vinci
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
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Filing date
Publication date
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Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP0551466A1 publication Critical patent/EP0551466A1/de
Application granted granted Critical
Publication of EP0551466B1 publication Critical patent/EP0551466B1/de
Anticipated expiration legal-status Critical
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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    • C10M2219/088—Neutral salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2219/089—Overbased salts
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
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    • C10M2223/041—Triaryl phosphates
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
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    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
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    • C10N2010/00—Metal present as such or in compounds
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    • C10N2010/02—Groups 1 or 11
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • compositions useful as additives for lubricants and functional fluids and to additive concentrates, lubricants and functional fluids containing said additives. More particularly, this invention relates to compositions comprising a major amount of an oil of lubricating viscosity, (A) a metal salt selected from the group consisting of sulfonates, phenates, carboxylates and mixtures thereof, (B) an aliphatic carboxylic acid or anhydride, or carboxylic acid containing derivative thereof, wherein the aliphatic group contains at least about 20 carbon atoms and optionally (C) a metal salt of (C) (I) at least one organic phosphorus acid or a mixture of (C) (I) at least one organic phosphorus acid and (C) (II) at least one carboxylic acid. Also disclosed are lubricants and functional fluids containing these additives and methods for improving the wet filterability of lubricants and functional fluids. This invention also lubricants and functional fluids containing these additives and
  • lubricants are required to meet a variety of performance requirements. It is known in the art to add various chemical additives to a lubricating oil basestock in order to provide or reinforce needed properties.
  • the lubricant may contain nothing more than the lubricating base stock, although even in this case, additives such as oxidation and corrosion inhibitors and antifoam agents are often included.
  • Chemical additives to provide extreme pressure and antiwear performance are known. These include, but are not limited to, phosphorus-containing additives, sulfur-containing additives and others. Phosphorus additives include metal-free and metal-containing derivatives of phosphorus acids.
  • Hoke U. S. Patents 4,032,461; 4,208,357; and 4,282,171, refers to various phosphorus and sulfur-containing amides and thioamides.
  • Metal salts of phosphorodithioic acids are known lubricant additives. See, for example, Le Suer et al, U.S. 3,390,082 and Chamberlin, U.S. 4,326,974.
  • Metals salts of mixtures of carboxylic and phosphorus acids are also known, as are post-treated metal salts of phosphorus acids. See, for example, Clason et al, U.S. 4,308,154, Schroeck, U.S. 4,289,635, Schroeck, U.S. 4,507,215 and Schroeck, U.S. 4,263,150.
  • Metals salts of organic acids, and particularly overbased metal salts of organic acids are also well-known lubricating oil additives.
  • lubricating oil compositions such as functional fluids, and especially hydraulic fluids, are used in equipment designed to very close tolerances.
  • a hydraulic fluid which is employed as the lubricant and power transmitting fluid in hydraulic pumps must provide extreme pressure, antiwear and oxidation performance. Because of the close operating tolerances, it is usually necessary that hydraulic fluids be kept meticulously clean. To accomplish this end, very fine filters are employed to remove solid contaminants from the circulating hydraulic fluid. The filter must remove abrasive contaminants, but still must allow free fluid flow through the system. ,
  • lubricating oil compositions including hydraulic fluids, containing metal salts of organic acids, and particularly those containing overbased metal salts, when exposed to mois ⁇ ture, may clog filters.
  • moisture may arise from, for example, environmental contamination or condensation of atmospheric moisture.
  • filters become clogged, fluid flow is reduced, or in extreme cases, essentially stops. Filterability of moisture (water) containing lubricating compositions is referred to herein as wet filterability.
  • the nature of the moisture-contaminated lubricating oil is not understood, that is, it is not known with certainty whether, for example, the moisture (water) is simply dispersed within the oil composition, whether a chemical reaction has taken place or if the moisture is incorporated in some other fashion. What is known is that when the oil composition is contaminated with moisture, filterability, especially filterability through fine filters, " is impaired.
  • moisture contamination contributing to filterability difficulties is present in the oil composi ⁇ tion in amounts ranging up to about 1% by weight of the oil composition, although more than 1% by weight of water may be present as a contaminant and may contribute to filterability di iculties.
  • a lubricant or functional fluid that does not tend to generate materials that clog filters when the fluid is exposed to moisture.
  • a zinc-containing lubricating oil composition resisted loss of zinc when the oil is exposed to water.
  • the present invention provides compositions useful as additives for lubricants and additive concentrates and lubricants containing these additives.
  • Lubricants and functional fluids containing these additives have a reduced tendency to clog filters when the lubricants are exposed to moisture and resist depletion of zinc when exposed to water.
  • the present invention provides a composition com ⁇ prising a major amount of an oil of lubricating viscos ⁇ ity, and minor amounts of (A) a metal salt selected from the group consisting of sulfonates, phenates, carbox- ylates and mixtures thereof, (B) an aliphatic carboxylic acid or anhydride, or carboxylic-acid group containing derivative thereof, wherein the aliphatic group contains at least about 20 carbon atoms and optionally (C) a metal salt of (C) (I) at least one organic phosphorus acid or mixture of (C) (I) at least one organic phosphorus acid and (C) (II) at least one carboxylic acid.
  • Component (B) is present in an effective amount to improve wet filter- ability of the composition.
  • the composition may comprise a phosphite.
  • the present invention provides a method for improving the wet filterability of lubricants and func ⁇ tional fluid compositions. Also provided is a method for imparting to lubricating oil compositions the ability to resist depletion of zinc when the compositions are exposed to water.
  • hydrocarbon based group is used throughout this specification and in the appended claims to denote a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character within the context of this invention.
  • hydrocarbon based group includes hydrocarbon, as well as substantially hydrocarbon, groups.
  • substantially hydrocarbon describes groups may contain non-hydrocarbon substituents, or non-carbon atoms in a ring or chain, which do not alter the predominantly hydrocarbon nature of the group.
  • Hydrocarbon based groups can contain up to three, preferably up to one, non-hydrocarbon substituent, or non-carbon heteroatom in a ring or chain, for every ten carbon atoms, provided this non-hydrocarbon substituent or non-carbon heteroatom does not significantly alter the predominantly hydrocarbon character of the group.
  • hydrocarbon-based groups are purely hydrocarbon, that is, they are substantially free of non-hydrocarbon substituents or heteroatoms.
  • heteroatoms such as oxygen, sulfur and nitrogen, or substituents, which include, for example, hydroxyl, halo (especially chloro and fluoro) , alkoxyl, alkyl mercapto, alkyl sulfoxy, etc.
  • hydrocarbon based groups include, but are not necessarily limited to, the following:
  • hydrocarbon groups that is, aliphatic (e.g., alkyl or alkenyl) , alicyclic (e.g., cycloalkyl, cycloalkenyl) groups, 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 (that is, for example, any two indicated substituents may together form an alicyclic radical) ;
  • substituted hydrocarbon groups that is, those groups containing non-hydrocarbon groups or atoms which, in the context of this invention, do not alter the predominantly hydrocarbon character of the group; those skilled in the art will be aware of such groups (e.g., halo (especially chloro and fluoro) , hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.);
  • hetero groups that is, groups which will, while having a predominantly hydrocarbon character within the context of this invention, contain atoms other than carbon present in a ring or chain otherwise composed of carbon atoms.
  • Suitable heteroatoms will be apparent to those of ordinary skill in the art and include, for example, sulfur, oxygen, nitrogen and such substituents as, e.g., pyridyl, furyl, thienyl, imidazolyl, etc.
  • substituents e.g., pyridyl, furyl, thienyl, imidazolyl, etc.
  • no more than about 2 preferably no more than one, non-hydrocarbon substituent or non-carbon atom in a ring moiety, will be present for every ten carbon atoms in the hydrocarbyl group.
  • the hydrocarbyl groups are purely hydrocarbon and contain substantially no such non-hydrocarbon groups or substituents.
  • Component (A) is a metal salt selected from the group consisting of sulfonate ⁇ , phenates or carboxylates. These salts may be normal salts or they may be overbased salts. Overbased salts are preferred.
  • the metals may be alkali or alkaline earth metals, copper or zinc. In a preferred embodiment the metals are alkali or alkaline earth metals, more preferably, sodium, potassium, calcium or magnesium.
  • the Normal Metal Salt is alkali or alkaline earth metals, more preferably, sodium, potassium, calcium or magnesium.
  • Component (A) may be a normal metal salt, that is, a salt wherein the metal content is substantially that which is present according to the stoichiometry of the metal and the particular organic compound reacted with the metal.
  • These salts are sometimes referred to as "neutral” salts despite the fact that, depending upon the nature of the anion and cation, the salt may ,display basic properties, i.e., may display basic character as opposed to neutral or acidic character, especially in aqueous media.
  • metal salts of sulfonic acids, phenols and carboxylic acids are preferred.
  • Preferred metals are alkali or alkaline earth metals, copper or zinc.
  • Normal metal salts are readily prepared by the reaction of an acid with a metal compound such as a hydroxide or carbonate, double displacement reactions, such as the reaction of a sodium salt with calcium chloride, etc.
  • a metal compound such as a hydroxide or carbonate
  • double displacement reactions such as the reaction of a sodium salt with calcium chloride, etc.
  • the skilled worker is aware of numerous means for preparing normal metal salts, and further elaboration here is unnecessary.
  • overbased is characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular organic compound reacted with the metal, e.g., a carboxylic or sulfonic acid or phenol.
  • a monocarboxylic acid e.g., a monocarboxylic acid
  • the "normal" metal salt produced will contain one equivalent of calcium for each equivalent of acid, i.e.,
  • the actual ⁇ toichiometric excess of metal can vary considerably, for example, from about 0.1 equivalent to about 50 or more equivalents depending on the reactions, the process conditions, and the like.
  • the overbased materials useful in accordance with the present invention contain from about 1.1 to about 40 or more equivalents of metal, more preferably from about 1.5 to about 30 and most preferably from about 2 to about 25 equivalents of metal for each equivalent of material which is overbased.
  • overbased is used to designate materials containing a stoichiometric excess of metal and is, therefore, inclusive of those materials which have been referred to in the art as overbased, superbased, hyperbased, etc. , as discussed supra, and hereinbelow.
  • metal ratio is used in the prior art and herein to designate the ratio of the total chemical equivalents of the metal in the overbased material (e.g., a metal sulfonate or carboxylate) to the chemical equivalents of the metal in the product which would be expected to result in the reaction between the organic material to be overbased (e.g., sulfonic or carboxylic acid) and the metal-containing reactant (e.g., calcium hydroxide, barium oxide, etc.) according to the known chemical reactivity and stoichiometry of the two reactants.
  • the metal-containing reactant e.g., calcium hydroxide, barium oxide, etc.
  • the equivalent weight of the acidic organic compound is its molecular weight divided by the number of acidic groups (i.e., sulfonic acid, carboxy or acidic hydroxy groups) present per molecule.
  • the acidic organic compound contains a diluent such as oil or unreacted alkylate. Often the acidic organic compound is not a pure single species.
  • the equivalent weight of the acidic organic compound can be determined by a suitable analytical technique such as acid number (e.g. ASTM procedures D-664 and/or D-974) .
  • the metal ratio is one, and in the overbased carboxylate, the metal ratio may be 4.5.
  • the "metal ratio" of the product will depend upon whether the number of equivalents of metal in the overbased product is compared to the number of equivalents expected to be present for a given single component or a combination of all such components.
  • the metal ratio may be expressed in terms of percentages. For a normal metal salt, the percentage is 100%; for overbased materials, the percentage is greater than 100. For the overbased calcium carboxylate example above, the percentage is 450.
