JPH04500234A - Lubricating oil compositions and concentrates - Google Patents

Abstract

A lubricating oil composition is described which is useful in internal combustion engines and which exhibit improved oxidation and wear performance. More particularly, lubricating oil compositions are described which comprise (A) a major amount of oil of lubricating viscosity; (B) at least about 1.0 % by weight of at least one carboxylic derivative composition produced by reacting (B-1) at least one substituted succinic acylating agent with (B-2) at least one amine compound characterized by the presence within its structure of at least one HN< group wherein said substituted succinic acylating agents consist of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene, said polyalkene being characterized by an Mn value of 1300 to about 5000 and an Mw/Mn value of about 1.5 to about 4.5, said acylating agents being characterized by the presence within their structure of an average of at least 1.3 succinic groups for each equivalent weight of substituent groups; and (c) at least one manganese compound in an amount sufficient to provide from 1 to about 500 ppm of manganese as metal, provided that the manganese compound is not a neutral manganese dihydrocarbyl phosphorodithioate. The oil compositions also may contain other desirable additives including (D) at least one metal dihydrocarbyl phosphorodithioate ; (E) detergent effective amounts of at least one neutral or basic alkali metal salt of a sulfonic or carboxylic acid; and/or (F) at least one carboxylic ester derivative is defined herein. In one embodiment, the oil compositions of the present invention contain the above additives and other additives described in the specification in an amount sufficient to enable the oil to meet all the performance requirements of the API Service Classification identified as "SG".

Description

[Detailed description of the invention] name of invention Lubricating oil compositions and concentrates field of invention TECHNICAL FIELD This invention relates to lubricating oil compositions. In particular, the present invention provides improved oxidation performance and The present invention relates to a lubricating oil composition exhibiting wear performance.

Background of the invention Hydrants used in internal combustion engines (especially spark ignition engines and diesel engines) Lubricating oils are constantly being modified and improved to provide superior performance. various organizations (This includes SAE (Society of Automotive Engineers) tive Engineers), ASTM (officially, Testing and Materials The American Society for Tes ting and Materials) and API (American Petroleum Institute, rfcan Petroleum In5titud)) Automotive manufacturers are also constantly demanding improved lubricant performance. child Through the efforts of these organizations, standards have been established and revised over the years. Good things are being done. Engines are becoming more powerful and more complex, so the following The performance requirements for such lubricants are increasing.

This means that the lubricant exhibits a low tendency to degrade under conditions of use, thereby reducing wear. lubricating oils that reduce the formation of undesirable deposits such as: For example, varnishes, sludges, carbon-bearing substances and resinous substances. this These deposits tend to stick to various engine parts and reduce engine efficiency. Let it go down.

Crank chamber lubrication that can generally be used in spark ignition engines and diesel engines Regarding lubricating oils, there are differences in the requirements for lubricating oils for these applications, and due to these requirements, Different oil classifications and performance requirements have been established for this purpose. Until recently, the spark point Good quality commercially available oils designed for fire engines include rSFJ oil and was identified and displayed. These oils are classified as API Service Classification S. capacity requirements.

In recent years, a new API service classification classification S character has been established, and this oil is designated as "SGJ". has been done. The oil, called SG, meets API Service Classification Classification S Performance Requirements. Must take a bus. This SG performance requirement is that these new oils It has more desirable properties and performance that exceed those required for SF oil. It has been established to ensure that This SG oil is suitable for engine wear. lubricant thickening during use. It is well designed. This SG oil is sold for spark ignition engines. Improves engine performance and durability compared to all conventional engine oils. It is intended to be a sea urchin. Further features of SG oil include API service classification. The requirements for the CC category (diesel) have been included in the SG specifications.

In order to meet the performance requirements of SG oil, this oil meets industry standards. Successfully bus following established gasoline engine tests and diesel engine tests Must do: Ford Sequence VE Test; Vinic Sequence ■E Test; Oldsmobile sequence ffD test; CRCL-38 test; and Caterpillar Single Cylinder Test Engine IH2゜This Caterpillar test The oil is also suitable for output diesel applications (?Easel performance classification rCCJ”) This performance requirement includes: In addition, SG classification oil is It is desirable to match the output to diesel applications (diesel classification rCDJ). This oil formulation was used in the Caterpillar single cylinder 17 cylinder test engine IG2. More stringent performance requirements must be met. All procedures for these tests and performance standards are established in the industry, and these tests are further detailed below. It is described in

When it is desired that an S0 class lubricant also exhibits superior fuel economy, this oil Sequence ■Fuel Efficiency Engine Oil Dynamometer Test Requirements Must be compatible.

The new classification of diesel engine oils is also 5AII: SASTM and A Established through joint efforts of PIs. The new diesel oil is rCE J is displayed. The oil that meets the new diesel classification CE is the current CD category oil. (This includes Mack T-6 test, Mack T-7 test and Cumm 1ns (includes the NTC-400 test). It is necessary to

The ideal lubricant for most purposes should have the same viscosity at all temperatures. It is. However, available lubricants deviate from this ideal. temperature Substances added to lubricants to minimize viscosity changes associated with They are called viscosity index improvers, viscosity index improvers or V+ improvers.

Generally, materials that improve the V+ properties of lubricating oils are oil-soluble organic polymers. this These polymers include polyisobutylene, polymethacrylate ester (i.e. copolymers of alkyl methacrylates of various chain lengths); copolymers of ethylene and propylene hydrogenated block copolymer of styrene and isoprene: and polyacrylic Lyric acid esters (i.e., copolymers of alkyl acrylates of various chain lengths) are included. Included.

Other substances may be included in the oil composition to enable the lubricating oil composition to meet various performance requirements. be done. These include dispersants, detergents, friction modifiers, corrosion inhibitors, etc. Ru. Dispersants sludge impurities, especially those formed during the operation of internal combustion engines. in the lubricant to keep it in suspension rather than allowing it to precipitate as a used in Materials exhibiting both viscosity-improving and dispersing properties have been described in the prior literature. It is stated. One type of compound that has both properties is 1 with polar groups. It consists of a polymeric backbone with species or more monomers attached to the backbone. this Such compounds are often prepared by grafting operations. In this operation , this backbone polymer is reacted directly with suitable monomers.

Reaction of hydroxy compounds or amines with substituted succinic acids or their derivatives Dispersant additives for lubricants containing products have also been described in the prior literature. child Typical dispersants of the type are described, for example, in U.S. Pat. No. 3,272,746; ．． No. 522.179; No. 3.219.666; and No. 4.234.435 has been disclosed.

The compositions described in the '435 patent, when mixed with lubricating oils, contain dispersants/detergents and and functions as a viscosity index improver.

Lubricating oil compositions containing oil-soluble transition metal-containing compounds have also been described in the prior literature. It is. This transition metal compound is often used with acidic substances (e.g. carboxylic acids) , sulfonic acids or mixtures thereof). For example, U.S. Pat. i No. 62°986 (Alkaitfs et al.) transition metal salts of carboxylic acids and sulfonic acids or second carboxylic acids; describes its use as a lubricant additive. This transition metal compound is also a catalyst , anti-knock agent, combustion improver, smoke suppressant, curing agent, desiccant, micro-nourishing agent, etc. It has been suggested that this is useful. U.S. Patent No. 3.762.890 (Collins) Colfins) is a hydrolyzable compound that is stabilized by containing propionic acid. Manganese soaps have been described as useful in greases, lubricants, fuels, etc. Ru.

Demonstrates the use of various manganese salts and compounds as additives in lubricating oil compositions. Other patents and publications that suggest include, for example, U.S. Patent No. 2.364.283 No. (Freuler): No. 2.378.820 (Amott ( Amott); No. 2.389.527 (McCIear y) N; i3,346,493 (LeSuer); No. 3.8 No. 27.979 (Piotrovski et al.); No. 4.25 2.6s9q (Ali); No. 4゜SO5,718 (Trail (D) .

rer)); No. 4.633.001 (Cells); No. 4.6 No. 64.677 (Dorer et al.); European Patent Application No. 0271363 No. 0.290.457; and European Patent Application No. 0.290.457. U.S. Patent No. 3. No. 941.606 (71 Lins et al.) describes hydrocarbon-soluble compositions. The composition of for example, MnO, Coo and N1p) and at least] species of acidic compounds. compounds (e.g. fatty acids) and at least one poly(b-hydroxy compound). Contains reaction products with compounds. This composition is suitable for paints and similar paint drying compositions. Useful as a desiccant in materials, a fuel additive, and a stabilizing agent for plastics. It is stated that it is for use.

U.S. Patent No. 4.505.718 and European Patent Application No. 0°290.457 are describes a hydrocarbon-soluble composition, the composition comprising at least one organic carboxylic acid. one or more transition metal salts of a bonic acid and at least one hydrocarbon soluble Contains a decomposable ashless dispersant. The transition metal salts described in these patents include: 1. below dicarboxylic acid, sulfuric acid, and phosphoric acid, including manganese salts of organic acids, including Containing acid. Overbased transition metal salts, including manganese salts, of these organic acids are preferred. It is described as (~ru).

Overbased metal salts are defined in the art and are defined herein as as a salt in which the metal is present in excess of the stoichiometric amount required to react with , defined as L'l.

A large number of ashless dispersants are useful in combination with this transition metal salt. is disclosed. The bibliography contains numerous patents describing ashless dispersants, and several textbook publications. Acylated nitrogen-containing dispersants dispersants of the type used in lubricating compositions. U.S. Patent No. 4. SO5 No. 718 contains 1 to about 500 ppm of transition metals and about 5 to about 10 ppm of metals. A lubricating oil composition containing 0.00 ppm ashless dispersant is described.

U.S. Pat. No. 4.6.54.677 contains a mixture of manganese and copper salts. Describes the composition. This composition is described as being useful in fuel compositions. There is. Fuels containing copper and manganese compositions are When a diesel engine is operated with It is disclosed that it is useful for lowering the ignition temperature of particulate matter.

European Patent Publication No. 271 363 describes an oil-soluble composition, which composition detergent materials, detergent materials, zinc dihydrocarbyldithiophosphate antiwear materials, and and compatibilizer (this is a hydrocarbyl-substituted monocarboxylic or dicarboxylic acid) (including metal salts of bonic acids). Many dispersants have been described, including long-chain of hydrocarbyl-substituted monocarboxylic or dicarboxylic acid substances (e.g., α long-chain hydrocarbons substituted with - or β-unsaturated dicarboxylic acids, generally polyols. (lefins) are included. This dispersant is generally , at least about 1.05 moles (e.g., 1.05 to 142 moles or more) Contains . This olefinic polymer usually has a number average content of 1 around 700. molecular weight I7, which includes number average molecular weights ranging from 1500 to 5000. . Polyisobutylene is mentioned as a particularly suitable starting material. This dispersant is a dicarboxylic acid substance and an amine, alcohol/aminoalcohol-1, etc. Obtained by reaction. Compatibilizers and suitable metal salts in 17 have periodic Group Tb, group ■b, group mb, rod group b, group vb, group vrb, group ■b in the table Included are salts of metals from Groups 1 and 2. Preferred metals are Group 1b and The most preferred metal is copper. This salt is basic, neutral or a reactive metal compound and at least one free carboxylic acid group; form by reacting with any of the substances described as dispersant substances with It can be done. Specific examples of compatibilizers include copper salts of polyisobutenyl succinic anhydride. and zinc salts.

Summary of the invention A lubricating oil composition useful in internal combustion engines and exhibiting improved oxidation and wear performance is disclosed. It has been described. More specifically, it contains the following (A), (B) and (C) Lubricating oil compositions are described that: (A) a major amount of oil of lubricating viscosity; (B) a minor amount of at least about 1.0% by weight; At least one carboxylic acid derivative composition, the composition comprising the following (B-1): & Produced by reaction with (B-2): (B-1) At least one substituted succinic acylating agent: (B-2) at least one atom characterized by the presence of at least one HN< group; compound; wherein the substituted succinic acid acylating agent has a substituent and a succinic acid group; wherein the substituent is derived from a polyalkene; Mn values of 1300 to about 5000 and MII/Mn of about 1.5 to about 4.5 characterized by the value; the acylating agent has, on average, for each equivalent of substituent Characterized by the presence of at least 1.3 succinic acid groups in its structure and (C) to provide from 1 to about 500 ppm manganese as metal; a sufficient amount of at least one manganese compound; provided that the manganese compound Manganese dihydrocarbyl phosphorodithioate.

The lubricating oil composition may also contain other desirable additives, including ( D), (E) and/or (F) include: (D) at least one dihydrogen Drocarbyl phosphorodithioic acid metal; (E) an effective amount of a neutral or basic sulfonic or carboxylic acid; at least one alkali metal salt; and/or (F) At least one carboxylic acid ester derivative as defined herein.

In one embodiment, the lubricating oil composition of the present invention comprises the additives described above and as described herein. API service classification performance requirements for other additives to be recognized as rSGJ Contains in sufficient amount to meet all of the requirements.

Detailed description of the invention Throughout this specification and claims, references to weight percentages of various ingredients refer to With the exception of component (A), which is a chemical standard, unless otherwise indicated, Ru. For example, the oil composition of the invention contains at least 2% by weight of (B) , the oil composition contains at least 2% by weight on a chemical basis. Contains (B). Therefore, component (B) is entered as a 50% by weight oil solution. If available, at least 4% by weight oil solution is included in the oil composition. Ru.

The number of equivalents of acylating agent depends on the total number of carboxylic acid functional groups present. This reed When determining the number of equivalents of the carboxylic acid acylating agent, consider Boxyl functional groups are excluded. However, in general, in these acylating agents There is one equivalent of acylating agent for each carboxy group.

For example, by reaction of 1 mole of olefinic polymer with 1 mole of maleic anhydride, In the derived anhydride, there are two equivalents of acylating agent. carboxyl functional group Conventional methods are readily available to determine the number of It is possible. Therefore, the number of equivalents of acylating agent can be readily determined by one skilled in the art. Ru.

The equivalent weight of an amine or polyamine is the molecular weight of the amine or polyamine. The value is divided by the total number of nitrogen atoms present in the molecule. Therefore, ethylenediamine has an equivalent weight equal to 172 of its molecular weight; has an equivalent weight equal to 173 of the molecular weight of Commercial mixture of polyalkylene polyamines The equivalent weight of a substance is the atomic weight (14) of nitrogen contained in this polyamine. It can be determined by dividing by a percentage and multiplying by 100; therefore , a polyamine mixture containing 34% nitrogen has an equivalent weight of 41.2. Ann The equivalent weight of a monia or monoamine is its molecular weight.

Hydroxyl position reacted with acylating agent to form carboxylic acid derivative (B) The equivalent weight of a converted amine is its molecular weight divided by the total number of nitrogen groups present in its molecule. It is a value. For the purposes of the present invention, when preparing component (B), the hydroxyl group is Ignored when calculating. Therefore, ethanolamine is equal to its molecular weight has an equivalent weight, and jetanolamine has an equivalent weight equal to its molecular weight! (Nitrogen base) evening).

The hydrogen used to form the carboxylic acid ester derivative (F) useful in the present invention The equivalent weight of a droxyl-substituted amine is its molecular weight divided by the number of hydroxyl groups present. It is. Any nitrogen atoms present are ignored. Therefore, for example, jetanolamine When extracting ml of ester from a sample, the equivalent weight is 1 ml of the molecular weight of jetanolamine. It is 72.

The terms "substituent", "acylating agent" and "substituted succinic acid unlyzing agent" include: their usual meanings are given. For example, a substituent may be added to a molecule as a result of a reaction. An atom or group of atoms that can be replaced by another atom or group within. Acylating agent or The term substituted succinic acylating agent refers to the compound itself; unreacted reactants used to form the acylating agent or substituted succinic acylating agent. does not include.

A　°　Oil The oil used in preparing the lubricant of the present invention may be natural oil, synthetic oil, or the like. It may be based on a mixture of these.

Natural oils include animal and vegetable oils (e.g. castor oil, lard oil), as well as Mineral lubricating oils (e.g. liquid petroleum oil and paraffin type, naphthene) paraffin type or mixed paraffin-naphthenic type and solvent treated. acid-treated mineral lubricating oils or acid-treated mineral lubricating oils). coal or Oils of lubricating viscosity derived from shale are also useful. synthetic lubricant includes the following hydrocarbon oils and halo-substituted hydrocarbon oils. This hydrocarbon Oils and halo-substituted hydrocarbon oils include, for example, polymerized olefins and - Polymerized olefins (e.g. polybutylene, polypropylene, propylene) Pyrene-isobutylene copolymer, chlorinated polybutylene, etc.): Poly(1- hexene), poly(l-octene), poly(1-decene), etc., and their Mixture; alkylbenzene (e.g. dodecylbenzene, tetradecylbenzene , dinonylbenzene, di(2-ethyl)-benzene, etc.); (e.g., biphenyl, terphenyl, alkylated polyphenyls, etc.) ): Alkylated diethyl ether and alkylated diphenyl sulfur These include fi, do and their derivatives, analogues and homologs thereof.

Alkylene oxide polymers and interpolymers and their derivatives In derivatives, the terminal hydroxyl group is modified by esterification, etherification, etc. lubricants constitute another class of well-known synthetic lubricants that may be used. these are, Oils prepared by polymerization of ethylene oxide or propylene oxide; Alkyl ethers and ethers of these polyoxyalkylene polymers ( For example, methylpolyisopropylene glycol with an average molecular weight of about 1000 ether, diphthalate of polyethylene glycol having a molecular weight of about 500-1000 phenyl ether, a polypropylene glyph with a molecular weight of about 1000-1500 diethyl ether, etc.), or their mono- and polycarboxylic acid esters. ster (e.g. acetate ester of tetraethylene glycol, mixed C3-8 fatty acid ester or C13 oxoacid diester).

Other suitable classes of synthetic lubricants that may be used include dicarboxylic acids (e.g. Ruric acid, Succinic acid, Alkyl succinic acid, Alkenyl succinic acid, Maleic acid, Azera Inic acid, schenic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid timer -, malonic acid, alkyl malonic acid, alkenyl malonic acid, various alcohol (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, gotylene glycol, diethylene glycol ethers, brobylengelifur, etc.). These Specific examples of esters include dibutyl adipate, di(2-, f-thyl sebacate), Sil), Shi-n-hexyl fumarate, Sebacin tm/f/y Chil, Azera In Diisooctyl acid, azeyl-isodecyl inate, dioctyl heptatalate, lid Didecyl phosphate, sebacic acid 1:''/2, linoleic acid coumer 2-functional tk hexyl diester, 1 mole of sebacic acid and 2 moles of tetraethyleneglyfur and 2 = complex ester formed by reaction with 2 moles of ethylhexanoic acid, etc. Esters useful as 3° synthetic oils include Cs-CI2 monocarboxylic acids and polyols and polyol ethers (e.g., neopentyl glyco, , To-11 methylolpropane, Pentaeryth 1.1 Toll, Dipenta-Elithri It also includes EST-1 formed from Ru.

Silicon-based oils (e.g., polyalkyl, boria 1, etc.) , polyalkoxy-1 or polyaryloxy-70 xane oil and silica Cate oil) constitutes another useful class of synthetic lubricating oils. For this, there is an example For example, tetraethyl silicade, tetraisopropyl silicate, tetra( 2-ethylhexyl)noricate, tetra-(4-methyl-,xyl)silicate cate, tetra-(p-tert~) tylphenyl silicate, hexyl- (4-Methyl-2-pentoxy7)di/loxane, poly(methyl)siloxane, poly Examples include li(methylphenyl)siloxane. Other synthetic lubricants include phosphorus-containing acids. liquid esters (e.g. tricresyl phosphate, trioctyl phosphate, decanephosate) (such as diethyl ester of sulfonic acid), polymerized tetrahydrofuran, etc. It will be done.

