JPH05508186A - lubricating composition - Google Patents

Abstract

The invention relates to a lubricating oil composition, comprising: a major amount of an oil of lubricating viscosity; and (A) an amount of at least one alkali metal overbased salt of an acidic organic compound to provide at least about 0.0019 equivalents of alkali metal per 100 grams of the lubricating composition; (B) at least about 1.60 % by weight of at least one dispersant; (C) at least one metal dihydrocarbyl dithiophosphate; (D) at least one antioxidant; and (E) at least one magnesium overbased metal salt of an acidic organic compound provided that the lubricating oil composition is free of calcium overbased sulfonate and calcium overbased phenate; provided that the composition contains less than about 0.08 % by weight calcium; and provided that (C) and (D) are not the same.

Description

[Detailed description of the invention] 1 and 7 ldan dongdan! The present invention provides an overbased alkali of at least one acidic organic compound. metal salt, at least one dispersant, at least one metal salt of dithiophosphate, less at least one antioxidant and at least one acidic organic compound magnesium The present invention relates to lubricating oil compositions containing metal overbased salts.

μjiυ1 theory Engines, especially spark ignition engines and diesel engines, preferably spark ignition engines As the power and complexity of ignition engines increases, lubricants such as: performance requirements for lubricants are increasing. This lubricant deteriorates under the conditions of use. less tendency to form A lubricating oil that tends to reduce the formation of sludge, carbonaceous materials and residues. Ru. These deposits adhere to various engine parts and reduce the efficiency of the engine. There is a tendency to

An alkaline earth metal detergent is used to suspend decomposition products in motor oil; Neutralizes acid products in engine oil. This alkaline earth metal is usually calcium detergents, especially overbased calcium sulfonates or calcium It is phenate.

Canadian Patent No. 1,055.700 discloses basic alkali metal sulfonate dispersions. and on methods. U.S. Pat. No. 4,326,972 discloses a fuel for internal combustion engines. Concentrates, lubricating compositions and methods that improve economy. These compositions are Contains as essential ingredients a specific sulfide composition and basic alkali metal sulfonates. do. US Pat. No. 4,904,401 relates to lubricating oil compositions. these pairs The composition comprises at least lti of basic alkali metal sulfonic or carboxylic acids. May contain salt. U.S. Pat. No. 4,938,881 discloses lubricating oil compositions and concentrates. relating to things. These compositions and concentrates contain sulfonic or carboxylic acids. At least one basic alkali metal salt is included. U.S. Patent No. 4.952. No. 3211 relates to lubricating oil compositions. These compositions contain sulfonic acids or carbon from about 0.01% to about 2% by weight of at least one basic alkali metal salt of rubonic acid. Contained in weight%.

l 匪dan1且 The present invention comprises a major amount of oil of lubricating viscosity and the following (A), (B), (C), Regarding a lubricating oil composition containing (D) and (E): (A) The lubricating composition 10 per 0 grams, the acid provides a small amount (about 0.001 g equivalent) of alkali metal. (B) at least one alkali metal overbased salt of the organic compound; (C) at least about 1.60% by weight of at least one dispersant; (C) at least one dispersant; hydrocarpyldithiophosphate metal salt (D) at least one antioxidant; and (E) At least one magnesium overbased metal salt of an acidic organic compound : However, the lubricating oil composition contains overbased calcium sulfonate and Contains no bar-based calcium phenate, the composition contains about o, og % contains more calcium, and (C) and (D) are not the same.

1 rabbit presentation plate The term "hydrocarpyl" includes hydrocarbon groups and substantive hydrocarbon groups. Ru. A substantial hydrocarbon group is primarily a non-hydrocarbon group that does not change the hydrocarbon nature of the group. Indicates a group having an elementary substituent.

Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e. aliphatic substituents (e.g. alkyl or alkenyl), cyclic substituents (e.g. (e.g., cycloalkyl or cycloalkenyl), aromatic substituted aromatic substituents , aliphatic-substituted aromatic substituents and ring-substituted aromatic substituents, and cyclic substituents, etc. Here, the ring of this cyclic substituent is completely (i.e., for example, any two indicated substituents are - together) (can form a ring group).

(2) substituted hydrocarbon substituents, i.e., these substituents are non-hydrocarbon groups; Contains. This non-hydrocarbon group, within the context of the present invention, is primarily a hydrocarbon substituted does not change the group; such groups, such as halo (particularly chloro and fluoro) ), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nito lon, sulhogyushi, etc.) are known to those skilled in the art; (3) heterosubstituents, i.e., within the context of the present invention, are primarily hydrocarbon in nature; has carbon atoms other than those present in the chain or ring, but other carbon atoms are present in the chain or ring. It is a group composed of children. Suitable heteroatoms will be clear to those skilled in the art and may be Examples include sulfur, oxygen and nitrogen. Such substituents include, for example, pyri Examples include zyl, frill, chenyl, and imidazolyl. Generally, this hydrocarbyl For each 10 carbon atoms, no more than ), preferably no more than one non-hydrocarbon substituent of non-hydrocarbon substituents are present. This hydrocarbyl group is often There are no other non-hydrocarbon substituents present, and this hydrocarbyl group is a pure carbon It is hydrogen.

Throughout this specification and claims, unless indicated otherwise, the weight percentages of the various ingredients are References to cents are chemical standards.

The equivalent weight of an amine or polyamine is the molecular weight of the amine or polyamine. It is the value divided by the total number of nitrogens present in the child. The number of equivalents of this acylating agent is then depends on the total number of carboxylic acid functionalities present. Formed by carboxylic acid ester derivatives The equivalent weight of hydroxyamine used to form The value divided by the number of nitrogen atoms present is ignored. Reacts with this acylating agent The equivalent weight of hydroxy-substituted amine to form a carboxylic acid amine derivative is It is the value obtained by dividing the molecular weight by the total number of nitrogen groups present in the molecule.

The equivalent weight of a polyhydric alcohol is calculated by dividing its molecular weight by the total number of hydroxyl groups present in the molecule. This is the value.

In the terms "substituent" and "acylating agent" or "substituted monopolic acid acylating agent" are given their usual meaning.

For example, a substituent is replaced with another atom or group within a molecule as a result of a reaction. An atom or group of atoms. The term for acylating agent or substituted succinic acylating agent is , refers to the compound itself and refers to this acylating agent or substituted co/percent acylating agent does not include unreacted reactants used to form.

A Arshika 1 Overbase: The lubricating composition of the present invention comprises: A) an alkali metal overbased salt of an acidic organic compound; Contains. This O/K-based salt contains metals and specific compounds that react with the metals. by a metal content in excess of the amount that would be present according to the stoichiometry of the organic compound. It is a characterized single-phase, homogeneous Newtonian system. Excess amounts of metal are usually Expressed in terms of metal ratios. The term "metal ratio" refers to the equivalent amount of acidic organic compound. It is the ratio of the total equivalents of metals.

A salt with 4.5 times as much metal as is present in the normal salt has a 3.5 equivalent excess of metal, That is, it has a metal ratio of 4.5. In the present invention, these salts are preferably about A metal ratio of 1.5 to about 40, preferably a metal ratio of about 3 to about 30, more preferably It has a metal ratio of about 3 to about 25.

This overbased material converts acidic substances (typically carbon dioxide) into a reaction medium comprising at least one inert organic solvent for the acidic organic substance; , a stoichiometric excess of a metal compound (typically a metal hydroxide or metal oxide) ) and a promoter. Other implementation In embodiments, the basic alkali metal salt separates water from the acidic organic compound, the reaction medium and It is prepared by reacting with a mixture containing a stimulant and an accelerator. These metal salts and methods of their manufacture are described in U.S. Pat. No. 4.627.928. . This disclosure is set forth herein.

These acidic organic compounds include carboxylic acids, sulfonic acids, phosphorus-containing acids, and phenols. and derivatives thereof. Preferably, this overbase Substances are prepared from carboxylic or sulfonic acids. This carboxylic acid and sulfonic acids may have substituents derived from polyalkenes. This polya Lukene has at least about 8 carbon atoms, preferably at least about 30 carbon atoms. from carbon atoms, more preferably from at least about 35 carbon atoms, from about 300 carbon atoms, preferably about 200 carbon atoms, more preferably about 10 carbon atoms Characterized as having up to 0 carbon atoms. In one embodiment, this The polyalkene has a number average molecular weight of at least about 400, preferably about 500. quantity) is characterized by its value. Generally, the polyalkene ranges from about 500 to Preferably from about 700, more preferably from about 800, even more preferably from about 900 to about 5000, preferably about 2500, more preferably characterized by an h value of up to about 2000, even more preferably up to about 1500. It will be done. In other embodiments, the basket is from about 500, preferably from about 700, and even more. preferably varies from about 800 to about 1200 or 1300.

The abbreviation is a common symbol representing number average molecular weight. Gelver Mini - Silane Chroma (GPC) determines both the weight average molecular weight and number average molecular weight of the polymer. and a method that gives the total molecular weight distribution of this polymer. For the purposes of this invention, iso Polyisobutyne, a series of fractionated polymers of butyne, has been used as a calibration standard for GPC. used.

These polyalkenes contain from 2 to about 16 carbon atoms, usually from 2 to about 6 carbon atoms. elementary atoms, preferably 2 to about 4 carbon atoms, more preferably 4 carbon atoms Including homopolymers and interpolymers of polymerizable olefinic moles 7- be done. These olefins are monoolefins (e.g. ethylene, propylene 1-butene, isobutene and 1-octene), or polyolefinic molecules monomers, preferably diolefinic monomers (e.g. 1,3-butadiene and and isoprene). Preferably the interpolymer is a homopolymer. Ru. Examples of preferred homopolymers include polybutene, preferably about 50% of the polymer. There are polybutenes derived from inbutylene. These polyalkenes are usually It is prepared by the method of

Suitable carboxylic acids from which useful alkali metal salts can be prepared include acetylenically unsaturated Aliphatic, cycloaliphatic and aromatic monobasic carboxylic acids and polysalts with no sum Basic carboxylic acids include naphthenic acid, alkyl-substituted or Kenyl III cyclopentanoic acid, and alkyl-substituted or alkenyl-substituted cyclopentanoic acid rohesanoic acids, preferably alkenyl-substituted succinic acids or anhydrides thereof. Ru. These aliphatic acids generally have about 8 to about 50 carbon atoms, preferably about It has 12 to about 25 carbon atoms. Cycloaliphatic carboxylic acids and aliphatic carboxylic acids Bonic acids are preferred; they may be saturated or unsaturated.

Exemplary carboxylic acids include 2-ethyl hexanic acid, palmitic acid, stearic acid, myristic acid, oleic acid, linoleic acid, behenic acid, hexatriacontanoic acid, Tetrapropylene-substituted glutaric acid, polybutene (Mn is about 200-1500. preferably equal to about 300-1500, more preferably about 800-1200 ) polybutenyl-substituted succinic acid, polypropene (fil is 200 ~2000, preferably about 300-1500, more preferably about 800-12 polypropylene-substituted succinic acid, petrolatum or is an acid formed by the oxidation of a hydrocarbon wax, two or more carboxylic acids, e.g. , tall oil acids and rosin acids), octadecyl-substituted adipic acids, Lorostearic acid, 9-methylstearic acid, dichlorostearic acid, stearic acid Benzoic acid, eicosane-substituted naphthoic acid, dilauryl-decahydro-naphthalene Carboxylic acids and mixtures of these acids, their metal salts and/or their Anhydrides of.

In other embodiments, the carboxylic acid is alkyloxyalkylene-acetic acid or Alkylphenoxy-acetic acid, more preferably alkylpolyoxydialkylene- Acetic acid or its salts. Certain examples of these compounds include: Isostearyl pentaethylene glycol acetic acid; Isostearyl-0- (CH2CH20)scH2cO2Na Nilauryl-〇-(CH2CH20) 25CH2C02)! ;Lauryl punishment-(CH2Cl(20)z3cH2cOJ ;oleyl-〇-(CH2CH20)acH2co2H;lauryl-0-(CH 2CH20)J, 5CH2CO2)1 Nilauryl-〇-(CH2CH20)+ θC)12CO2)1; lauryl-〇-(CH2CH20)+8ct12c Q2H; octyl-phenyl-〇-(CH2CH20)I]CH2C02H; Cutyl-phenyl-〇-(CH2CH20)+5CH2CChH; 2-octyl Rudecanyl-0(CH2CH20)sC)12GO2Ho These acids are Sandopan acid products from Sandoz Chemical It is marketed under the name

In a preferred implementation, the carboxylic acid is an aromatic carboxylic acid. useful aroma The group of aromatic carboxylic acids includes those of the formula: Here, R1 is preferably an aliphatic hydrocarbon derived from the above polyalkene. is a building group, a is a number ranging from 0 to about 4, usually 1 or 2, and Ar is an aromatic group group, each X is independently sulfur or oxygen, preferably oxygen, b is a number ranging from 1 to about 4, typically 1 to 2, and C is a number ranging from 0 to about 4, typically Usually 1 to 2, provided that the sum of a, b and C does not exceed the valence number of Ar. stomach. Examples of aromatic acids include substituted and unsubstituted benzoic acids, phthalic acids, and saline acids. Includes lytic acid.

This R1 group is a hydrocarbyl group directly bonded to the aromatic group Ar. R1 group Examples include substituents derived from the following polymerized olefins: tyrene, polypropylene, polyisobutylene, ethylene-propylene copolymer, Chlorinated olefin polymers and oxidized ethylene-propylene copolymers body.

The aromatic group Ar can have the same structure as any of the aromatic groups Ar discussed below.

Examples of aromatic groups useful here include benzene, naphthalene, anthracene, etc. Preferably, polyvalent aromatic groups derived from benzene) are included. Specification of Ar group Examples include phenylene and naphthylene, e.g. methylphenylene, ethoxyphthylene Phenylene, isopropylphenylene, hydrobovine diphenylene, dipropoxynaf Includes tyrene and the like.

Among this group of aromatic acids, the most useful carboxylic acids include those of the formula: where R1 is as defined above and a is a number ranging from 0 to about 4, preferably b is a number ranging from 1 to about 3; b is a number ranging from 1 to about 4, preferably 1 to about 2; a number in the range, C is a number in the range from 0 to about 4, preferably a number in the range from 1 to about 2; More preferably, it is 1; provided that the sum of asb and C does not exceed 6.

Preferably b and C are each 1 and the carboxylic acid is salicylic acid. It is.

The salicylic acid is preferably an aliphatic hydrocarbon substituted salicylic acid.

Overbased salts prepared from salicylic acid are particularly useful, such as: In this salicylic acid, the aliphatic hydrocarbon substituents include the polyalkenes mentioned above, especially polymerized lower 1-monoolefins (e.g. polyethylene, polypropylene, poly isobutylene, ethylene/propylene copolymers, etc.), and Based on average molecular weight, it has an average carbon content of about 50 to about 400 carbons.

The above aromatic carboxylic acids are well known or can be prepared according to methods well known in the art. It can be prepared by Carboxylic acids of the types exemplified by these formulas, and their Methods for the preparation of neutral and basic metal salts are well known and are described, for example, in U.S. Pat. ．． No. 197,832: No. 2.197,835; No. 2.252.662; No. 2 ．． No. 252.664; East No. 2.714.092; No. 3.410,798: and It is disclosed in Bicha 3.595 Ba No. 91.

These sulfonic acids preferably contain mono-, di- and tri-aliphatic hydrocarbon groups. It is a converted aromatic sulfonic acid. This hydrocarbon substituent is It can be derived from either. Such sulfonic acids include mahogany sulfonic acid , brightstock sulfonic acid, petroleum sulfonic acid, mo/- and polywax converted naphthalenesulfonic acid, cetylchlorobenzenesulfonic acid, cetylphenol Sulfonic acid, cetylphenol disulfide sulfonic acid, cetoxylic acid prilbene Zenesulfonic acid, dicetylthianthrenesulfonic acid, dilauryl-β-naphthol Rusulfonic acid, cicapril nitronaphthalene sulfonic acid, saturated paraffin wax Sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin 7x sulfonic acid, tetraisobutylene sulfonic acid, tetraamylene sulfonic acid Phonic acid, chloro-substituted paraffin wax Sulfonic acid, nitroso-substituted paraffin wax xsulfonic acid, cetylcyclopentylsulfonic acid, laurylcyclohexyl Sulfonic acids, mono- and polywax substituted cyclohexyl sulfonic acids, dodecyl Rubenzenesulfonic acid, didodecylbenzenesulfonic acid, dinonylbenzenesulfonic acid fonic acid, cetylchlorobenzenesulfonic acid, dilauryl-β-naphthalenesulfonate chlorofluoric acid, at least one of the above polyalkenes (preferably polybutene) Sulfonic acid, nitronaphthalene sulfonic acid, paraffin wax sulfonic acid, Treat methylcyclopentanesulfonic acid and laurylcyclo with bovine sansulfonic acid. sulfonic acid derived from polyethylene (Mn=300-1500, Preferably about 600-1500, more preferably about 800-1200, preferably Polybutenyl-substituted sulfonic acids derived from Examples include ``ruchelate'' and sulfonic acid.

Alkyl-substituted benzenesulfonic acid (where this alkyl group has a small number (total of 8) carbon atoms), including dodecylbenzene "bottoms" sulfonic acids, Particularly useful.

The latter is alkylated with propylene tetramer or imbutene trimer, One, two, three or more branched HICl disubstituents on the benzene ring This is an acid derived from benzene that is introduced. Dodecylbenzene bottoms (mainly mixtures of mono- and didodecylbenzenes) from the manufacture of household detergents. It is available as a by-product of Production of linear alkyl sulfonate (LAS) Similar products obtained from alkylated bottoms formed during production may also be used in the present invention. It is useful in producing sulfonate salts.

Preferred groups of sulfonic acids include mono-, di- and trialkylated benzenes. and naphthalene (including their hydrides) sulfonic acids. synthetically Examples of alkylbenzenes and naphthalene sulfonic acids produced include about 8 to about 30 carbon atoms, preferably about 12 to about 30 carbon atoms, advantageously about 24 carbon atoms Some have alkyl substituents with carbon atoms. Such acids include di- Isododecylbenzenesulfonic acid, wax-substituted phenolsulfonic acid, Wa Nox substituted benzene sulfonic acid, polybutenyl substituted sulfonic acid, approx. having a number average molecular weight (Mn) of 00 to 1000, more preferably 500 to 700. Polypropylene-substituted sulfonic acid derived from polypropylene, cetylchloride lobenzenesulfonic acid, dicetylnaphthalenesulfonic acid, dilauryl diphene Nyl ether sulfonic acid, diisononylbenzenesulfonic acid, di-isooctade Included are silbenzenesulfonic acid, stearnaphthalenesulfonic acid, and the like.

For example, the production of sulfonic acids from by-products of detergent production by the reaction of SO37 This is well known to those skilled in the art. For example, Kirk-Othmer's -Encyc ropedia of Chemical Technology-, 2nd edition, Vol, 19. From page 291, John Wiley & 5ons, NY (1969) publication.

Phosphorus-containing acids useful in preparing the salts of the invention include certain phosphorus-containing acids, e.g. , phosphoric acid or its ester; and thiophosphoric acid or its ester. This includes mono- and dithiophosphorus-containing acids or esters thereof.