  • overbased materials are prepared by treating a reaction mixture compri ⁇ ing the organic material to be overbased, a reaction medium consisting es ⁇ entially of at lea ⁇ t one inert, organic ⁇ olvent for said organic material, a stoichiometric excess of a metal base, and a promoter with an acidic material.
  • a reaction mixture compri ⁇ ing the organic material to be overbased
  • a reaction medium consisting es ⁇ entially of at lea ⁇ t one inert, organic ⁇ olvent for said organic material, a stoichiometric excess of a metal base, and a promoter with an acidic material.
  • organic materials which are overbased are their solubility in the particular reaction medium utilized in the overbasing process.
  • the reaction medium used frequently comprises petroleum fractions, particularly mineral oils
  • these organic materials have generally been oil-soluble.
  • another reaction medium e.g., aromatic hydrocarbons, aliphatic hydrocarbons, kerosene, etc.
  • many organic materials which are soluble in mineral oils will be soluble in many of the other indicated suitable reaction media.
  • Materials which can be overbased are generally oil-soluble organic acids including sulfonic acids, phosphorus acids, thiophosphorus acids, sulfur acids, alkylphenols, coupled alkylphenols, carboxylic, acids, thiocarboxylic acids, and the like, as well as the corresponding - alkali and alkaline earth metal salts thereof.
  • Representative examples of each of these classes of organic acids, as well as other organic acids, e.g., nitrogen acids, arsenic acids, etc. are disclosed along with methods of preparing overbased products therefrom in the above-cited patents and are, accordingly, incorporated herein by reference.
  • U.S. Patent No. 2,777,874 identifies organic acids suitable for preparing overbased materials.
  • U.S. Patent No. 2,777,874 identifies organic acids suitable for preparing overbased materials.
  • Patent NOS. 2,616,904; 2,695,910; 2,767,164; 2,767,209; 3,147,232; 3,274,135; etc. disclose a variety of organic acids suitable for preparing overbased materials as well as representative examples of overbased products prepared from such acids.
  • Overbased acids wherein the acid is a phosphorus acid, a thiophosphorus acid, phosphorus acid-sulfur acid combination, and sulfur acid prepared from polyolefins are disclosed in U.S. Patent Nos. 2,883,340; 2,915,517; 3,001,981; 3,108,960 and 3,232,883.
  • Overbased phenate ⁇ are disclosed in U.S. Patent No. 2,959,551, while overbased ketones are found in U.S. Patent No.
  • mixtures of alkylated phenols and the oil-soluble reaction product of alkylene polyamines such as propylene diamine or N-alkylated propylene diamine with formaldehyde or formaldehyde producing compound can be overbased.
  • alkylene polyamines such as propylene diamine or N-alkylated propylene diamine with formaldehyde or formaldehyde producing compound (e.g., paraformaldehyde)
  • formaldehyde or formaldehyde producing compound e.g., paraformaldehyde
  • formaldehyde or formaldehyde producing compound e.g., paraformaldehyde
  • the metal compounds used in preparing the overbased materials are normally the basic salts, oxides and hydroxides of alkali and alkaline earth metals, although corresponding metal compounds such as lead, zinc, manganese, copper, etc. , can be used in the preparation of overbased materials.
  • Mixture ⁇ of different metal compounds can be used to prepare mixed metal overbased products.
  • the anionic portion of the metal compound can be hydroxyl, oxide, carbonate, hydrogen carbonate, acetate, hydrogen ⁇ ulfite, halide, amide, borate, etc., as disclosed in the above-cited patents.
  • the preferred overbased materials are prepared from alkali and alkaline earth metal oxides, hydroxides, and alcoholates such as the alkaline earth metal lower alkoxides.
  • the more preferred metals are calcium, magnesium, sodium, lithium, and/or barium.
  • the most preferred alkali metal is sodium, and calci ⁇ un is the most preferred alkaline earth metal.
  • mixed metal overbased products are also useful.
  • the promoters that is, the materials which permit the incorporation of the excess metal into the overbased material, are also quite diverse and well known in the art as evidenced by the cited patents. A particularly comprehensive discussion of suitable promoters is found in U.S. Patent Nos. 2,777,874; 2,695,910 and 2,616,904. These include the alcoholic and phenolic promoters which are preferred.
  • the alcoholic promoters include the alkanols of one to about eighteen carbon atoms, preferably one to about twelve carbon atoms, and more preferably one to about five carbon atoms, ⁇ uch as methanol, ethanol, n-butanol, amyl alcohol, octanol, isopropanol, isobutanol, and mixtures of these and the like.
  • Polyols are also useful promoters.
  • a particularly preferred polyol is ethylene glycol.
  • Phenolic promoters include a variety of hydroxy- substituted benzenes and naphthalenes.
  • a particularly useful class of phenols are the alkylated phenols of the type listed in U.S. Patent No. 2,777,874, e.g., heptylphenols, octylphenols, and nonylphenols. Mixtures of various promoters are sometimes used.
  • Suitable acidic materials are also disclosed in the above-cited patents, for example, U.S. Patent No. 2,616,904. Included within the known group of useful acidic materials are liquid acids such as formic acid, acetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrobromic acid, carbamic acid, substituted carbamic acids, etc.
  • Acetic acid is a very useful acidic material, although inorganic acidic materials such as boric acid, HCI, SO., SO,, C0 2 r H 2 S ' N 2° 3 ' etc *' are ordinarily employed as the acidic materials.
  • the most preferred acidic materials are carbon dioxide and acetic acid, with carbon dioxide being especially preferred.
  • H_0 When the metal reactant used in the overbasing process is an oxide or alkoxide, H_0 can be used as the acidic material. Examples include overbasing with MgO or aluminum isopropoxide.
  • overba ⁇ ed materials In preparing overba ⁇ ed materials, the material to be overbased, an inert, non-polar, organic solvent therefor, the metal base, the promoter and the acidic material are brought together and a chemical reaction ensues.
  • the exact nature of the resulting overbased product is not known. However, it can be adequately described for purposes of the present specification as a single phase homogeneous mixture of the solvent and (1) either a metal complex formed from the metal base, the acidic material, and the material being overbased and/or (2) an amorphous metal salt formed from the reaction of the. acidic material with the metal base and the material which is said to be overbased.
  • mineral oil is used as the reaction medium
  • carboxylic acid as the material which is overbased, Ca(OH).
  • the resulting overbased material can be described for purposes of this invention as an oil solution of either a metal-containing complex of the acidic material, the metal base, and the carboxylic acid or as an oil solution of amorphous calcium carbonate and calcium carboxylate.
  • the temperature at which the acidic material is contacted with the remainder of the reaction mass depends to a large measure upon the promoting agent used. With a phenolic promoter, the temperature usually ranges from about 80*C to 300"C, and preferably from about 100'C to about 200 * C. When an alcohol or mercaptan is used as the promoting agent, the temperature usually will not exceed the reflux temperature of the reaction mixture and preferably will not exceed about 100*C.
  • the overbased materials may retain all or a portion of the promoter. That is, if the promoter is not volatile (e.g., an alkyl phenol) or otherwise readily removable from the overbased material, at least some promoter remains in the overbased product. The presence or absence of the promoter in the overbased material does not represent a critical aspect of the invention. Obviously, it is within the skill of the art to select a volatile promoter such as a lower alkanol, e.g., methanol, ethanol, etc., so that the promoter can be readily removed prior to incorporation within the compositions of the present invention.
  • a volatile promoter such as a lower alkanol, e.g., methanol, ethanol, etc.
  • overbased materials are the metal-overbased water-insoluble organic acids, preferably those containing at least eight aliphatic carbons, although the acids may contain as few as six aliphatic carbon atoms if the acid molecule includes an aromatic ring such as phenyl, naphthyl, etc.
  • Representative organic acids suitable for preparing these overbased materials are discussed and identified in detail in the above-cited patents. In particular, U.S. Patent Nos. 2,616,904 and 2,777,874 disclo ⁇ e a variety of very suitable organic acids. Overbased carboxylic and sulfonic acids and phenols are particularly suitable.
  • Suitable carboxylic acids include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids free from acetylenic unsaturation, including naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, and alkyl- or alkenyl-substituted aromatic carboxylic acids.
  • the aliphatic acids generally contain from about 8 to about 50, and preferably from about 12 to about 25, carbon atoms.
  • the cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated.
  • Specific examples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer- ⁇ ubstituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalene-carboxylic acid, ⁇ tearyl-octahydroindenecarboxylic acid, palmitic acid, alkyl- and alkenylsuccinic acids, acids formed by oxidation of petrolatum or of hydrocarbon waxes, and commercially available mixtures of two or more carboxylic acids, such as tall oil acids, rosin acids, and the like.
  • carboxylic acids include propenyl- substituted glutaric acid, polybutenyl-substituted succinic acids derived from a polybutene (Mn equals about 200-1500, preferably about 300-1500), propenyl-substituted succinic acids derived from polypropylenes (Mn equals 200-1000) , acids, acids formed by oxidation of petrolatum or of hydrocarbon waxes, available mixtures of two or more carboxylic acids and mixtures of these acids, their metal salts, and/or their anhydrides.
  • the carboxylic acids are aromatic carboxylic acids.
  • a group of useful aromatic carboxylic acids are those of the formula
  • R. is an aliphatic hydrocarbon based group preferably derived from polyalkenes
  • a is a number in the range of 1 to about 4, usually 1 or 2
  • Ar is an aromatic group
  • each X is independently sulfur or oxygen, preferably oxygen
  • b is a number in the range of from 1 to about 4, u ⁇ ually 1 or 2
  • c is a number in the range of zero to about 4, usually 1 to 2, with the proviso that the sum of a, b and c does not exceed the number of valences of Ar.
  • aromatic carboxylic acids include substituted benzoic, phthalic and salicylic acids.
  • the R. group is a hydrocarbon based group that is directly bonded to the aromatic group Ar.
  • R groups include substituents derived from polymerized olefins such as polyethylenes, polypropylenes, polybutylenes, ethylene-propylene copolymers, chlorinated olefin polymers and oxidized ethylene-propylene copolymers.
  • the aromatic group Ar may have the same structure as any of the aromatic groups Ar discussed below.
  • the aromatic groups that are useful herein include the polyvalent aromatic groups derived from benzene, naphthalene, anthracene, etc., preferably benzene.
  • Specific examples of Ar groups include phenylenes and naphthylene, e.g., methylphenylene ⁇ , ethoxyphenylenes, isopropylphenylenes, hydroxyphenylenes> dipropoxynaphthylenes, etc.
  • R. is defined above, a is a number in the range of from 1 to about 4, preferably 1 to about 3; b is a number in the range of 1 to about 4, preferably 1 to about 2, c is a number in the range of zero to about 4, preferably 1 to about 2, and more preferably 1; with the proviso that the sum of a, b and c does not exceed 6.
  • b and c are each one and the carboxylic acid is a salicylic acid.
  • polyalkenes particularly polymerized lower 1-mono-olefins such as polyethylene, polypropylene, polyisobutylene, ethylene/propylene copolymer ⁇ and the like and having average carbon contents of about 50 to about 400 carbon atoms are particularly useful.
  • Zinc, calcium and magnesium salt ⁇ of the aromatic carboxylic acids, and especially the salicylic acids, are preferred.
  • the ⁇ ulfonic acids for use in the preparation of component (A) include those represented by the formulas R a (SO- • ⁇ •)H)i and (R b )_r_>T(S0O,H)y.
  • R a is an aliphatic or aliphatic-sub ⁇ tituted cycloaliphatic hydrocarbon or e ⁇ entially hydrocarbon radical free from acetylenic un ⁇ aturation and containing up to about 60 carbon atoms.
  • R is aliphatic, it usually contains at least about 15 carbon atoms; when it is an aliphatic-substituted cycloaliphatic radical, the aliphatic substituent ⁇ usually contain a total of at least about 12 carbon atoms.