Unrefined oils, refined oils and rerefined oils (which include natural oils of the types disclosed above or It is either a synthetic oil; it is a mixture of two or more of any of these. compounds) may be used in the concentrates of the present invention. Unrefined oil is 44 oil obtained directly from natural or synthetic raw materials without further purification. It is le. For example, if the oil obtained directly from the retort operation, the first stage distillation or petroleum oil obtained directly from the esterification process, and further Ester oils used without treatment are unrefined oils. Refined oil is one type or another. further processed in one or more purification steps to improve further properties. Other than that, it is similar to unrefined oil. Many of these purification methods are readily available to those skilled in the art. It is well known. This method includes, for example, solvent extraction, hydrogen treatment, secondary distillation, acid or base extraction, filtration, and osmosis. Re-refined oil is added to refined oil that has already been used. , obtained by applying a process similar to that used to obtain refined oil.

Such rerefined oils are also known as recycled or reprocessed oils. 1. Directed to remove spent additives and oil breakdown products. Depending on the method, it is often further processed.

(B) #. ＋l 2 tama tori 1 trouble Component (B) used in the lubricating oil of the present invention includes the following (B-1) and <B-2). At least one carboxylic acid derivative composition produced by reacting (B-1) At least one substituted succinic acylating agent: (B-2) At least one amine compound containing at least one HN< group. here, The arylating agent consists of a substituent and a 7-acid group. Here, this substituent is Derived from polyalkenes, the polyalkenes have a molecular weight of about 1,300 to about 500,041 Mn value and about 1.5 to about 4. It is characterized by a My/Mn ratio of 5.

The acylating agent has an average of at least about 1.3 chains for each equivalent of substituent. Characterized by the presence of a citric acid group within its structure. Generally, this reaction reacts with about 0.5 equivalents to about 2 moles of amine compound per equivalent of acylating agent. include.

This carboxylic acid derivative (B) modifies the dispersibility and v1 properties of this oil composition. It is included in this oil composition to improve the quality of the oil.

Generally, from about 1% to about 10% or 15% by weight of component (B) is present in this oil. can be included in the composition. However, this oil composition preferably contains less than Each contains 2% by weight of component (B), for example, 3% by weight or more.

Substituted rice-phosphate acylating agent (used in preparing carboxylic acid derivative (B)) B-1) is characterized by the presence of two groups or moieties within its structure. It can be done. The groups or moieties hereinafter referred to as "substituents" for convenience are , derived from polyalkenes. The polyalkene from which this substituent is derived is about 1 Mn value (number average molecular ffi) of from 300 to about 5000 and of at least about 1.5. MW/Mn values, more generally from about 1.5 to about 4.5 or from about 1,5 to about 4. It is characterized by an l+1w/Mn value of 0. The abbreviation My stands for weight average molecular weight. This is the traditional symbol used to represent Gel permeation chromatography (GPC) , both the weight average molecular weight of the polymer and the thousands-equal fraction “Tjl” as well as this polymerization It is a method of measuring molecular size that determines the total molecular weight distribution of the body. For the purposes of this invention, minutes A series of polymers of isobutyne and polyisobutyne have been used as calibration standards for GPC. It is used.

Methods for determining the Mn and My values of polymers are well known and extensively documented. and described in the paper. For example, to determine the Mn and molecular weight distribution of a polymer, The method to do this is described by W. W. Yan, J. J. Kirkland nd) and Tori, D. Buy) Nor latest size exclusion liquid chromatograph (J. Wiley & Sons, Inc., 1979 2004).

The second group or moiety in the acylating agent is referred to herein as a "succinic acid group." It is. The succinic acid group is a group characterized by the following structure: Here, X and X' are the same or different. However, at least one and Xo, this substituted acid acylating agent functions as a carboxylic acid acylating agent. It is possible. That is, at least one of X and Xo is The binding agent is a group capable of forming an amide or amine salt with the amino compound. must be taken as such. Otherwise, this acylating agent is a traditional carboxyl Functions as an acid acylating agent. Transesterification and transamidation reactions are For purposes of clarity, it is considered a conventional acylation reaction.

Therefore, X and/or Xo are usually −0)! , -〇-hydrocarbyl, -0-M”, where M+ is one equivalent of metal, ammonium cation or represents an amine cation, -Nl2, -CL　-Br, and X and Xo are - can be -0- so that together they form an anhydride. any of the above groups It is important to specifically identify X or Xo groups that do not occur due to their presence. It is not critical as long as it does not prevent the other groups from participating in the acylation reaction. but However, preferably X and Xo each represent both groups of this acid group. carboxyl functionality (i.e., both -C(0)X and 10(0)Xo) It is likely to be involved in the sylation reaction.

One of the following incomplete valences in a group of formula I is co-existing with a carbon atom in this substituent: form a carbon-carbon bond: other such imperfect valences may be identical or Although such valences can be completed by similar bonds of different substituents, All but one are typically filled with hydrogen (ie, -H).

The substituted succinic acylating agent has an average of at least 1.3 succinic acid groups (i.e., groups corresponding to formula 1) are present in the structure. It is characterized by:

For the purposes of this invention, the number of equivalents of a substituent refers to the Mn value of the polyalkene from which the substituent is derived. by the total weight of substituents present in the purchased succinic acylating agent. It is considered that the number of

Therefore, substituted succinic acylating agents are characterized by a total fi of 40,000 for the substituents. and the Mn value of the polyalkene from which this substituent is derived is 2000. , then this substituted succinic acylating agent has a total of 20 (40,000/ 2000≠20) of substituents. Therefore, certain The citric acid acylating agent is also one of the requirements for the succinic acylating agent used in the present invention. the presence of at least 26 succinic acid groups in its structure to satisfy the must be characterized by.

Another requirement for substituted succinic acylating agents is that the substituent group is at least about 1.5 It must be derived from a polyalkene characterized by a My/Mn value of That is. The upper limit for I+Lv/Mn is generally about 4.5. 1.5 to about 4. A value of 5 is particularly useful.

Polyalkenes having the Mn and Mv values mentioned above are well known in the art. and can be prepared according to conventional methods.

For example, some of these polyalkenes are described in U.S. Pat. stated and illustrated. The disclosure of this patent regarding such polyalkenes is , shown here. Some of these polyalkenes (especially polybutenes) It is commercially available.

In one preferred embodiment, the succinic acid group typically corresponds to the formula: Here, R and Ro are each independently -OH, -CI, -〇-lower atom Lucille, and when taken together, R and Ro is −〇−. In the latter case, the succinic acid group is a conolyl anhydride group. . In a particular co/% phosphoric acid acylating agent, all succinic acid groups need not be identical. However, they can be the same. Preferably, the cono monophosphate group has the following formula: Also, a mixture of (IIT (A)) compound and (III (B)) compound corresponds to: (A) (B) To provide a substituted succinic acylating agent in which the succinic acid groups are the same or different. is within the ordinary skill in the art and may be performed by conventional methods. This conventional method Methods include, for example, treating the substituted succinic acylating agent itself, e.g. Hydrolyzing the water to the free acid, or converting this free acid with thionyl chloride. acid chloride) and/or a suitable maleic acid reactant or fumarate Acid reactants may be selected.

As mentioned earlier, the minimum number of acid groups for each equivalent of substituent is 1.3. be. The maximum number generally does not exceed 4.5. In general, this minimum number is the replacement For each equivalent of groups, there are approximately 1.4 succinic acid groups. A range based on this minimum number range from at least 1.4 to about 3.5 per equivalent of substituent, and more specifically Then, it is about 1.4 to about 2.5.

The preferable point is derived from the number and type of cono-acid groups for each equivalent of the substituent. In addition to the preferred substituted cono\hydric acid group, a further preferred point is that this substitution It is based on the type and characteristics of the polyalkene from which the substituent is derived.

For example, for the value of Mn, a minimum value of about 1300 and a maximum value of about 5000 are preferred. Preferably, a range of about 1500 to about 5000 is also preferred.

More preferred Mn values range from about 1,500 to about 2,800. most preferred The range of Mn values is from about 1500 to about 2400.

We will further discuss polyalkenes from which substituents are derived. These preferred characteristics of the phosphoric acid acylating agent are unique and dependent on others. It is intended to be understood as both. : should be pointed out. be. These include, for example, 14 or 15 succinic acids per equivalent of substituent. The preferred minimum value of the group is coupled with the more preferred value of Mn or My7'Mn. It is considered independent in the sense that it is not. They are, for example, 1 ．． A preferred minimum value of 4 or 1.5 succinic groups is Mn and 1, or My When combined with a more preferred value of /Mn, this preferred combination are in fact dependent on each other in the sense of indicating further preferred embodiments of the invention. It is also considered as Therefore, the various parameters are considered isolated, but in order to confirm further favorable points may be combined with other parameters to This same concept applies to preferred values, ranges, Concerning descriptions of ranges, ratios, reactants, etc., are there clearly opposing objectives? or unless otherwise apparent, is intended to apply throughout this specification.

In one embodiment, the Mn of the polyalkene is at the lower end of this range (e.g., about 1300 ), with this acylating agent, the substituent derived from the polyalkene is The ratio of succinic acid groups is preferably higher than, for example, when Mr+ is 1500.

Conversely, when the Mn of the polyalkene is higher (e.g. 2000), this ratio The Mn of Rialken is lower than, for example, 1500.

The bob alkene from which the substituent is derived is a polymerizable olefin monomer (which is , having from 2 to about 16 carbon atoms, usually from 2 to about 6 carbon atoms) alone Polymers and interpolymers. This interpolymer may contain two or more or more olefin monomers can be made into interpolymers [hyperfluorocarbons] by well-known conventional methods. The polyalkene is a polymer that is derived from each of the two or more olefin monomers in the structure of It has a unit of Therefore, "interpolymer" as used herein This includes copolymers, ternary copolymers, quaternary copolymers, etc. obvious to those skilled in the art Polyalkenes from which substituents are derived, such as referred to as "Refin".

The olefin monomer from which this polyalkene is derived may contain one or more esters. Polymerizable compounds characterized by the presence of thyrenically unsaturated groups (i.e., >C=C) i.e., they are monoolefin monomers with (e.g. ethylene, propylene, butene-1, imbutene, and octene-1) 1) or polyolefin monomers (usually diolefin monomers; e.g. Tagene-1,3 and isoprene).

These olefin monomers are typically polymerizable terminal olefins (i.e. An olefin characterized by the presence of a >C=CH2 group in its structure (in). However, polymerizable internal olefin monomers (these are When l&: is indicated in the literature as a medial olefin. are characterized by the presence of the following groups within their structure: ) can also be used to form polyalkenes: When internal olefin monomers are used, they are usually combined with terminal olefins. Used together to form an interpolymer, a polyalkene. Purpose of the invention Above, certain polymerized olefin monomers form terminal and internal olefins. If it can be classified as both, it is considered a terminal olefin. therefore , 1,3-pentadiene (i.e., piperylene), for purposes of this invention, It is thought to be a lefin.

Substituted succinic acylating agent ( B-1) are well known in the art, e.g. 34.435. These disclosures are This is shown here.

The acylating agents described in the '435 patent have Mn values of about 1300 to about 5000. and containing substituents derived from polyalkenes having a My/Mn value of from about 1.5 to about 4. It is characterized as something that does.

Aliphatic hydrocarbon polyalkenes without aromatic and cycloaliphatic groups are generally preferable. Among these generally preferred ones are those derived from the group consisting of: Rialkenes are further preferred: this group has from 2 to about 16 carbon atoms. Composed of homopolymers and interpolymers of terminal hydrocarbon olefins.

This further preference is limited by the following conditions: Up to about 16 carbon atoms, although interpolymers of olefins are usually preferred. optionally containing up to about 40% polymer units derived from internal olefins having Also included in the preferred group are interpolymers that polyarche A further preferred class of members is selected from the group consisting of: Terminal olefin having ~6 carbon atoms, preferably 2 to 4 carbon atoms consisting of homopolymers and interpolymers of terminal olefins with but However, other preferred classes of polyalkenes include the latter, more preferred polyalkenes. It is. This polyalkene is an internal olefin having up to about 6 carbon atoms. optionally containing up to about 25% polymer units derived from.

Apparently, the above polyalkenes (meeting various criteria for Mn and My/Mn) It is within the skill of the art and does not form part of this invention. . Techniques that will be readily apparent to those skilled in the art include controlling the polymerization temperature, controlling the polymerization initiator, and/or adjusting the catalyst group size, using chain-terminating groups in the polymerization process. This includes things such as: Other conventional techniques (e.g. stripping very light fragments) stripping (including vacuum stripping) and/or high molecular weight polyamide Oxidative or mechanical decomposition of lukene to produce low molecular weight polyalkenes ) can also be used.

In preparing the substituted succinic acylating agents of the present invention, one or more of the above polymers may be used. Rialken consists of a maleic acid reactant or a fumaric acid reactant with the following general formula: reacted with one or more acidic reactants selected from the group: X(0)C- CH=CH-C(0)X' (IV) where X and X' are the above in formula I is defined in

Preferably, the maleic acid reactant and the fumaric acid reactant are 1 corresponding to the formula: species or more compounds: RC(0)-CH=Cl1-C(0) It' (V) Here, R and R' are those defined earlier in the formula ■ in the specification. is the same as Typically, this maleic acid reactant or fumaric acid reactant is acid, fumaric acid, maleic anhydride, or a mixture of two or more of these. It is. Maleic acid reactants are generally preferred over fumaric acid reactants. The former is easy polyalkenes (or their derivatives) and are generally readily available. ) to prepare the substituted cono-phosphate acylating agent of the present invention. Special Preferred reactants are maleic acid, maleic anhydride, and mixtures thereof. Ru.

Maleic anhydride is usually used because of availability and ease of reaction.

Examples of patents describing various methods for preparing useful acylating agents include U.S. National Patent No. 3.215.707 (Rense); No. 3,219,666 (N orman et al.); No. 3.231.587 (Rense); No. 3.912.7 No. 64 (Palmer); No. 4.110.349 (CQhen); and and British Patent No. 4.234.435 (Meinhardt et al.); and British Patent No. 1.4. No. 40.219 is included. The disclosures of these patents can be found here .

For convenience and brevity, the term "maleic acid reactant" is often used hereafter. used in As it is used, the term refers to formula (IV) above and formula ( an acidic reaction selected from maleic acid reactants and fumaric acid reactants corresponding to V) (which includes mixtures of such reactants) can be formed into a film. should be understood.

In the method for preparing the carboxylic acid derivative composition (B), the above-mentioned noacylating reagent is It is an intermediate body. This method: Well, (B-1) one or more acylating reagents and , (B-2) ζ in its structure is characterized by the presence of at least one HN< group. It includes reacting with at least one type of amino compound that is

At least one HN < fundamental force f exists in the structure (characterized by this) Amino compound (B-2) it, monoamine metal or polyamine compound could be. A mixture of two or more amino compounds may be used in one or more amino compounds of the invention. It can be used in reactions with one or more acylating reagents. Preferably C, this ami The compound contains at least one primary amine group (i.e. -Nl2). , more preferably (yo, this amine C±, bo-1-noamine (especially at least two -NO- group-containing bonoamine). This -Nl(- group) Either it is a primary amine or a secondary amine. This amine (yo, fat) Aliphatic amines, cycloaliphatic amines, aromatic amines (also can be heterocyclic amines) . From this polyamine, a carboxylic acid derivative composition (which is usually a monoamine as a dispersant/detergent additive compared to derivative compositions derived from Not only are these preferred 0-polinoamineka) and ( Moreover, a carboxylic acid derivative composition exhibiting more remarkable viscosity index improvement properties can be obtained.

Among the preferred amines are alkylene polyamines, including polyalkylene monoamines. There is a rearmin force f. This alkylene polyamine includes those conforming to the formula: where n is from 1 to about 10; each R3 is independently a hydrogen atom, a locarbyl group or hydroxy-substituted hydrocarbyl group or amine-substituted hydrocarbyl group rubyl groups (these have up to about 30 atoms), or different nitrogen Two R3 groups on an atom may - taken together, form a U group; provided that at least One R3 group is a hydrogen atom, and U is an atom having about 2 to about 10 carbon atoms. It is a lekylene group. Preferably U is ethylene or propylene. Each R alkylene polyamide in which 3 is hydrogen or amine-substituted hydrocarbyl group Particularly preferred are Ethylene polyamines and mixtures of ethylene polyamines is most preferred. Typically, n has an average value of about 2 to about 7. Al like this Kylene polyamines include methylene polyamine, ethylene polyamine, and butylene polyamine. Reamine, propylene polyamine, pentylene polyamine, hexylene polyamine and hexylene polyamines. Higher analogues of such amines and related aminoalkyl-substituted piperazines are also included.

Alkylene polyamines useful in preparing the carboxylic acid derivative composition (B) include , ethylenediamine, triethylenetetramine, propylenediamine, trimethylene Diamine, hex 7th, 7diamia, decamethylene diamine, octamethyl /diamine, di(hebutamethylene)triaminino, tripropylenetetramine , tetraethylbenthyl alcohol: /, 2-methylenediamine, pentaethylene to cattle Samin, Ji()! /methylene)-triamini/, N-(2-terminoethyl)pi Perazine, 1,4-bis(2,ami/edil)piperazine, and the like are included.

Higher grade compounds obtained by condensation of two or more of the above alkylene amines Group I bodies, as well as mixtures of two or more of the above polyamines, It is nurturing.

Ethylene polyamines (e.g. those mentioned above) are preferred due to price and effectiveness. , is particularly useful. Such polyamines include ``diamines, and higher amines.'' Encyclopedia of Chemical Technology (2nd edition), published by Irk and Ozmar (2nd edition). d 0thtaer), Vol. 7 h D, 27-39, Interscience Publishing, Ji John Wrley and 5ons Department, 1965), and these contents are a useful guide to the development of For illustration purposes, it is shown here. Such colored substances are alkylene chloride by reaction with ammonia or ethyleneimine with a ring-opening reagent (e.g. monium, etc.). These reactions lead to A complex of alkylene polyamines (including cyclic polyamines such as piperazine) (including condensation products) are formed.

This mixture is particularly useful when preparing the carboxylic acid derivative (B) useful in the present invention. It is for use. On the other hand, by using pure alkylene polyamine, it is completely satisfactory. A product can also be obtained that can be washed.

Other useful types of polyamine mixtures include the stripping of Boriamia mixtures described above. In this case, a mixture of low molecular weight polyamine and volatile Chemical impurities are removed from alkylene polyamine mixtures, often by A residue called nobottomsuyo remains. In general, al-gyushin polyamino bottoms contains substances boiling below about 200°C in an amount of less than 2%, usually 1% (heavy It can be characterized as having less than the standard). Ethylene boryaminium Nobottoms (which are readily available and have been found to be quite useful) ), the bottoms must contain less than approximately 2% (by weight) diethylenetriamine (DETA) or triethylenetetramine (TETA) ). Etile obtained from Dow Chemical Company (Freeboard, Texas) A typical sample of the ) has a specific gravity of 1.0168(') at 15.6℃, and a nitrogen content of 33.15% by weight. , and a viscosity of 121 centistokes at 40°C.

Gas chromatography analysis of such a sample shows that this is approximately 0.93% Light entco (mostly DETA), 0.72% TETA, 2 1.74% tetraethylenepentamine, and 76.61% and more It was shown to contain pentaethylene hexamino (heavy I group T$). these Alkyleneboriyaminobottoms include cyclic condensation products (e.g. piperazine) , and higher congeners such as diethylenetriamine and triethylenetetramine The body is included.

Other polyamines which can be reacted with the acylating agent (B-1) according to the invention are e.g. , as described in U.S. Patent Nos. 3.219.666 and 4.234.435. There is. The content of these patents is that the carboxylic acid inducer of the present invention reacts with the above-mentioned acylating agent. Reference is made herein to the disclosure of amines that can form the conductor (B).