In a preferred embodiment, the phosphorus-containing acid reacts with the above polyalkene and phosphorus sulfide. It is a reaction product. Useful phosphorus sulfide-containing raw materials include phosphorus trisulfide, phosphorus sesquisulfide, Includes phosphorus heptasulfide, etc.

The reaction of this polyalkene with phosphorus sulfide is generally carried out at temperatures above 80°C, preferably or by simply mixing the two at a temperature between 100°C and 300°C. can be obtained. Generally, these products have a phosphorus content of about O,OS% to about 10%, preferably or having a phosphorus content of about 0.1% to about 5%. for this olefin polymer The relative proportions of phosphating agents are generally as follows: The north side of phosphorus is 0.1 part to 50 parts.

Phosphorus-containing acids useful in the present invention include those published by Le 5uer U.S. Patent No. 3.232. It is described in No. 1H3. The content of this document is A disclosure of containing acids and methods of making them is provided herein.

Phenols useful in making the overbased salts of this invention have the formula (R+) a -Ar-(OH)h. where R7 is defined above; Ar is is an aromatic group; a and b are independently a number of at least 1; The sum is from 2 to the number of replaceable hydrogens on the aromatic nucleus of Ar. Preferably a and b are independently numbers ranging from 1 to about 4, more preferably from 1 to about 4. It is 2. R1 and a are preferably on average small for each phenolic compound. The value is such that at least about 8 aliphatic carbon atoms are provided by the R1 group.

Although the term "phenol" is used here, this term refers to the phenolic aroma. It is understood that there is no intention to limit the family group to benzene. Therefore, in rArJ Aromatic groups represented may be used elsewhere in the specification and appended claims in other formulas. as well as mononuclear (e.g. phenyl, pyridyl, or chenyl) or polynuclear It is understood that it can be sexual. This polynuclear group has one aromatic nucleus attached to two other nuclei. may be of the fused type (eg naphthyl, anthranyl, etc.). child A polynuclear group is also a polynuclear group in which at least two nuclei (either mononuclear or polynuclear) It may also be of a bond type that is bonded by cross-linking. These crosslinks are May be selected from the group consisting of: alkylene bonds, ether bonds, keto bonds, Sulfide bonds, polysulfide bonds having from 2 to about 6 sulfur atoms, and the like.

The number of aromatic nuclei in Ar, whether fused type, bonded type, or both , a and b. For example, Ar has a single aromatic nucleus. In this case, the sum of a and b is 2 to 6. When Ar has two aromatic nuclei , a and b are 2 to 10 in total. In the trinuclear Ar part, the combination of a and b The total is 2-15. The total value of a and b is the replaceable hydrogen on the aromatic nucleus of Ar. limited by the fact that it does not exceed the total number of .

Also accelerators, i.e. substances that promote the incorporation of excess metal into the overbased material. They are also quite diverse and well known in the art. A particularly wide range of suitable accelerators For a comprehensive discussion, see U.S. Patent Nos. 2.777,874; 2.695.910. No. 2.616.904; No. 3.384.586; and Measure 3,492. Found in No. 231. The contents of these patents are hereby incorporated by reference with respect to disclosure of accelerators. is shown. In one embodiment, the accelerator includes an alcoholic accelerator and a Included are nolic promoters. Alcoholic accelerators contain from 1 to about 12 carbons. Atomic alkanols (e.g. methanol, ethanol, amyl alcohol, tools, such as tools, tools, and mixtures thereof). centre Phenolic promoters include various hydroxy-substituted benzenes and naphthalenes. be done. Particularly useful phenols are described in U.S. Pat. No. 2,777.874. Alkylated phenols of the types mentioned, e.g. heptylphenol, octyl phenol and nonylphenol. Mixtures of various accelerators are sometimes used. I can stay.

Acidic substances that react with mixtures of acidic organic compounds, promoters, metal compounds and reaction media Quality is also disclosed in the patents cited above, e.g., U.S. Patent No. 2.616.904. It is. A well-known group of useful acidic substances includes liquid acids (e.g., formic acid, acetic acid, nitric acid) , boric acid, sulfuric acid, hydrochloric acid, hydrobromic acid, carbamic acid, substituted carbamic acid, etc.) Included. Inorganic acidic compounds (e.g. HCI, SO2, so3 , co2, H2S, N2O3, etc.) are commonly used, but acetic acid is a very useful It is an acidic substance. Preferred acidic substances are carbon dioxide and acetic acid, more preferred Preferably carbon dioxide.

The alkali metal present in the overbased alkali metal salt is primarily includes sodium, sodium and potassium, with sodium and potassium being preferred. Of course, sodium is most preferred. This overbased metal salt prepared using alkali metal compounds. Exemplary basic alkali metal compounds include alkali metal hydroxides, oxides, and alkoxides (ordinarily, the alkoxy group is (containing up to 10 carbon atoms, preferably up to 7 carbon atoms), hydrogen compounds and amides. Therefore, useful basic alkali metal compounds include Sodium oxide, potassium hydroxide, lithium hydroxide, sodium propoxide, Lithium methoxide, potassium ethoxide, sodium butoxide, lithium hydride um, sodium hydride, potassium hydride, lithium amide, sodium amide and potassium amide. Sodium hydroxide and sodium lower acetate Rukoxides (ie those having up to 7 carbon atoms) are particularly preferred.

A study of this overbased material and a very different group of O/C based materials. Methods of manufacture are well known in the prior literature and are disclosed, for example, in the following US patents: : No. 2.516.904; No. 2, 616.905; No. 2.616.906 ; No. 3.242.080; No. 3.250.710; No. 3.256.186 ; No. 3.27'4.135; Kan No. 3.492.231; and No. 4.230. No. 586. These patents cover methods and materials that can be based on metal bases, accelerators, and acidic substances, and these disclosures are are presented here for their disclosure.

Other descriptions of basic sulfonate salts that can be mixed into the lubricating oil compositions of the present invention, and Methods for their manufacture can be found in the following US patents: No. 2.174.110 ; No. 2.202.781; No. 2.239°974; No. 2.319.121 ; No. 2.337.552; No. 3.488.284; No. 3,595.790 ; and No. 3.798.012. These details are subject to disclosure regarding this matter. and is shown here.

The temperature at which this acidic material comes into contact with the rest of the reaction mass depends in large part on the acceleration used. Depends on the agent. With phenolic accelerators, the temperature typically ranges from about 0°C to about 3°C. 00°C, preferably in the range of about 100°C to about 200°C. This accelerator When alcohols or mercaptans are used, this temperature Do not exceed the flow temperature.

In other embodiments, the alkali metal overbased salt is a boronated alkali metal overbased salt. alkali metal overbased salt.

Boronated overbased metal salts are produced by reacting a boron compound with a cleaning agent. or by overbased organic acids with boric acid. prepared. Boron compounds include boron oxide, boron oxide hydrate, and boron trioxide. , boron trifluoride, boron tribromide, boron trichloride, boron-containing acids (e.g. boronie acid, boric acid, tetraboric acid and metaboric acid, Boron hydrides, boron-containing amides) and various esters of boron-containing acids are mentioned. It will be done. This boron-containing ester is preferably a lower alkyl boric acid (from 1 to 7 carbon atoms) ester. Preferably the boron-containing compound is boric acid. be. Generally, the overbased metal salt is heated between about 50°C and about 250"C, preferably Preferably, it reacts with a boron compound at 100°C to about 200°C. This reaction is In the presence of solvents (e.g. mineral oil, naphtha, solvent oil, toluene or xylene) It can get stiff. The overbased metal salt is suitable for the composition at least about 0.5% to about 5% by weight boron, preferably about 1% to about 4% by weight boron react with a boron compound in an amount that provides about 3% by weight of boron, more preferably about 3% by weight of boron. Ru.

Borated overbased compositions, lubricating compositions containing the same, and boronated overbased compositions, and lubricating compositions containing the same. A method for preparing urinated overbased compositions is described by Fischer (F1 U.S. Pat. No. 4,744,922 issued by Scher et al.; Schwinn No. 4,792,410, issued by Schvind et al. and PCT Publication WO38103144. The disclosure regarding the above is as follows: Shown here.

(Margin below) The overbased alkali metal salts of the invention and their preparation can be carried out as follows. Illustrated in an example.

Example A-1 Alkylated benzene sulfonic acid (100% neutral mineral oil and unreacted alkylated benzene) (57% by weight) 780 parts (1 equivalent) and 119 parts of polybutenyl succinic anhydride (0.2 equivalents) in mineral oil, 800 parts (20 equivalents) of sodium hydroxide. and 704 parts (22 equivalents) of methanol. Temperature slowly rises to 97°C Add 7 cfh (cubic feet per hour) to this mixture while rising to Bubble carbon dioxide for 11 minutes. Reduce carbon dioxide flow rate to 6 cfh and the temperature slowly decreases to 88°C over about 40 minutes. diacid The carbon flow rate was reduced to 5 cfh in approximately 35 minutes, and the temperature slowly increased to 7 cfh. The temperature drops to 3℃. Add this carbonated mixture while slowly increasing the temperature to 160"C. Volatiles were removed by bubbling the mixture with nitrogen at 2Cfh for 105 minutes. stripping. After completing the stripping, the mixture was heated at 160° C for an additional 45 minutes and then filtered to have a metal ratio of approximately 19.75. An oil solution of the desired basic sulfonic acid IJ is obtained.

Example A-2 According to the method of Example A-1, petroleum sulfonic acid) l) 100% of 48% of rum 836 parts (1 equivalent) of a neutral mineral oil solution, and 63 parts of polybutenyl succinic anhydride (0 , 11 eq.) to 60"C, and 280 parts of sodium hydroxide (7 eq. amount) and 320 parts (10 equivalents) of methanol. To this reaction mixture, add 4 Blow carbon dioxide at cfh for approximately 45 minutes. During this period, the temperature was 8 It increases to 5°C and then slowly decreases to 74°C. The temperature gradually increases to 160 By blowing nitrogen at 2 cfh while heating to °C, volatile substances are removed. Stripping. After completing the stripping, the mixture was heated to 160°C. Heat for an additional 30 minutes and then filter to get the sodium salt in solution. child The product has a metal ratio of 8.0.

Example A-3 Sodium carbonate overbased (20:1 equivalent) Sodium sulfonate (l ooo parts, 7.84 equivalents) were mixed with 130 parts of 100 neutral mineral oil in a reaction vessel. Ru. This mixture of sodium carbonate overbased sodium sulfonate and mineral oil Heat the mixture to 75°C. The mixture is then heated without substantially changing its temperature. Then, slowly add boric acid (486 parts, 7.84 moles).

The reaction mixture was then stirred for about an hour while removing substantially all of the distillate. or slowly heat to 100°C.

Approximately half of the carbon dioxide is removed with virtually no foaming. all distillates The product is then further heated to 150°C for about 3 hours while removing Heat. At the latter temperature, virtually all the water is removed and the product leaves very little water. It is observed that some carbon dioxide is further evolved. The water content of the product is then The product is held at 150° C. for an additional hour until the amount is less than about 0.3%. .

The product is cooled to 100°C to 120°C, followed by filtration. to recover. This i! ! The solution contains 6.12% boron, 14.4% Na, and 3 Contains 5% 100 neutral mineral oil.

Example A-4 In a reaction vessel, 1122 parts (2 equivalents) of polybutenyl-substituted succinic anhydride and tetrapropylene were added. 105 parts of penylphenol (0.4 equivalents) in 1122 parts of xylene and 100 Fill with 1000 grams of mineral oil. The reaction mixture was stirred and under nitrogen Heat to 80°C, then add 580 parts of a 50% aqueous solution of sodium hydroxide to 1 Add to container for 0 minutes. The reaction mixture was stirred at 80° C. for 1.3 hours. Heat from to 120°C. Water was removed by azeotropic reflux and 300 parts of water During assembly the temperature increases to 150°C over 6 hours.

(1) The reaction was cooled to 80°C, where a 50% aqueous solution of sodium hydroxide was added. Add 540 parts to the container. (2) The reaction mixture was heated at 140° C. for 1.7 hours. Heat to °C and remove water at reflux. (3) Remove water for 5 hours. The reaction mixture was pumped at a rate of 15 cfh (standard cubic feet) per hour while Carbonate with.

Repeat the above steps (1) to (3) using 560 parts of 17um aqueous solution (hydroxide). return. Repeat steps (1) to (3) using 640 parts of sodium hydroxide aqueous solution. return. Next, step (1) is carried out using an additional 640 parts of aqueous sodium hydroxide solution. Repeat ~(3). Then, add 640 parts of 50% sodium hydroxide aqueous solution. Using this method, steps (1) to (3) are repeated. Cool the reaction mixture and Add 1000 parts of 100% neutral mineral oil to the reaction mixture. This reaction mixture was heated to 115°C. , vacuum stripping to 30 mm mercury. This reaction mixture was Filter through sawdust. This filtrate has a total base number of 361 (theoretical value 398), 43.4 % (theoretical value 50.3) and a specific gravity of 1.11.

Example A-5 Mobil 150 Bright Stock (molecular weight 600 ．． Brightstock sulfone derived from 72% Brightstock dilution) 1561 parts of acid oil solution (11 parts per 1,11), sulfur-coupled tetite Lapropylene-substituted phenol (27% 100 neutral mineral oil) 107 parts (0.27 parts) amount), polybutenyl-substituted anhydride derived from polybutene (liver equal to 960) 178 parts of succinic acid (0.31 equivalents), 118 parts of 100 neutral mineral oil, and toluene Fill 1000 parts. This mixture was heated to 100°C, where it was heated to 591 parts (7.4 equivalents) of a 50% aqueous solution of thorium are added to the reaction mixture.

The reaction mixture was bubbled with carbon dioxide at 15 cfh for 1.75 hours. nothing. During this time, 275 parts of water are removed. The reaction was cooled to 90°C and the reaction Add 275 parts of water back to the mixture. The reaction was heated to 100°C and this temperature Maintain temperature for 2 hours. Therefore, 31 parts of the above polybutenyl succinic anhydride (0°05 equivalent), and 36 parts of sulfur-coupled tetrapropenylphenol ( 0.0 g equivalent) in 100 parts of toluene.

The reaction mixture is bubbled with carbon dioxide for 4 hours at 117°C. this During this period, 350 parts of water are removed. The reaction system was cooled to 80°C, where the 434 parts (54 equivalents) of an aqueous sodium hydroxide solution are added to the reaction mixture. This mixture The mixture is bubbled with carbon dioxide for 3.5 hours. During this time, 550 parts of water was removed. be done.

The reaction was cooled to 90°C whereupon sodium hydroxide was added to the reaction mixture. Add 600 parts (7.5 equivalents) of aqueous solution. To this mixture, add 105°C to 112°C. Bubble carbon dioxide for 8 hours at a temperature of C. During the cooking period, 870 parts of water was removed. be removed. The reaction mixture was cooled to 40°C, whereupon the reaction mixture contained Add 601 parts (7.5 equivalents) of an aqueous sodium hydroxide solution. This reaction mixture was Heat to 10°C to 112°C and sparge with carbon dioxide for 7 hours. child During this time, 1150 parts of water are removed. The reaction was cooled to 60°C, where the 164 parts (2.1 eq.) of an aqueous sodium hydroxide solution are added to the reaction mixture. this The reaction mixture was heated to 110°C to 120°C and heated with carbon dioxide for 7 hours. Infuse the essence. During this time, a total of 1410 parts of water is removed.

This mixture is sparged with nitrogen at 25 cfh for 6 hours at 140″C.

When this product is filtered through diatomaceous earth, the filtrate is the desired product. This filtrate has a total number of bases of 446.

[Hosankari The lubricating composition contains at least one dispersant.

This dispersant is one of the following (a), (b), (c), (d), (e) and (f). selected from the group consisting of = (a) nitrogen-containing carboxylic acid dispersant, (b) amine dispersant (C) ester dispersant, (d) Mannich dispersant, (e) dispersant viscosity improver , and (f) mixtures thereof. In one embodiment, these dispersants include: Can be post-treated with reagents such as: urea, thiourea, carbon disulfide, aldehydes, ketones , carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron elementary compounds, phosphorus compounds, etc.

This nitrogen-containing carboxylic acid dispersant contains hydrocarbyl tm carboxylic acid acyl. Reaction of amines with binding agents (e.g. substituted carboxylic acids or their derivatives) reaction products are included.

This hydrocarbyl-substituted carboxylic acid acylating agent is a monocarboxylic or polycarboxylic acid acylating agent. may be derived from rubonic acid. Polycarboxylic acids are generally preferred. This acylation The agent may be a carboxylic acid or a derivative of a carboxylic acid (e.g., a halide, an ester, preferably acids, esters or anhydrides, more preferably anhydrides. things). Preferably, the carboxylic acylating agent is succinic acid acylating agent. It's on the side. This hydrocarbyl-substituted carboxylic acid acylating agent includes the above-mentioned polyalkylene Included are reagents having hydrocarbyl groups derived from ions.

In one embodiment, the hydrocarbyl group has at least about 1300 to about 500 mos It is derived from polyalkenes with a My/Mn value of approximately 1. 5-about 4, preferably about 1.8 to about 3.6, more preferably about 2.5 to about 3. It is 2. Substituted acyl succinates whose substituents are derived from such polyalkenes The preparation and use of Northside is described in U.S. Patent No. 4.234.435, which The content is shown here.

The hydrocarbyl-substituted carboxylic acid acylating agent comprises one or more polyalkenes; Prepared by reaction with one or more unsaturated carboxylic acid reagents. This unsaturated carb Acid reagents generally contain alpha-beta olefinic unsaturation. This carboxylic acid test Drugs include carboxylic acids themselves and their functional derivatives (e.g. anhydrides, esters, etc.). (esters, amides, imides, salts, acyl halides and nitriles).

These carboxylic acid reagents are either basic or polybasic in nature. obtain. Tricarboxylic and tetracarboxylic acids are used when they are polybasic. It can be a dicarboxylic acid, preferably a dicarboxylic acid. Useful monobasic unsaturated cal Specific examples of bonic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, -Phenylpropenoic acid, etc. Exemplary polybasic acids include maleic acid, fumaric acid , mesaconic acid, itafonic acid and citraconic acid. In general, this insatiability maleic anhydride or maleic acid or fumaric acid. maleic acid or its ester, preferably maleic acid or its anhydride, more preferably maleic acid or its anhydride; Or maleic anhydride.

The polyalkene is at least 1 mole for each mole of polyalkene reacted. can be reacted with a carboxylic acid reagent such that a reagent of Preferably an excess of Medicine is used.

In other embodiments, these acylating agents are combined with the polyalkene and excess anhydrous macerate. The number of succinic acid groups for each equivalent of substituents is small (both 1.3 is prepared by providing a substituted acyl succinate. The most Major numbers do not exceed 4.5. A suitable range is about 1.4 to 1.4 per equivalent of substituent. 3.5 succinic acid groups, more specifically about 1°4 to about 2.5 succinic acid groups. It is a citric acid group. In this embodiment, the polyalkene is preferably as described above. The most preferred range is about 1,300 to about 50, and the most preferred range is about 1,500 to about 2,800. A preferred range of i values is from about 1500 to about 2400.

For purposes of this invention, the number of equivalents of substituents present in the substituted succinic acylating agent is by dividing the total weight of a substituent by the weight of the polyalkene from which it is derived. It is thought that this is the number obtained. Therefore, the substituted acyl succinate north side is The total weight of substituents is 40,000 and the polyester from which the substituents are derived is If the E value of the alkene is 2000, the substituted acyl succinate It is characterized by an equivalent weight of 20 (40,000/2000=20). Therefore, special Certain acyl succinates or mixtures of acyl succinates may also be used in the present invention. At least 26 It must be characterized by the presence of succinic acid groups.