  • Example ⁇ of R a are alkyl, alkenyl and alkoxyalkyl radicals, and aliphatic- ⁇ ub ⁇ tituted cycloaliphatic radicals wherein the aliphatic ⁇ ub ⁇ tituents are alkyl, alkenyl, alkoxy, alkoxyalkyl, carboxyalkyl and the like.
  • the cycloaliphatic nucleu ⁇ i ⁇ derived from a cycloalkane or a cycloalkene such a ⁇ cyclopentane, cyclohexane, cyclohexene or cyclopentene.
  • R a are cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, and radical ⁇ derived from petroleum, ⁇ aturated and un ⁇ aturated paraffin wax, and olefin polymers including polymerized monoolefin ⁇ and diolefin ⁇ containing about 2-8 carbon atom ⁇ per olefinic monomer unit.
  • R a can also contain other substituents such as phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitroso, lower alkoxy, lower alkylmercapto, carboxy, carbalkoxy, oxo or thio, or interrupting groups such as -NH-, -O- or -S-, as long as the essentially hydrocarbon character thereof is not destroyed.
  • R is generally a hydrocarbon or substantially hydrocarbon radical free from acetylenic unsaturation and containing from about 4 to about 60 aliphatic carbon atom ⁇ , preferably an aliphatic hydrocarbon radical ⁇ uch a ⁇ alkyl or alkenyl. It may also, however, * contain substituent ⁇ or interrupting group ⁇ such as those enumerated above provided the es ⁇ entially hydrocarbon character thereof is retained. In general, any non-hydrocarbon atoms pre ⁇ ent in R a or R do not account for more than 10% of the total weight thereof. Preferably, R a and R are substantially free of non-hydrocarbon atoms.
  • the radical T is a cyclic nucleus which may be derived from an aromatic hydrocarbon such a ⁇ benzene, naphthalene, anthracene or biphenyl, or from a heterocyclic compound such a ⁇ pyridine, indole or i ⁇ oindole.
  • T i ⁇ an aromatic hydrocarbon nucleu ⁇ , especially a benzene or naphthalene nucleu ⁇ .
  • the ⁇ ubscript x is at least 1 and is generally 1-3.
  • the sub ⁇ cript ⁇ r and y have an average value of about 1-4 per molecule, more often about 1.
  • Illustrative sulfonic acids useful in the preparation of component A are mahogany sulfonic acids, petrolatum ⁇ ulfonic acid ⁇ , mono- and polywax- ⁇ ub ⁇ tituted naphthalene ⁇ ulfonic acid ⁇ , cetylchlorobenzene ⁇ ulfonic acids, cetylphenol ⁇ ulfonic acid ⁇ , cetylphenol di ⁇ ulfide sulfonic acid ⁇ , cetoxycapryl benzene ⁇ ulfonic acid ⁇ , dicetyl thianthrene sulfonic acid ⁇ , dilauryl beta-naphthol ⁇ ulfonic acids, dicapryl nitronaphthalene sulfonic acids, saturated paraffin wax ⁇ ulfonic acid ⁇ , un ⁇ aturated paraffin wax sulfonic acid ⁇ , hydroxy- ⁇ ub ⁇ tituted paraffin wax sulfonic acids, tetrai ⁇ obutylene sulfonic acids, tetra-
  • the overba ⁇ ed material ⁇ have a metal ratio of at lea ⁇ t about 1.1, preferably at lea ⁇ t about 1.5, and more preferably at lea ⁇ t 2 to about 4.
  • An especially suitable group of the preferred sulfonic acid and carboxylic acid overba ⁇ ed material ⁇ has a metal ratio of at lea ⁇ t about 7.0. While overba ⁇ ed material ⁇ having a metal ratio of 75 have been prepared, normally the maximum metal ratio will not exceed about 50 and, in mo ⁇ t ca ⁇ es, not more than about 40.
  • the overbased material ⁇ utilized in the compo ⁇ ition ⁇ of the invention u ⁇ ually contain from about 10% to about 70% by weight of metal-containing component ⁇ .
  • the remainder of the overbased materials comprise the inert organic reaction medium and any promoter which i ⁇ not removed from the overbased product.
  • the organic material which is subjected to overbasing i ⁇ considered a part of the metal-containing components.
  • the liquid reaction medium constitutes at least about 30% by weight of the reaction mixture utilized to prepare the overbased materials.
  • component A is prepared from phenols; that is, compounds containing a hydroxy radical bound directly to an aromatic ring.
  • phenol as used herein include ⁇ compounds having more than one hydroxy group bound to an aromatic ring, such as catechol, resorcinol and hydroquinone. It also includes alkylphenols such as the cre ⁇ ol ⁇ and ethylphenol ⁇ , and alkenylphenol ⁇ .
  • phenol ⁇ containing at lea ⁇ t one alkyl or alkenyl substituent containing about 3-100 and especially about 6-50 carbon atom ⁇ ⁇ uch a ⁇ heptylphenol, octylphenol, dodecylphenol, tetrapropenealkylated phenol, octadecylphenol and polybutenylphenol ⁇ .
  • Phenol ⁇ containing more than one ⁇ ubstituent may also be used, but the monoalkylphenols are preferred becau ⁇ e of their availability and ea ⁇ e of production.
  • aldehydes include formaldehyde, acetaldehyde, propionaldehyde, the butyraldehydes, the valeraldehyde ⁇ and benzaldehyde.
  • Al ⁇ o suitable are aldehyde-yielding reagents such as parafor aldehyde, trioxane, methylol, Methyl Formcel and paraldehyde. Formaldehyde and the formaldehyde-yielding reagents are especially preferred.
  • the metal phenates are overbased metal phenate ⁇ , more preferably overba ⁇ ed ⁇ ulfurized metal phenate ⁇ , preferably alkaline earth metal phenate ⁇ , and e ⁇ pecially calcium phenate ⁇ .
  • the phenol group of the phenate ⁇ include ⁇ an aromatic moiety with at lea ⁇ t one hydrocarbon-ba ⁇ ed radical and an oxygen atom attached to such aromatic moiety, a ⁇ indicated in Formula I, below.
  • the phenol group may be sulfurized and reacted with a metal, as discussed below, to form component (A) .
  • (R C_L - Ar - 0-) is the phenol group; M i ⁇ a metal; x i ⁇ the valence of M.
  • Ar i ⁇ an aromatic moiety which i ⁇ preferably benzene; R i ⁇ a hydrocarbon-ba ⁇ ed radical; and a i ⁇ an integer of from 1 up to the number of unsatisfied valences in Ar, preferably 1 or 2.
  • the term overbased metal phenates refers to metal phenates wherein the ratio of metal to the phenol group i ⁇ greater than that of normal metal phenate ⁇ .
  • Such phenate ⁇ are ⁇ ometime ⁇ referred to interchangeably a ⁇ "ba ⁇ ic” or "overba ⁇ ed”.
  • Component (A) generally contain ⁇ up to about 1000%, preferably up to about 500%, of the metal pre ⁇ ent in the corresponding normal metal phenate.
  • component (A) contains from about 250% to about 450%, preferably up to about 350%, of the metal pre ⁇ ent in the corresponding normal metal phenate.
  • alkali or alkaline earth metal ⁇ , copper or zinc may be u ⁇ ed in the phenate of component (A) ; however, alkaline earth metal compounds are preferred, and calcium i ⁇ especially preferred.
  • component (A) preferably comprises a sulfurized metal phenate and the metal contents referred to hereinabove apply equally to this preferred embodiment.
  • component (A) is a sulfurized phenate it has a phenol to sulfur group molar ratio of from about 2:1 to about 1:2, preferably about 2:1 to about 1:1, and advantageously about 4:3.
  • the neutral and ba ⁇ ic salt ⁇ of phenol ⁇ ulfide ⁇ provide antioxidant and detergent properties to the oil compositions of the invention.
  • component (A) include ⁇ , for example, ba ⁇ ic sulfurized tetrapropenyl phenate with, for example, about 230% or 380% of the calcium present in the corresponding normal calcium phenate, and a phenol to sulfur group molar ratio of about 4:3.
  • the alkylphenols from which the neutral and overbased salt ⁇ are prepared generally compri ⁇ e phenol ⁇ containing hydrocarbon substituents with at least about 6 carbon atoms; the sub ⁇ tituent ⁇ may contain up to about 700 aliphatic carbon atom ⁇ . Also included are substantially hydrocarbon substituents, as defined hereinabove.
  • the preferred hydrocarbon sub ⁇ tituent ⁇ are derived from the polymerization of olefins such as ethylene, propene, etc.
  • alkylphenol sulfides is meant to include di-(alkylphenol)monosulfides, disulfides, polysulfide ⁇ , and other product ⁇ obtained by the reaction of the alkylphenol with sulfur monochloride, sulfur dichloride or elemental sulfur.
  • the molar ratio of the phenol to the ⁇ ulfur compound can be, depending on the ⁇ ulfur compound, from about 1:0.5 to about 1:1.5, or higher.
  • phenol ⁇ ulfides are readily obtained by mixing, at a temperature above about 60*C, one mole of an alkylphenol and about 0.5-1 mole of sulfur dichloride.
  • the reaction mixture is usually maintained at about 100 ⁇ C for about 2-5 hours, after which time the resulting sulfide is stripped of volatiles and filtered.
  • temperatures of about 200 ⁇ C or higher are sometimes desirable. It i ⁇ al ⁇ o de ⁇ irable that the drying operation be conducted under nitrogen or a ⁇ imilar inert gas.
  • a commonly employed method for preparing the basic (or overbased) salt ⁇ of the ⁇ e phenol ⁇ comprises heating the phenol with a stoichiometric excess of a metal neutralizing agent such as a metal oxide, hydroxide, carbonate, bicarbonate, sulfide, etc., at temperatures above about 50 ⁇ C.
  • a metal neutralizing agent such as a metal oxide, hydroxide, carbonate, bicarbonate, sulfide, etc.
  • promoter ⁇ may be u ⁇ ed in the overbasing proces ⁇ to aid in the incorporation of the excess metal.
  • Promoter ⁇ include such compound ⁇ a ⁇ phenolic substances including phenol; alcohols ⁇ uch a ⁇ methanol, 2-propanol, octyl alcohol, etc.; amines such as aniline and dodecyl amine, etc.
  • the basic salt i ⁇ treated with carbon dioxide after it ha ⁇ been formed Preferably, the basic salt i ⁇ treated with carbon dioxide after it ha ⁇ been formed.
  • the technique ⁇ of overba ⁇ ing various phenols are described in the prior art and can be utilized as proces ⁇ e ⁇ for preparing the basic or overba ⁇ ed phenol ⁇ u ⁇ ed in the pre ⁇ ent invention.
  • Neutral salt ⁇ are prepared by mixing and heating a ba ⁇ ic metal compound with the de ⁇ ired phenol compound.
  • ba ⁇ ic (overba ⁇ ed) phenate ⁇ can be accomplished by any of the standard technique ⁇ known to those skilled in the art for producing basic sulfurized metal phenates. These techniques include, for example, one-step proces ⁇ e ⁇ wherein ⁇ ulfurization and ba ⁇ ing (or overbasing) with the metal are effected ⁇ imultaneou ⁇ ly, and two- ⁇ tep proce ⁇ e ⁇ wherein the phenol i ⁇ fir ⁇ t ⁇ ulfurized, forming an alkylphenol sulfide, then based.
  • Each of the ⁇ e technique ⁇ is well known to those skilled in the art and, accordingly, need not be further discu ⁇ ed herein.
  • the source of ⁇ ulfur i ⁇ generally elemental sulfur, or ⁇ ulfur halide, for example, SC1_ or S-C1-.