Manufactured from the previously described acylation reagent (B-1) and amino compound (B-2) The carboxylic acid derivative composition (B) contains an acylated amine. This reed amines include amine salts, amides, imides and imidacillins as well as their Mixtures thereof are included. Carboxylic acid derivatives from acylating reagents and amine compounds To prepare the conductor, one or more acylating reagents and one or more The amino compound on it pi is approximately 0°C to the decomposition point (here, this decomposition point is as required, at temperatures ranging up to Heat is applied in the presence of an active organic liquid solvent/diluent. However, usually around Range from 00°C to approximately 300'C (if 300°C does not exceed this decomposition point) heated at a temperature of Temperatures of about 25° C. to about 250° C. are typically used.

The acylation reagent and amide/compound are approximately 172 Enough to obtain equivalent to about 2 moles of amine compound! A. Let it react.

In this acylation reagent (B-1), a conventional high molecular weight acylating agent reacts with an amine. It can be reacted with amino compound <B-2) in the same manner as License No. 3.172.892; No. 3.219.666; No. 3.272.746 and No. 4.234.435 discloses that acylating reagents and the above amino/compounds Regarding the methods that can be applied to reactions with substances, this is shown in ζ.

To produce carboxylic acid derivative compositions that exhibit improved viscosity index performance, generally The need to react this acylating reagent with a polyfunctional amine reactant was discovered. ing. For example, two or more primary amino groups and/or secondary amino groups Polyamines having amine groups are preferred. However, clearly this acyl Not all of the amine compounds that are reacted with the chemical reagent need to be polyfunctional. That's it In addition, a combination of a monofunctional amine compound and a polyfunctional amino compound is used.

In one embodiment, the acylating agent is about 0.70 equivalents per equivalent of acylating agent. to less than 1 equivalent (e.g., about 0,695 equivalents It) of the amino compound. will be responded to. The lower limit of the equivalent amount of the amino compound is o, 75 per 1 acylating agent. equivalent weight or exactly 0.80 equivalents, with an upper limit of about 0.90 equivalents or o,9 It can be up to 5 equivalents. Therefore, the acylating agent for amino compound (B-2) A narrower range of equivalents for (B-1) is about 0.70 equivalents to about 0.90 equivalents, or About 1 to about 0.90 equivalents per 0475, or about 1 to about 0.85 equivalents per 0475. can be obtained. In at least some situations, equivalents of amino compound per equivalent of acylating agent. When the amount is about 0.75 or less, the dispersant and 16. It is clear that the effectiveness is reduced. In one embodiment, the acylating agent and the amino The relative amount of the carboxylic acid derivative preferably contains free carboxylic groups. It is assumed that there is no such amount.

In other embodiments, the acylating agent is about 1.0 parts I per 1 part acylating agent. ~1.1 equivalents, or up to about 155 equivalents of the amine compound. This is it Numerous amino compounds may also be used.

The amount of amine compound (B-2) reacted with the acylating agent (B-1) within the above range may also depend in part on the number and type of nitrogen atoms present. For example, certain reeds Polymers containing one or more -NH2 groups are used to react with the Amines have the same number of nitrogen atoms but -N+ (2 groups are fewer or absent). Less amounts are required than -polyamines. One -NH2 group is 2 This is because an imide can be formed by reacting with -COOI (group). If only secondary nitrogen is present in the compound, each >NH group has one -COOH It can only be reacted with groups. Therefore, within the above range, the reaction with this acylating agent is The amount of polyamine that is added to form the carboxylic acid derivative of the present invention is determined by considering the number and type of nitrogen atoms (i.e. -NH2, >NH and >N-) in Therefore, it can be easily determined.

The acylating agent used to form this carboxylic acid derivative composition (B) and In addition to the relative amounts of carboxylic acid derivatives and amino compounds used in the present invention, Other important characteristics are the Mn value and My/Mn value of the polyalkene, and For each equivalent of substituents, on average at least 1.3 succinic acid groups are present as acylating agents. It is to exist within. This carboxylic acid derivative composition (B) has all of these When characterized, the lubricating oil compositions of the present invention exhibit new and improved properties. child Lubricating oil compositions are characterized by exhibiting improved performance in internal combustion engines. Ru.

The ratio of succinic acid groups to the equivalents of substituents present in the acylating agent is It can be determined from the saponification value of the mixture. This saponification value is the saponification value at the end of the reaction. reaction mixture (which is generally indicated as filtrate or residue in the following examples) is corrected by revealing unreacted polyalkenes present in This saponification value is determined using the ASTM D-94 method.

The formula for calculating this ratio from the saponification number is: The corrected saponification number is , obtained by dividing the saponification number by the percentage of polyalkene reacted. Ru. For example, 10% of the polyalkene is not reacted and the filtrate or residue If the saponification value is 95, the corrected saponification value is the value obtained by dividing 95 by 0.90. It is 105.5.

The preparation of this acylating agent is illustrated in Examples 1-3 below.

The preparation of carboxylic acid derivative composition (B) is illustrated in Examples B-1 to B-26 below. do. As otherwise set forth in the Examples below and elsewhere in the specification and claims. Unless explicitly indicated, all percentages and parts are by weight and temperatures are by weight. mr, and the pressure is at or near atmospheric pressure.

(Margin below) “Nijo” YoL: Example 1 Polyisobutyne (Mn=1845: Mv=5325) 510 parts (0.28 parts ) and 59 parts (0.59 mol) of maleic anhydride at 110'C Heat until. Heat this mixture to 190'C for 7 hours. During this time, I 43 parts (0.6 mol) of physical chlorine are added from below the surface. At 190-192°C, An additional 11 parts (0.16 mol) of chlorine are added over a period of 3.5 hours. This reaction mixture The mixture was heated at 190-193°C for 10 hours with nitrogen bubbling. stripping. This residue is converted into the desired polyisobutyne-substituted succinic acid. Sil ([JIJ), which is the saponification rate of 87 determined by ASTM method D-94. has an equivalent number).

Example 2 Polyisobutyne (Mn=2020; Mw=6049) 1000 parts (0.49 5 mol) and 115 parts (1.17 mol) of maleic anhydride. Heat to 0'C. This mixture is heated to 184°C for 6 hours.

During this time, 85 parts (1.2 moles) of gaseous chlorine are added from below the surface. 184-189 At °C, an additional 59 parts (0.83 mol) of chlorine are added over 4 hours. This anti Heating the reaction mixture at 186-190°C for 26 hours with nitrogen bubbling. Stripping is performed. This residue is the desired polyisobutylene substituted succinate. Acid acylating agents (which have a saponification equivalent of 87 as determined by ASTM method D-94) Quantity).

Example 3 Polyisobutyne chloride (This is 3000 parts of polyisobutyne (Mn=1696; Mw=16594) was added with 251 parts of gaseous chlorine at 80°C for 4.66 hours. ) and 345 parts of maleic anhydride were prepared by adding 0 ．． Heat to 200°C over 5 hours. The reaction mixture was heated at 200-224°C. 6.3 Hold for 33 hours, strip at 210°C under vacuum and filter.

This filtrate is then converted to the desired bo-11 isobutyne-substituted succinic acylating agent (which is AS with a saponification equivalent number of 94 as determined by TM Method D-94).

,! L-Tuesday Z-Scattered participation and defeat Danhosa U: Example B-1 10.2 parts (025 parts jl) of a commercially available mixture of ethishishi/polyamine <This is 1 having about 3 to about 10 nitrogen atoms per molecule) with 113 parts of mineral oil and substituted 161 parts (0 , 25 equivalents). This reaction mixture was mixed with 2 Heat up to 150°C for an hour [2. Stripping is done by blowing in nitrogen. Ru. The reaction mixture is filtered to obtain the product as an oil solution.

Example B-2 57 parts (138 equivalents) of a commercially available mixture of ethylene polyamine (this is equivalent to 1 molecule per (having about 3 to 10 nitrogen atoms) in 1067 parts of mineral oil and direct conversion 893 parts of acid acylating agent (which was prepared in Example 2 at 140-145°C) A mixture is prepared by adding (1,38 eq.). This reaction mixture , stripped by heating to 155°C for 3 hours and blowing with nitrogen. do. The reaction mixture is filtered to obtain liquid 1a as the desired product.

Example B-3 1132 parts of mineral oil and 70 parts of substituted succinic acid unlying agent prepared as in Example 1 Prepare 9 parts (1,2 equivalents) of the mixture. Piperazine 56.8 parts (1°32 parts) A solution of i) in 200 parts of water was added dropwise at 130-140″C for approximately 4 hours. Slowly add to mixture from top of funnel. Heat to 160°C while removing water Continue. The mixture was maintained at 160-165°C for 1 hour and then cooled overnight. do. The mixture is reheated to 160°C and then maintained at this temperature for 4 hours.

Mineral oil (270 parts) is added and the mixture is filtered through filter aid at 150°C.

This filtrate contains 65% oil and 0.65% nitrogen (theoretical 0.86%). The desired product is

Example B-4 1968 parts of mineral oil and 15 parts of substituted succinic acylating agent prepared as in Example 1 08 parts (2,5 equivalents) of the mixture are heated to 145°C. Then, examples 125.6 parts of the commercially available mixture of ethylene polyamine used in B~1 (3.0 parts) , over a period of 2 hours, maintaining the reaction temperature at 145-150°C. this The reaction mixture was heated at 150-152°C for 5.5 hours with nitrogen bubbling. Stir. The mixture is filtered at 150° C. using a filter aid. This filtrate is , 55% oil and 1.20% nitrogen (theoretical value 1.17). It is a product.

Example B-5 1503 parts of mineral oil and 1220 parts of the substituted succinic acylating agent prepared in Example 1 (2 equivalents) is heated to 110'C. Then, used in Example B-1. 120 parts (3 parts N) of a commercially available mixture of type ethylene polyamine was added for about 50 minutes. Add over time. The reaction mixture was stirred for an additional 30 minutes at 110"C. , then increase the temperature and maintain at about 151"C for 4 hours. Add filter aid, Filter this mixture. This filtrate contains 53.2% oil and 1,44% nitrogen. The desired product contains the following: (theoretical value 149).

Example B-6 3111 parts of mineral oil and a commercially available mixture of ethylene polyamine used in Example B-1 844 parts (21 parts ji) of the mixture are heated to 140°C. Then, implement 3885 parts (70 parts!) of the substituted succinic acylating agent prepared as in Example 1 were is added over a period of about 1.75 hours while increasing the temperature to about 150°C. blow nitrogen The mixture was maintained at 150-155°C for about 6 hours at 1 and then at 130°C. Filter using filter aid at °C. This filtrate contains 40% oil and 3.5% 5, Example B, -7, the desired product containing nitrogen (theoretical value 3.78) 182 parts (0,433 parts jl) of a commercially available mixture of ethylene polyamine (this is 1 having about 3 to 10 nitrogen atoms per molecule) in 392 parts of mineral oil and gastric Huccinic acid acylating agent (prepared at 140°C in Example 2) 348 parts (0 , 52 equivalent It) to prepare compound a. This reaction mixture is Stripping by heating to 150℃ for 1.8 hours and blowing nitrogen do. The reaction mixture was filtered to yield the desired product containing 55% oil. A filtrate is obtained.

Example B-8 Appropriately sized flask (this includes a stirrer, nitrogen inlet tube, addition funnel and Dean-Stark (equipped with a trap/cooler) was fitted with the assembly described in Example 3. Filled with a mixture of 2483 parts of silting agent (4°2, our JIi) and 1104 parts of oil. do. Heat this mixture to 210°C. During this time, slowly sparge the mixture with nitrogen. Let the cream bubble. Ethylene polyamine bottoms (134 parts, 3°14 equivalents) , at this temperature, slowly over about an hour.

The temperature was maintained at about 210° C. for 3 hours, then 3688 parts of oil was added and the temperature to 125°C. After being stored at 138°C for 17.5 hours, the mixture was Filtration through diatomaceous extract yields the desired acylated amino acid containing 65% oil. Musu is obtained.

Example B-9 3660 parts (6 equivalents) of the substituted succinic acylating agent prepared in Example 1 in diluent oil 46 A mixture in 64 parts is prepared and heated to about 110°C.

This mixture is then sparged with nitrogen. This mixture was then added to the ethylene polyethylene Commercially available amines (which contain from about 3 to about 10 nitrogen atoms per molecule) 210 parts (5.25 equivalents) of the mixture were added over the course of 1 hour and the mixture was Maintain at 0°C for an additional 0.5 hour. Heat at 155"C for 6 hours while removing water. After that, the filtrate was added and the reaction mixture was heated at about 150°C to 111! treat This filtrate is is the desired product.

Example B-10 0.8 equivalents of the substituted succinic acylating agent prepared in Example 1 was added to ethylene polyamine. The general method of Example B-9 was followed except that 0.67 equivalents of a commercially available mixture of repeat. The product obtained in this way is an oil solution containing 55% diluent oil. It is.

Example B-11 The polyamine used in this example is a mixture of equivalent amounts of the following alkylene polyamines: The general method of Example B-9 is repeated except that: This alkylene polyamine The mixture was made of ethylene polyamino bottoms 80 obtained from Union Carbide. %, and the city of ethylene polyamine corresponding to diethylene triamine in the empirical formula Consists of 20% commercial mixture. This polyamine mixture has an equivalent weight of about 43.3 It is characterized as having.

Example B-12 The polyamine used in this example was an ethylene polyamine bottle obtained from Dow. Contains a mixture of 80 parts by weight of Mus and 20MjIi parts of diethylenetriamine The general method of Example B-9 is repeated except as follows. This amine mixture has approximately 41 ．． It has an equivalent weight of 3.

Example B-13 444 parts (0.7 equivalents) of a substituted conoester acylating agent prepared as in Example 1; and 563 parts of mineral oil are prepared and heated to 14Q'c. Then, the sutra Ethylene polyamine mixture 22.2 corresponding to triethylenetetramine in empirical formula (0,5 & eq.) over 1 hour while maintaining the temperature at 140°C. Ru. Bubble the mixture with nitrogen while heating to 150'C to remove water. Maintain this temperature for 4 hours. This mixture was then filtered at about 135°C. Filter with aid. This filtrate is the desired product containing approximately 55% mineral oil.

Example B-14 422 parts (0.7 parts jl) of substituted succinic acylating agent prepared as in Example 1 , and 188 parts of mineral oil are prepared and heated to 210"C. Then, A commercially available mixture of ethylene polyamino bottoms (E-100> obtained from Dow Company) 22.1 parts (0.53 equivalents) are added over 1 hour while blowing with nitrogen. . The temperature is then increased to about 210-216°C and maintained at this temperature for 3 hours. ore Add oil (625 parts) and maintain the mixture at 135°C for approximately 17 hours. Then filter this mixture. This filtrate contains the desired product containing 65% oil. It is.

Example B-15 414 parts (0.71 parts jl) of the substituted succinic acylating agent prepared in Example 1, and A mixture of 184 parts of mineral oil and mineral oil is prepared and heated to about 80'C. Then, Melami Add 22.4 parts (0,534 parts) of Heat to 50"C and maintain at this temperature for 5 hours. After cooling overnight, the mixture is Heat to 170°C for 2.5 hours, then to 215°C for 1.5 hours. Heat.

The mixture was maintained at about 215°C for about 4 hours and at about 220'C''C' for 6 hours. maintain. - After cooling overnight, the reaction mixture is filtered through a filter aid at 150'C. Ru. This filtrate is the desired product containing 30% mineral oil.

Example B-16 414 parts (0.71 equivalents) of the substituted acylating agent prepared in Example 1 and 18 parts of mineral oil Heat the 4 parts mixture to 210°C. Then, using the empirical formula, tetraethylene 21 parts (0.53 equivalents) of a commercial mixture of ethylene polyamines corresponding to pentamine is added over 0.5 hour while maintaining the temperature at about 210-217°C. Po Once the addition of reaamine was complete, the mixture was heated to 217° C. with nitrogen bubbling. Maintain for 3 hours. Mineral oil (613 parts) was added and the mixture heated at about 135°C for 17 Hold for an hour and filter. This filtrate contains the desired product containing 65% mineral oil. It is.

(C) Niotsffy Tokoso The lubricating oil compositions of the present invention obtain from 1 to about 500 ppm manganese as metal. contains at least one manganese compound in an amount sufficient to. However, this manga The compound is not a neutral manganese dihydrocarbyl phosphorodithioate. Real In embodiments, the manganese compound is soluble in the lubricating oil compositions of the present invention. child The manganese compound (C) is generally a salt of an acidic substance, especially a carboxylic acid, It is a salt of sulfonic acid and phenol. In other embodiments, manga in oil Compound snow provides about 50 to about 300 ppm manganese as a metal. It is. This manganese compound is a neutral manganese compound, or It can be a oxidized manganese compound.

Overbased manganese compounds are generally preferred. used in the present invention The term "overbased" applied to manganese compounds refers to indicates that the substance contains manganese in an amount greater than that required to neutralize the acid.

Therefore, the overbased manganese salt is more than 1 equivalent per 1 equivalent of acid. Contains a lot of metal. Acidic substances (e.g. carboxylic acids, sulfonic acids, phenols) Overbased manganese salts of (and phosphorus-containing acids) are well known and described in the technical field. For example, U.S. Patent No. 4.162.986 (Alka iHs); U.S. Patent No. 3.821.979 (Pfotrowskf); National Patent No. 3.312.618 (LeSuer et al.); U.S. Patent No. 2.616.9 No. 04 and.

No. 905 (Aseff et al.); and No. 4.252.659 (Ali). Yo. Neutral manganese dihydrocarbyl phosphorodithioate is present in the lubricating oil composition of the present invention. Although not contained in products, overbased dihydrocarbyl phosphoro It should be noted that manganese dithioate is considered a useful manganese compound. be.

Overbased manganese salts are preferred. They retain their solubility while Acidic compounds that give a high manganese content and are therefore introduced into the lubricating oil (this The amount of metal (which serves only as a carrier for the metal) is This is because it is useful for introducing Specifically mentioned here, overbasing The metal-acid molar ratio of the manganese compound prepared is greater than 1:1 and generally 2:1. : Greater than 1. The metal-acid molar ratio in overbased compounds is often I7 is called the "metal ratio."

The organic acid used in preparing this manganese salt contains carbon atoms5, carboxylic acids (especially carboxylic acids containing from 1 to about 30 carbon atoms), Sulfonic acids (especially one or more sulfonic acids having from 4 to about 22 carbon atoms) Sulfonic acids containing an aromatic ring structure replaced with an alkyl group), phenolic compounds (especially hydrocarbon-substituted phenols); and 4 manganese compounds When overbased compounds, from 1 to about 30 or more carbon atoms Phosphorus-containing compounds containing in their structure one or more organic groups with , is included. All of these acidic materials are well known in the art.

The carboxylic acids include aliphatic, cycloaliphatic or aromatic monocarbonic acids and It can be a polycarboxylic acid. Monocarboxylic acids include C2-7 lower acids (acetic acid, (e.g., propionic acid) and higher Ci acids (e.g., octanoic acid, decanoic acid, etc.) ) as well as the well-known fatty acids having about 12 to 30 carbon atoms. . This fatty acid is often a mixture of straight chain acids and branched chain acids; , for example, 5% to about 30% straight chain acids, and about 70% to about 95% (moles) branched. Contains chain acids.

Other commercially available fatty acid mixtures containing even higher proportions of straight chain acids are also useful. . Mixtures formed by trimerization of unsaturated fatty acids can also be used.