The ratio of succinic acid groups to equivalents of substituents present in this acylating agent is It can be determined from the saponification value of the mixture.

This saponification value is the unreacted polyalkene present in the reaction mixture at the end of the reaction. (this is generally indicated as filtrate or residue in the following examples). clarified and corrected. This saponification value is determined using the ASTM D-94 method. be done. The formula for calculating this ratio from the saponification number is: The saponification number is obtained by dividing the saponification number by the percentage of polyalkene reacted. It will be done. For example, 10% of the polyalkene does not react and the filtrate or residue If the saponification value of is 95, the corrected saponification value is 95 divided by 0.90, the total In other words, it is 105.5.

Conditions for reacting acidic reactants with polyalkenes, i.e. temperature, agitation, solvent, etc. are well known to those skilled in the art. describes various methods of preparing useful acylating agents. Examples of patents include U.S. Patent No. 3.215.707 (Rense). ; No. 3.219.566 (Norman et al.); No. 3.231.5 No. 87 (Rense); No. 3.912.764 (Pa. lmar); No. 4.110.349 (Cohen); and and East No. 4.234.435 (Meinhardt et al.); British patent! No. 1,440.219 is mentioned.

The disclosures of these patents are provided herein.

The following examples illustrate carboxylic acylating agents and methods of their preparation. place The desired acylating agent sometimes, in this example, may be present in combination with other substances or amounts thereof. Referred to as "residue" without specific measurement or mention.

Example■ Polybutene (Mn□1g45; Mv115325) 510 parts (0.28 mol ) and 59 parts (0.59 mol) of maleic anhydride were heated to 110°C. heat. This mixture is heated to 190° C. for 7 hours. During this time, gaseous chlorine 4 Add 3 parts (0.6 mol) subsurface. At 190-192°C, additional chlorine 11 (0.16 mol) over 3.5 hours.

The reaction mixture was heated at 190-193°C for 10 hours with nitrogen bubbling. stripping. This residue was processed according to ASTM Method D Method 4. The desired polybutene-substituted succinic acyl having a saponification equivalent number of 87 determined by It is on the north side.

Example II Ho IJ border: / (Mn=2020; rv=6049) 1000ffi (0,495 parts), a mixture of O and 115 parts (1,17 moles) of maleic anhydride. Heat the mixture to 110°C. This mixture is heated to 184° C. for 6 hours.

During this time, 85 parts (1.2 moles) of gaseous chlorine are added subsurface. 184~189° At C, an additional 59 parts (0.83 mol) of chlorine are added over 4 hours. This anti The reaction mixture was heated at 186-190°C for 26 hours while blowing nitrogen. More than that, stripping. This residue was determined by ASTM Method D Method 4. on the north side of the desired polybutene-substituted acyl succinate with a saponification equivalent number of 87. be.

The above carboxylic acid acylating agent reacts with an amine to form the nitrogen-containing carboxylic acid of the present invention. Form a dispersant. The amine is a monoamine or a polyamine, typically Polyamines, preferably ethylene amines, amine bottoms or amine condensates It can be. These amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic. This includes aliphatic-substituted cycloaliphatic, aliphatic-substituted aromatic, and aliphatic-substituted cycloaliphatic. Heterocycle, cycloaliphatic substituted aliphatic, cycloaliphatic substituted heterocycle, aromatic substituted aliphatic group, aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic, heterocyclic-substituted aliphatic, heterocyclic Includes ring-substituted ring ring and heterocycle-substituted aromatic amines, including saturated or unsaturated amines. Can be saturated.

These monoamines generally contain from 1 to about 24 carbon atoms, preferably from 1 to about 24 carbon atoms. It has about 12 carbon atoms, more preferably 1 to about 6 carbon atoms. Main departure Examples of clear and useful monoamines include methylamine, ethylamine, and propylamine. , butylamine, cyclobeni/thylamine, cyclohexylamine, octylamine amine, dodecylamine, allylamine, cocoamine, stearylamine and Included are urylamines.

Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, Dibutylamine, dicyclopentylamine, dicyclohexylamine, methylbutylamine Includes thylamine, ethylhexylamine, and the like. Tertiary amines include Methylamine, tributylamine, methyldiethylamine, ethyldibutylamine This includes the following:

In other embodiments, the amine can be a hydroxyamine. Typically, this Hydroxyamines can be primary, secondary or tertiary alkanolamines or is a mixture of them. Such amines may be represented by the formula: and wherein each R'+ is independently a hydrocarbyl group of 1 to about 8 carbon atoms; or a hydroxyl group of 2 to about 8 carbon atoms, preferably 1 to about 4 carbon atoms. cyhydrocarbyl group, and more particularly Ro has about 2 to about 18 carbon atoms, preferably or a divalent hydrocarbyl group of 2 to about 4 carbon atoms. − of these expressions The R'-OH group represents a hydroxyhydrocarbyl group.

Ro can be an acyclic group, a ring group or an aromatic group. Typically, Ro is Acyclic linear or branched alkylene groups (e.g. Eva, ethylene group, 1.2-'; 7 'ropylene group, 1,2-butylene group, 1°2-octadecylene group, etc.).

When two R's groups are present in the same molecule, they form a direct carbon-carbon bond. or through a heteroatom (e.g. oxygen, nitrogen or sulfur) , a 5-membered ring structure, a 6-membered ring structure, a 7-membered ring structure, or an 8-membered ring structure. This way Examples of such heterocyclic amines include N-(hydroxyl lower alkyl)-morpholine, -thiomorpholine, -piperidine, -oxazolidine, -thiazolidine, etc. Included. However, typically each R'+ is independently a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.

Examples of these alkanolamines include mono-, di- and triethanolamines. diethylethanolamine, ethylethanolamine, butyljetanol Includes amines and the like.

This hydroxyamine is also an ether-N-(hydroxyhydrocarbyl)a It could be Min. These are the hydroxypoly(hydrocarbons) of the above hydroxyamines. Rubyloxy) analogs (these analogs include hydroxyl-substituted oxy- lukylene analogs are also included). Such N-(hydroxyhydrocarbon (Bi) amines can be conveniently prepared by reaction of epoxides with the above amines. , and can be expressed by: (Margin below) H2N - (R'0)7H.

and where X is a number from about 2 to about 15, and R1 and Ro are as described above. It is the same as the thing. R’+ is still a hydroxypoly(hydrocarbyloxy) group It can be.

Suitable amines also have average molecular weights ranging from about 200 to 4000, preferably about Polyoxyalkylene polyamines having an average molecular weight ranging from 400 to 2000 (e.g., polyoxyalkylene diamines and polyoxyalkylene triamines) ) are included. Illustrative examples of these polyoxyalkylene polyamines are: It can be characterized by the formula: NH2-alkylene (0-alkylene) mNH 2, where m has a value of about 3 to 70, preferably about 10 to 35. and R(alkylene(O-alkylene)nNH2) 3-6, Here, n is a value whose total value is approximately 1 to 40, provided that the total value of n is approximately 1 to 40. is about 3 to about 70, generally about 6 to about 35, and R is a valence of 3 to 6. is a polyvalent unsaturated hydrocarbon radical of up to 10 carbon atoms. These alki A ren group can be straight or branched and contains 1 to 7 carbon atoms, usually 1 It may have from 1 to 4 carbon atoms.

The various alkylene groups present may be the same or different.

Preferred polyoxyalkylene polyamines include average polyamines ranging from about 200 to 2000. Polyoxyethylene diamine and polyoxyalkylene diamine with uniform molecular weight - Includes amines and polyoxypropylene triamines. This polyoxia Lukylene polyamines are commercially available, for example from Jefferson Chem From icalCompany, Inc.-Jeffamines D-230 , D-400, D-1000, D-2000, T-403, etc.” It can be done.

The contents of U.S. Pat. Nos. 3.804.763 and 3.948.800 are polyoxyalkylene polyamines, and their carboxylic acid acylating agents acylation method (this method is applicable to the reaction with the acylation reagent used in the present invention) This disclosure is expressly set forth herein.

The nitrogen-containing carboxylic dispersant may be derived from a polyamine. This polyamide The ring can be aliphatic, cycloaliphatic, heterocyclic or aromatic. These polyamide Examples include alkylene polyamines, hydroxy-containing polyamines, and aryl polyamines. Included are amines and heterocyclic polyamines.

The alkylene polyamine is represented by the formula: where n is an average of 1 to about 10. average value, preferably an average value of about 2 to about 7, more preferably an average value of about 2 to about 5. and the "alkylene" group has from 1 to about 10 carbon atoms, preferably having about 2 to about 6 carbon atoms, more preferably about 2 to about 4 carbon atoms Ru. R2 is independently preferably hydrogen; or aliphatic of up to about 30 carbon atoms group or hydroxy-substituted aliphatic group. Preferably R2 is similar to Rol defined.

Such alkylene polyamines include methylene polyamine, ethylene polyamine, butylene polyamine, propylene polyamine, pentylene polyamine, etc. Included. Higher congeners and related heterocyclic amines (e.g. piperazine) N-aminoalkyl-substituted piperazines) are also included. this Specific examples of polyamines such as ethylenediamine, triethylenetetraamine , tris-(2-aminoethyl)amine, propylene diamine, trimethylene diamine amine, tripropylenetetraamine, tetraethylenepentaamine, hexaethyl These include lenhebutamine, pentaethylenehexamine, etc.

Higher homologues obtained by condensation of two or more of the above-mentioned alkylene amines are: Also useful are mixtures of two or more of the above polyamines.

Ethylene polyamines (eg, those mentioned above) are useful. A port like this Reamin, under the title ethylene amine, is an encyclopedia by Kirk Othmer. opedia of Chemical Technology-, 2nd edition, V ol, pp. 7.22-37, Interscience Publishers , New York (1965). Such polyamines is most conveniently produced by the reaction of ethylene dichloride with ammonia or by the reaction of ethylene dichloride with ammonia. prepared by the reaction of renimine with a ring-opening reagent (e.g., water, ammonia, etc.) Ru. The results of such reactions include cyclic condensation products (e.g. the piperazine described above). A complex mixture of polyalkylene polyamines is produced. Ethylene polyamine mixture Things are useful.

Other useful types of polyamine mixtures include strippers of the polyamine mixtures listed above. This process often leaves behind a residue called a “polyamine mixture”. There are things that can be done.

Generally, alkylenebolyamine bottoms contain substances that boil below about 200°C. Characterized as containing less than 2% by weight, usually less than 11% by weight. It can be done. Dot Chemical Cowpany of Freeport Typical of such ethylene polyamine mixtures obtained from The sample (which is designated as ``rE-100'') has a temperature of 1.016 at 15.6°C. specific gravity of 8, nitrogen content of 33.15% by weight, and 121 centistokes at 40°C. It has a viscosity of In gas chromatography analysis of such samples, this , about 0.93% by weight of "light end" (mostly DETA), 0.72% by weight TETA, 21.74% by weight tetraethylenepentamine, and contains 76, 61% and more pentaethylene hexamine by weight. . These alkylene polyamine bottoms contain cyclic condensation products (e.g. perazine), and diethylenetriamine and triethylenetetraamine. Higher congeners are included.

These alkylene polyamine bottoms can react only with acylating agents or with other amines, polyamines or mixtures thereof.

Other useful polyamines include at least one hydroxy compound and at least one At least one polyamide containing 7 primary amino groups or 7 secondary amine groups It is a condensation reaction product between the reaction product and the reaction product. This hydroxy compound is preferably a polyvalent alcohols and amines. These polyhydric alcohols are described below There is. (Collagen carboxylic acid ester dispersant). Preferably this hydroxylation The compound is a polyvalent amine. Polyhydric amines have from 2 to about 20 carbon atoms, preferably or an alkylene oxide having from 2 to about 4 carbon atoms (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) Any of the following is included. Examples of polyvalent amines include tri(hydroxypropylene) ) amine, tris-(hydroxymethyl)aminomethane, 2-amino-2-methane Chil-1,3-propanediol, N,N,No,N-tetrakis(2-hydro (xypropyl) ethylenediamine, and N, N, No, N'-tetraki tris(2-hydroxyethyl)ethylenediamine, preferably tris(hydroxyethyl) methyl)aminomethane (T)JAM).

Reacts with polyhydric alcohols or amines to form condensation products or amines Polyamine reactants are described above. Preferred polyamine reactants include Liethylenetetraamine (TE-A), Tetraethylenepentaamine (TEPA) ), pentaethylenehexamine (PEHA), and polyamine mixtures (e.g. For example, the above-mentioned "amine bottoms") are included.

This condensation reaction between the polyamine reactant and the hydroxy compound is carried out in the presence of an acid catalyst. , high temperature, typically from about 60"C to about 265°C (preferably from about 20"C to about 250°C) C) occurs.

This amine condensate and its manufacturing method are described in PCT publication WO36105501. The contents of which are presented herein for the disclosure of this condensate and its method of preparation. has been done. Such polyamine condensates can be prepared as follows: Stirrer, thermowell, subsurface N2 inlet tube, DG Stark trap, and 3 liter 4 bottle with Friedrich cooler. Fill a round bottom flask with the following materials: 1299 grams of HPA tufts Amines (Tart Aa+1nes) (Union Carbide (llnion Amine bottoms commercially available from Carbide, Inc., typically 341% by weight. of nitrogen, and 12.3% by weight of eastern amines, 14.4% by weight of secondary amines. amine and 7.4 wt% tertiary amine nitrogen distribution), and 727 grams of 40% aqueous tris(hydroxymethyl)aminomethane (THAM). child Heat the mixture to 60° C. and add 23 grams of 85% H3P0a.

The mixture is then heated to 120° C. for 0.6 hours.

The mixture was then heated to 150° C. for 1.25 hours by blowing with N2. Heat to 235°C for an additional hour, then 230-235°C. maintained at °C for 5 h, then heated to 240 °C for 0.75 h, It is then maintained at 240-245°C for 5 hours. Cool the product to 150℃ and filter through diatomaceous earth filter aid. Yield = 84% (1221 grams).

In other embodiments, these polyamines are hydroxy-containing polyamines.

Hydroxy-containing polyamine analogs of hydroxymonoamines, especially alkoxyl alkylene polyamine (e.g., N, N (jetanol) ethylenediamine) can also be used. Such polyamines include the above alkylene amine and one type of polyamine. It can be produced by reacting the above alkylene oxides. similar Alkylene oxide-alkanolamine reaction products, e.g. secondary or tertiary alkaline amines and ethylene, propylene or higher It was produced by reacting with a grade epoxide at a molar ratio of 1.1 to 1.2. Products may also be used.

Reactant ratios and temperatures for carrying out such reactions are well known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines include ) ethylenediamine, N,N-bis(2-hydroxyethyl)-ethylenediamine Amine, 1-(2-hydroxyethyl)-piperazine, mono(hydroxypropylene) pyru) substituted tetraethylenepentaamine, N-(3-hydrobov dibutyl)-tet Ramethylene diamine and the like are included. of the hydroxy-containing polyamines exemplified above. Higher homologs obtained by condensation via amine or hydroxyl groups are equally useful. It is. Condensation via the amino group produces higher amino acids with removal of ammonia. In contrast, condensation through hydroxyl groups, with removal of water, A product containing tel bonds is obtained. Two or more of any of the above polyamines Mixtures are also useful.

In other embodiments, the amine is a heterocyclic polyamine.

These heterocyclic polyamines include aziridine, azetidine, azolidine, tetra- and and dihydropyridine, virol, indole, piperidine, imidazole, dihydropyridine, - and tetrahydroimidazole, piperazine, isoindole, purine, mole luforin, thiomorpholine, N-aminoalkylmorpholine, N-aminoalkyl ruthiomorpholine, N-ami/alkylpiperazine, N,N'-diaminoalkyl Luviperazine, azepine, azocine, azocine, azecine and each of the above Tetra-, di- and perhydro derivatives, and two or more of these heterocyclic amines Mixtures of are included. Preferred heterocyclic amines include nitrogen, oxygen and / or saturated five- and six-membered heterocyclic amines containing only sulfur; In particular, piperidine, piperazine, thiomorpholine, morpholine, pyrrolidine, etc. It is. piperidine, aminoalkyl-substituted piperazine, piperazine, aminoalkyl Kyl-substituted piperazine, morpholine, aminoalkyl-substituted morpholine, pyrrolidine , and aminoalkyl-substituted pyrrolidines are particularly preferred. Usually, this amino alcohol A kill substituent is substituted on a nitrogen atom that forms part of a heterocycle. like this Specific examples of heterocyclic amines include N-aminopropylmorpholine, N-aminoethyl Included are lupiperazine, and N,N'-diaminoethylpiperazine. Hi Droxyheterocyclic polyamines are also useful. Examples include N-(2-hydroxyethyl Chill) cyclo\xylamine, 3-hydroxycyclopentylamine, barahi Included are drooxyaniline, N-hydrobovine diethylpiperazine, and the like.

Hydrazine and substituted hydrazines also form nitrogen-containing carboxylic acid dispersants. It can be used for At least one nitrogen in this hydrazine is directly bonded to it. must contain combined hydrogen. Preferably bonded directly to the hydrazine nitrogen and more preferably both hydrogens are the same nitrogen Substituents that may exist on this hydrazine include alkyl, Included are alkenyl, aryl, aralyl, alkaryl, and the like. Usually this These substituents include alkyl (especially lower alkyl), phenyl, and substituted phenyl. (e.g., lower alkoxy-substituted phenyl or lower alkyl-substituted phenyl) It is. Specific examples of substituted hydrazines include methylhydrazine, N,N-dimethyl -hydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-phenylhydrazine Nyl-N-ethylhydrazine, N-(para-tolyl)-No-(n-butyl )-hydrazine, N-(para-nitrophenyl)-hydrazine, N-(para-nitrophenyl)-hydrazine trophenyl)-tomethyl-hydrazine, N, N'-di(Barack 00 phenyl )-hydrazine (N, N'-di (para-chlorophenol) )-hydrazine), N-phenyl-N-cyclohexylhydrazine, etc. There is.

Nitrogen-containing carboxylic acid dispersants and methods for their preparation are described in U.S. Pat. No. 4,234. , 435; No. 4.952.328; No. 4.938.881; No. 4,957 ．． No. 649; and Measure No. 4,904,401. These patents Disclosures of included nitrogen-containing carboxylic dispersants and other dispersants are provided herein. It is.

(Margin below) The following examples illustrate nitrogen-containing carboxylic dispersants and methods of their preparation. Ru.

Example B-1 Commercial mixtures of ethylene polyamines having about 3 to 10 nitrogen atoms per molecule 8.16 parts (0.20 equivalents) of the compound at 138°C, 113 parts of mineral oil, and Example Add to 161 parts (0.24 equivalents) of the substituted acyl succinate prepared in step I. A mixture is prepared by: The reaction mixture was heated to 150″C for 2 hours. , and stripped by blowing with nitrogen. Filter this reaction mixture A filtrate is then obtained as an oil solution of the desired product.