  • Patent ⁇ di ⁇ clo ⁇ ing ⁇ uitable procedure ⁇ for preparing component (B) include U.S. Pat. No ⁇ . 2,680,096; 3,036,971; 3,178,368; 3,437,595; and Re 29,661, these patents being ' incorporated herein by reference.
  • Suitable basic alkyl phenol sulfides are disclosed, for example, in U.S. Pat. Nos. 3,372,116, 3,410,798 and 3,562,159, 4,021,419 and 4,740,321 which are hereby incorporated by reference.
  • the metal salts, component (A) are generally employed in the composition ⁇ of thi ⁇ invention in amounts ranging from about 0.1 to about 10% by weight of the total lubricating oil composition. More often, they are u ⁇ ed in amounts ranging from about 0.02 to about 5%, frequently up to about 2% and preferably from about 0.04% to about 1% by weight of the lubricating compositions.
  • Examples A-l through A-10 are non-limiting examples of the preparation of metal carboxylates, sulfonates and mixtures thereof.
  • Example A-l To 790 parts of an oil solution containing 1 equivalent based on neutralization number of an alkylated benzenesulfonic acid and 71 part ⁇ of polybutenyl succinic anhydride (equivalent weight about 560) containing predominantly i ⁇ obutene units in 176 parts of mineral oil is added 320 parts (8 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. The temperature of the mixture in ⁇ rease ⁇ to 89*C (reflux) over 10 minute ⁇ due to exother ing. During thi ⁇ period, the mixture i ⁇ blown with carbon dioxide at 4 cfh (cubic feet per hour) .
  • the methanol and other volatile materials are stripped from the carbonated mixture by blowing nitrogen through it at 2 cfh while the temperature i ⁇ slowly increa ⁇ ed to 150 'C over 90 minute ⁇ . After ⁇ tripping is completed, the remaining mixture is held at lSS'C-l ⁇ S'C for about 30 minutes and filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 7.75.
  • Example A-2 Following the procedure of Example A-l, a ⁇ olution of 780 part ⁇ (1 equivalent) of an alkylated benzene ⁇ ulfonic acid (57% by weight 100 neutral mineral oil and unreacted alkylated benzene) and 119 part ⁇ of the polybutenyl ⁇ uccinic anhydride in 442 part ⁇ of mineral oil i ⁇ mixed with 800 part ⁇ (20 equivalents) of sodium hydroxide and 704 parts (22 equivalents) of methanol. The mixture is blown with carbon dioxide at 7 cfh for 11 minutes as the temperature slowly increase ⁇ to 97*C. The rate of carbon dioxide flow is reduced to 6 cfh and the temperature decreases slowly to 88"C over about 40 minutes.
  • an alkylated benzene ⁇ ulfonic acid 57% by weight 100 neutral mineral oil and unreacted alkylated benzene
  • 119 part ⁇ of the polybutenyl ⁇ uccinic anhydride in 442 part ⁇ of mineral oil i ⁇ mixed with 800 part ⁇
  • the rate of carbon dioxide flow is reduced to 5 cfh for about 35 minutes and the temperature slowly decreases to 73*C.
  • the volatile material ⁇ are ⁇ tripped by blowing nitrogen through the carbonated mixture at 2 cfh for 105 minute ⁇ a ⁇ the temperature i ⁇ ⁇ lowly increa ⁇ ed to 160*C. After stripping i ⁇ completed, the mixture i ⁇ held at 160*C for an additional 45 minute ⁇ and then filtered to yield an oil solution of the de ⁇ ired ba ⁇ ic ⁇ odium ⁇ ulfonate having a metal ratio of about 19.75.
  • Example A-3 A mixture of 906 part ⁇ of an oil solution of an alkyl phenyl ⁇ ulfonic acid (having a molecular weight of 450), 564 part ⁇ mineral oil, 600 parts toluene, 98.7 part ⁇ magnesium oxide and 120 parts water is blown with carbon dioxide at a " temperature of 78 , -85*C for 7 hours at a rate of about 3 cubic feet of carbon dioxide per hour.
  • the reaction mixture i ⁇ con ⁇ tantly agitated throughout the carbonation. After carbonation, the reaction mixture i ⁇ ⁇ tripped to 165"C/20 torr and the re ⁇ idue filtered.
  • Example A-4 A polybutenyl ⁇ uccinic anhydride i ⁇ prepared by reacting a chlorinated polybutene (having an average chlorine content of 4.3% and derived from a polybutene con ⁇ i ⁇ ting predominantly of i ⁇ obutene unit ⁇ having a number average molecular weight of about 1150) with maleic anhydride at about 200'C. To a mixture of 1246 parts of thi ⁇ succinic anhydride and 1000 parts of toluene there is added at 25*C, 76.6 parts of barium oxide. The mixture i ⁇ heated to 115*C and 125 part ⁇ of water i ⁇ added drop-wise over a period of one hour. The mixture is then allowed to reflux at 150*C until.all the barium oxide is reacted. Stripping and filtration provides a filtrate containing the desired product.
  • a chlorinated polybutene having an average chlorine content of 4.3% and derived from a polybutene con ⁇ i ⁇ ting predominantly of i ⁇ obutene unit
  • Example A-5 A basic calcium sulfonate having a metal ratio of about 15 i ⁇ prepared by carbonation, in increment ⁇ , of a mixture of calcium hydroxide, a neutral ⁇ odium petroleum sulfonate, calcium chloride, methanol and an alkyl phenol, followed by removal of volatile material ⁇ and filtration of the re ⁇ idue.
  • Example -6 A mixture of 323 part ⁇ of mineral oil, 4.8 part ⁇ of water, 0.74 part ⁇ of calcium chloride, 79 part ⁇ of lime, and 128 part ⁇ of methyl alcohol i ⁇ prepared, and warmed to a temperature of about 50*C. To thi ⁇ mixture there is added 1000 parts of an alkyl phenyl sulfonic acid having a molecular weight of 500 with mixing. The mixture then i ⁇ blown with carbon dioxide at a temperature of about 5 'C at a rate of about 5.4 pounds per hour for about 2.5 hours. After carbonation, 102 additional parts of oil are added and the mixture is ⁇ tripped of volatile material ⁇ at a temperature of about 150-155*C at 55 mm. pres ⁇ ure. The re ⁇ idue i ⁇ filtered and the filtrate i ⁇ the desired oil solution of the overbased calcium ⁇ ulfonate having calcium content of about 3.7% and a metal ratio of about 1.7.
  • an alkyl phenyl sulfonic acid having a mo
  • Example A-7 A mixture of 490 part ⁇ (by weight) of a mineral oil, 110 part ⁇ of water, 61 parts of heptylphenol, 340 parts of barium mahogany sulfonate, and 227 parts of barium oxide is heated at 100*C for 0.5 hour and then to 150 * C. Carbon dioxide is then bubbled into the mixture until the mixture is substantially neutral. The mixture is filtered and the filtrate found to have a sulfate ash content of 25%.
  • Example A-8 Add to a flask about 512 parts by weight of a mineral oil solution containing about 0.5 equivalent of a sub ⁇ tantially neutral magne ⁇ ium salt of an alkylated salicylic acid wherein the alkyl group has an average of about 18 aliphatic carbon atoms, about 30 parts by weight of an oil mixture containing about 0.037 equivalent of an alkylated benzenesulfonic acid together with about 15 part ⁇ by weight (0.65 equivalents) of magnesium oxide and about 250 parts by weight of xylene. Heat to a temperature of about 60*C to 70*C. Increase the heat to about 85*C and add approximately 60 parts by weight of water.
  • the filtrate will compri ⁇ e the ba ⁇ ic carboxylic magnesium salt containing 200% of the ⁇ toichiometrically equivalent amount of magnesium.
  • Example A-9 Prepare a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have from 16 to 24 aliphatic carbon atoms by reacting approximately stoichiometric amounts of magnesium chloride with a substantially neutral potassium salt of the alkylated salicylic acid.
  • Charge a flask with a reaction ma ⁇ comprising approximately 6580 parts by weight of a mineral oil solution containing about 6.50 equivalents of the substantially neutral magnesium salt of the alkylated salicylic acid and about 388 parts by weight of an oil mixture containing about 0.48 equivalent of an alkylated benzenesulfonic acid together with approximately 285 parts by weight (14 equivalents) of magnesium oxide and approximately 3252 parts by weight of xylene.
  • Example A-10 A reaction mixture comprising 2900 grams (3 equivalents) of an oil solution of the magnesium salt of polyisobutylene (average molecular weight—480)- ⁇ ub ⁇ tituted salicyclic acids, 624 grams of mineral oil, 277 grams (l equivalent) of a commercial mixture of tall oil acids, 1800 grams of xylene, 195 grams (9 equivalents) of magnesium oxide, and 480 grams of water are carbonated at the reflux temperature (about 95"C) for one hour. The carbonated mixture i ⁇ then stripped by first heating to 160"C with nitrogen blowing (3 cubic feet per hour) and thereafter heating to 165*C at a pressure of 30 mm. (Hg) . This stripped carbonated product is filtered, the filtrate being an oil solution of the desired basic magnesium salt.
  • the salt is characterized by a metal ratio of 2.7.
  • Example A-ll A phenol sulfide is prepared by reacting sulfur dichloride with a polyisobutenyl phenol in which the polyisobutenyl substituent has an average of 23.8 carbon atoms, in the presence of sodium acetate (an acid acceptor used to avoid discoloration of the product) .
  • Example A-12 To 6072 parts (22 moles OH) of a tetrapropenyl- substituted phenol (prepared by mixing, at 138"C and in the pre ⁇ ence of a sulfuric acid treated clay, phenol and tetrapropylene) , there are added at 90*-95'C, 1134 parts (11 moles) of ⁇ ulfur dichloride. The addition is made over a 4-hour period whereupon the mixture is bubbled with nitrogen for 2 hour ⁇ , heated to 150*C and filtered. To 861 part ⁇ (3 equivalent ⁇ ) of the above product, 1068 part ⁇ of mineral oil, and 90 part ⁇ of water, there are added at 70"C, 122 parts (3.3 equivalents) of calcium hydroxide.
  • the mixture i ⁇ maintained at 110°C for 2 hour ⁇ , heated to 165"C and maintained at thi ⁇ temperature until it i ⁇ dry. Thereupon, the mixture i ⁇ cooled to 25*C and 180 part ⁇ of methanol are added. The mixture i ⁇ heated to 50°C and 366 part ⁇ (9.9 equivalents) of calcium hydroxide and 50 parts (0.633 equivalent) of calcium acetate are added. The mixture is agitated for 45 minutes and i ⁇ then treated at 50-70*C with carbon dioxide at a rate of 2-5 cubic feet per hour for 3 hours. The mixture i ⁇ dried at 165*C and the residue is filtered. The filtrate has a calcium content of 3.3%, a neutralization number of 39 (basic) and a metal ratio of 4.4.
  • Example A-13 To 5880 parts (12 moles OH) of a polyisobutene- substituted phenol (prepared by mixing, at 54'C and in the presence of boron trifluoride, equimolar amounts of phenol and a polyisobutene having a number average molecular weight of about 350) and 2186 part ⁇ of mineral oil, there are added over 2.5 hours and at 90-110*C, 618 parts (6 moles) of sulfur dichloride. The mixture is heated to 150*C and bubbled with nitrogen. To 3449 parts (5.25 equivalents) of the above product, 1200 parts of mineral oil, and 130 parts of water, there are added at 70 * C, 147 parts (5.25 equivalents) of calcium oxide.