Higher carboxylic acids can be obtained by alkylating 71-twin acid anhydride or its derivatives. The well-known dicarboxylic acids produced by The production of such a reaction Products include hydrocarbon-substituted succinic acid and its anhydrides. low molecular weight from about C Substituted acids up to 3B as well as low molecular weight dicarboxylic acids (e.g. polymer tyrene-linked acids; glutaric acid, adipic acid, etc.) also make the salts of the invention. It can be used to

High molecular weight substituted succinic anhydride as described above in preparing dispersant (B) and its homologs are also useful in making the manganese salts of the present invention.

The fatty acid generally contains at least 8 carbon atoms, preferably less than 8 carbon atoms. Contains at least 12 carbon atoms. Usually these acids are greater than about 400 Contains no carbon atoms.

Generally, if the aliphatic carbon chain is branched, the acid Oil-solubility increases relative to the content. Cycloaliphatic carboxylic acids and aliphatic carboxylic acids can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, α- Lyrinic acid, propylene tetramer substituted succinic acid, behenic acid, isostearic acid Phosphoric acid, pelargonic acid, capric acid, palmitoleie acid), sulfuric acid, lauric acid, oleic acid, ricinoleic acid, undecane acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldehyde lonafucrenecarboxylic acid, stearyl-octahydroindenecarphonic acid, lumitic acid, commercially available mixtures of two or more carboxylic acids (e.g. tall oil acids, rosin acids, etc.) This Manrikisha salt also contains oil-soluble organic sulfur-containing acids (e.g. sulfonic acid, sulfuric acid, Sulfamic acid, thiosulfonic acid, sulfinic acid, sulfenic acid, partially esterified sulfate, sulfite, and thiosulfate) Ru. Generally, the manganese salt is a salt of a carboxylic or aliphatic sulfonic acid. .

Examples of such carboxylic or aliphatic sulfonic acids include mahogany sulfonic acid ;Bright Stock Sulfonic Acid; Approximately 100 seconds at 100'F ~ Approximately at 210'F Sulfonic acid derived from lubricating oil fraction with Saybolt viscosity of 200 seconds: petroleum Sulfonic acids; monowax-substituted and polywax-substituted sulfonic acids and polysulfonic acids (e.g. benzene, naphthalene, fairol, diphenylene, etc.) Nyl ether, naphthalene disulfide, diphenyl γmino, thiophene, α- chloronaphthalenato sulfonic acids and polysulfonic acids); other substituted sulfonic acids There is ruhoni/acid. Other substituted sulfonic acids include, e.g. surnanic acid (in the case of 1, this alkyl group has at least 8 carbon atoms) ), cetyl phenyl monosulfide sulfonic acid, dicetylthiane di-sulfonate acid, dilauryl-β-naphthylsulfonic acid, capril nitronaphthalene sulfonic acid fonic acid, and alkaryl sulfonic acid, dodecylbenzene (bottoms) ) sulfonic acid). Dodecylbenzene (bottoms) is primarily a monodode. It is a mixture of silbenzene and didodecylbenzene.

This aliphatic sulfonic acid includes paraffin wax sulfonic acid, unsaturated paraffin Wax Sulfonic Acid, Hydroxy Substituted Paraffin Wax Sulfonic Acid, Hexap Lopyrene sulfonic acid, tetraamylene sulfonic acid, polyisobutyne sulfonic acid ( Here, the polyisobutyne has 20 to 700 (4 or more H carbon atoms) ), chlorosubstituted paraffin wax sulfonic acid, nitroparaffin wax cycloaliphatic sulfonic acids (e.g., petroleum naphthalene sulfonic acids); cetylcyclopentylsulfonic acid, laurylcyclohexylsulfonic acid, Bis-(di-isobutyl)cycloto-bovine silsulfonic acid, monowax substituted or polywax-substituted cyclohexylsulfonic acid.

A more detailed description of the sulfonic acids used herein can be found in U.S. Patent No. 2.61 No. 6.905; No. 3.027.325; No. 3.312,618; No. 3, 35 No. 0.308: No. 3.471.403; No. 3.488.2!14; No. 3.5 No. 95.790; No. 3.798.012; No. 3.829°381; No. 4.1 No. 00.083; and No. 4.326.4172. these The content is set forth herein for the disclosure regarding -J.

Neutral or overbased manganese salts of phenolic compounds (phenates) ) are also useful in the lubricants of the present invention. Hydrocarbon substituted phenol, sulfur phenols, and phenols with alkylene (e.g. methylene) attached. It is also useful. To prepare this manganese salt, a mixture of phenols is used. I can stay. Alternatively, mixtures of separately prepared mancamphenate can be used in accordance with the present invention. It can be included in lubricating oils.

Typically, the organic acid used in producing the manganese salt used in the present invention is carbon rubonic acid, sulfonic acid, or a mixture thereof. A particularly useful series of manga U.S. Pat. No. 4.162 by A. Kaitis et al. ．． No. 986, the contents of which are described in Manga No. 986, which are useful in the composition of the invention DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference is made herein for disclosure of compositions, particularly manganese salts of organic acids.

The manganese salt used in the present invention is preferably overbased. It is worth paying attention to. Such salts are well known in the art. For example, In addition to the previously cited U.S. Pat. No. 4.162.986, U.S. Pat. ．． No. 827.979; No. 4.252.659; No. 4.505.718; and See also No. 4.664.677. The contents of these patents are -based disclosure of manganese salts is provided herein.

Organic compositions of manganese metal with a high proportion of overbased overbasing of organic acids (including oxide-hydroxylated homogeneous carbonate complexes) Manganese salts are particularly useful. In this complex, the metal content is partially polynuclear It is chemically combined with oxygen in the crystal nucleus of the metal oxide, and some are combined with at least two species. different monocarboxylic acids or one or more monocarboxylic acids and monosulfur mixture with fonic acid (which contains hydroxyl-metal-carbonate and hydroxyl-metal-sulfuric acids) (containing at least 2 carbon atoms as a phonate group) Ru. At least one of the acids is a monocarboxylic acid containing at least 7 carbon atoms. carboxylic acid and the second acid is also a monocarboxylic acid, the second acid is the longest chain (This differs by at least two carbon atoms from the total number of carbon atoms in the other acids.) ) contains a large number of carbon atoms. This carboxylate group and sulfonate At least a portion of the group is hydrogen bonded to the nuclear oxygen atom, and this carboxylic acid The remainder of the ate and sulfonate groups are unbonded and the sulfonate groups are is in equilibrium. The molar ratio of all metals to the total number of moles of organic acid is greater than 1. stomach. These preferred compositions, and methods of their preparation, are described in U.S. Patent No. 4.16 No. 2゜986, particularly in columns 8 to 14, are described in more detail, and the contents of the entire patent are as follows: A disclosure regarding such manganese salts is provided herein.

Useful overbased manganese salts containing high concentrations of manganese include the following products: 4 as a bimetallic product commercially available from Mooney Chemical Company under the name FOA 910T″ liquid carboxylate containing 0% manganese: 12% CEM-ALL” containing manganese.

Overbased manganese 'fm' produced from phosphorus-containing acids also Useful in lubricants. This phosphorus-containing acid can be represented by the following formula: Here, R' and R2 are each independently a hydrocarbon group; and x4 are each independently oxygen or sulfur; and a and b are each 0 or l.

The preparation of such overbased manganese salts of phosphorous acids is described in U.S. Pat. No. 695.910 (Asseff et al.). this The content of the patent is here for the disclosure of such overbased manganese salts. It is shown.

In addition to the above necessary carboxylic acid derivative dispersant (B) and manganese compound (C) This lubricant has favorable performance in gasoline and diesel engines. Contains other additives to further give the oil the desired properties needed to obtain Generally, it contains. Such additives include metal phosphorodithioates. anti-wear additives, detergents, and other dispersants including carboxylic acid ester derivatives. Included.

(margin below) (D) Dihydrocarbyl phosphorodithio gold: In other embodiments, the present invention (D) at least 18! Dihydro Contains local phosphorodithioic acid metal: Here, R1 and R2 each independently contain 3 to about 13 carbon atoms. is a hydrocarbyl group having a metal, and n is an integer equal to the valence of M. It is a number.

Generally, the oil compositions of the present invention will contain one or more of the above identified phosphors. Metal rhodithioates can be added to various I (e.g., about 0.0 1% to about 5% or about 0.1% to about 2% by weight, more generally , about o,oi% to about 1% by weight). This metal phosphorodithioate is In order to improve the anti-wear properties and anti-oxidation properties of the lubricating oil composition of the present invention, added to the composition.

The hydrocarbyl groups R1 and R2 in the phosphorodithioate of formula (2) are alkyl groups. , cycloalkyl, aralkyl or alkaryl groups, or entities of similar structure. It can be a qualitative hydrocarbon group. "Substantial hydrocarbon" means the hydrocarbon nature of the group. substituents that do not significantly alter the refers to hydrocarbons containing chlorogen).

Exemplary alkyl groups include isopropyl, isobutyl, n-butyl, 5ee-butyl, various amyl groups, n-hexyl, methyl7. isobutyl, carbinyl, heptyl 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, Includes decyl, dodecyl, tridecyl, and the like. Examples of lower alkylphenyl The bases include quinryl, cresyl, methyl phenyl, amyl phenyl, and heptyl phenyl. and phenyl. Cycloalkyl groups are useful as well, and these primarily include , cyclohexyl group and lower alkylcyclohexyl group. many Substituted hydrocarbon groups (e.g. chloropentyl, dichlorophenyl and dichlorophenyl) lolodecyl) can also be used.

The phosphorodithioic acids from which the metal salts useful in this invention are prepared are well known.

Examples of dihydro-rubyl phosphorodinaic acid and its metal salts, and such acids Examples of methods for preparing salts and salts include, for example, U.S. Pat. No. 4.263.150; No. 289.635; No. 4.308.154; and No. 4.417.990. be found. The contents of these patents are hereby incorporated by reference with respect to such disclosure. ing.

This phosphorodithioic acid combines phosphorus trisulfide with an alcohol or phenol or alcohol. alcohol mixture, phenol mixture or mixture of alcohol and phenol It is prepared by reaction with In this reaction, 4 moles per mole of phosphorus trisulfide reactions of alcohols or phenols. This reaction occurs between approximately 0°C and approximately carried out at a temperature in the range of 200°C, preferably in the range of about 0°C to about 150°C. I can. Therefore, for the preparation of 010-non-n-hexylphosphorodithioic acid, React phosphorus trisulfide and 4 mol n-hexyl alcohol at about 100°C for about 2 hours. This includes letting people do so. Hydrogen sulfide is liberated and the residue is the specified acid. this acid Metal salts of can be prepared by reaction with metal oxides. To cause a reaction, this Simply mixing and heating these two reactants is sufficient and the resulting product is , is sufficiently pure for the purposes of this invention.

Metal salts of dihydrocarbylbosphorodithioic acids useful in the present invention include Group I metals, Contains Group III metals, aluminum, lead, tin, manganese, cobalt and nickel. These salts are included. Group ■ metals, tin, iron, cobalt, lead, manganese, Nickel and copper are among the preferred metals. Zinc and copper are particularly useful metals It is. 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, acid Zinc oxide, copper oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, Barium oxide, iron carbonate, copper hydroxide, lead hydroxide , tin butyrate, cobalt hydroxide, nickel hydroxide, nickel carbonate, etc. .

In some cases, certain components (e.g., small amounts of metal acetate) may be present along with this metal reactant. salt or acetic acid) to facilitate the reaction and yield improved products. Ru. For example, using up to about 5% zinc acetate in conjunction with the required amount of zinc oxide , zinc phosphorodithioate is easily formed.

In one preferred embodiment, the alkyl groups R1 and R2 are secondary alcohols (e.g. For example, isopropyl alcohol, 2'Q1 alcohol, 2-pentanol , 4-methyl-2-pentanol, 2-hexanol, 3-hexanol, etc.) derived from.

A particularly useful metal phosphorodithioate is the reaction of phosphorus trisulfide with alcohol mixtures. can be prepared from phosphorodithioic acids prepared in the following order: Furthermore, such a By using alcohol mixtures, it is possible to generate oil-soluble phosphorodithioic acids by themselves. 〇 Therefore, isopropyl A mixture of alcohol and hexyl alcohol is a very useful oil-soluble phosphor. It can be used to produce metal phorodithioates. For the same reason, phospho Mixtures of rhodithioic acids can react with metal compounds to form inexpensive oil-soluble salts.

Mixtures of alcohols include mixtures of different primary alcohols, different secondary alcohols, or a mixture of primary and secondary alcohols. Ru. Examples of useful mixtures include: n-butanol and n-octane. Tatool; n-pentanol and 2-ethyl-1-hexanol; isobutano alcohol and n-benzenol; isobutanol and isoamyl alcohol; Sopropatool and 4-methyl-2-pentanol: Isopropatool and 5ea-butyl alcohol; such as isopropanol and inoctyl alcohol degree. Particularly useful alcohol mixtures include at least about 20 mole percent isopropyl alcohol. alcohol (in a preferred embodiment, at least 40 mol% isopropyl alcohol) It is a mixture of secondary alcohols containing alcohol.

In other embodiments, the lubricating oil compositions of the present invention include dihydrocarbyl phosphorodithio containing a mixture of metal salts of acids, wherein at least one dihydrocarbyl phosphorus In phorodithioic acid, one hydrocarbyl group (D-1) is an isopropyl group or It is a secondary butyl group, and the other hydrocarbyl group (D-2) has at least 5 contains carbon atoms, and at least one of all hydrocarbyl groups present in (D) Approximately 20 mol% of both are isopropyl groups, secondary butyl groups, or mixtures thereof. be.

In yet other embodiments, the lubricating oil composition comprises a dihydrocarbyl phosphoroditone. a mixture of metal salts of phosphorodithioic acids, wherein at least one of the phosphorodithioic acids In , one hydrocarbyl group (D-1') is an isopropyl group or a secondary butylene group. the other hydrocarbyl group (D-2) contains at least 5 carbon atoms. and this lubricating oil composition has an inpropyl group derived from (D), a secondary butylene group, or mixtures thereof in a proportion of at least about 0.05 1% by weight.

In yet other embodiments, the lubricating oil compositions of the present invention comprise isopropylene derived from (D). and/or secondary butyl groups in an amount of at least about 0.08% by weight. may have.

Isopropylene derived from (D) present in or added to this oil The amount of ru groups or secondary butyl groups can be calculated using the following formula: Weight % of iPr groups or S-butyl groups = weight % of P in niobyl x carbonization of (D) in a hydrogen mixture °43 is isopropyl group molding °57 is the molding of secondary butyl group 31 is the atomic weight of phosphorus The alcohol mixture used in preparing the phosphorodithioic acid of this last embodiment. The compound is a mixture of isopropyl alcohol, a mixture of secondary butyl alcohol or or a mixture of isopropyl alcohol and secondary butyl alcohol, and approx. at least one primary alcohol or aliphatic containing ~13 carbon atoms Includes alcohol. In particular, this alcohol mixture has at least 20.25 or 30 mol% isopropyl alcohol and/or secondary butyl alcohol L containing alcohol, generally from about 20 mol% to about 90 mol% inpropyl alcohol or or secondary butyl alcohol. In a preferred embodiment, this alcohol The alcohol mixture contains from about 30 mol% to about 70 mol% isopropyl alcohol. species or more primary aliphatic alcohols.

The primary alcohol contained in this alcohol mixture includes n-amyl alcohol. Coal, in-amyl alcohol, n-hexyl alcohol, 2-ethyl-l-hexyl alcohol xyl alcohol, isooctyl alcohol, nonyl alcohol, isodecyl Alcohol, dodecyl alcohol, tridecyl alcohol, etc. are included. child The primary alcohols may also contain various substituents (eg, \logen).

Particular examples of useful alcohol mixtures include, for example, isopropyl/2-ethyl- 1-hexyl; isopropyl/isooctyl; isopropyl/isodecyl; iso Included are propyl/dodecyl; and isopropyl/tridecyl. preferable In one embodiment, the primary alcohol contains 6 to 13 carbon atoms; The total number of carbon atoms per phosphorus atom in the phosphorodithioic acid required for It's at least 9.

Alcohol mixtures (e.g. mixtures of iPrOH and R”OH) and phosphorus trisulfide The phosphorodithioic acid composition obtained by the reaction with A statistical mixture of exemplified phosphorodithioic acids: In the present invention, two or more species reacting with P2S5 to obtain the following mixture: It is preferable to choose the amount of alcohol above: in this mixture, dithioline The acid includes one isopropyl or secondary isobutyl group and at least five an acid containing one primary or secondary alkyl group having carbon atoms (or multiple acids) are extremely common. The relative amounts of the three phosphorodithioic acids in this mixture are: It depends in part on the relative amounts of alcohol in the mixture, steric effects, etc.

Examples D-1 to D-6 below demonstrate metal phosphorodithioates from alcohol mixtures. The preparation of

Example D-1 Alcohol mixture (this consists of 6 moles of 4-methyl-2-pentanol and 4 moles of (containing isopropyl alcohol) with phosphorus trisulfide. and prepare phosphorodithioic acid. This phosphorodithioic acid was then treated with zinc oxide. react with the oil slurry. The amount of zinc oxide in this slurry is This is approximately 1.08 times the theoretical amount required to completely neutralize rhodithioic acid. this method The oil solution (10% is oil) of zinc phosphorodithioate obtained in of phosphorus, 20.0% sulfur and 10.5% zinc.

Example D-2 Fine powder phosphorus trisulfide and alcohol mixture (this is inpropyl alcohol 11. 53 moles (692 parts by weight) and 7.69 moles (1000 parts by weight) of isooctanol The phosphorodithioic acid is prepared by reacting the phosphorodithioic acid with the following:

The phosphorodithioic acids obtained by this method have an acid value of about 178-186 and are 10.0% and 21.0% sulfur. This phosphorodithioic acid is then Then, it is reacted with an oil slurry of zinc oxide. Contained in this oil slurry The amount of zinc oxide is 1.10 times the theoretical equivalent determined by the acid value of phosphorodithioic acid. It is. The zinc salt oil solution prepared in this manner was 12% oil, 8.6% of phosphorus, 18.5% sulfur, and 9.5% zinc.

Example D-3 Inoctyl alcohol tsaoN (12 mol) and isopropyl alcohol A mixture of 180 parts (3 mol) of trisulfide phosphorus and 56 parts (3.4 mol) of trisulfide are reacted. The phosphorodithioic acid is prepared by: This reaction is based on this alcohol Heat the mixture to about 55°C and then while maintaining the reaction temperature at about 60-75°C. , by adding phosphorus trisulfide over a period of 1.5 hours.

After all the phosphorus trisulfide has been added, heat the mixture for an additional 1 hour at 70-75°C. Stir for an hour and then filter through filter aid.

Zinc oxide (282 parts, 6.87 moles) was charged to the reactor along with 278 parts of mineral oil. Ru. The phosphorodithioic acid prepared above (2305 parts, 6.

28 moles) are added to the zinc oxide slurry over a period of 30 minutes.

An exotherm of up to 60°C occurs. This mixture is then heated to 80°C and this temperature Maintain temperature for 3 hours. ], O 0°C and 6 in. Stripping to Hg After that, the mixture is filtered twice through a filter aid. This filtrate is This is the desired oil solution.

The solution was 10% oil, 7.97% zinc (theoretical value 7°40); 7.21 % phosphorus (theoretical value 7.06); and 15.64% sulfur (theoretical value 14.5) 7).

Example D-4 Isopropyl alcohol (396 parts 76.6 mol) and inoctyl alcohol Fill a reactor with 1,287 parts (9.9 moles) of 1,287 parts (9.9 moles) and heat to 59°C while stirring. Ru. Next, phosphorus trisulfide (833 parts, 3.75 mol) was added while blowing nitrogen. Add. Addition of phosphorus trisulfide takes about 2 hours at a reaction temperature between 59 and 63°C. Complete. The mixture was then stirred at 45-63°C for approximately 1.45 hours and then and filter. This filtrate is the desired phosphorodithioic acid.