Example B-2 Commercial mixtures of ethylene polyamines having about 3 to 10 nitrogen atoms per molecule 18.2 parts (0,433 equivalents) of 392 parts of mineral oil at 140°C and Add to 348 parts (0.52 equivalents) of substituted acyl succinate prepared in Example I+ A mixture is prepared by: The reaction mixture was heated to 150°C for 1.8 hours. Heat and strip by blowing with nitrogen. This reaction mixture The filtrate is obtained as an oil solution (55% oil) of the desired product. It will be done.

The products of Examples B-3 to B-8 were prepared according to the general method shown in Example B-1. do.

B-3 Pentaethylene 4.3° 40% Bovine Amine 6 B-4 tris(2-amino 5:4 so% ethyl)amine B-5 imino-bis-8nia 40% propylamine B-6 hexamethylene 4:340% diamine B-71-(2-aminoethyl)-5:4 40% B-8N-aminopropyl- 8 Near 40%a The experimental formula is ethylene polymer corresponding to pentaethylene hexamine. Commercial mixture of riamin Example B-9 3660 parts (6 equivalents) of substituted acyl succinate prepared in Example ① diluent oil 46 A mixture in 64 parts was prepared and heated to about 110°C whereupon the mixture Blow nitrogen into things. This mixture is then added to the alkylene polyamine mixture (this This is Union Carbide ethylene polyamide. 80% bottoms, and in the empirical formula, ethylene corresponding to diethylenetriamine. 210 parts (5.25 equivalents) of a commercially available mixture of polyamines (containing 20%) were added at 1 hour. and the mixture is maintained at 110° C. for an additional 0.5 h. . This polyamine mixture is characterized by having an equivalent weight of about 43.3. Ru. After heating at 155°C for 6 hours with removal of water, the filtrate was added and the reaction mixture is filtered at approximately 150°C. This filtrate is an oil solution of the desired product.

The dispersant may also be an amine dispersant. Amine dispersants are hydrocarbyl It is a substituted amine. These hydrocarbyl substituted amines are well known to those skilled in the art. . These amines are described in U.S. Pat. No. 3,275.554; No. 3.454.555; No. 3.565.804; No. 3.755.433 No.: and No. 3.822.289. The content of these patents is For the disclosure of hydrocarbylamines and methods of their preparation, set forth herein: There is.

Typically, olefins and olefin polymers (polyalkenes) and amines ( Amine dispersants are prepared by reacting with monoamines or polyamines. It will be done. The polyalkene can be any of the polyalkenes described above. these The amine can be any of the amines listed above. Examples of amine dispersants include poly(propylene) N,N-dimethyl-N-poly(ethylene/propylene)amine (So: monomer molar ratio of 50); polybutenamine; N,N-di(hydrocarbon); (oxyethyl)-N-polybutenamine; N-(2-hydroxypropyl)- N-polybuteneamine; N-polybutene-aniline; N-polybutenemorpholine ; N-poly(butene)ethylenediamine; N-poly(propylene) trimethylene N-diamine; N-poly(butene)diethylenetriamine: ho, rCo-poly (butene)tetraethylenepentaamine;) J, l+-tumethyl-N'-poly( propylene)-1,3-propylene diamine and the like.

In other embodiments, the dispersant may also be an ester dispersant. This beauty salon The dispersant contains at least one (and at least one) hydrocarpyl-substituted carboxylic acid acylating agent. , a small amount (with one organic hydroxy compound and optionally an amine) It is prepared by In other embodiments, the ester dispersant is prepared by reacting the north side with at least one of the above hydroxyamines be done.

The organic hydroxy compounds include compounds of the general formula R-(OH)□. child Here, R- is a monovalent or polyvalent organic group bonded to the 10H group via a carbon bond. m is an integer from 1 to about 10, where the hydrocarbyl group is , containing at least about 8 aliphatic carbon atoms. This hydroxy compound aliphatic compounds (e.g. -hydric and polyhydric alcohols), or aromatic compounds (e.g. for example, phenol and naphthol). The aromatic properties from which this ester can be derived Aromatic hydroxy compounds are exemplified by the following specific examples: phenol, β- naphthol, α-naphthol, cresol, resorcinol, catechol, p, p-dihydroxypiphenyl, 2-chlorophenol, 2,4-dibutylphenol This is exemplified by the rules.

The alcohol from which this ester can be derived preferably has up to about 40 aliphatic carbons. elementary atoms, preferably from 2 to about 30 carbon atoms, more preferably from 2 to about 10 It contains carbon atoms.

These include -hydric alcohols (e.g. methanol, ethanol, alcohol dodecanol, cyclohexanol, etc.). In one embodiment, this These hydroxy compounds are polyhydric alcohols (e.g. alkylene polyols) It is. Preferably these polyhydric alcohols contain from 2 to about 40 carbon atoms, More preferably 2 to about 20 carbon atoms, and preferably 2 to about 1 carbon atoms. It has 0 hydroxyl groups, more preferably 2 to about 6 hydroxyl groups. polyhydric alcohol Ethylene glycol (this includes di-, tri-, and tetraethylene glycols) Propylene glycol (this includes G, T and T); (contains trapropylene glycol); glycerol; butanediol; Sandiol; sorbitol; arabitol; mannitol; sucrose; full Cutose; Glucose; Cyclohedoxandiol; Erythritol; and Pen taerythritol (this includes g- and tripentaerythritol) ), preferably diethylene glycol, triethylene glycol, glycol Ricerol, sorbitol, pentaerythritol and dipentaerythritol It is le.

The polyhydric alcohol has from 2 to about 30 carbon atoms, preferably from about 8 to about 18 carbon atoms. may be esterified with a monocarboxylic acid having at least One hydroxyl group remains unesterified. Examples of monocarboxylic acids include acetic acid , propionic acid, butyric acid, and fatty carboxylic acids.

The fatty monocarboxylic acids have about 8 to about 30 carbon atoms and octa oleic acid, stearic acid, linoleic acid, dodecanoic acid and tall oil acid. Included. Specific examples of these esterified polyhydric alcohols include sorbitol, Tall oleate (including mono- and dioleate), sorbitol stearate (including mono- and distearates), glycerol oleate (including glycerol oleate) (including role mono-, di- and trioleate), and erythritol octane. Included are tanoates.

This carboxylic ester dispersant is prepared by any of several well-known methods. can be done. Preferred method due to convenience and superior properties of the esters produced The above-mentioned carboxylic acid anchor is on the north side and one or more alcohols or phenols. The ratio of about 0.5 to about 4 equivalents of hydroxy compound per equivalent of the north side of the antle. reactions are included. This esterification is typically carried out at temperatures above about 100"C, Preferably it is carried out at a temperature between 150°C and 300°C. Formed as a by-product The water is removed by distillation as the esterification progresses. useful carvone Preparation of acid ester dispersants is described in U.S. Pat. 4.435.

The carboxylic ester dispersant further comprises at least one of the above amines, preferably Alternatively, it can be reacted with at least one of the polyamines mentioned above. added in an amount sufficient to neutralize any unesterified carboxyl groups. It will be done. In one preferred embodiment, the nitrogen-containing carboxylic ester dispersant is About 1.0 to 2.0 equivalents of hydroxy compound per equivalent of north side of the sill, preferably or about 1.0 to 1.8 equivalents of the hydroxy compound and up to about OJ equivalents of the polyamine. amine, preferably about 0.02 equivalents to about 0.25 equivalents of polyamine. It is prepared by

In other embodiments, the carboxylic acylating agent comprises the alcohol and the amine. Both can be reacted simultaneously. The total number of equivalents in this formulation is per equivalent of acyl north side. generally should be at least about 0.5 equivalents; ．． 0.01 equivalents of alcohol and at least 0.01 equivalents of aminka are present.

These nitrogen-containing carboxylic ester dispersant compositions are well known in the art. The preparation of a large number of these derivatives is described, for example, in U.S. Pat. No. 3.957.85. No. 4 and No. 4.234.435, the contents of which were previously indicated. There is.

This carboxylic acid ester dispersant and its manufacturing method are well known in the art. Yes, U.S. Patent No. 3,219,666: i3,381.022; No. 3,52 No. 2.179; and No. 4.234.435, the contents of which are: Reference is made herein for disclosure of the preparation of carboxylic acid ester dispersants.

The following examples demonstrate this ester dispersant and methods for preparing such esters. Illustrate.

Example B-10 Polybutene with a number average molecular weight of 1000 was chlorinated to a chlorine content of 4.5%. Then, at a temperature of 150 to 220°C, this chlorinated polybutene was heated to 1.2 Substantial hydrocarbon displacement by heating with molar proportions of maleic anhydride Prepare succinic anhydride. 874 grams (1 mole) of succinic anhydride and A mixture of 104 grams (1 mole) of opentyl glycol in one 240-bl. and a mixture of esters obtained from esterification of both hydroxyl groups.

Example B-11 3225 parts (5,0 equivalents) of the polybutene-substituted acyl succinate prepared in Example 11 ), a mixture of 289 parts (8,5 equivalents) of pentaerythritol and 5204 parts of mineral oil. The mixture is heated at 224-235°C for 5.5 hours.

The reaction mixture is filtered at 130″C to obtain an oil solution of the desired product. .

Acylating agents and hydroxy-containing compounds (e.g. alcohols or phenols) The above carboxylic acid ester derivative obtained from the reaction with With any of the above amines (4!, polyamine) using the method described above for the agent. can be reacted.

In other embodiments, the carboxylic acylating agent comprises the alcohol and the amine. can be reacted simultaneously with both. The total number of equivalents in this formulation is 1 equivalent on the north side of the acyl. generally at least about 0.5 equivalents, but generally at least about 0.5 equivalents. There are 0.01 equivalents of alcohol and at least 0.01 equivalents of amine. child These carboxylic acid ester derivative compositions are well known in the art and very popular. Many of these derivatives are described, for example, in U.S. Pat. No. 3,957,854 and No. 4.234.435, the contents of which are presented here.

The specific examples below show that both the alcohol and the amine were reacted with the acylating agent. The preparation of esters is illustrated.

Example B-12 1000 parts of polybutene having a number average molecular weight of about 1000, and maleic anhydride A mixture of 108 parts (1.1 mol) of acid is heated to about 190°C and the temperature is 100 parts (1.43 mol) of chlorine was added for about 4 hours while maintaining the temperature at about 185 to 190°C. Add under the surface. This mixture is then added to nitrogen for several hours at this temperature. The residue is then blown into the desired polybutenyl-substituted acyl succinate. be.

A solution of 857 parts of mineral oil containing 1000 parts of the north side of the acyl prepared above was added with stirring to about 1 Heat to 50°C and, with stirring, add 109 parts of pentaerythritol (3, 2 equivalents). This mixture was sparged with nitrogen and for about 14 hours. Heat to approximately 200°C to form an oil solution of the desired carboxylic acid ester intermediate. to be accomplished.

This intermediate has an ethythmyl alcohol containing an average of about 3 to about 10 nitrogen atoms per molecule. 19.25 parts (0.46 equivalents) of a commercial mixture of renpolyamine are added. this reaction The mixture was stirred by heating at 205°C for 3 hours with nitrogen bubbling. Ping and filter. This filtrate was added to the desired aqueous solution containing 0.35% nitrogen. An oil solution (45% in 100 neutral mineral oil) of a amine-modified carboxylic acid ester.

The dispersant may also be a Mannich dispersant. Mannich dispersants are generally , at least one aldehyde, at least one of the above amines and at least Formed by the reaction of one alkyl-substituted hydroxyaromatic compound. this reaction from room temperature to 225°C, usually from 50°C to about 200°C (75°C to 150°C is most preferred). (preferably) and the amounts of these reagents are The molar ratio of aldehyde to amine is in the range of about (1:1:1) to about (1:3:3). The amount is such that

This first reagent is an alkyl-substituted hydroxyaromatic compound. This term includes , phenol (preferred), carbon-1 oxygen-, sulfur- and nitrogen cross-linked phenols and phenols linked directly via covalent bonds (e.g. 4. Hydrocarbons derived from 4-bis(hydroxy)biphenyl), fused ring hydrocarbons) droxy compounds (e.g. naphthol, etc.); and polyhydroxy compounds (e.g. Examples include catechol, dinordicinol and hydroquinone). 1 type A mixture of the above hydroxyaromatic compounds can be used as this first reagent. .

The hydroxyaromatic compound may contain at least about 6 (usually as few as about 3) 0, more preferably at least 50) up to about 400 carbon atoms, preferably preferably up to 300 carbon atoms, more preferably up to 200 carbon atoms. substituted with at least one, preferably not more than two, aliphatic or ring group It is something. These groups can be derived from the polyalkenes described above. In one embodiment This hydroxyaromatic compound has a door of about 420 to about io, ooo Phenols substituted with aliphatic or ring hydrocarbon-based groups.

The second reagent is a hydrocarbon-based aldehyde, preferably a lower aliphatic aldehyde. It is. Suitable aldehydes include formaldehyde, benzaldehyde, and acetate. Aldehydes, butyraldehyde, hydroxybutyraldehyde and heptaners and an aldehyde precursor that reacts as an aldehyde under the reaction conditions (e.g. , paraformaldehyde, valaldehyde, formalin and metal) be done. Formaldehyde and its precursors (e.g. paraformaldehyde, Trio Beef San) is preferred. A mixture of aldehydes is used as the second reagent. It can be done.

The third reagent is any of the amines listed above. Preferably, the amine is This is the polyamine described below.

Mannich dispersants are described in the following patents: U.S. Patent No. 3.980.5 No. 69; U.S. Pat. No. 3,877.899; and U.S. Pat. No. 4.454. O5 No. 9 (the contents of these patents are set forth herein for their disclosure of Mannich dispersants). ing).

The dispersant can also be a dispersant-viscosity modifier. This dispersant-viscosity modifier contains a polymeric backbone that is functionalized by reaction with an amine source. true bond Regular block copolymers, random block copolymers, or a combination of both. combination is used. These remove virtually all olefinic double bonds. It is hydrogenated prior to use in the present invention. The method for carrying out this hydrogenation is It is well known to business operators.

In summary, hydrogenation is performed using metal catalysts (e.g. colloidal nickel, supported on charcoal). This copolymer is processed at superatmospheric pressure in the presence of metals (such as palladium) This is done by contacting with hydrogen.

Generally, these pro-1 copolymers have a low carbon content in the average molecule for reasons of oxidative stability. Based on the total number of elementary-carbon covalent bonds, approximately 5% or less (no rsore tha n) residual olefinic unsilence, preferably about 0.5% or less (no more han) Contains residual olefinic acid. Such unsaturation is well known to those skilled in the art. It can be measured by a large number of known methods (eg, infrared, NMR, etc.). most Preferably these copolymers are indistinguishable as determined by the analytical method described above. Contains no unsaturation.

The block copolymers typically range from about 10.000 to about 500.000 range, preferably from about 30.000 to about 200.000. ). The weight average molecular weight (My) of these copolymers is generally about so, ooo to about 500,000, preferably about 30,000 to about 300,000 It is in the range of 0.

This amine source is an unsaturated amine compound or an unsaturated carboxyl compound that can react with the amine. Can be an acid reagent. This unsaturated carboxylic acid reagent and amine are described above. There is.

Examples of saturated amine compounds include N-(3,6-thioxaheptyl)maleimide, N -(3-dimethylaminopropyl)maleimide, and diethyl)maleimide. Preferred amines are ammonia and It is a primary amine-containing compound. Examples of such primary amine-containing compounds include a ammonia, N,N-dimethylhydrazine, methylamine, ethylamine, butyl Amine, 2-methoxyethylamine, N.

N-dimethyl-1,3-propanediamine, N-ethyl-N-methyl-1,3- Propanediamine, N-methyl-1,3-propanediamine, N-(3-amino propyl) morpholine, 3-methoxypropylamine, 3-isobutoxypropylamine amine and 4,7-di-oxyoctylamine, N-(3-aminopropylamine) )-N-1-methylpiperazine, N-(2-aminoethyl)piperazine, (2 -aminoethyl)pyridine, aminopyridine, 2-aminoethylpyridine, 2- 7minomethylfuran, 3-amino-2-oxotetrahydrofuran, N-(2- aminoethyl)pyrrolidine, 2-7minomethylpyrrolidine, 1-methyl-2-a Minomethylpyrrolidine, 1-amino-pyrrolidine, 1-(3-aminopropyl) -2-methylpiperidine, 4-aminomethylpiperidine, N-(2-aminoethyl ) Morpholine, 1-ethyl-3-aminopiperidine, 1-aminopiperidine, Included are N-ami7morpholine and the like. Among these compounds, N-(3-a (minopropyl) morpholine and N-ethyl-N-methyl-1,3-propanedi Amines are preferred, and N,N-dimethyl-1,3-propanediamine is highly preferred. Yes.

Another group of primary amine-containing compounds are various amine-terminated polyethers. child The less than amine polyethers of ine)■J, commercially available from Texaco Chemical Company. It is. Specific examples of these substances include Jeffamine "M-600; M(000; M-2005; and M-2070 amines Included.

Examples of dispersants-viscosity modifiers are listed in the following references: EP 17L, 167 3.587.90S3, 687.849 4.670. 1733, 756.954 4.320.0124, 320.019 (These contents are presented here with respect to the dispersant-viscosity modifier disclosure) .

The above dispersant is one or more post-treatment reagents selected from the group consisting of: Can be = boron compounds (described above), carbon disulfide, hydrogen sulfide, sulfur, salts sulfur chloride, alkenyl cyanide, carboxylic acid acylating agent, aldehyde, ketone, Urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphate, phosphorus Hydrocarbyl phosphate, Hydrocarbyl thiophosphate, Hydrocarbyl thiophosphite , phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl inthiocyanate, epoxide, episyl formaldehyde or formaldehyde-generating compounds and phenols, and sulfur and phenol.

The following U.S. patents describe post-treatments that can be applied to the carboxylic acid derivative compositions of the present invention. Disclosures of methods and post-treatment reagents are provided herein: U.S. Pat. ．． No. 087.936; No. 3,254,025; No. 3.256.185; No. 3 ．． No. 278.550; No. 3.282.955; No. 3.284.410; Kan 3 ．． No. 338,1132; No. 3.533.945; No. 3.639.242; No. No. 3.708.522; No. 3.859.318; No. 3,865.813: No. 4, 234.435 etc. British Patent Nos. 1,085.903 and 1.16 No. 2.436 also describes such a method.

In one embodiment, these dispersants are treated with at least one boron compound. Ru. The reaction between the dispersant and the boron compound is accomplished by simply mixing these reactants at the desired temperature. This can occur due to the combination of Typically this temperature is between about 50°C and about 250°C. be.

In some cases, this temperature may be below 25°C. The upper limit of this temperature is point of decomposition of the reaction mixture and/or product.

The amount of boron compound that reacts with this dispersant is determined for each mole of dispersant (i.e., atomic ratio of nitrogen or hydroxyl groups contained in the powder), about 0.1 to about 1 The amount is sufficient to provide 0 atomic percentage of boron. Preferred amounts of reactants are so as to provide from about 0.5 atomic percent to about 2 atomic percent boron per mole of dispersant. It is a large amount. For illustration purposes, an amine dispersant with 5 nitrogen atoms per molecule boron compounds with one boron atom per molecule used with 1 mole The amount of is in the range of about 0.1 moles to about 50 moles, preferably about 0.5 moles to about 10 moles. Within the molar range.