  • a polyisobutene- substituted phenol prepared by mixing, at 54'C and in the presence of boron trifluoride, equimolar amounts of phenol and a polyisobutene having a number average molecular weight of about 350
  • Example A-14 A mixture of 485 part ⁇ (1 mole ⁇ OH) of a polyi ⁇ obutene-substituted phenol wherein the substituent has a number average molecular weight of about 400, 32 parts (1 equivalent) of ⁇ ulfur.
  • Component (B) is an aliphatic carboxylic acid or an anhydride thereof, wherein the aliphatic group contains at least about 20 carbon atom ⁇ and up to about 500 carbon atom ⁇ , preferably from about 30 to about 300 carbon atom ⁇ and often from about 30 to about 150 carbon atom ⁇ .
  • component (B) is an aliphatic substituted succinic anhydride or acid containing from about 20 to about 500 carbon atoms in the aliphatic substituent, preferably from about 30 to about 400 carbon atoms, and often from about 50 to about 200 carbon atoms.
  • Patents de ⁇ cribing u ⁇ eful aliphatic carboxylic acid ⁇ or anhydrides and methods for preparing them include, among numerous others, U.S. Pat. Nos.
  • the carboxylic acid ⁇ (or variou ⁇ derivatives thereof) are usually derived by the reaction of a carboxylic acid containing compound with a polyalkene or halogenated derivative thereof or a suitable olefin.
  • the polyalkenes from which the carboxylic acids (B) are derived are homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms.
  • the interpolymer ⁇ are tho ⁇ e in which two or more olefin monomer ⁇ are interpolymerized according to well-known conventional procedure ⁇ to form polyalkene ⁇ having units within their structure derived from each of said two or more olefin monomers.
  • interpolymer( ⁇ )" as used herein i ⁇ inclu ⁇ ive of copolymer ⁇ , terpolymers, tetrapolymers, and the like.
  • the polyalkenes from which the substituent groups are derived are often conventionally referred to as "polyolefin(s)".
  • polymerizable internal olefin monomer ⁇ ( ⁇ ometime ⁇ referred to in the literature a ⁇ medial olefins) characterized by the pre ⁇ ence within their structure of the group
  • internal olefin monomer ⁇ When internal olefin monomer ⁇ are employed, they normally will be employed with terminal olefin ⁇ to produce polyalkene ⁇ which are interpolymer ⁇ .
  • terminal olefin ⁇ When a particular polymerized olefin monomer can be cla ⁇ ified a ⁇ both a terminal olefin and an internal olefin, it will be deemed to be a terminal olefin.
  • Preferred carboxylic acids include polyolefin substituted succinic acids, succinic anhydrides, ester acids or lactone acids.
  • Component (B) i ⁇ generally u ⁇ ed in the lubricating oil compositions of this invention in amounts ranging from about 0.01% to about 10% by weight of the lubricating oil composition, preferably from about 0.01% to about 5% by weight and often up to about 1% by weight. Most preferably, component (B) i ⁇ pre ⁇ ent in amount ⁇ ranging from about 0.02% to about 1% by weight.
  • Non-limiting example ⁇ of compounds useful as component (B) include those in the following examples:
  • Example B-l A mixture of 6400 part ⁇ (4 ole ⁇ ) of a polybutene comprising predominantly i ⁇ obutene unit ⁇ and having a molecular weight of about 1600 and 408 part ⁇ (4.16 moles) of maleic anhydride i ⁇ heated at 225-240 ⁇ C for 4 hours. It i ⁇ then cooled to 170*C and an additional 102 part ⁇ (1.04 mole ⁇ ) of maleic anhydride i ⁇ 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 an additional 3 hours at 215*C and is then vacuum stripped at 220"C and filtered through diatomaceous earth. The product i ⁇ the de ⁇ ired polybutenyl- ⁇ ubstituted succinic anhydride having a saponification number of 61.8.
  • Example B-2 A monocarboxylic acid is prepared by chlorinating a polyisobutene having a molecular weight of 750 to a product having a chlorine content of 3.6% by weight, converting the product to the corre ⁇ ponding nitrile by reaction with an equivalent amount of pota ⁇ ium cyanide in the pre ⁇ ence of a catalytic amount of cuprou ⁇ cyanide and hydrolyzing the re ⁇ ulting nitrile by treatment with 50% exce ⁇ of a dilute aqueous sulfuric acid at the reflux temperature.
  • Example B-3 A high molecular weight mono-carboxylic acid is prepared by telomerizing ethylene with carbon tetrachloride to a telomer having an average of 35 ethylene radical ⁇ per molecule and hydrolyzing the telomer to the corresponding acid in according with the procedure described in British Patent No. 581,899.
  • Example B-4 A polybutenyl ⁇ uccinic anhydride i ⁇ prepared by the reaction of a chlorinated polybutylene with maleic anhydride at 200'C.
  • the polybutenyl radical ha ⁇ an average molecular weight of 805 and contain ⁇ primarily i ⁇ obutene unit ⁇ .
  • the re ⁇ ulting alkenyl ⁇ uccinic anhydride is found to have an acid number of 113 (corresponding to an equivalent weight of 500) .
  • Example B-5 A lactone acid is prepared by reacting 2 equivalent ⁇ of a polyolefin (Mn about 900) substituted Succinic anhydride with 1.02 equivalents of water at a temperature of about 90*C in the presence of a catalytic amount of concentrated sulfuric acid. Following completion of the reaction, the sulfuric acid catalyst is neutralized with sodium carbonate and the reaction mixture is filtered.
  • Example B-6 An ester acid is prepared by reacting 2 equivalents of an alkyl ⁇ ub ⁇ tituted ⁇ uccinic anhydride having an average of about 35 carbon atom ⁇ in the alkyl group with 1 mole of ethanol.
  • Example B-7 A reactor i ⁇ charged with 1000 part ⁇ of polybutene having a molecular weight determined by vapor pha ⁇ e i ⁇ ometry of about 950 and which con ⁇ i ⁇ t ⁇ primarily of isobutene units, followed by the addition of 108 parts of moleic anhydride.
  • the mixture i ⁇ heated to 110'C followed by the sub-surface addition of 100 parts Cl 2 over 6.5 hours at a temperature ranging from 110 to 188'C.
  • the exothermic reaction is controlled as not to exceed 188'C.
  • the batch is blown with nitrogen then stored.
  • Example B-8 The procedure of Example B-7 is repeated employing 1000 parts of polybutene having a molecular weight determined by vapor phase isometry of about 1650 and con ⁇ isting primarily of isobutene units and 106 parts moleic anhydride. Cl, is added beginning at 130 * C and added a near continuous rate such that the maximum temperature of 188*C is reached near 1;he end of chlorination. The residue is blown with nitrogen and collected.
  • composition ⁇ of the pre ⁇ ent invention may also contain (C) a metal salt of (C) (I) at lea ⁇ t one organic phosphorus acid or mixture of (C) (I) at least one organic phosphorus acid and (C) (II) at least one carboxylic acid.
  • the phosphorus acid (B) (I) is preferably at least one acid of the general formula
  • R 1 and R2 is the same or different and each of R1 and R 2 is independently H or a hydrocarbon-based group with the proviso that at least one of R 1 and R2 is a hydrocarbon-based group and each X is independently S or
  • the phosphorus acid in a preferred embodiment, the phosphorus acid
  • R 1 and R2 are as defined hereinabove.
  • the ⁇ e are referred to a ⁇ pho ⁇ phorodithioic acid ⁇ .
  • the hydrocarbon-ba ⁇ ed groups R 1 and R2 may be alkyl, cycloalkyl, aralkyl or alkaryl groups.
  • Illustrative alkyl groups include isopropyl, i ⁇ obutyl, n-butyl, sec-butyl, the variou ⁇ amyl group ⁇ , n-hexyl, ethyli ⁇ obutyl carbinyl, heptyl, 2-ethylhexyl, dii ⁇ obutyl, i ⁇ ooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc.
  • Illu ⁇ trative alkaryl groups include lower alkylphenyl group ⁇ ⁇ uch a ⁇ butylphenyl, amylphenyl, heptylphenyl, etc. Cycloalkyl group ⁇ likewi ⁇ e are u ⁇ eful and the ⁇ e include chiefly cyclohexyl and the lower alkyl-cyclohexyl radical ⁇ . Lower alkyl group ⁇ contain from one to about ⁇ even carbon atom ⁇ . Many ⁇ ub ⁇ tituted hydrocarbon group ⁇ may also be u ⁇ ed, e.g., chloropentyl, dichlorophenyl, and dichlorodecyl.
  • phosphorus pentasulfide (-P H * 3 *) with an alcohol or mixture ⁇ of alcohol ⁇ .
  • the reaction involve ⁇ mixing at a temperature of about 20'C to about 200'C, 4 mole ⁇ of the alcohol with one mole of pho ⁇ phorus pentasulfide. Hydrogen ⁇ ulfide is liberated in this reaction.
  • the oxygen-containing analogs of these acids are conveniently prepared by treating the dithioic acid with water or steam which, in effect, replaces one or both of the sulfur atoms.
  • the mixed phosphates (RO)xP(0H)y are readily prepared by reacting 3 moles of an alcohol with 1 mole of phosphorus pentoxide (P_0 g ) .
  • hydrocarbon-based group as u ⁇ ed herein with re ⁇ pect to and R 2 i ⁇ u ⁇ ed to define a monovalent radical derived from a hydrocarbon-ba ⁇ ed material by removal of a hydrogen from a carbon atom of the hydrocarbon-based material. Thi ⁇ carbon atom is directly bonded to the remainder of the molecule.
  • the hydrocarbon-based groups may be straight chains, e.g., isopropyl-, n-pentyl, ⁇ ec-butyl-, etc. or branched, e.g., 2-methyl-4-pentyl-, i ⁇ ooctyl-, etc.
  • the group ⁇ R1 and R2 are ⁇ ub ⁇ tantially ⁇ aturated.
  • acetylenic unsaturation e.g., benzene
  • -C ethylenic linkage
  • substantially saturated there will be no more than an average of one ethylenic linkage per substantially saturated monovalent radical as described hereinbefore.
  • all the carbon-to-carbon bonds in a substantially ⁇ aturated radical will be ⁇ aturated linkages; that is, the radical will be free from acetylenic and ethylenic linkages.
  • aromatic unsaturation is not to be con ⁇ idered ethylenic un ⁇ aturation.
  • the hydrocarbon-ba ⁇ ed radical may contain at lea ⁇ t 3 carbon atom ⁇ and up to about 100 carbon atom ⁇ with a preferred range from 3 to about 50 carbon atom ⁇ , more preferably from about 3 to about 16 carbon atom ⁇ . Other preferred range ⁇ are from about 6 to about 18 carbon ⁇ , more preferably from about 6 to about 8 carbon ⁇ .
  • R 1 and R2 are different are useful.
  • Typical example ⁇ of R and R include i ⁇ opropyl-, n-butyl-, n-pentyl-, 4-methyl-2-pentyl-, isooctyl-, n-dodecyl-, etc.
  • Mixtures such as isopropyl- and isooctyl, sec-butyl and n-decyl-, i ⁇ opropyl- and 4-methyl-2-pentyl- and the like are useful.
  • Mixtures are often ⁇ tati ⁇ tical mixture ⁇ which comprise a mixture wherein some of the molecule ⁇ have both R 1 and R2 alike and additional molecule ⁇ wherein R 1 and R2 are different.
  • Method ⁇ for preparing the metal ⁇ alt ⁇ (C) are well known and are de ⁇ cribed in detail in the patent literature. Mo ⁇ t frequently, the ⁇ alt ⁇ are prepared by reacting one or more of the pho ⁇ phoru ⁇ -containing acids de ⁇ cribed hereinabove with a metal base.