The reactor is charged with 312 parts (7.7 equivalents jl) of zinc oxide and 580 parts of mineral oil.

While stirring at room temperature, add <2287 parts, 6.97 equivalents, of the phosphorodithioic acid prepared above. 11) over a period of approximately 1.26 hours.

An exotherm of up to 54°C occurs. Heat this mixture to 78 °C and 78-85 °C. Maintain at C for 3 hours. The reaction mixture was heated to 119 mm at 100°C.

Vacuum strip to Hg. This residue is filtered through a filter aid. This filter The liquid is an oil solution (19.2% oil) of the desired zinc salt. This solution is Contains 7.86% zinc, 7.76% phosphorus and 14.8% sulfur.

Example D-5 The molar ratio of isopropyl alcohol to isooctyl alcohol is 1.1. The general method of Example D-4 is repeated except that: Products obtained by this method is a solution of zinc phosphorodithioate in oil (10% oil). This solution is , 8.96% zinc, 8.49% phosphorus and 18.05% sulfur. Ru.

Example D-6 Alcohol mixture (this consists of 520 parts (4 moles) of inoctyl alcohol and containing 360 parts (6 moles) of inpropyl alcohol) and 504 parts of phosphorus trisulfide. (2.27 mol) of Prepare oxic acid. 950.8 parts (3,20 mol) of the phosphorodithioic acid prepared above and an oil solution containing 116.3 parts of mineral oil and 141.5 parts (3.44 moles) of zinc oxide. The zinc salt is prepared by reacting with the zinc salt. prepared in this way The product is a solution of the desired zinc salt in oil (10% mineral oil). This oil solution contains 9.36% zinc, 8.81% phosphorus and 1L65% sulfur .

Further identification of metal phosphorodithioates useful as component (D) in the lubricating oils of the present invention Examples are listed in the table below. The compounds of Examples D-7 to D-11 have a single The compounds of Examples D-12 to D-15 are prepared from alcohols, and the compounds of Examples D-12 to D-15 are Prepared from an alcohol mixture according to the general method of D-1: Component D: Phospho gold gold rhodithioate Genketsu Wataru [[and... D-7n-nonyl n-nonyl Ba 2D-8 cyclohexyl cyclohexy Zn 2D-9 Inbutyl Isobutyl Zn 2D-10 Hexyl Hexy Le Ca 2D-11 Indecyl Isodecyl Zn 2D-12<n-) Zn 2D-13 (Isopropyl + Isopropyl) (1:1) sooctyl) (1:1) v Ba 2D-14 (iso7'thyl + isoamyl ) (65:35) o + Zn 2D-15 (isopropyl 15 ec-) ) (40:60)m Zn2 Hosts considered for use in the lubricating compositions of the present invention Other classes of phosphorodithioate additives include the phosphorodithioate metals and epoxies listed above. adducts with de are included. Phosphorologies useful in preparing such adducts The metal thioate is most often zinc phosphocythioate. This epoxide is , alkylene oxide or aryl alkylene oxide.

This aryl alkylene oxide is styrene oxide, p-ethylstyrene oxide, oxide, α-methylstyrene oxide, 3-β-naphthyl-1,1,3-butylene chlorostyrene oxide, m-dodecylstyrene oxide, and p-chlorostyrene oxide This is exemplified by This alkylene oxide mainly contains an alkylene group. includes lower alkylene oxides containing 8 or fewer carbon atoms. Ru. Examples of such lower alkylene oxides include ethylene oxide, propylene oxide, oxide, 1,2-butene oxide, trimethylene oxide, tetramethylene oxide, butadiene monoepoxide, 1,2-hexene oxide, and shrimp There's chlorohydrin. Other epoxides useful herein include, for example, 9,10- Epoxy butyl stearate, epoxidized soybean oil, epoxidized oil, and epoxidized copolymers with styrene butadiene.

This adduct is produced by simply mixing the metal phosphorodithioate and the epoxide. ,can get. This reaction is usually exothermic and can be carried out over a wide range of temperatures from about O'C to about 300C. within the limits of the degree range. This reaction is exothermic, so the reaction temperature can be controlled carefully. One reactant (usually an epoxide) is added in small amounts to the other to make This is best done by: This reaction is carried out using a solvent (e.g. benzene, Mineral oil, naphtha or n-hexane).

The chemical structure of this adduct is unknown. For the purposes of the present invention, the phosphorodithioate salt 1 moles and lower alkylene oxides (especially ethylene oxide and propylene oxide). oxide) from about 0.25 moles to 5 moles (usually up to about 0.75 moles, or about 0.5 moles) The adducts obtained by reacting (up to molar) with found and therefore preferred.

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

Example D-16 ! [2365 parts (333 mol) of zinc phosphorodithioate prepared in Example D-2 was added to the reaction Fill the container. While stirring at room temperature, add 7138.6 parts of propylene oxide (0.6 parts). 7 mol). An exotherm of 24-31°C occurs. The mixture of the two is 80=-90 ℃ for 3 hours, then vacuum stripped to 101'C17m*, Hg Google. This residue is filtered using a filter aid. This filtrate is filtered with the desired salt solution. oil solution (11.8% oil). This solution contains 17.1% sulfur, 8 ．． Contains 17% zinc and 7.44% phosphorus.

Example D-17 7% i7) 394 g of zinc dioctyl phosphorodithioate with 1,1 content (Weight basis Tja) at 75-85°C. )'13 parts (0.5 mol per mol of zinc phosphorodithioate) over 20 minutes. Stand and add. The mixture was heated at 82-85°C for 1 hour and filtered. Ru. This filtrate (399 parts) contains 6.7% phosphorus, 7.4% zinc and 4.1% It has been found that it contains sulfur.

Phos d10 dithistate additives ( Other classes of D) include at least one of 2 to 1 defined and exemplified above in (a); (b) at least one aliphatic carboxylic acid or alicyclic carboxylic acid; Mixed metal salts with rubonic acids are included. This carboxylic acid is a monocarboxylic acid or polycarboxylic acids (which usually contain 1 to about 3 carboxylic groups) (preferably containing only one caleboxy group). This carbo The acid has about 2 to about 40 carbon atoms, preferably about 2 to about 20 carbon atoms. , may conveniently contain from about 5 to about 20 carbon atoms. The preferred carboxylic acid is , formula R'C0OH (where R3 is preferably a fatty acid free of acetylenonic unsaturation) A carboxylic acid having an aliphatic or alicyclic hydrocarbon-based group).

Suitable acids include butanoic acid, pentanoic acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, Canoic acid, dodecanoic acid, octadecanoic acid, and arachidic acid as well as olefinic acid For example, oleic acid, linoleic acid and linoleic acid, and linoleic acid (mar) or included. In most cases R3 is a saturated aliphatic group, especially a branched It is an alkyl group (eg, isopropyl group or 3-hebutyl group). illustrative Polycarboxylic acids include succinic acid, alkylsuccinic acid and alkenylsuccinic acid, There are adipic acid, sebacic acid and citric acid.

This mixed metal salt includes a metal salt of phosphorodithioic acid and a metal salt of carboxylic acid. They can be prepared by simply mixing in the desired proportions. For carboxylates The equivalent ratio of sforodithioate salts is between about O15:1 and about 400:1. preferred Preferably, this ratio is between about 0.5:1 and about 200:1. Conveniently, this The ratio is from about 0.5+1 to about 100:1, preferably from about 0.5:1 to about 50 :1, more preferably about 0.5:1 to about 20:1. Furthermore, this The ratio is about 0.5:I to about 4.5+1, preferably about 2.5:1 to about 4.25:1. For this purpose, the equivalent weight of phosphorodithioic acid is It is the value obtained by dividing the molecular weight of by the number of -PSSH groups in it, and the equivalent weight of carboxylic acid is , its molecular weight divided by the number of carboxy groups in it.

A second preferred method for preparing mixed metal salts useful in the invention includes the desired Prepare a mixture of acids in proportions and react this acid mixture with a suitable metal base. Sometimes. When this preparation method is used, with respect to the number of equivalents of acid present, It is often possible to prepare salts containing excess metal; therefore, acid Mixed metal salts containing about 2 equivalents of metal per equivalent, especially up to about 1.5 equivalents Mixed metal salts containing metals can be prepared. For this purpose, the metal equivalent is , is its atomic mass divided by its valence.

Variations on the above methods may also be used to prepare mixed metal salts useful in the present invention. It can be done. For example, metal salts of either acid can be mixed with other acids. obtained The mixture may be further reacted with a metal base.

Suitable metal bases for preparing mixed metal salts include the free metals listed above; and their oxides, hydroxides, alkoxides and basic salts. example contains sodium hydroxide, potassium hydroxide, magnesium oxide, calcium hydroxide. aluminum, zinc oxide, lead oxide, and nickel oxide.

The temperature at which the mixed metal salt is prepared generally ranges between about 30°C and about 150°C, preferably The temperature is said to be up to about 125°C. Mixed gold by neutralization with a mixture of acids and gold, space If the genus salts are prepared, temperatures above about 50°C, especially above about 75°C, may be used. It is preferable to use Substantially inert, normally liquid organic diluents (e.g. It is best to carry out this reaction in the presence of Often advantageous. The diluent is mineral oil or physically or chemically similar to mineral oil. Similar, often mixed metal salts as additives in lubricants or functional fluids There is no need to remove this diluent before using.

U.S. Patent Nos. 4.3011.154 and 4.417.990 are describes a method for preparing mixed metal salts, and provides many examples of such mixed metal salts. Disclosed. Such disclosures of these patents are set forth herein.

The preparation of this mixed salt is illustrated by the following example.

Example D-18 A mixture of 67 parts of zinc oxide (11 parts of 1,63 parts) and 48 parts of mineral oil was stirred at room temperature. Ru. 401 parts (1 equivalent jl) of di(2-ethylhexyl)phosphorodithioic acid and 36 parts of 2-ethylhexanoic acid (0.25 parts) was added to the mixture over 10 minutes. Add. During the addition, increase the temperature to 40°C. When the addition is complete, the temperature of . Raise the temperature to 80℃ in 3 hours. This mixture was then vacuum stripped at 100°C. Ping yields the desired mixed metal salt as a 91% solution in mineral oil.

Example D-19 According to the method of Example D-18, dialkylphosphorodithioic acid (which is 65% (containing isobutyl groups and 35% amyl groups) 383 parts < 1,2 equivalents), 43 parts (o, 3 equivalents) of bovine acid to 2-ethyl, 71 parts (1,73 equivalents) of zinc oxide and 47 parts of mineral oil. Mixture obtained as 90% mineral oil solution The metal salt contains 11.07% zinc.

(E) alkali metal salts of the present invention also contain at least and at least one neutral or basic sulfonic acid or carboxylic acid. May contain alkali metal salts. The amount of alkali metal salts in this lubricating oil is the amount effective to impart the desired cleaning properties to the bottle. Generally, this lubricant is approximately Contains from 0.01% to about 5% alkali metal salts, often from about 0.01% to about Contains 3% alkali metal salts. Certain alkali golds useful as component (E) A general description of salts of the genus Chamberlin (C Hamberlin)). This patent describes the use of useful alkali metals. Provided herein are disclosures of genus salts and methods of preparing the salts.

The alkali metals present in this basic alkali metal salt mainly include lithium. , including sodium and potassium, with sodium and potassium being preferred .

The equivalent weight of this acidic organic compound is the molecular weight of the acidic group present per molecule ( In other words, it is the value divided by the number of sulfonic acid groups or carboxyl groups).

In one preferred embodiment, the alkali metal salt (E) contains at least about 2 metals. more generally from about 4 to about 40, preferably from about 6 to about 30. A basic alkali metal salt having a metal ratio, particularly a metal ratio of about 8 to about 25.

The acidic organic compound from which the salt of component (E) is derived is at least one sulfur-containing acid. , carboxylic acids, phosphorous acids, or phenols or mixtures thereof . Sulfur-containing acids include sulfonic acids, thiosulfonic acids, sulfinic acids, and sulfonic acids. The oral composition (E), which includes phosphoric acid, partial ester sulfuric acid, sulfite and thiosulfuric acid, was prepared. The sulfonic acids useful in the preparation include those represented by the following formulas (■) and (X). Things are included: RXT (SO3H) 7 (■) R' (SO3111), (X) In these formulas, Ro is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon group or or substantial hydrocarbon groups (these are free of acetylenic unsaturation and contain about 60 or more containing carbon atoms). When Ro is an aliphatic group, it usually has a small containing at least about 15 carbon atoms; when Ro is an aliphatic-substituted cycloaliphatic group; , the aliphatic substituents usually contain a total of at least about 12 carbon atoms. . Examples of Ro include alkyl, alkenyl and alkoxyalkyl groups. , and there are aliphatic-substituted cycloaliphatic groups in which the aliphatic substituents are: alkyl , alkenyl, alkoxy, alkoxyalkyl, carboxyalkyl, etc. one Generally, the cycloaliphatic prokaryote is a cycloalkane or cycloalkene (e.g. Clopentane, cyclohexane, cyclohexene or cyclopentene) be guided. Specific examples of Ro include cetylcyclohexyl, laurylcyclohexyl ru, cetyloxyethyl, octadecenyl, and groups derived from Dipetroleum saturated and unsaturated paraffin waxes, and olefinic polymers ( This includes about 2 to 8 carbon atoms per unit of olefinic monomer. and 4 to 8 carbon atoms per monomer unit. (includes diolefins containing). Ro can also be used for other substitutions, e.g. may contain the following radicals, as long as their substantially hydrocarbon character is not impaired: phenyl cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitro So, lower alkoxy, lower alkyl mercapto, carboxy, carbalkoxy , oxo or thio, or an interrupting group (for example, -NH-1-〇- or -S-> .

R in formula (2) is generally a hydrocarbon group or a substantial hydrocarbon group (these are acetic Thyrenically unsaturated (containing from about 4 to about 60 aliphatic carbon atoms), preferably or an aliphatic hydrocarbon group such as alkyl or alkenyl. However However, it may also be used to may contain substituents or interrupting groups such as.

Generally, any non-carbon atoms present in Ro or R account for 1 of their total weight. It never exceeds 0%.

T is an aromatic hydrocarbon (e.g. benzene, naphthalene, anthracene or bicarbonate) phenyl) from which a cyclic nucleus can be derived, or a heterocyclic compound (Pl, pyridine , indole or isoindole) can be derived. Usually, T is , an aromatic hydrocarbon nucleus, in particular a benzene nucleus or a naphthalene nucleus.

The subscript X is at least 1, and generally 1-3. Subscripts r and y are 1 minute It has an average value of about 1-2 per child and is also generally l.

The sulfonic acid is generally a petroleum sulfonic acid or a synthetically prepared alkali. It is lylsulfonic acid. The most useful products of this petroleum sulfonic acid include: Sulfonation of suitable petroleum fractions with continuous removal and purification of acid sludge Some products are prepared by Synthetic alkaryl sulfonic acids are usually Kylated benzenes (e.g., the reaction between benzene and a polymer such as tetrapropylene) Riedel-Crafts reaction product). The following is how to prepare salt (E). A specific example of a sulfonic acid useful in Such examples also include component (E) and It should be understood that this also serves to illustrate useful sulfonic acid salts. . In other words, for each listed sulfonic acid, their corresponding basicity Alkali metal salts are also intended to be considered exemplified. (same This applies to the list of other acid substances listed below). Sulfo like this Acids include mahogany sulfonic acid, brightstock sulfonic acid, and petroleum sulfonic acid. Acid, mono- and polywax-substituted naphthalene sulfonic acid, cetylchlorobenze sulfonic acid, cetylphenol sulfonic acid, cetylphenol disulfide sulfonic acid, cetoxycaprylbenzenesulfonic acid, dicetylthianthrene sulfonate dilauryl-β-naphtholsulfonic acid, capril nitronaphthalene Sulfonic acid, saturated paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid Phonic acid, hydroxy-substituted paraffin wax sulfonic acid, tetraisobutylene Sulfonic acid, tetraamylene sulfonic acid, chlorine-substituted paraffin wax sulfonic acid , nitroso-substituted paraffin wax sulfonic acid, petroleum naphthalene sulfonic acid, Tylcyclopentylsulfonic acid, 5-urylcyclohexylsulfonic acid, mono- and polywax-substituted cyclohexylsulfonic acid, dodecylbenzenesulfonic acid , "dimer alkylate" sulfonic acid, etc.

alkyl-substituted benzenesulfonic acid wherein the alkyl group has at least 8 carbon atoms), including dode/rubenzene "bottoms" sulfonic acids , is particularly useful.

The latter is an acid derived from benzene. This is also known as propylene tetramer is alkylated with an inbutene trimer to form 1, 2, and 3 molecules on the benzene ring. One or more branched CI2 substituents are introduced. dodecylbenzene bottom (primarily mixtures of mono- and didodecylbenzenes) are used in the manufacture of household detergents. It is available as a by-product of manufacturing. Linear alkyl sulfonate (LAS) Similar products obtained from alkylated bottoms formed during the production of It is useful in producing the sulfonate salts used.

For example, sulfonates are produced from detergent manufacturing by-products by reaction with SOa. It is well known to those skilled in the art to do so. For example, Cf, Kirk Oz? -<Kirk- ``Ihi Academic and Technological UI Encyclopedia'' by Othmer), 2nd edition, Volume 19, 9.291 and below (this to John Wiley & Sons (1969, published in Ninny York), chapter ``Sulfonates'' Shine on.

A basic sulfonate salt that can be mixed with the lubricating oil composition I of the present invention as component (E); and other descriptions of their manufacturing methods may be found in the following U.S. patents: U.S. Pat. License 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. Of these patents The details of the disclosure in this regard are shown below.

Useful alkaline earth metal salts (E) are prepared therefrom using suitable calcium salts such as Bonic acids include aliphatic carboxylic acids, cycloaliphatic carboxylic acids, and aromatic monobasic carboxylic acids. In addition to 7 levonic acids and polybasic acids, naphthenic acids and alkyl cyclopentanoic acid, alkyl-substituted cyclohexanoic acid, alkenyl-substituted cyclopentanoic acid , and alkyl-substituted or (alkenyl-substituted aromatic carbo) acids are included. Ru. The aliphatic acid generally has from about 8 to about 50 carbon atoms, preferably from about 1 to about 1. Contains 12 to about 25 carbon atoms. Cycloaliphatic carboxylic acids and fats Good too. Specific examples include 2-ethyl hexanic acid, lylunic acid, propylene tetramer -Substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid , balmitic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, Decylic acid, dioctylcyclobencunecarboxylic acid, myristic acid, dilaurylde Cahydronaphthalenecarboxylic acid, stearyl octahydroindenecarboxylic acid, Valmitic acid, 7'lukyl succinic acid and alkenyl succinic acid, petrolatum and Acids formed by the oxidation of hydrocarbon waxes, as well as tall oil acids and rosin acids. Commercially available mixtures of two or more carboxylic acids and the like are included.

In one preferred embodiment, the basic sulfonate (E) has the following (E-1) and (E-2) at a temperature between the solidification temperature of the reaction mixture and its decomposition temperature. prepared by contacting for a sufficient period of time to form a uniform dispersion. It is an oil-soluble dispersion that: <E-1) selected from the group consisting of carbon dioxide, hydrogen sulfide and sulfur dioxide At least one acidic gaseous substance; (E-2> (E-2-a) below, (E-2 -b), (E-2-e) and (E-2-d) reaction mixture: (E-2-a) at least one oil-soluble sulfonic acid or overbased (E-2-b) at least one alkali metal or salt; 'M alkali metal compound; (E-2-c) at least one lower aliphatic alcohol, alkylphenol, or sulfurized alkylphenol; and (E-2-d) at least one oil-soluble Carboxylic acids, or their functional derivatives.