C dihydrocarbyl dithioline The oil composition of the present invention also includes (C) at least 18 Contains 1i dihydrocarbyl dithiophosphate metal salt: wherein R3 and R1 each independently have from 3 to about 13 carbon atoms, preferably preferably a hydrocarbyl group having from 3 to about 8 carbon atoms, where M is a metal; , and 2 is an integer equal to the valence of M.

The hydrocarbyl groups R3 and R4 in this dithiophosphate are alkyl groups, It can be a loalkyl group, an aralkyl group or an alkaryl group. Exemplary alkyl The groups include isopropyl group, isobutyl group, n-butyl group, 5ec-butyl group, species amyl group, n-hexyl group, methylisobutyl group, carbinyl group, heptyl group group, 2-ethylhexyl group, diisobutyl group, inoctyl group, nonyl group, behe Included are a nyl group, a decyl group, a dodecyl group, a tridecyl group, and the like. Example of a lower grade Rukylphenyl groups include butylphenyl, amyl phenyl, heptylphenyl, etc. which are included. Cycloalkyl groups are also useful and include: Mainly includes cyclohexyl and lower alkyl-cyclohexyl groups. Ru. A number of substituted hydrocarbon groups may also be used, e.g. chloropentyl, dichloro There are lophenyl and dichlorodecyl.

The dithiophosphoric acids from which metal salts useful in the present invention are prepared are well known. dihydrocal Bildithiophosphoric acids and their metal salts and methods of preparing such acids and salts Examples of laws include, for example, U.S. Pat. No. 4,263,150; ; No. 4.308.154; and No. 4.417.990. child The contents of these patents are hereby incorporated by reference for such disclosure.

This dithiophosphoric acid is a combination of phosphorus trisulfide and alcohol or phenol or alcohol. It is prepared by reacting a mixture of This reaction requires 1 mole of phosphorus trisulfide. contains 4 moles of alcohol or phenol per portion, and has a temperature of about 0°C to about 2°C. It can be carried out at temperatures in the range of 00°C. Therefore, 0.0-Gi-n- to bovine sildithio To prepare phosphoric acid, phosphorus trisulfide and 4 moles of n-hexyl alcohol are mixed into about 10 This includes reacting at a temperature of 0° C. for about 2 hours. Hydrogen sulfide is liberated and its residue A distillate is an acid in the definition. Metal salts of this acid are prepared by reaction with metal oxides. obtain. Simply mixing and heating these two reactants is sufficient for the reaction to occur. It is. The product obtained is sufficiently pure for the purposes of the present invention.

Dihydrocarpyldithiophosphate metal salts useful in the present invention include Group 1 metals, Group 1I metals, group metals, aluminium, lead, tin, molybdenum, manganese, cobalt and nickel. Salts containing Kel are included. Groups 1 and 1I (these are Groups 1a, 1I) tl, group 11a and group 11b) are listed in the Merck Index, 9th edition ( It is defined in the periodic table of elements (1976). Group 1I metal, aluminum , tin, iron, cobalt, lead, molybdenum, manganese, nickel and copper are preferred. Enter the new metal.

Zinc and copper are particularly useful metals. In one embodiment, the lubricating composition comprises: Contains zinc dihydrocarbyl dithiophosphate and copper dihydrocarbyl dithiophosphate. have Examples of metal compounds that can react with this acid include lithium oxide, lithium hydroxide, Mu, Sodium hydroxide, Sodium carbonate, Potassium hydroxide, Potassium carbonate, Oxide Silver, magnesium oxide, magnesium hydroxide, calcium oxide, zinc hydroxide, water Strontium oxide, cadmium oxide, cadmium hydroxide, barium oxide, oxide Aluminum, iron carbonate, copper hydroxide, copper oxide, lead hydroxide, tin butyrate, cobal hydroxide Nickel hydroxide, nickel carbonate, zinc oxide, etc.

In some cases, certain ingredients (e.g. small amounts of metal acetate or acetic acid) may be added to this Mixing with metal reactants accelerates the reaction and yields improved products. It will be done. For example, up to about 5% zinc acetate can be used in combination with the required amount of zinc oxide. The formation of zinc dithiophosphate is promoted by the use of zinc dithiophosphate.

In one preferred embodiment, the alkyl groups R3 and R4 are secondary alcohols. (e.g. isopropyl alcohol, secondary butyl alcohol, 2-pentanoyl alcohol, 2-methyl-4-pentanol, 2-hexanol, 3-hexanol, etc. ) is derived from

Particularly useful metal dithiophosphates are produced by the reaction of phosphorus trisulfide with an alcohol mixture. can be prepared from dithiophosphoric acids prepared in the following order: Furthermore, such mixtures Use alone cannot produce oil-soluble dithiophosphoric acids or their salts It becomes possible to use inexpensive alcohol. Therefore, isopropyl alcohol and A mixture of dithiophosphate and hexyl alcohol is a highly effective oil-soluble dithiophosphate metal salt. can be used to generate For the same reason, mixtures of dithiophosphoric acids are can react with other compounds of the genus to form cheaper oil-soluble salts.

This alcohol mixture is a mixture of different primary alcohols, different secondary alcohols, A mixture of coals or a mixture of primary and secondary alcohols. can be obtained. Examples of useful mixtures include: n-butanol and n- Octatool; n-pentanol and 2-ethyl-1-hexanol; isobutane Tanol and n-hexanol; isobutanol and isoamyl alcohol ; isopropanol and 2-methyl-4-pentanol; isopropanol and and secondary butyl alcohol; isopropanol and inoctyl alcohol etc. are included. Particularly useful alcohol mixtures include as little as about 20 mole parts isopropyl alcohol, [: In embodiments, at least 40 moles] is a mixture of secondary alcohols containing % isopropyl alcohol. Ru.

Generally, the oil compositions of the present invention have different compositions, based on the weight of the total oil composition. amount of one or more of the dithiophosphate metal salts identified above (e.g., about 0.01 % to about 2% by weight, more typically from about 0.01% to about 1% by weight). Ru. The dithiophosphate metal salt improves the anti-wear properties and oxidation properties of the oil compositions of the present invention. It is added to this composition to improve its preventive properties.

(Margin below) The following examples illustrate the preparation of dithiophosphate metal salts.

Example C-t 41 f / l / - 6 moles of 2-pentanol and 4 moles of isopropyl alcohol By reacting an alcohol mixture containing phosphorus with phosphorus trisulfide, Prepare phosphoric acid. This dithiophosphoric acid is then mixed with an oil slurry of zinc oxide. Make it react.

The amount of zinc oxide in this slurry is such that this dithiophosphoric acid is completely A solution of zinc acid in oil (10% oil) contains 9.5% phosphorus and 20.0% iodine. Contains corrugated iron and 10.5% zinc.

More specific examples of metal dithiophosphates useful in the lubricating oils of the present invention are listed in the table below. I'm getting lost. These dithiophosphate metal salts were prepared by the general method of Example C-1. prepared.

table Component C Nidithiophosphate metal salt Tenguse rowing R” R’ M construction C-2 (iso7° lobil + isooctyl) (60: 40) ll Zn 2 C-3n-nonyl n-nonyl Ba 2C-4 cyclohexyl cyclohexy Zn 2C-5 Inbutyl Isobutyl Zn 2C-6 Hexyl Hexy Le Ca 2 C-7n-decyl n-decyl Zn 2C-84-methyl-2-he°amyl 4-Methyl-2-ethyl amyl Cu 2C-9(n-)tyl + totyl) ( 1:1) v Zn2C-10 (iso7°ropyl + isooctyl) (1:1) w Ba2C-11 (iso7'rohydryl + 4-methyl-2-hemyl amyl) + (40 : 60) m Cu 2C-12 (Isofurobil + Isoamyl) (65: 35) m Zn 2C-13 (iso7°ropyru 15ec-7'fle) ( 40:60), Zn2 Other compounds considered for use in the lubricating composition of the present invention Las's dithiophosphate additives include the addition of the above dithiophosphate metal salts and epoxides. Things are included. Metal dithiophosphate salts useful in preparing such adducts are , most often zinc dithiophosphate. These epoxides are alkylene It can be an oxide or an aryl alkylene compound. these awalal Kylene oxide is styrene oxide, p-ethylstyrene oxide, α-methyl Rustyrene oxide, 3-β-naphthyl-1,1,3-butylene oxide, l- Illustrated by dodecylstyrene oxide, and p-chlorostyrene oxide Ru. These alkylene oxides mainly contain carbon atoms with 8 or less alkylene groups. Examples include lower alkylene oxides containing elementary atoms. Lower alki like this Examples of lene oxides include ethylene oxide, propylene oxide, 1,2-butene oxide, oxide, trimethylene oxide, tetramethylene oxide, butadiene mono There are epoxides, 1,2-hexene oxide and shrimp chlorohydrin. here Other epoxides useful in, for example, 9.10-epoxybutyl stearate , epoxidized soybean oil, epoxidized tung oil, and styrene and butadiene Examples include epoxidized copolymers with ene.

This adduct is created by simply mixing the dithiophosphate metal salt and the epoxide. can be obtained. This reaction is usually exothermic, with temperatures ranging from about 0°C to about 300°C. It can be carried out within wide temperature limits. Since this reaction is exothermic, it reduces the reaction temperature to For better control, one reactant (usually an epoxide) is added in small increments. This is best done by addition to the other reaction components. This reaction takes place in a solvent ( For example, in benzene, toluene, xylene, mineral oil, naphtha or n-hexane) And it can be done.

The chemical structure of this adduct is unknown. For the purposes of this invention, 1 mole of dithiophosphate and from about 0.25 moles to 5 moles (usually up to about 0.75 moles, or about 0.5 moles). 5 mol) of lower alkylene oxides (especially ethylene oxide and propylene) The adducts obtained by reaction with oxides) have been found to be particularly useful. , therefore preferred.

The preparation of such adducts is more particularly illustrated by the examples below.

Example c-14 2365 parts (3.33 moles) of inpropyl-isooctyldithioli were added to the reactor. zinc oxide (here, the molar ratio of isopropyl to inoctyl is (1:0) ．． 7)) and stirred at room temperature to generate an exotherm of 24-31 °C. At the same time, 38.6 parts (067 mol) of propylene oxide is added. This mixture Maintained at 80-9°C for 3 hours, then vacuum-stripped to 101°C at 7 nmHg. Rip it. This residue is filtered using a filter aid. This filtrate contains sulfur Oil of desired salts containing 17.1%, zinc 8.17% and lymph, 44% Solution (11.8% oil).

Other classes of dithiophosphates contemplated as useful in the lubricating compositions of the present invention The additive comprises (a) at least one dithiophosphoric acid as defined above; and (b) at least It also contains a mixed metal salt with an aliphatic carboxylic acid or a ring carboxylic acid.

The carboxylic acid usually has from 1 to about 3 carboxy groups, preferably 1 carboxy group. It can be a monocarboxylic or polycarboxylic acid containing carboxy groups. This card Rubonic acids have about 2 to about 40 carbon atoms, preferably about 2 to about 20 carbon atoms. It may contain elementary atoms, advantageously from about 5 to about 20 carbon atoms. This carboxylic acid can be any of the carboxylic acids listed above. Preferred carboxylic acids have the formula R5C0 0I (wherein R5 is preferably acetylenically unsaturated is an aliphatic or alicyclic hydrocarbon-based group containing no Suitable acids include Butanoic acid, pentanoic acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodeca acid, octadecanoic acid and arachidic acid, and olefinic acids (e.g. inic acid, linoleic acid, and lyric acid and lylic acid dimer).

In most cases R5 is a saturated aliphatic group, and especially a branched alkyl group (e.g. For example, isopropyl group or 3-hebutyl group). Examples of polycarboxylic acids include , succinic acid, alkylsuccinic acid, alkenylsuccinic acid, adipic acid, sebacic acid and citric acid.

Simply blending a metal salt of dithiophosphoric acid and a metal salt of carboxylic acid in the desired ratio. Mixed metal salts can be prepared by:

The equivalent ratio of dithiophosphate to carboxylate is from about 05:1 to about 400:1. It is between. Preferably, this ratio is between about 0.5:1 and about 200:1.

Advantageously, this ratio is from about 0.5:1 to about 100:1, preferably about 0.5:1. 1 to about 50=1, more preferably about 0.5:1 to about 20:1.

Further, this ratio may range from about 0.5:1 to about 4.5:1, preferably from about 2.5+1 to about 4.5:1. It can be about 4,25:1. For this purpose, the equivalent amount of dithiophosphoric acid is It is the value obtained by dividing the molecular weight by the number of -PSSH groups in it, and the equivalent weight of a carboxylic acid is its It is the value obtained by dividing the molecular weight of by the number of carboxy groups in it.

A second preferred method for preparing mixed metal salts useful in the present invention is to prepare mixtures of acids. are prepared in the desired ratio and this acid mixture is reacted with one of the above metal compounds. Is Rukoto. When this method of preparation is used, with respect to the equivalent amount of acid present, It is often possible to prepare salts containing excess metal; therefore, the acid 1 Mixed gold containing about 2 equivalents of metal per equivalent, especially up to about 15 equivalents of metal genus salts may be prepared.

The equivalent weight of a metal for this purpose is its atomic weight divided by its valence.

Alternatives of the above methods may also be used to prepare mixed metal salts useful in the present invention. It can be done. For example, a metal salt of either acid can be combined with another acid and the resulting formulation may react with additional metal bases.

The temperature at which the mixed metal salt is prepared is generally between about 30'C and about 150°C. , preferably up to about 125°C. This mixed salt is a mixture of acids and metal bases. If prepared by neutralization with It is preferred to use higher temperatures. Substantially inert, normally liquid organic diluent ( For example, the reaction is carried out in the presence of naphtha, benzene, xylene, mineral oil, etc. , often advantageous. If this diluent is mineral oil or is physically or If chemically similar, this mixed metal can be used as an additive in lubricants or functional fluids. There is no need to remove the genus salt before using it.

U.S. Patent Nos. 4.308.154 and 4.417.990 address these mixtures. describes a method for preparing mixed metal salts and discloses examples of such mixed metal salts. Ru. The disclosures of these patents are incorporated herein by reference.

The preparation of these mixed metal salts is illustrated by the examples below.

Example C-15 A mixture of 67 parts (1,63 equivalent jl) of zinc oxide and 48 parts of mineral oil was stirred at room temperature. , 401 parts (1 equivalent) of di(2-ethylhexyl)dithiophosphoric acid and 2 - Adding a mixture of 36 parts (0.25 equivalents) of bovine acid to ethyl over a period of 10 minutes. I can do it. During this addition, increase the temperature to 40'C. Once the addition is complete, this temperature is raised to 80°C in 3 hours. This mixture was then vacuum-steamed at 100'C. Tripping yields the desired mixed metal salt as a 91% solution in mineral oil.

Vomit! Kamibo-1 The composition of the invention also contains an antioxidant (D). However, (D) antioxidant and (C) the dithiophosphate metal salts are not the same. For example, (C) and (D ) are both dithiophosphate metal salts, provided that the metal (C) is the metal (D). is not the same as This antioxidant is useful in sulfur-containing compositions, alkylated aromatic amino acids, phenol, and an oil-soluble transition metal-containing compound.

The antioxidant may also be one or more sulfur-containing compositions. sulfurized book Substances that can form the sulfurized organic composition of the invention include oils, fatty acids or esters thereof. olefin or polyolefin produced therefrom, or Diels = Alder adducts are included.

Oils that can be sulphurized are natural or synthetic, including mineral oil, lard oil, , fatty alcohols and carbones derived from fatty acids or aliphatic carboxylic acids Acid esters (e.g. myristyl oleate and oleyl oleate), Whale oil, synthetic sperm whale oil substitutes, and synthetic unsaturated esters or glycans. Includes cerides.

Fatty acids generally contain about 3 to 30 carbon atoms.

Unsaturated fatty acids are generally contained in naturally occurring vegetable or animal fats and oils.

Such acids include palmitoleic acid, oleic acid, Included are linoleic acid, su/lenic acid and erucic acid. This fatty acid is a mixture of acids such as naturally occurring animal and vegetable oils, including beef tallow, stored fat (d el)Ot　fat), lard oil, tall oil, peanut oil, corn oil, Safflower oil, sesame oil, poppy seed oil, soybean oil, cottonseed oil, sunflower fM oil, or small malt oil).

Tall oil contains rosin acids (mainly abietic acid) and unsaturated fatty acids (mainly It is a mixture of oleic acid and linoleic acid). tall oil wood valve is a by-product of the sulfate process for the production of

This fatty acid ester also converts aliphatic olefinic acids of the above type into alcohols of the above type. and polyols. aliphatic Examples of alcohols include -hydric alcohols (e.g., methanol, ethanol, n- Proper tool or Improper tool; n-butanol, isobutanol, secondary (such as primary or tertiary butanol); and polyhydric alcohols (which include , ethylene glycol, propylene glycol, trimethylene glycol, neo pentyl glycol, glycerol, etc.).

The olefinic compounds that can be sulfurized are virtually diverse.

These compounds contain at least one olefin, defined as a non-aromatic double bond. Lefinic double bonds; i.e., those containing two aliphatic carbon atoms Ru. Broadly speaking, this olefin is defined by the formula R"'R"C=CR"3R"4 where each R'', R'', R'3 and R'4 are hydrogen or an organic group. Ru.

In general, the R" group in the above formula +, =te, hydrogen is -C(R")3, -C0OR' 5, -C0N(R")2, C00N(R">4, -COOM, -CN , -X, -YR'5 or -Ar, where each R5 is independently Hydrogen, alkyl, alkenyl, teryl, substituted alkyl, substituted alkyl kenyl or substituted aryl, and any two R°5 groups are alkylene or substituted alkylene, thereby having up to about 12 carbon atoms. A ring is formed; M is one equivalent of a metal cation (preferably Group 1 or Group II, e.g. lium, potassium, barium, calcium); X is halogen (e.g. chlorine, bromine or iodine); Y is oxygen or divalent ion cormorant; Ar is an aryl group or substituted aryl group having up to about 12 carbon atoms It is the basis.

Any two of cl, R-2, R"3 and R-4 can also be taken together, A kylene group or a substituted alkylene group may be formed. In other words, this olefin The ring-like compound may be a ring family.

In this olefinic compound, each non-hydrogen R group is usually independently an alkyl group. , an alkenyl group or an aryl group. Monoolefinic compounds and diolefinic compounds, especially the former are preferred, especially monoolefinic terminal Hydrocarbon; that is, R"3 and c4 are hydrogen;

1 and R'' have 1 to about 30 carbon atoms, preferably 1 to about 16 carbon atoms; elementary atoms, more preferably 1 to about 8 carbon atoms, even more preferably 1 alkyl or aryl having ~4 carbon atoms, especially alkyl (i.e. , the olefin being aliphatic) are preferred. Approximately 3 to 30 pieces carbon atoms, especially carbon atoms of about 3 to 16 (in most cases less than 9) Particularly desirable are olefinic compounds having children.

Isobutyne, propylene and their dimers, trimers and tetramers and mixtures are particularly preferred olefinic compounds. These compounds However, isobutylene and diisobutylene are particularly high in their usefulness and It is particularly desirable because sulfur-rich compositions can be prepared.

In other embodiments, the sulfurized organic compound is a sulfurized terpene compound. "Tell" As used herein and in the claims, the term "pen compound" includes Various isomeric terpene hydrocarbons with empirical formula c, aL6 (e.g. turpentine , pine oil (pine oH) and dipentene), and various Synthetic and naturally occurring oxygen-containing derivatives are intended to be included.