  • Suitable metal base ⁇ include the free metals previously enumerated and their oxides, hydroxides, alkoxides and ba ⁇ ic ⁇ alts. Examples include sodium hydroxide, calcium hydroxide, zinc oxide, copper oxide, calcium acetate and the like.
  • metal salt ⁇ of pho ⁇ phorus-containing acid ⁇ a ⁇ described hereinabove which have been post-treated with other reagents to improve various properties.
  • Example ⁇ include po ⁇ t-treatment ⁇ with pho ⁇ phites, epoxides, amines and the like. Such post-treatment ⁇ and product ⁇ ⁇ o obtained are described in the following U.S. Patents: - 42 -
  • the metal ⁇ alt ⁇ (C) useful in the lubricating composition ⁇ of thi ⁇ invention may be metal ⁇ alt ⁇ of a mixture of (C) (I) at lea ⁇ t one organic pho ⁇ phoru ⁇ acid and (C) (II) at lea ⁇ t one carboxylic acid wherein the various elements of the formula are as described hereinabove.
  • the carboxylic acid reactant (C) (II) may be a monocarboxylic or polycarboxylic acid, u ⁇ ually containing from 1 to about 3 carboxy group ⁇ and preferably only 1. It may contain from about 2 to about 40, preferably from about 2 to about 20 carbon atom ⁇ .
  • the preferred carboxylic acid ⁇ are tho ⁇ e having the formula R 3COOH,
  • R ⁇ an aliphatic or alicyclic hydrocarbon-ba ⁇ ed group preferably free from acetylenic unsaturation.
  • Suitable acid ⁇ include acetic, propionic, butanoic, hexanoic, decanoic, dodecanoic, octadecanoic and eico ⁇ anoic acid ⁇ , as well a ⁇ olefinic acids such as acrylic, oleic, linoleic, and linoleic acid dimer.
  • acetic, propionic, butanoic, hexanoic, decanoic, dodecanoic, octadecanoic and eico ⁇ anoic acid ⁇ as well a ⁇ olefinic acids such as acrylic, oleic, linoleic, and linoleic acid dimer.
  • R l ⁇ a ⁇ aturated aliphatic radical and especially a branched alkyl radical such as the isopropyl or 3-heptyl radical.
  • Illu ⁇ trative polycarboxylic acid ⁇ are oxalic, malonic, succinic, alkyl- and alkenylsuccinic, glutaric, adipic, pimelic, sebacic, maleic, fumaric and citric acid ⁇ .
  • the ⁇ alt of a mixture of (C) (I) and (C) (II) may be prepared by merely blending a metal salt of compoment (C) (I) with a metal ⁇ alt of component (C) (II) in the de ⁇ ired ratio.
  • Thi ⁇ ratio i ⁇ between about 0.5:1 and about 500:1 on an equivalent basis.
  • the ratio is between about 0.5:1 and about 200:1.
  • the ratio can be from about 0.5:1 to about 100:1, preferably from about 0.5:1 to about 50:1, and more preferably from about 0.5:1 to about 20:1.
  • the ratio can be from about 0.5:1 to about 4.5:1, preferably about 2.5:1 to about 4.25:1.
  • the equivalent weight of a phosphoru ⁇ containing acid (C) (I) i ⁇ it ⁇ molecular weight divided by the number of acidic groups, and that of a carboxylic acid is its molecular weight divided by the number of carboxy groups therein.
  • the information required to determine equivalents can u ⁇ ually be determined from the ⁇ tructural formula of component ⁇ (C) (I) and (C) (II) or empirically through well-known titration procedure ⁇ .
  • a second and preferred method for preparing the metal salts of mixtures of acids (C) (I) and (C) (II) is to prepare a mixture of the acid ⁇ in the de ⁇ ired ratio and to react the acid mixture with a suitable metal base.
  • thi ⁇ method of preparation i ⁇ u ⁇ ed, it i ⁇ frequently po ⁇ ible to prepare a neutral ⁇ alt or a ⁇ alt containing an exces ⁇ of metal with re ⁇ pect to the number of equivalent ⁇ of acid pre ⁇ ent; thus, mixed metal ⁇ alt ⁇ containing a ⁇ many a ⁇ 2 equivalent ⁇ and especially up to about 1.5 equivalents of metal per equivalent of acid may be prepared.
  • the equivalent of a metal for this purpose is its atomic weight divided by its valence.
  • neutral salt refers to salt ⁇ characterized by metal content equal to that which would be pre ⁇ ent according to the stoichiometry of the metal and the particular organic compound reacted with the metal. Thu ⁇ , if a pho ⁇ phorodithioic acid, (RO)-PSSH, i ⁇ neutralized with a ba ⁇ ic metal compound, e.g., zinc oxide, the neutral metal ⁇ alt produced would contain one equivalent of zinc for each equivalent of acid, i.e., [(R0) 2 PSS] 2 Zn.
  • component (C) can contain more or le ⁇ than the ⁇ toichiometric amount of metal.
  • the products containing le ⁇ s than the stoichiometric amount of metal are acidic material ⁇ .
  • the product ⁇ containing more than the ⁇ toichiometric amount of metal are overbased materials.
  • Component (C) may have about 80% to about 200%, preferably about 100% to about 150%, more preferably about 100% to about 135%, and advantageously about 103% to about 110% of the metal pre ⁇ ent in the corre ⁇ ponding neutral ⁇ alt.
  • Variants of the above-de ⁇ cribed method ⁇ may al ⁇ o be u ⁇ ed to prepare the mixed metal ⁇ alt ⁇ of thi ⁇ invention.
  • a metal ⁇ alt, component (C) may be blended with the free acid a ⁇ component (C) (II) , and the re ⁇ ulting blend reacted with additional metal base.
  • Suitable metal bases for the preparations of the metal ⁇ alt ⁇ (C) of thi ⁇ invention include the free metal ⁇ previously enumerated and their oxides, hydroxides', alkoxides and basic salt ⁇ .
  • Example ⁇ are ⁇ odium hydroxide, ⁇ odium methoxide, ⁇ odium carbonate, pota ⁇ ium hydroxide, pota ⁇ ium carbonate, magne ⁇ ium oxide, magne ⁇ ium hydroxide, calcium hydroxide, calcium acetate, zinc oxide, zinc acetate, lead oxide, nickel oxide, copper oxide, antimony trioxide and the like.
  • the temperature at which the metal salts used in this invention are prepared is generally between about 30'C and about 150*C, preferably up to about 125*C. If component (C) is prepared by neutralization of a mixture of acids with a metal base, it is preferred to employ temperatures above about 50"C and especially above about 75 * C. It i ⁇ frequently advantageou ⁇ to conduct the reaction in the pre ⁇ ence of a substantially inert, normally liquid organic diluent such as naphtha, benzene, xylene, mineral oil or the like. If the diluent is mineral oil or is physically and chemically ⁇ imilar to mineral oil, it frequently need not be removed before using component (C) in the compo ⁇ ition ⁇ of the invention.
  • a substantially inert, normally liquid organic diluent such as naphtha, benzene, xylene, mineral oil or the like. If the diluent is mineral oil or is physically and chemically ⁇ imilar to mineral oil, it frequently need not be removed before
  • Component (C) when pre ⁇ ent, i ⁇ generally u ⁇ ed in the lubricating oil compo ⁇ ition ⁇ of thi ⁇ invention in amount ⁇ ranging up to about 10% of the total weight of the lubricating oil composition. More often, component (C) , when u ⁇ ed, i ⁇ pre ⁇ ent in amount ⁇ ranging from about 0.05% to about 5%, preferably from about 0.1 to about 2% and more preferably from about 0.1 to about 1% by weight of the lubricating oil compo ⁇ ition.
  • the metal salts and derivatives thereof are well known in the art.
  • the following examples are provided to illustrate several of the metal salt ⁇ u ⁇ eful a ⁇ component (C) in thi ⁇ invention. It i ⁇ empha ⁇ ized that the ⁇ e example ⁇ are provided for illu ⁇ trative purposes and are not to serve as a limitation on the scope of the invention.
  • Example fC-l One mole of an 0,0-di(alkyl)phosphorodithioic acid containing 40 mole % isopropyl and 60 mole % 4-methyl-2-pentyl group i ⁇ reacted with an oil ⁇ lurry of 1.08 eguivalent ⁇ (0.54 mole ⁇ ) of zinc oxide at about 190'F (88 * C). H 2 0 is evolved. The reaction mixture is steam stripped followed by vacuum stripping. Oil is added if neces ⁇ ary to adjust the phosphoru ⁇ content of the residue to about 9.5%. The oil solution is filtered.
  • Example (C-2) The procedure of Example B-l is repeated employing 1 mole of di(4-methyl-2-pentyl)dithiophosphoric acid and
  • Example fC-3 The procedure of Example B-2 i ⁇ repeated except no oil diluent i ⁇ employed. The filtered product contains 9.25% phosphorus.
  • Example (C-4) A mixture of 67 parts (1.63 eguivalent ⁇ ) of zinc oxide and 48 part ⁇ of mineral oil i ⁇ prepared at room temperature. A mixture of 303 part ⁇ (l equivalent) of the 0,0-di(alkyl)pho ⁇ phorodithioic acid de ⁇ cribed in Example 2 and 36 part ⁇ (0.25 equivalents) of 2-ethylhexanoic acid is added over 10 minutes and a slight exotherm is observed. When addition is complete, the temperature is increased to 80*C for 3 hour ⁇ . The mixture is vacuum stripped at 100*C and filtered.
  • Example C-5 Following the procedure of Example C-4, a product is prepared from 383 part ⁇ (1.2 equivalent ⁇ ) of a dialkyl pho ⁇ phorodithioic acid containing 65% i ⁇ obutyl and 35 % amyl group ⁇ , 43 part ⁇ (0.3 equivalent) of 2-ethylhexanoic acid, 71 part ⁇ (1.73 equivalent ⁇ ) of zinc oxide and 47 part ⁇ of mineral oil.
  • the re ⁇ ulting metal ⁇ alt obtained a ⁇ a 90% ⁇ olution in mineral oil, contain ⁇ 11.07% zinc.
  • Example C-6 Following the procedure of Example C-4, a product is prepared from 474 parts (1.2 equivalents) of a dialkylphosphorodithioic acid containing 80% 2-ethylhexyl group ⁇ and 20% isobutyl group ⁇ , 43 part ⁇ (0.3 equivalent) of 2-ethylhexanoic acid, 80 part ⁇ (1.95 equivalent ⁇ ) of zinc oxide and 57 parts of mineral oil. The resulting metal ⁇ alt is obtained as a 91% solution in mineral oil.
  • Example C-7 A mixture of 118 part ⁇ (2.8 equivalent ⁇ ) of zinc oxide, 25 part ⁇ (0.25 equivalent) of sebacic acid and 72 part ⁇ of mineral oil i ⁇ ⁇ tirred at room temperature and a mixture of 584 parts (2 equivalents) of the dialkylphosphorodithioic acid of Example 2 and 36 parts (0.25 equivalent) of 2-ethyl-hexanoic acid i ⁇ added over 30 minutes. The temperature increases to 65"C during the addition. The solution i ⁇ heated to 80'C for 3 hour ⁇ and vacuum stripped at 180'C. The re ⁇ idue i ⁇ filtered to yield the desired metal salt (90% solution in mineral oil) containing 11.7% zinc.
  • Example C-8 A product is prepared by the procedure of Example C-4 except that an equivalent amount of oleic acid i ⁇ sub ⁇ tituted for the 2-ethylhexanoic acid.
  • the reaction condition ⁇ and results are given in Table I.
  • the salts are prepared by reacting zinc oxide with 4 equivalents of the dialkylphosphorodithioic acid and 1 equivalent of the carboxylic acid, a total of 1.3 equivalents of zinc oxide being used per equivalent of acid.