When (E-2-C) is alkylphenol or sulfurized alkylphenol, the formation The use of minute (E-2-d) is optional. A suitable basic sulfonate is a mixture ( E-2) can be prepared with or without carboxylic acids .

Reagent (E-1) is at least one acidic gaseous substance, which is carbon dioxide , hydrogen sulfide or sulfur dioxide; mixtures of these gases are also useful. be. Carbon dioxide is preferred.

As mentioned above, component (E-2) generally includes at least four components. Among these components, component (E-2-a) is a mixture of At least one oil-soluble sulfonic acid or their derivatives that are susceptible to overbased It is the body. Mixtures of sulfonic acids and/or their derivatives may also be used. Ru. Sulfonic acid derivatives that are easily overbased include metal salts of sulfonic acids, especially alkali metal salts, zinc salts and lead salts; ammonium salts and amine salts (e.g. (e.g., ethylamine salts, butylamine salts and ethylene polyamine salts); esters (e.g., ethyl esters, phthyl esters and glycerol esters) ) are included.

Component (E-2-b) preferably and generally contains at least one basic Examples of zero-basic alkali metal compounds include hydroxide, alkoxide (typically the alkoxy group has up to 10 carbon atoms, preferably are alkoxides containing up to 7 carbon atoms), hydrides and amides . Therefore, useful basic alkali metal compounds include sodium hydroxide, hydroxide Potassium, lithium hydroxide, sodium propoxide, lithium methoxide, carbon Lithium ethoxide, sodium butoxide, lithium hydride, sodium hydride , potassium hydride, lithium amide, sodium amide and potassium amide Included. Sodium hydroxide and sodium lower alkoxides (i.e. Particular preference is given to alkoxides containing up to 7 carbon atoms. Purpose of the invention Above, since these alkali metals are monovalent, the equivalent of component (E-2-b) is equal to the amount of particles.

Component (E-2-c) is at least one lower aliphatic alcohol, preferably It can be a monohydric alcohol or a dihydric alcohol. Exemplary alcohols include meth Nol, ethanol, 1-propanol, 1-hexanol, isopropanol , isobutanol, 2-pentanol, 2,2-dimethyl-1-propanol, Ethylene glycol, 1-3-7'lovandiol and 1. s-ventanedi There is an oar. This alcohol is also known as methyl cellosolve (MethylCe). glycerol esters such as 1losolve). Of these, the preferred Preferred alcohols are methanol, ethanol and propatool; Nols are particularly preferred.

Component (E-2-0) also contains at least one alkyltunol or sulfurized atom. It is lucylphenol. In particular, sulfurized alkylphenol (E-2-b ) is a potassium compound or one of its basic compounds (e.g. potassium hydroxide) It is preferable when . As used herein, the term "phenol" includes an aromatic ring Compounds having one or more hydroxyl groups bonded to are included. This aromatic ring is It may be a zyl ring or a naphthyl ring. Use Sgo “Alkylphenol rule Each alkyl substituent has about 6 to about 100 carbon atoms, preferably about 6 to about 5 carbon atoms. Contains 0 carbon atoms.

Exemplary alkylphenols include heptylphenol, octylphenol, Cylphenol, dodecylphenol, polypropylene (Mn is approximately 150) substitution Phenol, polyisobutyne (Mn is about 1.200) substituted phenol, cyclohexane Included are xyl phenols.

Condensation product of the above phenol and at least one lower aldehyde or ketone Things are also useful. The term "lower" means containing fewer than 7 carbon atoms. Shows aldehydes and ketones. Suitable aldehydes include formaldehyde, a Cetaldehyde, propionaldehyde, butyroaldehyde, valeroaldehyde and benzaldehyde. Aldehyde-producing reagents are also suitable. be. Examples of this reagent include paraformaldehyde, trioxane, and methyl mol, methylformce+ and paraaldehyde There is a de. Formaldehyde and formaldehyde-generating reagents are particularly preferred. Yes.

Sulfurized alkylphenols include phenol sulfides, disulfides or polysulfides. Sulfides are included. This sulfurized phenol can be prepared by methods well known to those skilled in the art. It may be derived from any suitable alkylphenol. Many sulfurized phenols are It's on sale. This sulfurized alkylphenol is composed of alkylphenol and elemental ionic acid. sulfur and/or monohalogenated sulfur (e.g. -sulfur chloride). It can be prepared by This reaction can be carried out in the presence of excess base. , sulfide, disulfide or polysulfide mixture salts (these are depending on the application conditions). Preparing component (E-2) according to the present invention The substances used in this case are the products obtained in this reaction. US Patent No. 2. 9 71, 940 and 4, 309. No. 293 is the component (E-2-c) Various exemplary sulfurized phenols are disclosed. The disclosures of these patents are This is shown here.

The equivalent weight of component (E-2-c) is calculated by dividing its molecular weight by the number of hydroxyl groups per engineering molecule. It is a value.

Component (E-2-d) is at least one oil-soluble carboxylic acid described above, or They are functional derivatives. Particularly suitable carboxylic acids are of the formula R5(COOH), is a carboxylic acid. Here, n is an integer of 1 to 6, preferably 1 or 2. , and R5 is a saturated or substantially aliphatic carbon group having at least 8 aliphatic carbon atoms. A saturated R)te aliphatic group (preferably a hydrocarbon group). Depending on the value of n, R 5 is a monovalent to pentavalent group.

R5 may contain non-hydrocarbon substituents. However, these substituents does not substantially change its elementary properties. Such substituents preferably contain about 20 wt. Present in amounts less than %. Illustrative substituents include those for component (E-2-a). Included are the non-hydrocarbon substituents listed above. R5 also has up to about 5% May contain olefinic unsaturation, preferably as little as 2% less olefinic bonds (this value is based on the total number of carbon-carbon covalent bonds present). R5 The number of carbon atoms in it is usually about 8 to 700, depending on the source of R5. below A series of preferred carboxylic acids and their derivatives include olefinic acids, as described in polymer or halogenated olefinic polymer and an α,β-unsaturated acid or its anhydrides (e.g. acrylic acid, methacrylic acid, maleic acid or fumaric acid) , or maleic anhydride) to form the corresponding substituted acid or its derivative. Prepared by forming. The R5 groups in these products range from about 150 to about 1 A number average molecular weight of 0.000, usually a number average molecular weight of about 700 to about 5000 (determined, for example, by kervermeation chromatography) has.

Monocarboxylic acids useful as component (E-2-d) have the formula R5C0OH.

Examples of such acids include caprylic/capric acid, palmitic acid, and stearic acid. acids, isostearic acid, linoleic acid and behenic acid. monocarboxylic acid A particularly preferred group is halogenated olefinic polymers (e.g. chlorinated polyesters). butene) with acrylic or methacrylic acid.

Suitable dicarboxylic acids include substituted succinic acids having the formula: R6C11COO)! CH2CQQH Here, R6 is the same as R5 defined above. R6 is an olefinic bond It can be a group derived from. This group is formed by polymerization of monomers as follows: Formed: ethylene, propylene, 1-butene, isobutyne, 1-pentene, 2-pentene, 1-hexene and 3-hexene. R6 is also a substance of high molecular weight. can be derived from highly saturated petroleum fractions. Hydrocarbon-substituted succinic acids and their derivatives The conductor is the most preferred class of carboxylates for use as component (E-2-d). It is an acid.

Carboxylic acids of the above classes derived from olefinic polymers and their derivatives Conductors are well known in the art.

Representative examples of the types useful in this invention, as well as methods of their preparation, include many is described in detail in the US patent.

Functional derivatives of the above-mentioned acids useful as component (E-2-d) include anhydrides, esters, Includes esters, amides, imides, amidines, and metal or ammonium salts. It will be done. Succinic acid substituted with olefinic polymers and monoamines or polyamines (especially polyalkylene polyamines; these have up to about 10 amine nitrogens) Particularly suitable are reaction products with These reaction products are generally 1 Contains a mixture of species or more amides, imides and amidines. Polie tyrenamine (which contains about 1 (contains up to 1 nitrogen atom)) and polybutene Substituted succinic anhydride, where the polybutene group is mainly composed of isobutyne units. Particularly useful are the reaction products with (containing) Functional derivatives of this group include: Amine-anhydride reaction products can be converted into carbon disulfide, boron-containing compounds, nitriles, urea, etc. prepared by post-treatment with , thiourea, guanidine, alkylene oxide, etc. Compositions that include. Such substituted succinic acid semiamides, semimetallic salts and Also useful are semi-esters and semi-metallic salt derivatives.

Substituted acids or anhydrides and monohydric or polyhydric hydroxy compounds esters prepared by reaction with substances (e.g. aliphatic alcohols or phenols). Stells are also useful. Succinic acid or the like substituted with olefinic polymers anhydride, a polyhydric aliphatic alcohol (which contains 2 to 10 hydroxyl groups, and about 4 (containing up to 0 aliphatic carbon atoms) are preferred. of this class Alcohols include ethylene glyfur, glycerol, sorbitol, and pentae. Lythritol, polyethylene glycol, jetanolamine, triethanol Included are amines, N,N-di(hydroxyethyl)gotylenediamine, and the like.

When this alcohol contains a reactive amine 7 group, the reaction product of - is an acid group. may contain products obtained by reaction of with both hydroxyl and amine functional groups . This reaction mixture is therefore half-ester, half-amide, ester, amide, and and imide.

The equivalent ratio of each component of reagent <E-2) can be varied within a wide range. -3 In general, the ingredients ( the ratio of component (E-2-b) to E-2-a) is at least about 4=1; It usually does not exceed about 40:1, preferably between 6:1 and 30:1, most preferably between 6:1 and 30:1. Preferably, it is between 8:1 and 25=1. This ratio can sometimes exceed 40:1. However, such excess amounts usually serve no useful purpose.

The equivalent ratio of component (E-2-e) to component (E-2-a) is approximately 1=20 and 80 :1, preferably about 2:1 and 50:10. As mentioned above, the ingredients When (E-2-c) is an alkylphenol or a sulfurized alkylphenol, the carbon The intervention of rubonic acid (E-2-d) is optional. In this mixture, the component (E-2-d ), the equivalent ratio of component (E-2-d) to component (E-2-a> is , generally from about 1:1 to about 1=20, preferably from about 1=2 to about 1:10.

Approximately stoichiometric amounts of acidic material (E-1) are reacted with (E-2). 1 fruit According to the method, this acidic substance is added to the (E-2) mixture in a fixed proportion. this The reaction proceeds rapidly. The addition ratio of (E-1) is not important. However, the reaction If the temperature of the mixture rises too rapidly due to exothermic properties, the addition of (E-1) Added flJ must be reduced.

If (E-2-c) is an alcohol, the reaction temperature is not critical.

Generally, this temperature is the solidification temperature of the reaction mixture and its decomposition temperature (i.e., its (lowest decomposition temperature of all components). Typically this temperature is approximately 5 °C to about 200 °C1 preferred (7 degrees is approximately 0 °C to about 150 °C. Reagent (E-1) and (E-2>) are conveniently contacted at the reflux temperature of the mixture. The degree clearly depends on the boiling points of the various components; therefore, the temperature of the component (E-2- When methanol is used as c), this contact temperature is equal to the reflux temperature of the methanol. degree or less.

When test g (E-2-c) is alkylphenol or sulfurized alkylphenol , the reaction temperature is at or below the azeotropic temperature of water so that the water formed during the reaction can be removed. must be greater than that.

This reaction is usually carried out under atmospheric pressure. However, pressures above atmospheric pressure are often It often speeds up the reaction and promotes optimal utilization of reagent (E-1). This process also reduces It can also be done under reduced pressure, but for obvious practical reasons it is rarely done under reduced pressure. Not possible.

This reaction is typically carried out using a substantially inert and usually liquid organic diluent, which is a dispersion medium. and a reaction medium). This diluent is , at least about 10% of the total weight of the reaction mixture.

Once the reaction is complete, all solids in the mixture are preferably removed by filtration or other removed by conventional methods. Easily removable diluent, alcohol, if necessary. The coal promoter, and the water formed during the reaction, are removed by conventional methods (e.g. distillation). can be removed. Typically, substantially all water is removed from the reaction mixture. is desirable. The presence of water makes filtration difficult and may result in unwanted This is because an undesirable emulsion is formed. All water that exists is under atmospheric pressure or easily removed by heating under reduced pressure or by azeotropic distillation . In one preferred embodiment, basic potassium sulfonate is desired as component (E). When fresh, this potassium salt contains carbon dioxide and sulfur as component (E-2-c). prepared using alkylphenols. Due to the use of sulfurized phenol, A basic salt with a lower metal ratio is produced, forming a more homogeneous and stable salt.

The basic salt or complex of component (E) can be prepared in solution or, more suitably, in a stable dispersion. It can be said that Selectively, they can be overbased on acidic substances, oil-soluble may be considered a "polymer salt" formed by the reaction of an acid and a metal compound. Up Considering that these compositions are most conveniently formed Defined in relation to the method of obtaining it.

Using alcohol as component (E-2-C), alkali metal salt of sulfonic acid ( It has a metal ratio of at least about 2, preferably between about 4 and 40. The above method for preparing , which corresponds to British Patent No. 1,481.553). There is. The contents of these patents are set forth herein with respect to their disclosure of such methods. There is. Alkali gold sulfonates useful as component (E) in lubricating oil compositions of the present invention The preparation of oil-soluble dispersions of genus salts is illustrated in the examples below.

Example E-1 790 parts of alkylated benzenesulfonic acid (per j and polybutenyl anhydride) 71 parts (approximately 560 equivalent It) of citric acid (which contains primarily isobutyne units) In a solution of 176 parts of mineral oil, 320 parts (8 parts jl) of hydroxide t)')'7 and 640 parts of metal/-ol (20 parts of fl) are added. The temperature of this mixture is Due to the heat it rises to 89'C (reflux) in 10 minutes. During this time, this mixture Blow carbon dioxide into the material at 4 cfh, (cubic feet/hr). temperature Carbonation is continued for about 30 minutes while gradually lowering the temperature to 74°C. carbonated mixture Methanol and and other volatile substances. During this time, let the temperature cool down for 90 minutes. Slowly raise the temperature to 150℃. After stripping is complete, add 1 portion of the remaining mixture Maintain at 55-165°C for approximately 30 minutes and filter to obtain the desired basic sulfonate. An oil solution of sodium phosphate (which has a metal ratio of approximately 7.75) is produced. . This solution contains 12.4% oil.

Example E-2 According to the method of Example E-x, 780 parts of alkylated benzenesulfonic acid (1 eq. ) and 119 parts of polybutenyl succinic anhydride in 442 parts of mineral oil were dissolved in sodium hydroxide. Mixed with 800 parts of thorium (20 equivalents) and 704 parts of methanol (22 equivalents) do. Add 1 to 7 cfh to this mixture while slowly increasing the temperature to 97°C. Bubble carbon dioxide for 1 minute. The blowing rate of carbon dioxide was 6 cf. h.

lower to Slowly reduce temperature to 88°C over approximately 40 minutes . The carbon dioxide blowing rate is reduced to 5 cfh in about 35 minutes. warm Slowly lower the temperature to 73°C.

Add 2 c to this carbonated mixture while slowly increasing the temperature to 1.60°C. The volatiles were stripped by bubbling nitrogen for 105 minutes at Ping. After the stripping of volatiles was completed, the mixture was heated to 160 Holding for an additional 45 minutes at 'C and then filtering yields the desired basic sulfonate An oil solution of thorium (which has a metal ratio of approximately 19.75) is obtained.

This solution contains 18.7% oil.

CF>htv: yonic acid ester/uf1 body composition composition: The lubricating oil composition of the present invention also has In many cases, (F-1) at least one substituted succinic acylating agent and (F-2 >React with at least one alcohol or phenol of the following general formula (F>at least one type of carbonic acid ester derivative group) 2, which may contain R3(OH)21(X　I　) Here, R3 is a monovalent or polyvalent organic group bonded to the 10H group via a carbon bond. and m is an integer from 1 to about 10.

This carboxylic acid ester derivative (F) is about 10% based on the total weight of the lubricating oil. Lubricating oil in an amount of up to 1% to about 10% by weight of snow, and more commonly from about 1% to about 10% by weight. contained in the composition. This carboxylic acid ester (F) further provides additional dispersion. and, in some applications, to the carboxylic acid esters (F) present in the oil. The ratio of the carboxylic acid derivative (B) in the oil composition depends on the properties of the oil composition (e.g. gender). Carboxylic acid ester derivative contained in this lubricating oil composition The amount of (F) can vary from about 1% by weight to about 1% by weight.

“Reacted with alcohol or phenol to form carboxylic acid ester derivatives” The substituted fluoric acid acylating agent (F-1) has the above-mentioned carboxylic acid acylating agent (F-1), except for one part. It is the same as the acylating agent (B-1) used when preparing the acid derivative (B). Ru. The polyalkene from which this substituent is derived has a number average molecular weight of at least about 700 It is characterized as having a quantity.

A molecular weight (Mn) of about 700 to about 5000 is preferred. In one preferred embodiment, The acylating agent substituents have Mn values of about 1300 to 5000, and about 1.5 to 5000. It is derived from polyalkenes characterized by a My/Mn value of approximately 4.5. child The acylating agent of this embodiment is a group of carboxylic acid derivatives useful as component (B) above. Regarding the preparation of the composition, it is identical to the acylating agent described above. Therefore, the above ingredients Any of the acylating agents described for the preparation of (B) may be used as component (F). It can be used to prepare useful carboxylic acid ester derivative compositions. carboxylic acid s The acylating agent used to prepare tel (F) is the same as that used in the preparation of component (B). When the same acylating agent is used, this carboxylic acid ester component (P) also has VI It is characterized as a dispersant with special properties. For use in the oil of the present invention These preferred types of combinations of component (F) and component (B) are also suitable for use in the present invention. Provides excellent wear resistance properties to the tile.

However, other substituted succinic acylating agents also include carboxylic acid ester derivatives. In preparing the composition, which is useful as component (F) in the present invention, can be used. For example, the substituents have a number average molecular weight of about 800 to about 1200. Substituted succinic acylating agents such as those derived from polyalkenes are useful.

The carboxylic acid ester derivative composition (F) consists of the above co/% phosphoric acid acylating agent and the following: is an ester composition with a hydroxy compound: this hydroxy compound is an aliphatic compounds (e.g. monohydric and polyhydric alcohols) or aromatic compounds ( for example, phenol and naphthol). Aromatics from which esters can be derived Aromatic hydroxy compounds are exemplified by the following specific examples: phenol, β - Naphthol, α-naphthol, cresol, resorcinol, catechol, p , p-dihydroxybiphenyl, 2-talolofueno, 2,4-dibutylphenyl Nord et al.

The number of alcohols (F-2) from which this ester can be derived is preferably about 40 or less. Contains aliphatic carbon atoms. These alcohols are monohydric alcohols such as: Can be called: methanol, ethanol, inoctatool, dodecanol , cyclohexanol, etc. The polyhydric alcohol preferably has from 2 to about 10 Contains hydroxyl group. These include, for example, ethylene glycol, diethylene glyco triethylene glycol, tetraethylene glycol, dipropylene glycol Coal, tripropylene glycol, diethylene glycol, tributylene glycol cole, and other alkylene glycols (where this alkylene group has two ~containing about 8 carbon atoms).

A particularly preferred class of polyhydric alcohols is an alcohol having at least three hydroxyl groups. It's a call. Some of them are monomers having about 80 to about 30 carbon atoms. Carboxylic acids (e.g. octanoic acid, oleic acid, stearic acid, sulfuric acid, esterified with decanoic acid or tall oil acid). Such partial esterification Examples of polyhydric alcohols include sorbitol monooleate, sorbitol distearate, monooleate of glycerol, monostearate of glycerol rate, didodecanoate of erythritol.