Mixtures of these various compounds are particularly useful for natural ingredients such as pine oil and turpentine. When natural products are used, they are generally utilized. For example, pine oil contains α-tetra Lupineol, β-terpineol, α-7 fenchol, Camphor, borneol/isoborneol, fenchone , estragole, dihydro-α-terpineol, a Contains a mixture of netol and other monoterpene hydrocarbons. indicated pine oil The specific ratios and amounts of the various components therein depend on the particular raw material and degree of purification. pine A group of products derived from root oils are manufactured by Hercules Inc. (H It is commercially available from Ercules Incorporated. hercules It is commercially available from Inc. and is commonly known as terpene alcohol. Pine oil products have been found to be particularly useful in preparing the sulfurized products of the present invention. ing. Pine oil products include α-Terpineol, α-Terpineol, Terpineol 318 Prime (Terpineol 3111 Pr1Ile ), Yar+wor 302, Hercovine Oil (Herco pineoil), Yarmol 302W, Yarmol F and Yarmol 60 It is commercially available from Hercules under the name .

In other embodiments, the sulfurized organic composition comprises a sulfur source and at least one diacetate. at least one sulfur-containing substance containing a reaction product with a Ruth-Alder adduct; be. Generally, the molar ratio of sulfur source to Diels-Alder adduct is about 0. ．． 75 to about 4.0, preferably about 1 to about 2.0, and More preferably, it is in the range of about 1 to about 1.8. In one embodiment, for the adduct The molar ratio of sulfur is about 0.8:1 to 1.2:1.

This Diels-Alder adduct can be used for diene synthesis or Diels-Alder reaction. is a well-known and art-recognized class of compounds prepared by chemical reactions. child A summary of the prior art for the class of compounds is given by A.S. Onischenko (A.S. Russian monograph by Dienov i S’ ntes, Izdatelstvo Ak ademii Nauk) 5SSR, found in 1963. (L, 7 Mandel (L, Mandel), A, S Onischenko, 4 (Dien e 5 synthesis).

New York, Daniel Devey & Company, Inc. (Daniel D. avey and Co Inc.), 1964, translated into English as ). The contents of this monograph, and the references cited herein, are incorporated herein by reference. It is shown as.

Basically, this diene synthesis (Diels-Alder reaction) requires at least one conjugated diene and at least one ethylenically or acetylenically unsaturated compound and the latter compound is a reaction with dienophiles. It is well known as Piperylene, isoprene, methylisoprene, chlorobrene and 1,3-butadiene in preparing this Diels-Alder adduct. Among the preferred dienes used are: Examples of cyclic dienes include cyclopentadiene , fulveneS, 1,3-cyclohexadiene, 1,3-cyclo Lohebutadiene, 1゜3.5-cyclohebutatriene (1,3,5-cyclo eptatrienes), cyclooctatetraene, and 1.3.5-cyclo There is Rononatrien.

Preferred classes of genophiles include formyl, cyano, nitro, carboxy, carbon small (and one electron) groups selected from groups such as It has an acceptor group. Typically, this hydrocarbyl group and substituted hydrocarbyl groups Bill groups, if present, each contain no more than 10 carbon atoms .

One preferred class of genophiles has at least 18i carboxylic acid ester groups. is represented by -C(0)O-Ra, where RiI represents up to about 40 carbon atoms. is a residue of a saturated aliphatic alcohol having a child, and the aliphatic alcohol from which -RQ is derived. The kohl can be any of the monohydric alcohols or polyhydric alcohols listed above. It is. Preferably, the alcohol is a lower aliphatic alcohol, and is preferably methanol, ethanol, propatool or butanol. .

In addition to this ethylenically unsaturated genophile, there are many useful acetyls such as: Renically unsaturated genophiles are present: propiolaldehyde, methylethini ketone, propylethynyl ketone, propenylethynyl ketone, propiolic acid , propionitrile, ethyl propiolate, tetrolic acid acid), propargyl aldehyde, acetylene dicarboxylic acid, acetylene dicarboxylic acid Dimethyl esters of carboxylic acids, dibenzoylacetylene, etc.

Typically, this adduct involves the reaction of equimolar amounts of diene and genophile. but However, if this genophile has more than one ethylenic bond, then it It is possible to react additional dienes if present in the reaction mixture .

Into this reaction mixture, substances useful as sulfurization promoters are often mixed. It's advantageous. These substances are acidic, basic or neutral. useful neutral substances and acidic substances, such as acidified clays (e.g. “Superfiltrol” (Sup erFiltrol) (sulfuric acid treated diatomaceous earth)), p-toluene sulfonate phosphoric acids, phosphorus-containing reagents (e.g., phosphorus-containing acids (e.g., dialkyldithiophosphoric acids) ), phosphorus-containing acid esters (e.g. triphenyl phosphate), phosphorus sulfide (phosphorus trisulfide), surfactants (eg lecithin), and surfactants (eg lecithin).

Preferred promoters are basic substances. These include inorganic acids (t[ and salts (e.g. for example, sodium hydroxide, calcium oxide and sodium sulfide). death However, the most desirable basic promoters include ammonia and amines. It is a nitrogen base.

The amount of accelerator material used generally depends on the total weight of the terpenic and olefinic compounds. approximately 0.0005 to 2.0% of the amount. Preferred ammonia and amine catalysts In this case, it is preferably about 0.0005 to 0.5 mol per mole of this total weight, About 0.001 to 0.1 mole is particularly preferred.

an accelerator, or any of the diluents for one or more of the accelerators listed above. Water is then also present in the reaction mixture. When water is present, the amount is , usually about 1 to 25% by weight of the olefinic compound. However, water The presence of substantially anhydrous water is not essential and when certain types of reactors are used, substantially anhydrous It may be advantageous to carry out this reaction under conditions of .

As described above, when a promoter is mixed into the reaction mixture, the reaction is It is generally accepted that the product is generally pale in color. ing.

a sulfur source used to prepare any of the sulfur-containing materials of the invention; Reagents include, for example, sulfur, sulfur halides (e.g. - sulfur chloride or di-salts) sulfur oxide), a mixture of hydrogen sulfide and sulfur or sulfur dioxide, etc.

Sulfur or a mixture of sulfur and hydrogen sulfide is often preferred. but However, it is understood that other sulfiding reagents may be substituted for it, if appropriate. It will be done. Commercially available sources of all sulfiding reagents are commonly used for the purposes of this invention; Impurities normally associated with commercial products of It can exist.

When this sulfidation reaction occurs by using only sulfur, the reaction is approximately This reagent at a temperature of 50 to 250°C, typically about 150 to about 210°C. occurs by simply heating it with sulfur. against sulfur in substances to be sulfided. The weight ratio is between about 5:1 and about 15=1, generally between about 5:1 and about 10=1. It is between. This sulfurization reaction is generally performed under an inert atmosphere (e.g. nitrogen). This is done with vigorous stirring. Either the components or reagents are significantly volatile at the reaction temperature. If so, the reaction vessel may be sealed and maintained under pressure. Sulfur is a component of other components. It is often advantageous to add portions to the mixture.

When a mixture of sulfur and hydrogen sulfide is used in the method of the invention, sulfur The amounts of sulfur and hydrogen sulfide per mole of each component are typically about 0.3 ~3 gram atoms, and about 0.1 to about 15 moles. The preferred range is that about 0.5 to about 2.0 gram atoms and about 0.4 to about 1.25 moles, respectively; The most desirable ranges are about 0.8 to about 1.8 gram atoms and about 0.4 gram atoms, respectively. ~0.8 mol. In this reaction mixture operation, these components are It is introduced at a level that provides scope.

In semi-continuous operation, these components can be mixed in any ratio, but the mass balance basis On a mass balance basis, within these ratios To be consumed in quantity, to exist. Therefore, for example, if the reaction vessel is initially filled with sulfur, If only terpenic and/or olefinic compounds and sulfides are loaded Hydrogen is added incrementally at such a rate that the desired ratio is obtained.

If a mixture of sulfur and hydrogen sulfide is used in this sulfidation reaction, The temperature range for the reaction is generally from about 50 to about 350°C. A preferred range is about 100'C to about 200C, with about 150 to about 180C being particularly suitable.

This reaction is often carried out at pressures above atmospheric (this is natural pressure, i.e. the reaction (can be, and usually is) under naturally occurring pressure during the process of Alternatively, pressure applied from the outside may be used. The exact pressure developed during the reaction is determined by the system Factors such as design and operation, reaction temperature, and vapor pressure of reactant and product components It depends on the factors and can change during the reaction process.

It is generally preferred that the reaction mixture consist primarily of the components and reagents described above. However, this reaction also requires inert solvents that are liquid within the temperature range used (e.g. For example, alcohols, ethers, esters, aliphatic hydrocarbons, halogenated aromatic carbons hydrogen, etc.). This reaction temperature is relatively high (e.g. approx. 200°C), sulfur can be evolved from the product. If the reaction temperature is low (e.g. , about 150-170''C) is used, this sulfur generation is avoided.

In some cases, in order to reduce active sulfur, the obtained It is desirable to treat the sulfurized products.

The term "active sulfur" includes sulfur in a form that can stain copper and similar materials. Standard tests are available to measure sulfur activity. activity An alternative method of treatment to reduce sulfur is to use lubricants containing sulfide compositions. A metal deactivator may be used.

The following examples relate to sulfurized compositions of the present invention.

Example D-1 In a reaction vessel, 780 parts of isopropyl alcohol, 752 m of water, 50% by weight hydroxide 35 parts of sl-'Jum aqueous solution, diatomaceous earth treated with sulfuric acid (Ingel hard coat) Poration (Engelhard Corporation) (Menloper) Superfil obtained from Menlo Park (Menlo Park, Niney Chassis) 60 parts of Super Filtrol, and 2 parts of sodium sulfide Fill 39 parts. The mixture is stirred and heated to 77-80°C. child The reaction temperature is maintained for 2 hours.

The mixture was cooled to 71°C, where it was cooled to a sulfurized olefin, which was 337 parts of C, 733 parts of 1-dodecene and 16 parts of Neodene 18 (obtained from Shell Chemical) Cl8-18 olefin mixture) and 1000 parts of the mixture. (prepared by reacting) is added to this mixture. This reaction mixture Heat to 77-80°C and maintain this temperature until the chlorine content reaches a maximum of 0.5 do. The reaction mixture was vacuum stripped to 80°C and 20 mInHg. do.

The residue is filtered through diatomaceous earth. This filtrate contains 19.0% sulfur and It has a specific gravity of 0.95.

Example D-2 A mixture of 100 parts of soybean oil and 50 parts of commercially available CI8 α-olefin was added under nitrogen. Heat to 175° C. and slowly add 17.4 parts of sulfur. Therefore, The exothermic reaction raises the temperature to 205°C. This mixture was heated to 188°C~2 Heating at 00°C for 5 hours, slowly cooling to 90°C and filtering yields 1 The desired product containing 0.13% sulfur results.

Example D-3 100 parts of soybean oil, 3.7 volumes of tall oil acid and commercially available Cl5-Illα-olefin A mixture of 46.3 parts of sulfur was heated to 165° C. under nitrogen and 17.3 parts of sulfur was added. Add 4 parts. The temperature of this mixture rises to 191°C. Temperature: 165°C Maintain at 200°C for 7 hours, then cool to 90°C and filter. this product contains 10.13% sulfur.

Example D-4 In a reaction vessel equipped with a condenser, thermometer and stirrer, add 93 parts of pine oil (0.5 equivalents). and 48 parts (1,5 equivalents) of sulfur. This mixture was heated with nitrogen. Heat to about 140° C. with blowing and maintain at this temperature for about 28 hours. cold After cooling, add the cue α-olefin (this is from Gulf Oil Chem. Gulf Oil Chemicals Company? (available under the generic trade name Gulftene 16) 111 Add part. After the addition is complete, replace the addition funnel with a nitrogen tube. this reaction The mixture is heated to 170°C while bubbling with nitrogen, and at this temperature Keep time. The mixture is cooled and filtered through filter aid. This filtrate is The desired product has a sulfur content of 19.01% (theoretical 19.04%).

Example D-5 (a) Contains 400 grams of toluene and 66.7 grams of aluminum chloride The mixture was cooled with a stirrer, nitrogen inlet tube, and solid carbon dioxide in a reflux condenser. Fill a 2 liter flask with a 640 grams of butyl acrylate (5 mo ) and 240.8 grams of toluene over a period of 0.25 hours. Add to AlCl3 slurry. During this time, the temperature is maintained in the range of 37-58°C.

Thereafter, 313 grams (58 moles) of butadiene was added to this stream over a period of 275 hours. Add to rally. During this time, the temperature of the reaction mass was maintained at 60-61°C by external cooling. Maintain at °C. The reaction mass was sparged with nitrogen for approximately 0.33 hours and then , transfer to a large separatory funnel, and add a solution of 150 grams of concentrated hydrochloric acid in 1100 grams of water. Wash with The product is then subjected to two further water washes.

In this water wash, 1000+ml of water is used for each wash. This washed reaction product is continuously distilled to remove unreacted butyl acrylate and toluene. child The residue of the first distillation step is further distilled at a pressure of 9-10 mmHg and its Afterwards, at 105-115°C, 785 grams of the desired adduct are collected.

(b) Diels-Alder adduct of butadiene-butyl acrylate (4550 grams, 25 moles), and 1,600 grams (50 moles) of sulfur in a stirrer, Fill a 12 liter flask equipped with a reflux condenser and nitrogen inlet. This anti The reaction mixture is heated at a temperature in the range of 150-155°C for 7 hours. During this time, 1 hour Nitrogen is passed through it at a rate of about 0.5 cubic feet per cubic foot. After heating, this mass is Upon cooling to warm temperature and filtering, the sulfur-containing product is the filtrate.

Component (D> can also be an alkylated aromatic amine. Examples include compounds represented by the following formula, where Ar3 and Ar' are independently and R8 is a mononuclear or polynuclear substituted or unsubstituted aromatic group; element, /10 gen, OH, NH2, SR, No2, or 1 to about 50 carbon atoms It is a hydrocarbyl group with a child. Ar3 and Ar' are the above aromatic groups. It can be either. When Ar' and/or Ar' is a substituted aromatic group, The number of substituents on Ar3 and/or Ar' (independently, the number of substituents on Ar3 and/or Ar' or up to the number of positions available for substitution on Ar'. These substituents are , independently, ]\logen (e.g., chlorine, bromine, etc.), 0HSNH2, SR, consisting of NO2, or a hydrocarbyl group having from 1 to about 50 carbon atoms selected from the group.

In a preferred embodiment, component (D) is represented by the formula: where R7 and and R8 are independently hydrogen or a hydrocarbon having from 1 to about 50 carbon atoms. a biyl group, preferably a hydrocarbyl group having from about 4 to about 20 carbon atoms; be. Examples of aromatic amines include p, p'-dioctyl diphenylamine; ruphenyl-β-naphthylamine; octylphenyl-α-naphthylamine; phenyl-α-naphthylamine; phenyl-β-naphthylamine; p-octylph phenyl-α-naphthylamine and 4-octylphenyl-1-octyl-β- Includes naphthylamine and di(nonylphenyl)amine; Nyl)amines are preferred.

U.S. Patent Nos. 2.558,2115; 3.601.632; 3.368. No. 975; and No. 3. SO5,225 is a diaryl within the scope of component (D) amines are disclosed. The contents of these patents are shown here for reference only. .

The antioxidant (D) of the present invention contains one or more of several types of phenolic compounds. It is possible. These phenolic compounds are metal-free phenolic compounds. It can be.

In one embodiment, the antioxidants of the invention include at least one metal-free Examples include hindered phenols.

Alkylene coupled derivatives of the hindered phenols may also be used. . Hindered phenol is (in the specification and claims) sterically hindered Defined as containing certain hydroxyl groups, these include hydroxyl groups that are in the Or a derivative of a dihydroboxydiaryl compound in the p-position.

This metal-free hindered phenol has the following formula I:

Can be represented by I+ and III: wherein each R9 is independently an alkyl group containing from 3 to about 9 carbon atoms; Each R11+ is hydrogen or an alkyl group, R11 is hydrogen or 1 to about 9 carbon atoms. an alkyl group containing an elementary atom, and each RI2 is independently hydrogen or methyl It is the basis. In a preferred embodiment, R1'' is about 3 to about 50 carbon atoms, preferably Preferably about 6 to about 20 carbon atoms, more preferably about 6 to about 12 carbon atoms. is an alkyl group containing carbon atoms. Examples of such groups include hexyl, Butyl, octyl, decyl, dodecyl, tripropenyl, tetrapropenyl, etc. is included. Examples of R9, R111 and R1+ groups include propyl, isopropyl, Lopyl, butyl, sec-butyl, tertiary-butyl, heptyl, octyl and noni files are included. Preferably, each R9 and R11 is a tertiary group (e.g. butyl, tertiary amyl, etc.). Phenols of the type represented by the formula ■ Such phenotypic compounds can be prepared by a variety of methods, and in one embodiment, such First, a substituted alkylphenol is prepared, and then, desirably, a 2-substituted alkylphenol is prepared. Alkylating this partially substituted phenol at the - and/or 6-positions. It is prepared in a stepwise manner. Tie represented by formula I+ and formula II+ When it is desired to prepare a coupled phenol, a second stage of alkaline Kylation is carried out under conditions that only one position ortho to the hydroxyl group is alkylated. be exposed. Examples of useful phenolic substances of the type represented by Formula I include: 2-t-butyl-4-heptylphenol: 2-t-butyl-4-oc Thylphenol; 2-t-butyl-4-dodecylphenol; 2,6-di-t- Butyl-4-butylphenol; 2,6-di-tert-butyl-4-hebutylphenol 2,6-di-t-butyl-4-dodecylphenol; 2-methyl-6-di -t-butyl-4-heptylphenol; 2,4-dimethyl-6-t-butylphenol phenol; 2,6-t-butyl-4-ethylphenol; 4-t-butyl catecho 2,4-di-t-butyl-p-cresol; 2,6-di-t-butyl-4 -methylphenol; and 2-methyl-6-di-tert-butyl-4-dotesylph henol.

Examples of ortho-coupled phenols of the type represented by formula I+ include: Included below = 2.2-bis(6-t-butyl-4-hebutylphenol); 2,2-bis(6-t-butyl-4-octylphenol); 2,5-bis(1 - A tie represented by formula 111 coupled with methylcyclohexylalkylene The phenolic compounds of formula I, in which R1+ is hydrogen, are chemical compounds and aldehydes (e.g. formaldehyde, acetaldehyde, etc.) ) or a ketone (eg acetone). phenol Methods for bridging chemical compounds with aldehydes and ketones are well known in the art. Well known, this method does not need to be described in detail here. Illustrate this method In order to prepare a phenolic compound represented by the formula (■) in which R1+ is hydrogen, a diluent ( (e.g., toluene or xylene) with a base and then this mixture. contacting the compound with an aldehyde or ketone. During this time, bring the mixture to reflux. and as the reaction progresses, water is removed. Formula II! Thailand represented by Examples of phenolic compounds include: 2.2'-methylene-bi- (6-tert-butyl-4-hebutylphenol); 2,2-methylene-bis(6-tert-butyl-4-hebutylphenol); -t-butyl-4-octylphenol): 2,2-methylene-bis-(4-do Decyl-6-t-butylphenol); 2,2'-methylene-bis-(4-octylphenol); 2,2-methylene-bis-(4-octyl phenol); 2,2-methylene-bis-(4-dodecylphenol); 2,2 ’-methylene-bis-(4-hebutylphenol); 2.2”-methylene-bis (6-t-butyl-4-dodecylphenol); 2.2°-methylene-bis( S-t-butyl-4-tetrabropenylfuninol); and 2,2°-methylene -bis(6-t-butyl-4-butylphenol).