  • the reactions are carried out in a small amount of mineral oil as diluent.
  • Example C-12 A reaction mixture is prepared by the addition of 3120 parts (24.0 moles) of 2-ethylhexanol and 444 parts (6.0 moles) of isobutyl alcohol. With nitrogen blowing at 1.0 cubic feet per hour, 1540 parts (6.9 moles) of P_S 5 is added to the mixture over a two-hour period while maintaining the temperature at 60-78 ⁇ C. The mixture is held at 75"C for one hour and is stirred an additional two hours while cooling. The mixture is filtered through diatomaceous earth.
  • Example C-13 A slurry i ⁇ prepared by the addition of 486.6 part ⁇ (.11.86 eguivalent ⁇ ) of ZnO and 243.1 part ⁇ diluent oil. With medium ⁇ peed ⁇ tirring 1204 part ⁇ (3.6 equivalents) of 0,0-di(4-methyl-2-pentyl)pho ⁇ phorodithioic acid are added to the ⁇ lurry and the temperature of the resulting mixture is increased from 56*C to 87'C over a period of 20 minutes. 2407 parts (7.2 equivalents) of 0,0-di-(4-methyl-2-pentyl)pho ⁇ phorodithioic acid are added to the mixture. The temperature of the mixture i ⁇ maintained at 86 ⁇ C for 4 hour ⁇ .
  • Example C-14 The process of Example C-l is repeated replacing the zinc oxide with about 1.15 equivalents of cuprou ⁇ oxide.
  • Example C-15 The proce ⁇ of Example C-l i ⁇ repeated employing O,O-di(2-ethylhexyl)pho ⁇ phorodithioic acid.
  • Example C-l6 The proce ⁇ s of Example C-15 is repeated employing 1 equivalent of copper (I) oxide for each equivalent of zinc oxide.
  • the triazole which may be used in this invention may be benzotriazole and alkyl-substituted benzotriazole.
  • the alkyl sub ⁇ tituent generally contain ⁇ up to 15 carbon atom ⁇ , preferably up to 8 carbon atom ⁇ .
  • the triazole ⁇ may contain other ⁇ ub ⁇ tituent ⁇ on the aromatic ring ⁇ uch a ⁇ halogens and nitro groups.
  • Example ⁇ of suitable compounds are benzotiazole and the tolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles, octylbenzotriazoles, chlorobenzo- triazole ⁇ and nitrobenzotriazole ⁇ .
  • Benzotriazole and tolyltriazole are particularly preferred.
  • the amount of triazole included in the compo ⁇ ition generally i ⁇ le ⁇ than 5%, more often le ⁇ than 1% by weight.
  • the compo ⁇ ition of the invention is to be u ⁇ ed in a lubricating oil ⁇ uch a ⁇ a hydraulic fluid, only ⁇ mall amounts of the triazole compound are required to obtain improved hydrolytic stability.
  • the composition of the invention will contain an amount of triazole compound which will provide an additive concentrate for lubricants and functional fluid which contains as little as 100 ppm of the triazole and preferably les ⁇ than 50 ppm of the triazole.
  • the composition ⁇ of the invention are prepared to provide the lubricant or functional fluid with a stabilizing amount of the triazole which generally is less than 20 ppm, and may be les ⁇ than 3 ppm of finished lubricant or functional fluid.
  • ba ⁇ i ⁇ other known additives which include, but are not limited to, disper ⁇ ant ⁇ , detergent ⁇ , antioxidant ⁇ , anti-wear agent ⁇ , extreme pre ⁇ ure agent ⁇ , emulsifiers, demul ⁇ ifier ⁇ , foam inhibitors, friction modifier ⁇ , anti-ru ⁇ t agents, corrosion inhibitors, visco ⁇ ity improver ⁇ , pour point depre ⁇ ant ⁇ , dyes, and solvents to improve handleability which may include alkyl and/or aryl hydrocarbons.
  • additives may be present in various amounts depending on the intended application for the final product or may be excluded therefrom.
  • Di ⁇ persants include, but are not limited to, hydrocarbon ⁇ ub ⁇ tituted succinimides, ⁇ uccinamides, carboxylic ester ⁇ , Mannich di ⁇ per ⁇ ant ⁇ and mixture ⁇ thereof a ⁇ well a ⁇ material ⁇ functioning both a ⁇ di ⁇ per ⁇ ant ⁇ and vi ⁇ co ⁇ ity improver ⁇ .
  • the di ⁇ per ⁇ ant ⁇ include nitrogen-containing carboxylic di ⁇ per ⁇ ant ⁇ , e ⁇ ter dispersants, Mannich dispersant ⁇ or mixture ⁇ thereof.
  • Nitrogen-containing carboxylic di ⁇ per ⁇ ant ⁇ are prepared by reacting a hydrocarbyl carboxylic acylating agent (u ⁇ ually a hydrocarbyl ⁇ ub ⁇ tituted ⁇ uccinic anhydride) with an amine (u ⁇ ually a polyamine) .
  • E ⁇ ter di ⁇ per ⁇ ants are prepared by reacting a polyhydroxy compound with a hydrocarbyl carboxylic acylating agent.
  • the ester disper ⁇ ant may be further treated with an amine.
  • Mannich dispersants are prepared by reacting a hydroxy aromatic compound with an amine and aldehyde.
  • the di ⁇ per ⁇ ant ⁇ li ⁇ ted above may be post-treated with reagents such as urea, thiourea, carbon disulfide, aldehydes, ketone ⁇ , carboxylic acid ⁇ , hydrocarbon ⁇ ub ⁇ tituted succinic anhydride, nitrile ⁇ , epoxides, boron compounds, phosphoru ⁇ compounds and the like.
  • reagents such as urea, thiourea, carbon disulfide, aldehydes, ketone ⁇ , carboxylic acid ⁇ , hydrocarbon ⁇ ub ⁇ tituted succinic anhydride, nitrile ⁇ , epoxides, boron compounds, phosphoru ⁇ compounds and the like.
  • the ⁇ e di ⁇ per ⁇ ant ⁇ are generally referred to a ⁇ ashless dispersants even though they may contain element ⁇ such as boron or phosphoru ⁇ which, on decompo ⁇ ition, will leave a non-metallic re ⁇
  • Extreme pressure agent ⁇ and corrosion- and oxidation-inhibiting agent ⁇ include chlorinated compound ⁇ , ⁇ ulfurized compound ⁇ , phosphorus containing compounds including, but not limited to, phospho ⁇ ulfurized hydrocarbons and phosphoru ⁇ ester ⁇ , metal containing compounds and boron containing compounds.
  • Chlorinated compound ⁇ are exemplified by chlorinated aliphatic hydrocarbons ⁇ uch a ⁇ chlorinated wax.
  • Example ⁇ of ⁇ ulfurized compounds are organic sulfides and polysulfides ⁇ uch a ⁇ benzyl disulfide, bi ⁇ (chlorobenzyl)di ⁇ ulfide, dibutyl tetra ⁇ ulfide. ⁇ ulfurized methyl e ⁇ ter of oleic acid, ⁇ ulfurized alkylphenol, ' ⁇ ulfurized dipentene, and sulfurized terpene.
  • Pho ⁇ pho ⁇ ulfurized hydrocarbons include the reaction product of a phosphorus sulfide with turpentine or methyl oleate.
  • Pho ⁇ phoru ⁇ e ⁇ ters include dihydrocarbon and trihydrocarbon phosphite ⁇ , pho ⁇ phate ⁇ and metal and amine salt ⁇ thereof.
  • Pho ⁇ phite ⁇ may be repre ⁇ ented by the following formulae:
  • each R 5 is independently hydrogen or a hydrocarbon based group, provided at least one R 5 is a hydrocarbon based group.
  • each R 5 is independently a hydrogen or hydrocarbon based group having from 1 to about 24, more preferably from 1 to about 18, and more preferably from about 2 to about 8 carbon atoms, provided that at least one R 5 is a hydrocarbon based group.
  • Each R 5 may be independently alkyl, alkenyl or aryl. When 5 is aryl it contains at least 6 carbon atoms; preferably 6 to about 18 carbon atom ⁇ . Examples of alkyl or alkenyl group ⁇ are propyl, butyl, hexyl, heptyl, octyl, oleyl, linoleyl, ⁇ tearyl, etc.
  • Example ⁇ of aryl group ⁇ are phenyl, naphthyl, heptylphenyl, etc.
  • each R 5 is independently propyl, butyl, pentyl, hexyl, heptyl, oleyl or phenyl, more preferably butyl, oleyl or phenyl and more preferably butyl or oleyl.
  • the R groups may also comprise a mixture of hydrocarbyl groups derived from commercial alcohols.
  • Alfol 810 is a mixture containing alcohols consi ⁇ ting e ⁇ entially of ⁇ traight-chain, primary alcohol ⁇ having 8 to 10 carbon atom ⁇ .
  • Alfol 812 i ⁇ a mixture compri ⁇ ing mo ⁇ tly C. - fatty alcohol ⁇ .
  • Alfol 1218 i ⁇ a mixture of ⁇ ynthetic, primary, ⁇ traight-chain alcohol ⁇ having from 12 to 18 carbon atoms.
  • Alfol 20+ alcohols are mixtures of 18-28 primary alcohols having mo ⁇ tly, on an alcohol ba ⁇ i ⁇ , C_ 0 alcohol ⁇ as determined by GLC (ga ⁇ -liguid- chromatography) .
  • Another group of commercially available alcohol mixture ⁇ includes the "Neodol” product ⁇ available from
  • Neodol 91 i ⁇ a mixture of
  • Pho ⁇ phite ⁇ and their preparation are known and many pho ⁇ phites are available commercially.
  • Particularly useful phosphite ⁇ are dibutylhydrogen phosphite, trioleyl phosphite and triphenyl phosphite.
  • Preferred phosphite ester ⁇ are generally dialkyl hydrogen pho ⁇ phites.
  • dialkyl hydrogen phosphites are commercially available, such as lower dialkyl hydrogen phosphite ⁇ , which are preferred.
  • Lower dialkyl hydrogen phosphite ⁇ include dimethyl, diethyl, dipropyl, dibutyl, dipenyl and dihexyl hydrogen pho ⁇ phite ⁇ .
  • Phosphate ester ⁇ include mono-, di- and trihydrocarbon-based phosphate ⁇ of the general formula
  • R_ is as defined for the pho ⁇ phite ⁇ described hereinabove.
  • Example ⁇ include mono-, di- and trialkyl ; mono-, di and triaryl and mixed alkyl and aryl.
  • Specific, non-limiting example ⁇ include, tri lower alkyl phosphate, dialkyl phosphates, and the like.
  • Particularly preferred are the reaction products of phosphoru ⁇ pentoxide (P ° c ) with alcohol ⁇ in a ratio of 3 hydroxyl group ⁇ to one P 2 0 5 yielding a mixture of mono- and dialkyl phosphates.
  • mixed alkyl hydrogen phosphite ⁇ are u ⁇ eful in the pre ⁇ ent invention.
  • Example ⁇ of mixed alkyl hydrogen pho ⁇ phite ⁇ include ethyl, butyl; propyl, pentyl; and methyl, pentyl hydrogen pho ⁇ phite ⁇ .
  • Metal containing compound ⁇ include > metal thiocarbamate ⁇ , ⁇ uch as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate and molybdenum compounds.
  • Boron containing compounds include borate esters and boron-nitrogen containing compounds prepared, for example, by the reaction of boric acid with a primary or secondary alkyl amine.
  • Viscosity improvers include, but are not limited to, polyisobutene ⁇ , polymethacrylate acid e ⁇ ter ⁇ , polyacrylate acid e ⁇ ters, diene polymers, polyalkyl styrene ⁇ , alkenyl aryl conjugated diene copolymer ⁇ , polyolefin ⁇ and multifunctional vi ⁇ co ⁇ ity improver ⁇ .