This ester (F) can be prepared by one of a variety of well-known methods. For convenience , a preferred method for producing esters with excellent properties involves the use of a suitable alkali. Reaction of coal or phenol with succinic anhydride substantially substituted with hydrocarbons Responses are included. This esterification is usually carried out at temperatures above about 100°C, preferably The process is preferably 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.

The relative proportions of succinic and hydroxyl reactants that can be used vary considerably. The extent to which the hydroxy reactant is intramolecular depends on the type of product desired, and depends on the number of hydroxyl groups present in For example, succinic acid half ester (i.e. 2 (in which only one of the two acid groups is esterified) Includes using 1 mole of monohydric alcohol for each mole of citric acid reactant. Ru. In contrast, the formation of diesters of succinic acid requires two moles for each mole of acid. This includes using 100% alcohol. On the other hand, 1 mole of hexahydric alcohol is , can be combined with about 6 moles of succinic acid to form the following ester. With this ester The six hydroxyl groups of each alcohol are one of the two acid groups of succinic acid. It has been stealthized. Therefore, succinic acid that can be used with polyhydric alcohols The maximum percentage is determined by the number of hydroxyl groups present in the molecule of this hydroxy reactant. be done. In one embodiment, an equimolar reaction of succinic acid and hydroxy reactants is performed. Esters obtained by reaction are preferred.

Methods for preparing this carboxylic acid ester (F) are well known in the art; There is no need to illustrate in more detail here.

See, eg, US Pat. No. 3,522,179. The content of this patent is that the ingredients With respect to the disclosure of the preparation of carboxylic acid ester compositions useful as (F), has been done. Acylating agent (wherein the substituent has at least about 1300 to about 5 000 and an ldv/Mn ratio of 1°5 to about 4. (derived from Rialken) to prepare a carboxylic acid ester derivative composition. This is described in US Pat. No. 4,234,435. The content of this patent is , shown above. As mentioned above, the application described in the '435 patent The sylating agent also contains on average less (1.3 co/·) for each substituent. It is characterized as having a phosphoric acid group within its structure.

The following examples illustrate esters (F) and methods for preparing such esters. Illustrated.

Example F-1 Polyisobutyne (which has a number average molecular weight of 1000) with 4.5% chlorine The chlorinated polyimbutene was then chlorinated to a 1.2 molar proportion of By heating with water maleic acid at a temperature of 150 to 220 °C, substantially A hydrocarbon-substituted succinic anhydride is prepared. Anhydrous amber thus obtained The acid has an acid number of 130. 874 g (1 mol) of this succinic anhydride and neo A mixture of pentyl glycol to 4 g (1 mol) was heated at 240 = -250° (:7 30 mm, and maintained for 12 hours. This residue contains one or two glycols. It is a mixture of esters obtained by esterifying hydroxyl groups. it is, It has a saponification number of 101 and an alcoholic hydroxyl content of 0.2%.

Example F-2 2185 g of anhydride of Example F-1, 480 g of methanol and 1000 g of toluene cc mixture at 50-65°C while bubbling hydrogen chloride into the reaction mixture. By heating for 3 hours at Prepare the dimethyl ester of hydrosuccinic acid. This mixture is then heated to 60-65 Heat for 2 hours at °C, dissolve in benzene, wash with water, dry and filter. Ru. The filtrate is heated at 150° C. and 760 mm to remove volatile components. This residue The distillate is the desired dimethyl ester.

acylating agents and hydroxy-containing compounds (e.g. alcohols or phenols) The above carboxylic acid ester derivative obtained by the reaction of can be reacted with amines (F-3) (especially polyamines): this method Regarding the reaction between the acylating agent (B-1) and the amine (B-2) when preparing (B) This is the method described first. In one embodiment, the amount of amine reacted with the ester is , for each equivalent of acylating agent initially used in the reaction with alcohol, at least Also, the amount is such that about Q, Gl equivalents of amine are present. For each equivalent of acylating agent whereas the acylating agent is present in an amount such that at least one equivalent of alcohol is present. When reacted with an alcohol, this small amount of amine reduces the esterification that may be present. This is sufficient to react with the small amount of carboxyl groups that are not present. Preferred implementation In embodiments, the amine-modified carboxylic ester used as component (F) is 1 unit of lubricating agent! about 1.0 to 2.0 equivalent Jl (preferably about 1.0 to 1.8 of the hydroxyl compound and up to about OJ equivalent (preferably from about 0.02 to about 0.25 equivalents) of a polyamine.

In other embodiments, the carboxylic acylating agent is both an alcohol and an amine. can be reacted at the same time. Generally, at least about 0.01 equivalents of alcohol and at least 0.0 r of the amine. However, the total equivalent of this conjugate should be at least about 0.5 equivalents per equivalent of acylating agent. Growth These carboxylic acid ester derivative compositions useful as fraction <F) are well known in the art. It is well known in the field. Methods for the preparation of a number of these derivatives are described, for example, in U.S. Pat. No. 57.854 and No. 4,234.435. These patents The contents are shown above. The specific example below illustrates the preparation of this ester. Show. Here both the alcohol and the amine are reacted with the acylating agent. Ru.

Example F-3 334 parts (0, 52 parts I, 548 parts mineral oil, 79:f-lisuride-Jlz3Q parts (0,88 parts amount) and Polyglycol 112-2 demulsifier (this This was obtained from the Dow Chemical Company, and a mixture of > 8.6 parts (0,0057 parts 1i) Heat the material at 150°C for 2.5 hours. The reaction mixture was mixed with 2I (1 Heat to ℃ and hold at 210'C for 3.2 hours. This reaction mixture was Cool to 90°C and mix with a commercially available mixture of ethylene polyamines (per molecule, having an average of about 3 to about 10 nitrogen atoms) 8.5 parts (plus 0.2 parts!) Ru.

The reaction mixture was heated at 205°C for 3 hours with nitrogen bubbling. Stripping and then filtration yields the desired product as an oil solution. An excess occurs.

Example F-4 322 parts of the polyisobutyne substituted succinic acylating agent prepared in Example F-2 (0, 5 parts of pentaerythritol (2,0 parts It) and 508 parts of mineral oil. The mixture is heated at 204-227°C for 5 hours.

The reaction mixture was cooled to 162°C and a commercially available ethylene polyamine mixture (this has an average of about 3 to lo nitrogen atoms per molecule) 5.3 parts (0 , add per ff13. The reaction mixture was heated at 162-163°C for 1 hour, Then cool to 130'C and filter. This II! The liquid contains the desired product It is an oil solution.

Example F-5 Polyisobutyne (which has a number average molecular weight of 2020 and a weight average molecular weight of 6049 molecular weight) 100 parts (0,495 mol) and 115 parts of maleic anhydride (1,17 mol) is heated to 184 °C for 6 hours1. During this time, 85 parts (12 moles) of chlorine are added subsurface. Additional 59 parts of chlorine (08 3 mol) over a period of 4 hours at 184-189°C. Add 1 to this mixture Blow nitrogen for 26 hours at 86-190°C. This residue has a total acid value of 95.3 It is a polyisobutyne-purchased succinic anhydride.

A solution of 409 parts (0.66 mol) of this substituted succinic anhydride in 191 parts of mineral oil was added to 1 Heat to 50'C and add 42.5 parts (11 parts per 1.1 g) of pentaerythritol. , with stirring, over 10 minutes at 145-150°C. this mixture When heated to 205-210℃ for about 14 minutes by blowing nitrogen into the An oil solution of the desired polyester intermediate results.

This polyester intermediate was mixed with 0.6 g equivalent of a substituted cono-phosphoric acid alkating agent and (containing 1.24 equivalents of pentaerythritol) was added with stirring to At 160°C for 1772 hours, Noetile: Notriamine 4.74 parts (0 , 138 it). Continue stirring at 160'C for 1 hour, then add 28% of mineral oil. Add 9 parts. The mixture was heated at 135°C for 16 hours and filtered at the same temperature. Filter using an auxiliary substance. This filtrate contains 35% of the desired amine-modified polyester. % mineral oil solution. It has a nitrogen content of 0.16% and a residual acid number of 2.0. do.

Example F-6 <a) 1000 parts of polyisobutyne having a number average molecular weight of about 1000, and A mixture of 108 parts (1.1 mol) of hydromaleic acid is heated to about 190°C, and 100 parts (1.43 moles) of chlorine are added from below the surface over a period of about 4 hours. child The temperature is maintained at about 185-190°C (1:1) during this time. bubbling with nitrogen for several hours at a temperature of . This residue is then converted into the desired polyisomer. It is a butyne-substituted succinic acid silating agent.

(b) Acylating agent preparation (a > 1000 parts in 857 parts of mineral oil solution with stirring) Heat to about 150°C and add 109 parts of pentaerythritol (3 parts) while stirring. , 2 thoughts) are added. This mixture was sparged with nitrogen to give about 2 Upon heating to 00°C, an oil solution of the desired carboxylic ester intermediate forms. be done. This intermediate contains ethylene polyamine (which has an average of 17 9.25 parts (0.46 parts) of a commercially available mixture of Add step 11). The reaction mixture was heated at 205°C for 3 hours with nitrogen bubbling. By heating, strain, twist and filter. This filtrate is Oil of amine-modified carboxylic acid ester (which contains 0.35% nitrogen) Solution (45% oil).

Example F-7 (a) Boisobutene, which has a number average molecular weight of 2020 and a weight of 6049 average molecular weight) 1000 parts (0,495 mol) and 1 maleic anhydride 15 parts (1,17 mol) of the mixture are heated to 184 °C for 6 hours. Ru. During this time, 85 parts (1.2 moles) of chlorine are added subsurface. additional chlorine 59 (0.83 mol) are added over 4 hours at 184-189°C. This mixture The mixture is sparged with nitrogen for 26 hours at 186-190°C. This residue is 95. Polyisobutyne-substituted co/% phosphoric anhydride having a total acid number of 3.

(b) 409 parts (0.66 parts IF) of this substituted cono-phosphoric anhydride in 191 parts of mineral oil of the solution was heated to 150°C, and 42.5 parts of pentacolythritol (1.1 g/g) was added. amount) over 10 minutes at 145-150° C. with stirring. This mixture When the mixture is bubbled with nitrogen and heated to 205-210°C for about 14 hours, , resulting in an oil solution of the desired polyester intermediate.

This polyester intermediate was prepared with the equivalent of 0.6 g of a substituted polyester acylating agent and (containing 1.24 equivalents of pentaerythritol), diethylene 4.74 parts (0,138 parts 11) of reaamine were added at 160°C with stirring for 17 hours. Add over 2 hours. Continue stirring for 1 hour at 160″C, then add 289% mineral oil Add part. The mixture was heated at 135°C for 16 hours and filtered at the same temperature. Filter using an auxiliary substance. This filtrate contains 35% of the desired amine-modified polyester. % mineral oil solution. It has a nitrogen content of 0.16% and a residual acid number of 2.0. do.

The lubricating oil compositions of the present invention contain other additives that impart certain desirable properties to the lubricant. It may contain, preferably contains. For example, this lubricant has suitable frictional properties. The lubricating oil may contain at least one friction modifier. various amines, especially , tertiary amines are effective friction modifiers. Examples of tertiary amine friction modifiers is N-fatty alkyl-N, N-jetanolamine, N-fatty alkyl~N, Included are compounds such as N-jethoxyethanolamine. Such tertiary amines is a reaction between a fatty alkylamine and an appropriate number of moles of ethylene oxide. It can be prepared by Naturally occurring substances (e.g. coconut oil and oleoamides) Tertiary amines derived from [Ethomeen J. It is available from Armor Chemical Company under the trade name Armour Chemical Company. In the specific example , Ethomeen-C and Ethoraeen-0 Sulfur-containing compounds, e.g. sulfurized Cl2-24 fats, alkyl sulfides and alkyl polysulfides, where the alkyl group has 1 to 8 carbon atoms. ) and sulfurized polyolefins are also present in the lubricating oil compositions of the present invention. May function as a friction modifier.

In one embodiment, preferred friction modifiers that may be included in the lubricating oil compositions of the present invention are , at least one partial fatty acid ester of a polyhydric alcohol. Generally, about 1 Partial fatty acid esters up to % by weight appear to impart desirable friction-modifying properties. . Such hydroxy fatty acid esters are dihydric alcohols or polyhydric alcohols. The hydroxy fatty acid esters of Le, Mac are their oxyalkylated oil-soluble selected from derivatives.

Suitable partial fatty acid esters of polyhydric alcohols include, for example, glycol monoesters. glycerol monoesters and diesters, and pentaerythritone and/or triesters. glycerol portion Fatty acid esters are preferred, and among the glycerol esters, monoesters, or mixtures of monoesters and diesters (7) are often used. Partial fatty acid esters of kohl can be prepared by methods well known in the art, e.g. prepared by direct esterification with alcohols, reaction of fatty acids with epoxides, etc.) can be done.

It is generally preferred that the cvu fatty acid ester contains olefinic unsaturation. Delicious. Olefinic unsaturation is usually found in the acidic portion of this ester . In addition, natural fatty acids containing olefinic unsaturation (e.g. oleic acid, octenoic acid, tetradecenoic acid, etc.) may be used in forming this ester. Ru.

The partial fatty acid ester used as a friction modifier in the lubricating oil composition of the present invention is various other components (e.g., unreacted fatty acids, fully esterified polyalcohols) It may be present as a component of a mixture containing substances such as alcohol, alcohol, and other substances). commercially available section Fatty acid esters often contain one or more of these components. and a mixture of monoesters and diesters of glycerol. Ru.

Among commercially available glycerol esters, at least about 30 at% nomodieste (generally from about 35% by weight to about 65% by weight monoester), and about 30% by weight i There are ester mixtures containing from % to about 50% diester by weight. The remainder of this total amount Rino I! (generally less than about 15%) triesters, free fatty acids and and other ingredients. Commercial products containing fatty acid esters of glycerol Specific examples of quality include Emery 2421 (Emery Industries) - Inc.), Cap City, GMO (Capital Inc.), D tlR-EM 114. DUR-EM GMO etc. (Durkee ) Kogyo Shokuhin Co., Ltd.), and various substances indicated by the trademarks of MAZOL GMO (Maze (Mazel Chemical Company). Partial fatty acid of polyhydric alfur Another example of Stell is K.

"Fatty acids" by S. Markley (2nd edition, parts 1 and 7, Interscience Publishing (1968).

A large number of commercially available fatty acid esters of polyhydric alcohols are maccutcheon (M "Emulsifiers and detergents" (North American and international Edition, 1981) lists its trade name and manufacturer.

The lubricating oil compositions of the present invention also include at least one of at least one acidic organic compound. It may contain a variety of neutral or basic alkaline earth metal salts. Such salt compounds are , generally referred to as a natural-containing cleaning agent. This acidic organic compound is at least one sulfur-containing acid, carboxylic acid, phosphorus-containing acid, or phenol, or It can be a mixture of these. Generally, its basic or overbased salts are preferred. Yes. The basic layer or overbased salt has a metal ratio of up to about 40; More particularly, it has a metal ratio of about 2 to about 30 or 40.

Preferred alkaline earth metals include calcium, magnesium, barium and There's trontium. Two or more ions of these alkaline earth metals Salts containing mixtures of can be used.

Usually used to prepare basic (i.e. overbased) salts. The method involves adding a mineral oil solution of the acid to a stoichiometric excess of a metal neutralizing agent (e.g. gold). oxides, hydroxides, carbonates, bicarbonates, sulfides, etc.) at temperatures above about 50°C. Heating at a temperature is included. Furthermore, this neutralization process removes a large excess of metal. Various promoters can be used to promote mixing. These accelerators include: Includes compounds such as: phenolic substances (e.g. phenol, naphtho) alkylphenols, thiophenols, sulfurized alkylphenols, and various condensation products of formaldehyde and phenolic substances); alcohols (e.g. For example, methanol, 2-propanol, octyl alcohol, cellosolve carpito alcohol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol amines (e.g. aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine). This basic salt Certain effective methods of preparation include phenolic accelerators and small amounts of water. mixing this acid with excess basic alkaline earth metal; carbonating the compound at elevated temperatures (e.g., 60°C to about 200°C). .

As mentioned above, the acidic organic compounds from which this alkaline earth metal salt is derived are At least one sulfur-containing acid, carboxylic acid, phosphorus-containing acid, or phenol or can be a mixture thereof. These acidic organic compounds (sulfonic acids and some of the alkali metal salts (component (E)) described above in connection with the preparation of the alkali metal salts (component (E)). All the acidic organic compounds mentioned above can be used to prepare alkaline earth metal salts. It can be used occasionally. In addition to sulfonic acids, sulfur-containing acids include thiosulfonic acid, sulfur Includes rufinic acid, sulfenic acid, partially esterified sulfuric acid, sulfite and thiosulfate be done.

The pentavalent phosphorus-containing acid is organic phosphoric acid, phosphonic acid or phosphinic acid, or It can be any thio homolog of

This alkaline earth metal salt is also a phenol, i.e., bound directly to the aromatic ring. It can be prepared from compounds containing hydroxyl groups. "Phenol" used here The term includes compounds containing more than one hydroxyl group attached to an aromatic ring, e.g. Included are catechol, resorcinol and hydroquinone. This term is also , alkylphenols (e.g. cresol and ethylphenol) and alkylphenols (e.g. cresol and ethylphenol) It also includes lukenylphenol. about 3 to 100 carbon atoms, especially 6 to 5 Phenols containing at least one alkyl substituent containing 0 carbon atoms ( For example, heptylphenol, octylphenol, dodecylphenol, tetylphenol, Phenol alkylated with lapropene, octadecylphenol and butenylphenol) is preferred. Fe containing more than one alkyl substituent Monoalkylphenols may also be used, but monoalkylphenols are It is preferred because it is easy to construct.

Condensation product of the above phenol and at least one lower aldehyde or ketone is also useful. The term "lower" means containing fewer than 7 carbon atoms. Represents an aldehyde or ketone. Suitable aldehydes include formaldehyde, a Included are cetaldehyde, propionaldehyde, and the like.

The amount of alkaline earth metal salt contained in the lubricants of the present invention can also be varied within a wide range. The amount useful in a particular lubricating oil composition can be readily determined by one of ordinary skill in the art.

This salt functions as an auxiliary detergent. The amount contained in the lubricant of the present invention is It can vary from about 0% to about 5% or more.

The lubricating oil of the present invention comprises at least one neutral or basic sulfurized alkylphenol. may contain alkaline earth metal salts.

The lubricating oil contains the sulfurized phenol in a proportion of about 0% to about 2% or 3%. obtain. Often, the lubricating oil contains a basic salt of sulfurized phenol, about 0.01% by weight. % to about 2% by weight. The term "basic" refers to other ingredients on is used here in the same format as used in defining . Sulfurized Fe, Nol Neutral and basic salts add antioxidant and detergent properties to the lubricating oil compositions of this invention. Give sex.

The lubricating oil composition of the present invention also exhibits its antiwear properties: 1. Extreme pressure properties and antioxidant properties may contain one or more sulfur-containing compositions useful in improving the O Sulfur-containing compositions prepared by sulfurization of various organic substances, including lefins, are useful It is. This olefin is a type of aliphatic, arylaliphatic or cycloaliphatic olefin. The hydrocarbon may be a olefinic hydrocarbon having about 3 to about 30 carbon atoms. contains.

U.S. Patent No. 4.119゜549, No. 4.505.11130 Apology Re No. 2 No. 7.331 discloses suitable sulfurized olefins useful in the lubricating oils of the present invention. As shown here. Some specific sulfide compositions are Described with examples.