The phenol coupled with this alkylene is phenol (2 equivalents) and 1 It is obtained by reacting with an equivalent amount of aldehyde or ketone. low molecular weight Aldehydes are preferred, and particularly preferred examples of useful aldehydes include formaldehydes. Hydehyde, their reversible polymers (e.g. paraformaldehyde), Trio Gyusan, Includes acetaldehyde and the like.

As used herein and in the claims, the term "formaldehyde" The term is considered to include such reversible polymers. This alkylene is a coupling The purified phenols are derived from phenols or substituted alkylphenols. and substituted alkylphenols are preferred. This phenol is It must have an ortho or rose position available for reaction with hydrogen.

In one embodiment, the phenol is a compound capable of producing sterically hindered hydroxyl groups. or contains one or more alkyl groups that cannot occur. This alkylene is a coupling Examples of hindered phenols that can be used in the formation of hindered phenols include: is included = 2,4-dimethylphenol; 2,4-di-t-butylphenol 2,6-di-t-butylphenol; 4-octyl-6-t-butylphenol rules etc.

In one embodiment, the alkylene-coupled phenol is prepared by Nor, as mentioned above, is an aliphatic compound with few rose positions (both containing 6 carbon atoms). It is a phenol substituted with a group. Generally, the alkyl group has 6 to 12 Contains carbon atoms. Preferred alkyl groups are ethylene, propylene, 1-butene. polymers of isobutyne and isobutyne, preferably propylene tetramer or trimer. It is derived from

The reaction between phenol and aldehydes, their polymers or ketones is usually carried out indoors. and about 150°C, preferably about 50-125°C. This reaction is , preferably acidic or basic substances (e.g. hydrochloric acid, acetic acid, ammonium hydroxide) sodium hydroxide, sodium hydroxide or potassium hydroxide). Usage The relative amounts of reagents used are not critical, but generally formaldehyde or It is preferable to use about 0.3 to about 2.0 moles of phenol per equivalent of aldehyde. This is the case.

The following example shows the formula! and of phenolic compounds of the type of formula II+ The preparation is illustrated.

Example D-6 A reaction vessel was charged with 3192 parts (12 moles) of 4-tetrapropenylphenol. Ru. Heat this phenol to 80°C for 30 minutes, and add 93% sulfuric acid solution to this container. Add 21 parts (0.2 mol) of liquid. Heat this mixture to 85°C and at 6 o'clock 1344 parts (24 moles) of isobutylene are added over time. This temperature is 85° and 91°C. After introducing inbutylene, the reaction system was heated at 85°C. Blow nitrogen at a rate of 2 standard cubic feet per hour for 30 minutes. . Calcium hydroxide (6 parts, 0.2 mol) was added to the reaction vessel along with 12 parts of water. I can do it. Heat this mixture to 130″C under nitrogen for 1.5 hours. . The reaction system was vacuum stored at 130'C and 20 mm of mercury for 30 minutes. Rip it. The residue is cooled to 90°C and filtered through diatomaceous earth. The desired product is obtained. The desired product has a specific gravity of 0901 and has a hydro The percentage of xyl (Grinard) is equal to 4.25 (theoretical value 4.49).

Example D-7 A reaction vessel is charged with 798 parts (3 moles) of 4-tetrapropenylphenol.

The phenol was heated to 95°C to 100°C, whereupon the container was charged with 93% Add 5 parts of sulfuric acid solution. This container was incubated for 1.7 hours at 100°C. Add 168 parts (3 moles) of tyrene. After introducing isobutylene, 1 Nitrogen at a rate of 2 standard cubic feet per hour for 172 hours at 00°C. Infuse the essence. 890 parts (2.98 moles) of the above phenol was added to this reaction vessel. Then heat to 34-40°C. In this container, add 37% formaldehyde water. Add solution (137 grams, 1.7 moles). This mixture, while removing water, Heat to 135°C. At 105-110°C, at a rate of 1.55 cfh, Start blowing nitrogen. The reaction system was maintained at 120°C for 3 hours under nitrogen. Ru. The reaction system was cooled to 83°C and the vessel was then filled with 50% sodium hydroxide. Add 4 parts (0.05 mol) of an aqueous solution of lium. This reaction system was heated at 135 mL under nitrogen. Heat to °C. The reaction was heated to 135°C and 20 ml for 10 min. Vacuum stripping down to 1 liter of mercury. This reaction system was cooled to 95°C, The residue is filtered through diatomaceous earth. This product has 5.47 hydroxyl Percentage of Grignard (theoretical value 5.5) and 682 (theoretical value 667) It has a molecular weight (vapor phase osmotic pressure) of

Example D-8 Replacing 4-hebutylphenol with an equivalent amount of tripropylenephenol Otherwise repeat the general method of Example D-6.

The substituted phenol obtained in this way contains 5.94% hydroxyl.

Example D-9 Except that the phenol of Example D-6 was replaced with the phenol of Example D-4t. repeat the general method of Example D-7. cup with methylene prepared in this way Blend phenol contains 5.74% hydroxyl.

In other embodiments, the lubricating compositions of the present invention are metal-free (i.e., ashless). ) may contain alkylphenol sulfides.

The alkylphenol from which this sulfide is prepared is also represented by the formula ■ discussed above. (where RI+ is hydrogen) type phenol. For example, Alkylphenols that can be converted to alkylphenol sulfide include 2-t- Butyl-4-hebutylphenol; 2-t-butyl-4-octylphenol; and 2-t-butyl-4-dodecylphenol.

The term "alkylphenol sulfide" refers to the term "alkylphenol sulfide" Monosulfides, disulfides, polysulfides, and alkylphenols Sulfur monochloride, sulfur dichloride or other products obtained by reaction with elemental sulfur It means to include things. 1 mole of phenol is 0°5 to 1.5 moles or more Reacts with sulfur compounds. For example, 1 mol of alkylphenol sulfide of alkylphenol and 0.5 to 2.0 moles of sulfur dichloride. can be easily obtained. The reaction mixture is typically heated at about 100°C for about 2 to 5 hours. maintained. The resulting sulfide is then dried and filtered. element sulfur is used Typically, temperatures of about 150-200°C or higher are used when It will be done. It is also desirable to carry out the drying operation under nitrogen or a similar inert gas. Yes.

Suitable basic alkylphenol sulfides are described, for example, in U.S. Pat. ．． No. 116, No. 3.410.798 and No. 4,021,419. , their contents are presented here for reference only.

These sulfur-containing phenols described in U.S. Pat. No. 4,021,419 The composition is made by sulfurizing a substituted phenol with sulfur or a sulfur halide. Afterwards, this sulfurized phenol is reacted with formaldehyde or their reversible polymers. It can be obtained by reacting. On the other hand, substituted phenols are first treated with formaldehyde. and then with sulfur or sulfur halides to form the desired alkyl Produces phenol sulfide. Disclosure of U.S. Patent No. 4.021.419 References are made for disclosure of such compounds and methods of preparing such compounds. It is presented here as a consideration. Synthetic oils of the type described below may be used in the present invention. It is used to replace mineral or natural oils used in preparing salts for use.

In other embodiments, the antioxidant (D) is a phenothiazine, a substituted phenothiazine, Jin, or expression! ■ Can be a derivative as represented by: Here, RI4 is a higher alkyl group, an alkenyl group, an aryl group, an alkyl group, or an alkenyl group. selected from the group consisting of karyl or aralkyl groups or mixtures thereof; R13 is an alkylene group, an alkenylene group, an aralkylene group, or a mixture of; each RI5 is independently alkyl, alkenyl, aryl, alkali aryl, arylalkyl, halogen, hydroxyl, alkoxy, alkylthio , arylthio, or fused aromatic rings, or mixtures thereof; a and b are , each independently greater than or equal to 0.

In other embodiments, the phenothiazine derivative may be represented by formula V: - where RI3, R14, RIS, a and b are as defined for formula IV is the same as

The above phenothiazine derivatives and methods for their preparation are described in U.S. Pat. No. 4,711 No. 5.095, the disclosure of this patent describes such methods and compounds. The teachings of are presented here for reference only. In one embodiment, dialkyl Diphenylamine reacts at high temperatures (e.g., in the range of 145°C to 205°C). treated with sulfur for a sufficient period of time to complete the process.

Catalysts such as iodine can be used to establish sulfur bridges.

Phenothiazine and its various derivatives are phenothiazines containing free NU groups. The compound has the formula R"SR+30H, where R1' and R13 are of formula IV. of formula IV by contacting with a thioalcohol of can be converted into a compound.

This thioalcohol is combined with mercaptan R1'SH and alkyl under basic conditions. Obtained by reaction with thioxide. On the other hand, this thioalcohol By reacting the terminal olefin and mercaptoethanol under Cal conditions, It can be obtained from The reaction between this thioalcohol and the phenothiazine compound is , in the presence of an inert solvent (eg, toluene, benzene, etc.). strength Acid catalysts (e.g. sulfuric acid or para-toluenesulfonic acid) Amounts of catalyst from about 1 part to about 50 parts per 00ffi are preferred. This reaction is generally , carried out at reflux temperature while removing the water formed. Conveniently, this reaction temperature may be maintained between 80°C and 170°C.

Compounds of the type of formula +y and V, where X is 1 or 2, That is, when it is desired to prepare a sulfone or sulfoxide, the above thios Derivatives prepared by reaction with alcohols are prepared under a blanket of inert gas. acid with an oxidizing agent such as hydrogen peroxide in a solvent such as glacial acetic acid or ethanol. be converted into Conveniently, partial oxidation occurs at about 20"C to about 150C. Examples include the use of non-phenolic antioxidants (D>) in the functional fluids of the present invention. 1 illustrates the preparation of phenothiazines that can be used.

Example D-10 1 mole of phenothiazine was added to a 1 liter round bottom flask along with 300 μl of toluene. Put it in Sco. A nitrogen blanket is maintained in the reactor. Phenothiazine and toluene, 0.05 mole of sulfuric acid catalyst is added. Then this mixture Heat the material to reflux temperature and add n-dodecylthioethanoate over approximately 90 minutes. Add 1.1 mol of alcohol dropwise. As water is formed during the reaction process, Remove continuously.

The reaction mixture was stirred continuously under reflux until virtually no water was evolved. do. The reaction mixture is then cooled to 90'C. This sulfuric acid catalyst is Neutralize with sodium chloride. This solvent was then heated to 2 Pa vacuum at 110″C. Remove it below. Filtration of this residue gave a 95% yield of the desired product. Ru.

In other embodiments, the antioxidant (D) is a transition metal-containing composition. this Transition metal-containing antioxidants are oil-soluble. The composition generally includes titanium, At least one selected from manganese, cobalt, nickel, copper, and zinc of transition metals, preferably selected from manganese, copper and zinc. i, more preferably copper. These metals are nitrates, nitrites Acid salts, halides, oxyhalides, carboxylates, borates, phosphates , phosphites, sulfates, sulfites, carbonates and oxide forms. this Transition metal-containing compositions are generally in the form of metal-organic compound complexes. This existence Organic compounds include carboxylic acids and esters, monothiophosphoric acids and dithiophosphoric acids , dithiocarbamic acid, and dispersants. Generally, this transition metal-containing The composition contains a small number of carbon atoms (about 5 do.

In one embodiment, the organic compound is a carboxylic acid. This carboxylic acid is one ~ about 10 carboxyl groups, and 2 to about 75 carbon atoms, preferably Containing 2 to about 30 carbon atoms, more preferably 2 to about 24 carbon atoms. It can be a monocarboxylic acid or a polycarboxylic acid with. An example of monocarboxylic acid are 2-ethylhexanoic acid, octanoic acid, decanoic acid, oleic acid, linoleic acid, Included are stearic acid and gluconic acid. Examples of polycarboxylic acids include amber acids, malonic acid, citraconic acid, and substituted forms of these acids.

This carboxylic acid is one of the above hydrocarbyl ltm carboxylic acid acyl north side. can be obtained.

In other embodiments, the organic compound is a monothiophosphoric acid or a dithiophosphoric acid. Ru. The dithiophosphoric acid can be any of the phosphoric acids listed above (dihydrocarbyl (see dithiophosphates). Monothiophosphoric acid can be converted to dithiophosphoric acid by steam or water. It is prepared by treating with

In other embodiments, the organic compound is a monothiocarbamate or a dithiocarbamate. It is bamic acid. Monothiocarbamic acid or dithiocarbamic acid is carbon disulfide Reaction between primary amine or carbon oxysulfide and primary amine or secondary amine. By reacting: II is produced. These amines can be any of the above amines It can be.

In other embodiments, the organic compound is a phenol, an aromatic amine, or It can be any dispersant. In a preferred embodiment, the transition metal-containing composition is a lower carboxylic acid-transition metal monodispersant complex. This lower alkyl cal Bonic acids contain from 1 to about 7 carbon atoms and include formic acid, acetic acid, propionic acid, examples include phosphoric acid, butanoic acid, 2-ethyl hexanic acid, benzoic acid and salicylic acid. Ru. The dispersant can be any of the dispersants described above, preferably the dispersant is , a nitrogen-containing carboxylic acid dispersant. This transition metal complex is up to the decomposition temperature of the reaction mixture, typically from about 25°C to about 100°C. It is prepared by blending a lower carboxylate of a transition metal with a dispersant. Ru. Solvents such as quinolene, toluene, naphtha or mineral oil may be used.

In Example D-1 50 parts of copper acetate hydrate, 283 parts of 100% neutral mineral oil, 250 ml of xylene and 507 parts of the acylated nitrogen intermediate were heated at 160"C for 32 hours, and an additional 10 Add 3240 parts of neutral mineral oil and heat at 130°C to 240°C for 3.5 hours. A metal composite is obtained. This acylated nitrogen intermediate is a polybutene-substituted anhydride 4.392 parts of citric acid (which has a number average molecular weight of 1000 and a chlorine content of 4.3%) By reacting a chlorinated polybutene with a 20 mol% excess of maleic anhydride with , prepared) and 3 parts by weight of triethylenetetramine and diethylenetriamine. and 540 parts of an alkyleneamine polyamine mixture. It is prepared from

The reaction system was vacuum stripped to 110°C and 5 mm of mercury. Ru. This reaction system was filtered through diatomaceous earth, resulting in 59% oil and 0.3% oil by weight. A filtrate is produced having 1.2% by weight of nitrogen and 1.2% by weight of nitrogen.

Example D-12 (a) 420 parts (7 moles) of isopropyl alcohol and n-butyl alcohol A mixture of 518 parts (7 moles) was prepared and heated to 60 °C under nitrogen atmosphere. Heat. Phosphorus disulfide (647 parts, 2 ．． 91 mol) is added over 1 hour. While cooling the mixture, add 1 Stir for an hour.

When this material is filtered through a filter aid, the filtrate is the desired dithiophosphoric acid.

(b) preparing a mixture of 69 parts (0.97 equivalents) of cuprous oxide and 38 parts of mineral oil; 239 parts (0.88 equivalents) of the dithiophosphoric acid prepared in Example D-13(a) was added to approximately Add over 2 hours. The reaction is slightly exothermic during the addition; The mixture is then stirred for a further 3 hours while maintaining the temperature at about 70°C. This mixture Strip the mixture to 105°C/10 m+sHg and filter . The filtrate is a dark green liquid containing 17.3% copper.

Magnesium overbase The lubricating compositions of the present invention also include at least an ill of magnesium overbased Sulfonic acids, carboxylic acids or phosphorous acids or derivatives thereof, preferably sulfonic acids Contains sulfonic acid.

These acids have been described above. Generally, these magnesium salts are It has the same metal ratios as described above for potassium metal salts.

These magnesium salts can be used in place of basic alkali metal compounds. using a sium compound, preferably magnesium oxide or magnesium hydroxide Otherwise, they are prepared in a similar manner to the alkali metal salts.

Magnesium overbased salts and methods of their preparation are disclosed in U.S. Pat. No. 29.109; No. 4.129.508; No. 4.627.9211; and No. 4.775.490. Regarding the disclosure of these contents, , shown here.

The following examples describe magnesium salts useful in the present invention.

Example F,-1 906 grams of an oil solution of alkylphenyl sulfonic acid (average molecular weight 450) (1,5 equivalents), 564 grams of mineral oil, 600 grams of toluene, magnesium oxide A reaction mixture containing 95.7 grams (4,4 equivalents) and 1 zO grams of water was , about 78°C to 85°C at a rate of about 3 cubic feet of carbon dioxide per hour. Carbonate for about 7 hours at a temperature of . Stir the reaction mixture constantly during this time. Stir. The carbonation was stopped and the reaction product was heated to 20 mra, (Hg, ) Stripping is performed by heating to 165°C at a pressure of . this strippy Filter the washing product. This filtrate contains the desired basic sulfonate having a metal ratio of approximately 3. This is an oil solution of magnesium phosphate.

Example E-2 135 parts mineral oil (all "parts" are parts by weight unless otherwise indicated), xylene 330 parts of alkylphenyl sulfonic acid (average molecular weight 425) in mineral oil 2 00 parts (0,235 equivalents), tall oil acid 19 parts (0,068 equivalents), magnesium oxide Contains 60 parts of Si (approximately 2.75 equivalents), 83 parts of methanol, and 62 parts of water. The reaction mixture was heated at the reflux temperature of methanol with 15 parts of carbon dioxide per hour. carbonate for about 2 hours. Next, the introduction rate of carbon dioxide is Reduce to about 7 parts per hour and increase to a temperature of about 98°C for 3 hours. Methanol is removed by removing the methanol. Add 47 parts of water and bring the temperature to approximately 95°C. Continue carbonation for an additional 3.5 hours at 1°C. This carbonated mixture by heating the material for 2.5 hours to a temperature of 140°C to 145°C. , to strip. This results in a basic matrix characterized by a metal ratio of approximately 10. An oil solution of the magnesium salt is obtained.

The carbonated mixture is then cooled to about 60°C to 65°C, and In addition, 208 parts of xylene, 60 parts of magnesium oxide, 83 parts of methanol and Add 62 parts of water. 2 at a rate of 15 parts per hour at the reflux temperature of methanol. Restart carbonation over time. The addition rate of carbon dioxide is 7 per hour. temperature to approximately 95°C for 3 hours. Remove tanol. Add 41.5 parts of water and at a rate of 7 parts per hour Continue carbonation for 3.5 hours at a temperature of about 90'C to about 95C.

The carbonated mass is then heated to about 150°C to 160°C for 3.5 hours. , then further reduce the pressure to 20 + u, (Hg,) at this temperature. stripping. This carbonated reaction product is then filtered. pass This filtrate contains the desired basic magnesium, characterized by a metal ratio of 20. It is an oil solution of um salt.