  • Pour point depre ⁇ ant ⁇ are a particularly u ⁇ eful type of additive often included in the lubricating oils described herein. See for example, page 8 of "Lubricant Additives” by C. V. Smalheer and R. Kennedy Smith (Lesius-Hile ⁇ Company Why it was not included in the lubricating oils described herein.
  • Anti-foam agent ⁇ u ⁇ ed to reduce or prevent the formation of ⁇ table foam include ⁇ ilicone ⁇ or organic polymers.
  • Example ⁇ of the ⁇ e and additional anti-foam compo ⁇ ition ⁇ are de ⁇ cribed in "Foam Control Agent ⁇ ", by Henry T. Kerner (Noye ⁇ Data Corporation, 1976) , pages 125-162.
  • the components may be blended together in any suitable manner and then admixed, for example with a diluent to form a concentrate a ⁇ discussed below, or with a lubricating oil, a ⁇ discussed below.
  • components can be admixed separately with such diluent or lubricating oil.
  • the triazole if used, be dis ⁇ olved fir ⁇ t in the diluent by heating to a temperature of about 80-90*C followed by cooling before the remaining component ⁇ are blended into the diluent.
  • the blending technique for mixing the component ⁇ i ⁇ not critical and can be effected u ⁇ ing any ⁇ tandard technique, depending upon the specific nature of the material ⁇ employed. In general, blending can be accompli ⁇ hed at room temperature; however, blending can be facilitated by heating the component ⁇ .
  • the compo ⁇ ition ⁇ of the pre ⁇ ent invention are u ⁇ eful a ⁇ additive ⁇ for lubricant ⁇ and functional fluid ⁇ . They can be employed in a variety of lubricant ⁇ ba ⁇ ed on diverse oils of lubricating visco ⁇ ity, including natural and ⁇ ynthetic lubricating oil ⁇ and mixture ⁇ thereof.
  • the lubricant ⁇ include crankcase lubricating oil ⁇ for ⁇ park-ignited and compre ⁇ sion-ignited internal combu ⁇ tion engine ⁇ , including automobile and truck engine ⁇ , two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. Also contemplated are lubricants for gas engines, stationary power engine ⁇ and turbine ⁇ and the like.
  • thi ⁇ invention provides ⁇ pecial benefits when the composition is exposed to water.
  • the lubricating compositions and methods of thi ⁇ invention employ an oil of lubricating viscosity, including natural or synthetic lubricating oils and mixtures thereof.
  • Natural oils include animal oils, vegetable oils, mineral lubricating oils, solvent or acid treated mineral oils, and oils derived from coal or shale.
  • Synthetic lubricating oils include hydrocarbon oils, halo-sub ⁇ tituted hydrocarbon oil ⁇ , alkylene oxide polymer ⁇ , e ⁇ ter ⁇ of carboxylic acids and polyols, esters of polycarboxylic acids and alcohol ⁇ , esters of phosphorus-containing acids, polymeric tetrahydrofurans, ⁇ ilicon-ba ⁇ ed oil ⁇ and mixture ⁇ thereof.
  • Patent 4,582,618 (column 2, line 37 through column 3, line 63, inclusive), herein incorporated by reference for its disclosure to oils of lubricating visco ⁇ ity.
  • Component (A) and component (B) are generally u ⁇ ed in relative amount ⁇ of A:B ranging from about 5:1 to about 1:5, more often from about 2:1 to about 1:2, by weight.
  • Components (B) and (C) are utilized in amounts within the above-specified amounts relative to component (A).
  • composition ⁇ of thi ⁇ invention are u ⁇ eful a ⁇ additive ⁇ for a wide variety of lubricating compo ⁇ ition ⁇ .
  • Preferred lubricating compo ⁇ ition ⁇ are functional fluid ⁇ , with hydraulic fluid ⁇ being particularly preferred.
  • the following are non-limiting example ⁇ of lubricating compositions of this invention.
  • Example 6 To a 100 neutral mineral oil base ⁇ tock i ⁇ added, with mixing and gentle heating, 1% by weight of the product of Example A-l, 0.3% by weight of the product of Example B-4, and 0.01 percent by weight of a ⁇ ilicone antifoam.
  • Example 7 To a mineral oil ba ⁇ e ⁇ tock (250 neutral) i ⁇ added 0.85 percent by weight of the additive concentrate of Example 1.
  • Example 8 Example 7 i ⁇ repeated except additive concentrate of Example 1 i ⁇ replaced with that of Example 4.
  • Example 9 To the lubricating oil compo ⁇ ition of Example 6 i ⁇ added 0.05% by weight of the product of Example C-l.
  • Example 10 To Sun Tul ⁇ a ISO 46 ba ⁇ e oil i ⁇ added 0.81 percent by weight of the additive concentrate of Example 3.
  • Example 11 To Sun Tul ⁇ a ISO 46 ba ⁇ e oil i ⁇ added 0.1 percent by weight of the additive concentrate of Example 2.
  • Example 12 Example 7 i ⁇ repeated except the additive concentrate of Example 4 replace ⁇ that of Example 1.
  • Example 13 To a hydraulic fluid ba ⁇ e ⁇ tock (ISO 46) i ⁇ added 0.1 part ⁇ of dibutyl hydrogen pho ⁇ phite, 0.01 parts of tolyltriazole, 0.1 parts of a magnesium salicylate, 0.05 part ⁇ of the reaction product of propylene oxide with tetrapropenyl ⁇ uccinic anhydride, 0.2 parts of tricresyl phosphate, 0.25 part ⁇ of hindered phenol, 0.25 parts of di(nonylphenyl) amine and 0.05 parts of the product of Example B-7.
  • ISO 46 i ⁇ added 0.1 part ⁇ of dibutyl hydrogen pho ⁇ phite, 0.01 parts of tolyltriazole, 0.1 parts of a magnesium salicylate, 0.05 part ⁇ of the reaction product of propylene oxide with tetrapropenyl ⁇ uccinic anhydride, 0.2 parts of tricresyl phosphate, 0.25 part ⁇ of hindered phenol, 0.25 parts of di
  • Example 14 A hydraulic fluid is prepared according to the procedure of Example 13 replacing 0.05 parts of the product of Example B-7 with 0.03 parts of the product of Example B-6.
  • Example 15 A compo ⁇ ition compri ⁇ ing an oil of lubricating vi ⁇ co ⁇ ity, 0.85 percent by weight of the product of Example A-4, 0.15 part ⁇ of the product of Example B-6, 0.2 parts of hindered phenol, 0.002 percent by weight of tolyltriazole and 0.01 percent by weight of an organic polymer antifoam.
  • Example 16 The composition of Example 7 replacing the product of Example C-ll with that of Example C-16.
  • the filterability of hydraulic fluids can be determined employing the AFNOR E48-690/1 test published by 1"Association Francaise DeNormali ⁇ ation, Tour Europe Cedex 7 92 080 Pari ⁇ -La Defense, France. This test - 62 -
  • Filterability indice ⁇ of the fluid (IF ⁇ and IF 2 ) are defined for a given fluid by the ratio ⁇ :
  • T_ 00 is the pas ⁇ age time, through the membrane, of 100 cm of fluid
  • a modification of thi ⁇ te ⁇ t entail ⁇ the u ⁇ e of a water-treated fluid.
  • the mixture is agitated, then stored. After the aging period, the water-treated fluid is evaluated as above.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Earth Drilling (AREA)
  • Paper (AREA)
EP92915925A 1991-07-31 1992-07-15 Verwendung einer Additivzusammensetzung zur Verbesserung der Filtrierbarkeit von mit Wasser kontaminierten Schmiermittelzusammensetzungen Revoked EP0551466B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US73901791A 1991-07-31 1991-07-31
US739017 1991-07-31
PCT/US1992/005928 WO1993003121A1 (en) 1991-07-31 1992-07-15 Improved lubricating compositions and additives useful therein

Publications (2)

Publication Number Publication Date
EP0551466A1 true EP0551466A1 (de) 1993-07-21
EP0551466B1 EP0551466B1 (de) 1998-06-17

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EP (1) EP0551466B1 (de)
JP (1) JP3212603B2 (de)
AT (1) ATE167512T1 (de)
AU (1) AU658218B2 (de)
CA (1) CA2088768A1 (de)
DE (1) DE69225947T2 (de)
ES (1) ES2119816T3 (de)
FI (1) FI931039A0 (de)
MX (1) MX9204467A (de)
NO (1) NO931202L (de)
WO (1) WO1993003121A1 (de)

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US5380448A (en) * 1994-02-07 1995-01-10 Ethyl Petrolium Additives, Inc. Process for metal salts of hydrocarbyl dithiophosphoric acid
GB9416838D0 (en) 1994-08-19 1994-10-12 Bp Chemicals Additives Overbased metal salts, their preparation and use
US5726133A (en) * 1996-02-27 1998-03-10 Exxon Research And Engineering Company Low ash natural gas engine oil and additive system
FR2762006B1 (fr) * 1997-04-11 2003-09-12 Chevron Res & Tech Utilisation de surfactants de haut poids moleculaire comme agents ameliorant la filtrabilite dans des lubrifiants hydrauliques
EP1078977B1 (de) * 1999-07-30 2010-01-27 Afton Chemical Limited Schmiermittelzusammensetzungen
US7435709B2 (en) * 2005-09-01 2008-10-14 Chevron Oronite Company Llc Linear alkylphenol derived detergent substantially free of endocrine disruptive chemicals
JP5230607B2 (ja) 2006-04-24 2013-07-10 ザ ルブリゾル コーポレイション 星形ポリマー潤滑組成物
US9771540B2 (en) 2009-01-20 2017-09-26 Exxonmobil Research And Engineering Company Hydraulic oil compositions with improved hydraulic motor efficiency
CN102356146A (zh) 2009-01-20 2012-02-15 卢布里佐尔公司 具有改进的抗磨特性的液压组合物
CA2801249A1 (en) 2010-06-02 2011-12-08 The Lubrizol Corporation Lubricating composition containing a carboxylic functionalised polymer

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GB1037985A (en) * 1963-02-19 1966-08-03 Cheuron Res Company Alkylbutyrolactone-ª‡-acetic acids
MX162168A (es) * 1981-09-14 1991-04-04 Lubrizol Corp Composicion lubricante mejorada para reducir el consumo de combustible
US4502970A (en) * 1982-06-08 1985-03-05 Exxon Research & Engineering Co. Lubricating oil composition
US4466894A (en) * 1983-04-20 1984-08-21 The Lubrizol Corporation Phosphorus-containing metal salts/sulfurized phenate compositions/aromatic substituted triazoles, concentrates, and functional fluids containing same
CA2030481C (en) * 1990-06-20 1998-08-11 William B. Chamberlin, Iii Lubricating oil compositions for meoh-fueled diesel engines

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Title
See references of WO9303121A1 *

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ES2119816T3 (es) 1998-10-16
AU2339692A (en) 1993-03-02
DE69225947T2 (de) 1999-03-25
NO931202D0 (no) 1993-03-30
JP3212603B2 (ja) 2001-09-25
WO1993003121A1 (en) 1993-02-18
JPH06502682A (ja) 1994-03-24
AU658218B2 (en) 1995-04-06
MX9204467A (es) 1994-06-30
NO931202L (no) 1993-05-14
ATE167512T1 (de) 1998-07-15
EP0551466B1 (de) 1998-06-17
CA2088768A1 (en) 1993-02-01
FI931039A (fi) 1993-03-09
FI931039A0 (fi) 1993-03-09
DE69225947D1 (de) 1998-07-23

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