The lubricating composition of the present invention is suitable for compression engines and spark ignition engines, preferably spark ignition engines. Effective in lubricating spark ignition engines. The composition of the present invention can be used under operating conditions. Provide effective protection to the engine underneath. This lubricating composition as described above contains a major amount of oil of lubricating viscosity, and (A) a sulfonic acid, a carboxylic acid or is an alkali metal overbase of at least one phosphorus-containing acid or derivative thereof. (B) at least one dispersant; (C) at least one dihydrocarbon salt; rubirdithiophosphate metal salt, (D) at least one antioxidant, and (E) at least a sulfonic, carboxylic or phosphoric acid containing acid or a derivative thereof; Contains one magnesium overbased metal salt.

The lubricating compositions and methods of the present invention use oils of lubricating viscosity. lubricating viscosity Certain oils include natural or synthetic lubricating oils and mixtures thereof. It will be done. Natural oils include animal oils, vegetable oils, mineral lubricating oils, and solvent-treated or acid-treated oils. mineral oils derived from coal or shale. synthesis Lubricating oils include hydrocarbon oils, halo-substituted hydrocarbon oils, alkylene oxide polymers, Esters of dicarboxylic acids and polyols, esters of phosphorus-containing acids, polymer tetra Includes hydrofuran and silicone-based oils.

Specific examples of oils of lubricating viscosity are described in U.S. Pat. State Patent Publication No. 107.282, the subject matter of both patents relates to lubricating oils. Disclosures are provided herein by reference. Basic and concise explanation of lubricant base oils The description is based on the paper “Lubricating Oil” by D. V. Brock. , Hao 1 cant E■mu group and■, vol. 43, p. 184-185 (1987 This was announced in March 2017). The content of this paper is based on disclosures regarding lubricants. It is shown here for reference. The description of oils of lubricating viscosity is Patent No. 4.582.618 (included in column 2, line 37 to column 3, line 63) ), which contains information on disclosure of oils of lubricating viscosity. It is presented here as a consideration.

The above components are generally present in amounts that provide effective protection to the engine. This Al The alkal metal salt (A) is present in an amount of at least about 0.001 g equivalent, preferably about 0.0025, more preferably about 0.00 31, even more preferably in an amount providing about 0,0037. in general, The alkali metal salt (A) is about 0.0075 g per 100 grams of the lubricating composition. present in an amount to provide an equivalent amount of alkali metal, preferably up to about a, ooso .

In other embodiments, the alkali metal salt (A) is about 0.15% by weight of the composition. %, preferably about 0.20% by weight, more preferably about 0.25% by weight, and even More preferably it is present in an amount of about 0.30% by weight. Generally, this alkali metal salt (A) up to about 0.60%, preferably up to about 0.40% by weight of the composition. Exists in amounts of . The dispersant (B) generally comprises at least about 1% of the composition. ．． 60% by weight, preferably about 1.8% by weight, more preferably about 2.25% by weight exists in an amount of The dispersant (B) generally comprises about 5.0% by weight of the composition. and preferably present in an amount up to about 4.0% by weight, more preferably about 3.5% by weight. Exists. The hydrocarbyl dithiophosphate metal salt (C) is generally used in the composition. from about 0.1%, preferably from about 0.5%, more preferably from about 0. ．． 7% by weight, up to about 2.0% by weight, preferably up to about 1.75% by weight, and even It is preferably present in an amount up to about 1.5% by weight. This antioxidant (D) is Generally, from about 0.01%, preferably from about 0.03% to about Present in an amount up to 2.0% by weight, preferably up to about 1.0% by weight. Other embodiments In the lubricating composition, the antioxidant preferably ranges from about 50 ppm to about 50 ppm of the lubricating composition. From about 100 ppm, more preferably from about 125 ppm to about 2000 ppm ppm, generally up to about 1000 ppm, preferably up to about soo ppm. and preferably up to about 200 ppm, more preferably up to about 150 ppll. present in an amount to provide a transition metal at This over-based sulfonic acid magnesi um(E) from at least about 0.15% by weight of the composition, preferably from about 0. ．． It is present in an amount from 20% by weight, more preferably from about 0.25% by weight. child Magnesium sulfonate (E) generally comprises up to about 2.0% by weight of the composition. , preferably in an amount up to about 1.5% by weight, more preferably up to about 1.0% by weight. exist.

The lubricating compositions of the present invention do not contain overbased calcium sulfonates.

Use of the term "does not contain" refers to substantially overbased sulfonic acid carboxylic acids. Represents a composition that does not contain sium. This overbased calcium sulfonate The metal ratio is typically between 1.5 and 40. In other embodiments, these compositions Calcium-overbased phenate (this includes -based alkylene-coupled phenate and calcium (contains bar-based and sulfur-coupled phenate). do not have. The lubricating compositions of the present invention generally contain less than about 0.08% by weight, preferably is less than about 0.07% by weight, more preferably less than about 0.05% by weight. Contains calcium metal. Certain additives of the invention contain some amount of calcium. Um may be present as an impurity. These small amounts of calcium make it possible for the present invention to It may be present provided it does not adversely affect the composition.

The lubricating compositions of the present invention may be used alone or in combination with any other well known additives. They can also be used together. These additives include, but are not limited to: Not specified: anti-wear agents, extreme pressure agents, emulsifiers, demulsifiers, friction modifiers, rust inhibitors, corrosion Food inhibitors, viscosity modifiers, pour point depressants, dyes and foam suppressants. These additives are , may be present in varying amounts depending on the needs of the final product.

Corrosion inhibitors, extreme pressure agents and anti-wear agents include, but are not limited to: metal salts of niphosphorus-containing acids, chlorinated aliphatic hydrocarbons; phosphorus-containing esters (This includes dihydrocarbyl phosphite and trihydrocarbyl phosphite. boron-containing compounds including boric acid esters; dimercaptothiadia Sol conductor; benzothiazole derivative; aminomercaptothiazole derivative; and molybdenum compounds.

Viscosity modifiers include, but are not limited to: polyisobutene , polymethacrylic acid ester, polyacrylic acid ester, diene polymer, polyamide alkylstyrene, alkenylaryl conjugated diene copolymer, preferably styrene. (maleic anhydride copolymer ester), polyolefin and multifunctional viscosity Improver.

Pour point depressants are a particularly useful type often included in the lubricating oils described herein. It is an additive. For example, C, V, Smalheer ) and R, Kennedy Smith (R, KennedySa+1th) -Lub ricant Additives-(Regius Heels Company Publications) Lezius-Hiles Co+mpany Publisher (S), Cleveland, Ohio, 1967), page 8.

Antifoam agents used to reduce or prevent the formation of stable foam include Included are silicone or organic polymers. These examples, and further antifoam combinations The product is “Foam C.

ntrol Agents” (Henry T, K. erner), Noyes Data Corporation 9.125-162 (1976).

These and other additives are described in U.S. Pat. No. 4.582.618 (No. (included in column 52, column 17, line 16) are described in great detail. , the contents of which include disclosure of other additives that may be used in combination with the present invention; Shown here.

The lubricating composition of the present invention contains the above components (A) to (D) in an oil with lubricating viscosity. by blending with or without any additional additives. prepared. The blend is made from room temperature to the decomposition temperature of this mixture or the individual components. By mixing these ingredients (usually by stirring) at a temperature of It will be done. Generally, these ingredients are heated at a temperature of about 25°C to about 250°C, preferably preferably at a temperature of up to about 200°C, more preferably at a temperature of up to about 150°C, or more preferably at a temperature of up to about 100°C.

The table below contains examples illustrating the lubricants of the present invention. In this table, r Ba1. J. represents that the remaining amount of this composition is oil. The amount of each component in Examples 1-9 is , measured in volume percent, and the amount of oil-containing product of the indicated additive It reflects.

Example lubricant (volume%) Gosohoko 123 Soil 1 A-10,350,26---0,350,35A-4-1---OJO--- ---1-B-15,5--5,55,55,58-i2 ---6.3- ------=-C-10,750,750!8 0,75 0.75D- 6-------0,31--(L'LT-Yu'a) Example lubricant (volume%) Raw m2, upper 23, soil i Silicone antifoaming agent 80ppm 80ppi 80ppm 80ppi 80pp o+oil Ba1. Ba1. Bat, Ba1. Bal.

(Margin below) Example lubricant (volume%) Double bottom Wataru I 89 A-10, 350, 250, 250, 32B-16, 05, 06, 35, 5 C-10,810,1140,771,0D-6---0,350,75-1- Glycerol monooleate or oleylamide 0.2 0.1 0.1 0.1 Example lubricant (volume%) ! Twin 22 6789 Silicone antifoaming agent 80ppm 80ppm 80ppm 80ppm oil B a1. Ba1. Ba1. Bal.

(Margin below) The lubricating oil compositions of the present invention exhibit a tendency to reduce degradation under conditions of use, thereby corrosion, abrasion, and undesirable deposits (face, sludge, carbonaceous material and wood Greasy substances (which adhere to various engine parts and reduce engine efficiency) tend to form)). Lubricating oils may also be formulated according to the present invention, As a result, fuel economy is improved when used in the crankcase of a passenger car.

Although the invention has been described with respect to a preferred embodiment thereof, various variations thereof may be described. Further, upon reading this specification, it should be understood that this will be apparent to those skilled in the art. follow Therefore, the invention disclosed herein should include such modifications as fall within the scope of the appended claims. It should be understood that this is intended to be

Essential book The present invention comprises a major amount of oil of lubricating viscosity; ), (D) and (E): (A) at least about 0.001 g equivalent of aluminum per 100 grams of the lubricating composition; an alkali metal salt of at least one acidic organic compound in an amount to provide potassium metal; (B) a dispersion of at least about 1.6011% of IN; (C) At least molf! Dihydrocarbyl dithiophosphate metal salt (D>less At least one antioxidant; (E) Magnesium overbased metal of at least one acidic organic compound Salt: Provided that the lubricating oil composition contains oat 1'-based calcium sulfonate and and oat <--based calcium phenate, and the composition contains about 0.0 contains less than 8% calcium by weight and (C) and (D) are not the same do not have.

Copy and translation of written amendment) Submission (Article 184-7, Paragraph 1 of the Patent Act) December 1992 21st-

Claims (1)

[Claims] 1. A major amount of oil of lubricating viscosity; and (A), (B), (C), ( A lubricating oil composition containing D) and (E): (A) 100 grams of the lubricating composition. in an amount to provide at least about 0.0019 equivalents of alkali metal per (B) at least one alkali metal overbased salt of an acidic organic compound; (C) about 1.60% by weight of at least one dispersant; (C) at least one dihydrogen; Drocarbyl dithiophosphate metal salt; (D) at least one antioxidant; (E) Magnesium overbased metal of at least one acidic organic compound Salt: Provided that the lubricating oil composition contains overbased calcium sulfonate and bar-based calcium phenate, the composition has a weight of about 0.08 % calcium and (C) and (D) are not the same. 2. The alkali metal in (A) is sodium, potassium or lithium. , the composition of claim 1. 3. Claims wherein the overbased salt (A) has a metal ratio of about 3 to about 40. Item 1. The composition according to item 1. 4. The acidic organic compound may be a sulfonic acid, a carboxylic acid, a phosphorus-containing acid or a phenolic acid. 2. A composition according to claim 1, wherein the composition is a polymer or a derivative thereof. 5. The overbased salt mentioned in the previous offense (A) is an overbased sodium sulfonate. 2. The composition of claim 1, wherein the composition is a potassium sulfonate or an overbased potassium sulfonate. thing. 6. The overbased salt of (A) is an overbased sodium carboxylic acid salt. 2. The composition of claim 1, wherein the composition is a potassium carboxylate or an overbased potassium carboxylate. . 7. 7. The carboxylic acid salt is a hydrocarbyl-substituted carboxylic acid salt. The compositions described, wherein the hydrocarbyl groups have an M of about 400 to about 5,000. A composition derived from a polyalkene having n. 8. 7. The polyalkene has a Mn of about 800 to about 2,500. The composition described in . 9. The overbased salt of (A) is an overbased sodium thiophosphate. The composition of claim 1, wherein the composition is a potassium thiophosphate or an overbased potassium thiophosphate. . 10. The dispersant (B) is (a) at least one nitrogen-containing carboxylic acid dispersant. , (b) at least one amine dispersant, (c) at least one ester dispersant. (d) at least one Mannich dispersant; (e) at least one dispersant. The viscosity modifier according to claim 1, which is a viscosity modifier, or (f) a mixture of two or more thereof. Composition. 11. The dispersant (B) comprises (a) a hydrocarbyl-substituted carboxylic acid acylating agent; , reacts with an amine having at least one primary or secondary amino group. at least one nitrogen-containing carboxylic acid dispersant prepared by 11. The composition of claim 10, wherein the hydrocarbyl groups are about 500 or more. A composition derived from a polyalkene having an Mn of about 5,000. 12. 7. The polyalkene has an Mn of about 800 to about 2,500. 12. The composition according to 11. 13. The hydrocarbyl-substituted carboxylic acid acylating agent is a hydrocarbyl-substituted carboxylic acid acylating agent. 12. The composition of claim 11, wherein the acylating agent is a succinic acid acylating agent. , an average value of at least 1.3 succinic acid groups for each equivalent of hydrocarbyl groups. and the hydrocarbyl group has an Mn value of about 1300 to about 5000 and and a polyalkene having a Mw/Mn value of about 1.5 to about 4. thing. 14. 12. The composition of claim 11, wherein the amine is an alkylene polyamine. . 15. The dispersant (B) comprises (b) a hydrocarbyl-substituted carboxylic acid acylating agent. Ester dispersion prepared by reaction with at least one polyhydroxy compound 11. The composition of claim 10, wherein the hydrocarbyl groups are about 50 A composition derived from a polyalkene having an Mn of 0 to about 5,000. 16. The polyhydroxy compound has 2 to about 8 hydroxyl groups and 2 to about 8 hydroxyl groups. 16. The composition of claim 15, which is a compound having 20 carbon atoms. 17. The polyhydroxy compound is pentaerythritol, trimethylol, Lopane, glycerol, sorbitol, ethylene glycol, tris(hydroxy) simethyl)aminomethane or dimers or trimers thereof. 15. The composition according to 15. 18. 16. The ester dispersant of claim 15, wherein the ester dispersant further reacts with an amine. Composition. 19. 19. The composition of claim 18, wherein the amine is an alkylene polyamine. . 20. The dihydrocarbyl dithiophosphate metal salt (C) contains at least one dihydrocarbyl dithiophosphate metal salt (C). 2. The composition of claim 1, which is zinc hydrocarbyl dithiophosphate. 21. The antioxidant (D) is present in at least one sulfur-containing composition, at least also one alkylated aromatic amine, at least one phenol, at least one 2. The antioxidant according to claim 1, wherein the antioxidant is an oil-soluble transition metal-containing antioxidant or a mixture thereof. Compositions as described. 22. The antioxidant (D) is alkylene-coupled phenol. 22. The composition of claim 21. 23. The antioxidant (D) is 2,6-di-t-alkyl-4-hydrocarbyl. 22. The composition of claim 21, which is phenol. 24. The antioxidant (D) is a sulfur-coupled phenol. A composition according to claim 21. 25. The antioxidant (D) is at least one transition metal-containing antioxidant. 22. The composition of claim 21. 26. 26. The composition of claim 25, wherein the transition metal is copper. 27. The antioxidant (D) is at least one dihydrocarbyldithioline. 22. The composition of claim 21, which is an acid copper. 28. Claim 1, wherein (E) is an overbased magnesium sulfonate. Compositions as described. 29. The composition of claim 1, containing less than about 0.01% calcium by weight. A product. 30. The composition of claim 1, which is a lubricant for spark ignition engines. 31. a major amount of oil of lubricating viscosity; and (A), (B), (C), A lubricating oil composition containing (D) and (E): (A) 100 grams of the lubricating composition; provides at least about 0.0019 equivalents of sodium or potassium per gram. of at least one sulfonic acid or carboxylic acid in an amount of based salt or potassium overbased salt; (B) at least about 1.60 wt. % of at least one dispersant; (C) at least one dihydrocarbyldithyl Zinc olinate; (D) at least one antioxidant; (E) at least one overbased magnesium sulfonate, provided that the The lubricating oil composition includes overbased calcium sulfonate and overbased does not contain calcium phenate, (D) and (C) are not the same, and The composition contains less than about 0.08% calcium by weight. 32. The dispersant (B) is (a) at least one nitrogen-containing carboxylic acid dispersant. , (b) at least one amine dispersant, (c) at least one ester dispersant. (d) at least one Mannich dispersant; (e) at least one dispersant. 32. A viscosity modifier, or (f) a mixture of two or more thereof. Composition of. 33. The dispersant (B) comprises (a) a hydrocarbyl-substituted carboxylic acid acylating agent; at least one nitrogen-containing carbon prepared by reacting with a polyamine 33. The composition of claim 32, wherein the composition is a rubonic acid dispersant, wherein the hydrocarbyl the group is derived from a polyalkene having an Mn of about 500 to about 5,000; Composition. 34. The hydrocarbyl-substituted carboxylic acid acylating agent is a hydrocarbyl-substituted carboxylic acid acylating agent. 34. The composition of claim 33, wherein the acylating agent is an acid acylating agent. Each equivalent of dorocarbyl groups has an average of at least 1.3 succinic acid groups. and the hydrocarbyl group has an Mn value of about 1300 to about 5000 and about A composition derived from a polyalkene having a Mw/Mn value of from 1.5 to about 4. 35. The antioxidant (D) is present in at least one sulfur-containing composition, at least also one alkylated aromatic amine, at least one phenol, at least one 32. A transition metal-containing antioxidant, or a mixture thereof. Composition of. 36. 36. The antioxidant (D) according to claim 35, wherein the antioxidant (D) is a copper-containing antioxidant. Composition. 37. The antioxidant (D) is 2,6-di-t-alkyl-4-hydrocarbyl. 32. The composition of claim 31, which is phenol. 38. 32. The composition of claim 31, which is a lubricant for a spark ignition engine. 39. a major amount of oil of lubricating viscosity; and (A), (B), (C), A lubricating oil composition containing (D) and (E): (A) 100 grams of the lubricating composition; provides at least about 0.0019 equivalents of sodium alkali metal per gram. an amount of at least one sodium overbased salt of an acidic organic compound; B) at least about 1.60% by weight of at least one dispersant; (C) at least one dihydrocarbyl dithiophosphate metal salt; (D) at least one copper-containing antioxidant; (E) at least one acidic organic Magnesium overbased metal salts of compounds: However, the lubricating oil composition contains overbased calcium sulfonate and calcium sulfonate. umphenate-free, the composition contains less than about 0.08% calcium by weight. and (C) and (D) are not the same. 40. Lubricating a spark ignition engine or a compression engine with the composition of claim 1 A method that includes causing. 41. Moisturizing a spark ignition engine or a compression engine with the composition of claim 31. A method that includes sliding. 42. A major amount of lubricating viscous oil is added to the following (A), (B), (C), (D ) and (E): (A) at least about 0.0019 equivalents of aluminum per 100 grams of the lubricating composition; an alkali metal salt of at least one acidic organic compound in an amount to provide potassium metal; (B) at least about 1.60% by weight of at least one dispersion; (C) at least one dihydrocarbyldithiophosphate metal salt; (D) at least one antioxidant; (E) Magnesium overbased metal of at least one acidic organic compound Salt: Provided that the lubricating oil composition contains an overbased calcium sulfonate. and overbased calcium phenate, the composition contains about contains less than 0.08% calcium, and (C) and (D) are the same. It's not the same.