Other extreme pressure agents and corrosion and antioxidant agents may also be included. these Reagents include chlorinated aliphatic hydrocarbons (e.g. chlorinated waxes): organic Sulfides and polysulfides (e.g. benzyl disulfide, bis(chloride) lobenzyl) disulfide, dibutyltetrasulfide, methyl sulfide of oleic acid esters and sulfurized alkylphenols); phosphorus sulfide hydrocarbons (e.g. sulfurized (reaction product of phosphorus with turpentine or methyl oleate); mainly sulfur Phosphorus-containing esters, including acid dihydrocarbons and trihydrocarbons (e.g., phosphorous Dibutyl, dihebutinope, dicyclohexyl phosphite, pentyl phosphite Phenyl, dibentylphenyl sulfite, tridecyl phosphite, diste phosphite Allyl, dimethylnaphthyl phosphite, oleyl-4-benthylphenyl phosphite , phenyl phosphite substituted with polypropylene (molecules! 1500), diisobutylene phenyl phosphite substituted with thyl); metal thiocarbamates (e.g. Zinc tyldithiocarbamate and barium heptylphenyldithiocarbamate This is exemplified by

Pour point depressants are a particularly useful type often included in the lubricating oils described herein. It is an additive. In oil-based compositions, the low-temperature properties of oil-based compositions The use of such pour point depressants to improve properties is well known in the art.

For example, C, V. Smalbeer and R. Kennedy Sumi Kennedy Sm1th's "Lubricant Additive" (Regius Heels) (Lezius-formerly 1es) Publishers, Cleveland, Ohio, 1967) See page 8.

Examples of useful pour point depressants include polymethacrylates; polyacrylates; Acrylamide; condensation product of haloparaffin wax and aromatic compound; vinyl Carboxylate polymers; vinyl esters and alkaline esters of sialkyl fumarates and fatty acids. There is a terpolymer with vinyl ether. Pour point depression useful for the present invention Agents, methods of their preparation and their uses are described in U.S. Pat. No. 2.387.501. ; No. 2.015,748; Measure 2.655゜479 No. 1.815.022 : No. 2.191,498; No. 2.666, 746; No. 2.721,877 ; No. 2.721.1178 and No. 3.250.71s, of which The relevant disclosures are set forth herein.

Defoamers are used to reduce or prevent the formation of stable foam.

Typical antifoam agents include silicones or organic polymers. Other antifoam compositions The product is "foam control agent" (Henry T., Kerner) , noise data (N.

Yes Data), 1976), p. 125-162.

The lubricating oil composition of the present invention is also particularly suited for use with multigrade oils. When formulated, it may contain one or more commercially available viscosity modifiers. Viscosity modification Good agents are polymeric substances that are generally characterized as hydrocarbon-based polymers. Ru. The polymer generally has a number average of between about 25,000 and soo,ooo Molecular weight, in most cases a number average molecular weight between about 50.000 and 200.000 has.

Polyisobutylene is used as a viscosity modifier in lubricating oils. polymetac Lyric acid ester (PMA) is a methacrylic acid ester with different alkyl groups. Prepared from a mixture of monomers. Most PMA is just a viscosity modifier. It is also a pour point depressant. The alkyl group has 1 to about 18 carbon atoms. It can contain either straight chain or branched chain groups.

When small amounts of nitrogen-containing monomers are copolymerized with alkyl methacrylates, the product contains is also given dispersion properties. Therefore, such products have improved viscosity, pour point It has multiple functions such as descent and dispersibility. Such products are In the technical field, it is called a dispersion type viscosity improver or simply a dispersion viscosity improver. . Vinylpyridine, N-vinylpyrrolidone and N,N-dimethylaminoethyl Methacrylate is an example of a nitrogen-containing monomer. one or more types of acrylic Polyacrylic esters obtained by polymerization or copolymerization of alkyl alkyl acids are also , useful as a viscosity modifier.

Ethylene-propylene copolymer (commonly referred to as OCP) Generally in a solvent, ethylene and It can be prepared by copolymerizing with propylene. Propylene in this polymer The ratio of ethylene to Affects descent performance and engine performance. The normal range of ethylene content is 4 5 to 60% by weight, typically 50% to about 55% by weight. A commercially available OC P is ethylene, propylene and a small amount of non-conjugated diene (N If, 1.4 It is a ternary copolymer of -H+"t diene".In the rubber industry, such ternary copolymers are The copolymer is called EPDM (ethylene-propylene-diene monomer). There is. The use of OCP as a viscosity improver in lubricating oils has been around since 1970. It has been increasing rapidly. This OCP is currently the most widely used automotive oil. It is one of the viscosity improvers that are widely used.

Copolymerization of styrene and maleic anhydride in the presence of a free radical initiator , then esterifying this copolymer with a mixture of Ct-0a alcohols. The resulting esters are also useful as viscosity improving additives in automotive oils. It is. This styrene ester is generally considered a multifunctional added viscosity modifier. is being given. In addition to its viscosity-improving properties, this styrene gostil It is also a purgative, and esterification is stopped before its completion, leaving unreacted anhydride groups or exhibits dispersion properties when carboxylic acid groups remain. These acid groups are then converted into primary It can be converted to an imide by reaction with an amine. Hydrogenated styrene-conjugated diene Copolymers are another class of commercially available viscosity improvers for automotive oils.

The above hydrogenated copolymers are described, for example, in the following prior literature, among which: Polymers and copolymers useful as viscosity modifiers in the oil compositions of this invention The disclosure of US Pat. No. 3,551,336; ．． No. 598.738; No. 3.554.911; No. 3.607.749; No. 3 ．． No. 687.849; and No. 4.181.6111. Lubricating oil composition of the present invention Hydrogenated styrene-butadiene copolymers useful as viscosity modifiers in e.g. For example, as the general trademark G11ssovicialJ, BASF It's on sale. A specific example includes a city with the name G11ssoviscal 5260. There are commercially available hydrogenated styrene-butadiene copolymers. This substance is Molecular weight approximately 120,000 determined by gel vermini-silane chromatography has. Hydrogenated styrene-isoprene copolymers useful as viscosity modifiers is, for example, the general trademark 5hellvjsj, from Shell Chemical Company. It is commercially available. Shell Chemical's 5hellvis 40 is made of styrene and It was identified as a diblock copolymer of isoprene and isoprene, which has a molecular weight of about 155. oo oO number average molecular weight, styrene content of about 19 mole percent and about 81 mole percent It has an isoprene content of cents.

Shell Chemical's 5hellvis So is a combination of styrene and isoprene. Original block copolymer and 1. , which has a number average molecular weight of approximately 100°000 about 28 mole percent styrene and about 72 mole percent isopropylene. It has a ren content. Generally, the polymeric viscosity modifier is present at a concentration of about 0.2% to about 8%. More specifically, approximately 0.5% to 1% by weight of the final lubricating oil is used. It is used in an amount of about 6% by weight.

The lubricating oil of the present invention has various components dissolved directly in the base oil, along with other additives that may be used. It can be prepared by letting or suspending. In many cases, the invention The chemical component is a substantially inert, usually liquid organic diluent (e.g. mineral oil, naphtha, vector). (e.g.) to form an additive concentrate. These concentrates are usually One or more of the following additive components (A) to (C) in an amount of about 0.01% by weight to about 80% by weight and further contains one or more of the other additives mentioned above. May contain.

Chemical concentrations such as 15%, 20%, 30% or 50% or more may be used. It can be done.

For example, the concentrate may contain from about 10% to about 50% carboxylic acid derivatives by weight on a chemical basis. body composition (B), and about 10 to about 5000 ppm manganese as a metal. may have. This concentrate also contains about 0.01% to 1% to about 1 phosphorodithioate metal. (D), about 1% to about 30% by weight of carboxylic acid ester (F) and/or is about 1% to about 20% by weight of at least one neutral or basic alkali metal. It may contain salt (F).

Typical lubricating oil compositions of the present invention are illustrated in the following lubricating oil examples. Here, par Cents are by volume and are exemplary additions used to form lubricating oil compositions. It shows the amount of solution diluted with common oil. For example, lubricant ■ is Example B- 10 products at 3.5% by volume, which is an example containing 55% diluent oil. This is an oil solution of carboxylic acid derivative (B).

Product of Example B-10 3.5 Product of Example D-1 0.4 Prepared from a mixture of amyl alcohol and isobutyl alcohol (35:65) m Zinc salt of phosphorodithioic acid 0.47 Product of Example E-1 0.25 alkylbenzenesulfonic acid Basic magnesium salt 0.33 alkylbenzenesulfonic acid Basic calcium salt 0.41 Overbased manganese carboxylate (40% 77g) (Mooney FOA-910) 250 ppm amide-based friction modifier 0. I C, mono- and C9-di-baralkylated diphenylamine 0.1 Sulfurized butyl acrylate-butadiene product 0.15 Silicone antifoaming agent 0.006 Mineral oil remaining amount ヱ剋五且 company percent Product of Example B-10 3.0 Zinc salt of diisooctylphosphorodithioic acid 1.07 Product of Example F-6 2 ．． 8 Basic sulfonate magutum 0.35 Basic calcium sulfonate 0. 92 Nonylphenoxypoly(ethyleneoxy)ethanol 0. l :t-bar/<-manganese carboxylate (40% manganese) (Moo ney FOA-910) Propylene reacted with 250 ppm sulfur dichloride hmm Tetramer phenol 2.3 Silicone antifoaming agent 0001 Mineral oil remaining amount According to the lubricating oil composition of the present invention, there is less tendency for quality deterioration under the conditions of use. , thereby reducing wear and the formation of undesirable deposits such as: Such precipitates include, for example, burnishing, sludge, and carbon. and resinous substances (these adhere to various engine parts and (tends to reduce performance).

In one embodiment, a lubricating oil may be formulated within the scope of the present invention as an SG oil. It can bus all the tests necessary for classification.

The lubricating oil of the present invention is also useful in diesel engines.

A lubricating oil formulation meeting the requirements of the new diesel classification CE is prepared according to the present invention. can be done.

The performance characteristics of the lubricating oil composition of the present invention make this lubricating oil composition suitable for use in many engine oils. It is evaluated by putting it to a test.

These tests are designed to evaluate various performance characteristics of engine oils. There is.

The ASTM Sequence I [ID engine oil test simulates high-speed, high-load operation. This is a simple test to evaluate the lubricating ability of oil under necessary conditions. This test , a 5.7-litre 12-barrel Olds with an 8.5:1 compression ratio on the production line. Uses a Mobil V-8 gasoline engine. In each test, the engine Must be manufactured according to certain instructions outlined in TM STP 315H . The test consisted of a 4-hour commissioning period followed by a <64-hour constant-state test period. This is done in two stages. The engine was tested at 100 bh during the 64-hour test period. Operated at p/74.6 kv and 300 Orpm. This exam is for 8 hours. This is recorded by extracting and analyzing the lubricant. sampling and Add new test oil to replace oil losses due to gas leaks.

The performance criteria for the sequence ID test (SF performance) is = after 64 hours Maximum viscosity increase measured at 45°C = 375%; Average engine sludge rating = 9.2 min; average engine piston rating = 9.2 min; average oil run Deposits = 4.8 minimum; Average Cam and Lifter Wear (inches) = 0. Maximum wear at 0040 is 0.0080; and oil loss (fort) = 6.3 8° modified to use a non-phosphate treated camshaft and lubricant I or Results of sequence mD tests conducted on lubricants I and ■ and control lubricants I and ■ are summarized in the table below. Control lubricants ■ and ■ do not contain manganese. They are the same as lubricants I and ①, respectively, except that they are different from each other. (normal sequence l lID tested camshafts are designed to increase resistance to wear scratches and contact treated with manganese salts of phosphoric acid to provide a lubricant reservoir in the area). trial The test results are reported in the table below.

(Margin below) L Yu ASTM Sequence III D Test Results Treated with Phosphate Treated with Phosphate Reason Not done Not done Average sludge 9.67 9,72 9.74 9.66 Average piston scar to Bernissini” 9.15 9J2 9.32 9J4 Average Ringland Precipitate "6,80 8.13 7.91 8.14 cam and lifter wear (inch) Maximum 0.0005 0.0087 0.00060.0023 Minimum 0.00 01 0.0002 0.00030.0002 Average 0.0003 0.00 15 0.00040.0006 Viscosity increase rate (%) 64 hours 283 44 36 50 Oil loss (four) 4.84 4.67 3.97 4.55 As mentioned above As such, in order to match the API service classification S side lubricant, this lubricant must be , must pass certain several engine oil bath tests. But long Lubricating oil compositions that pass one or more individual tests may also be suitable for certain applications. It is useful.

A　STM Sequence IIIE engine oil test How to determine anti-wear performance, anti-oil thickening performance and anti-sediment performance at high temperature Recently established as a law. This IIIE test is an alternative to the sequence IIID test. Used to protect camshafts and lids from wear at high temperatures and for oil concentration. Analytical capabilities have been improved regarding the control of This IIrE test (Bujck) uses a 3.8L V-6 model engine. Kono engine is At 67.8 bhp and 300 Orpm over a maximum test period of 64 hours. Operated on night lead fuel. A valve spring load of 230 pounds is used. workman Due to the high engine operating temperatures, a 100% glycol coolant is used. cooling The agent outlet temperature was maintained at 118°C and the oil temperature was maintained at an oil pressure of 30 psi. and maintained at 149°C. The air-fuel ratio is 16.5, the gas leakage rate is 1, 6 cfm. The initial oil charge is 146 ounces.

The test was performed with an oil level of 28 oz. during any of the 8 hour check intervals. It ends when the following is reached. Test ended 64 hours early due to low oil level When this low oil level is The oxidized oil remained intact, and the oil check temperature was 49℃. This was caused by oxidized oil not being drained into the oil pan. taken every 8 hours The viscosity is measured on the drawn oil sample. From this data, the engine A curve of the rate of increase in viscosity versus operating time is plotted. Applicable to API classification SG In order to achieve this, the viscosity must increase by at most 375% when measured at 40°C for 64 hours. need to join. The engine thrust requirements are based on the CRC merit evaluation system. Based on the stem, the minimum ratio is 9.2, and the piston Parnie Sosini has the highest ratio. The smallest is 8.9, and the smallest Ringland precipitate is 3.5. recent sequence For details on the HE test, see the Sequence Test for ASTM Oil Grade Channels. Sequence llID Surveillance Neunel Report for Published November 30, 1987, revised January 11, 1988) It is stated.

The results of the Sequence I [IE tests performed on Lubricants I and H are shown in the table below. It is summarized in ■. For comparison, a moisturizer with the exception of not containing manganese additives. Test results for control oils ■ and ■ corresponding to lubricants I and ■, respectively, are also summarized do.

(Margin below) ■ AS Ding M Sequence III-E Test −1−−−−−−−Second section 艷肱 Fruit−−−−−−−111 oil Viscosity mechanism E°stone link land VTW” loss bar IU2 Surprise, the master's ship was 4, 3, 21, 4, 2 -21 Sheng Max Otsu 7Δmu and Ni Control I 3300 9J 8.4 5.0 106/7/19 2.7N 210 9.6 8.9 6J i2/7/9 1.9 control n 2400 9.2 8.8 3.7 1175/3/176 3 ．． In? 40 9.3 9.0 4.5 133/6/70 3.6 The present invention , although described with respect to its preferred embodiments, various modifications thereof include: After reading this specification, it should be understood as would be obvious to one of ordinary skill in the art. Therefore, The invention disclosed herein includes such modifications as fall within the scope of the appended claims. It should be understood that it is intended to

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Claims (1)

[Claims] 1. A lubricating oil composition for internal combustion engines containing the following (A), (B) and (C): (A) a major amount of oil of lubricating viscosity; (B) a minor amount of at least about 1.0% by weight; At least one carboxylic acid derivative composition, the composition comprising the following (B-1): and (B-2) are produced by reacting: (B-1) at least 1 Species substituted succinic acylating agent; (B-2) at least one HN< group in the structure at least one amine compound characterized by the presence of A substituted succinic acylating agent consists of a substituent and a succinic acid group; The groups are derived from polyalkenes; the polyalkenes have a molecular weight of 1300 to about 5000 characterized by an Mn value of from about 1.5 to about 4.5; The sylating agent contains on average at least 1.3 succinic acid groups for each equivalent of substituent. characterized by the presence in its structure; and (C) as a metal. at least one species of manganese in an amount sufficient to provide from 1 to about 500 ppm manganese. However, the manganese compound is a neutral dihydrocarbyl phosphorodithio compound; Not manganese acid. 2. 2. The lubricating composition of claim 1, wherein the composition is substantially copper-free. . 3. The lubricating composition according to claim 1, wherein the manganese compound (C) is It is a based manganese compound. 4. The lubricating composition according to claim 1, wherein the composition also comprises (D): Has: (D) about 0.05% to about 5% by weight of at least one species characterized by the following formula: Dihydrocarbyl phosphorodithioic acid metal: ▲Mathematical formula, chemical formula, table, etc.▼( VIII) where R1 and R2 each independently represent 3 to about 13 carbon atoms; is a hydrocarbyl group containing an elementary atom, M is a metal, and n is the valence of M. is an integer equal to . 5. 5. The lubricating composition according to claim 4, wherein at least R1 and R2 in (D) Another one is bonded to an oxygen atom via a second carbon atom. 6. The lubricating composition of claim 1, wherein the composition also comprises (E): Has: (E) a detergent-effective amount of a neutral or basic atom of a sulfonic or carboxylic acid; At least one metal salt. 7. The lubricating oil composition according to claim 1, wherein the manganese compound (C) Salts of acidic substances selected from the group consisting of rubonic acids, sulfonic acids and phenols It is. 8. The lubricating oil composition according to claim 1, wherein the manganese compound (C) It is an overbased manganese salt of a mixture of rubonic acids. 9. 2. The lubricating oil composition of claim 1, wherein the composition has a metal content of from about 50 to Contains about 300 ppm manganese. 10. The lubricating oil composition according to claim 1, wherein the Mn value in (B) is small. The number is approximately 1,500 at most. 11. The lubricating oil composition according to claim 1, wherein the Mw/Mn value in (B) is , at least about 2.0. 12. 2. The lubricating oil composition according to claim 1, wherein (B) comprises an acylating agent (B- 1) About 0.5 equivalent to about 2 mol of the amine (B-2) per equivalent is reacted. will be responded to. 13. The lubricating oil composition according to claim 1, wherein the acylating agent (B-1) is at least about 1.5 to about 2.5 succinate groups for each equivalent of said substituents; It is characterized by the presence of within its structure. 14. Lubricating oil composition for internal combustion engines containing the following (A), (B) and (C) : (A) a major amount of oil of lubricating viscosity; (B) at least about 1% by weight; is also one kind of carboxylic acid derivative composition, which composition comprises the following (B-1) and ( B-2) is produced by reacting with: (B-1) At least one substituted succinic acylating agent; (B-2) at least one atom characterized by the presence of at least one HN< group; wherein the substituted succinic acylating agent has a substituent and a succinic acid group; wherein the substituent is derived from a polyalkene; the polyalkene is , with an Mn value of 1300 to about 5000 and a Mw/Mn value of about 1.5 to about 4.5. for each equivalent of substituent; on average, the acylating agent contains less than Both are characterized by the presence of 1.3 succinic acid groups in their structure. and (C) sufficient to provide from about 1 to about 500 ppm manganese as metal. of at least one overbased carboxylic acid or sulfonic acid manganese salt. 15. 15. The lubricating oil composition of claim 14, wherein the composition substantially comprises copper. do not. 16. 15. The lubricating oil composition according to claim 14, wherein the manganese compound (C) is , an overbased manganese carboxylate. 17. 15. The lubricating oil composition of claim 14, wherein the composition also comprises the following (D ) also contains: (D) about 0.01% to about 5% by weight of at least one species characterized by the following formula: Dihydrorubylphosphorodithioic acid metal: ▲Mathematical formula, chemical formula, table, etc.▼( VIII) where R1 and R2 each independently represent 3 to about 13 carbon atoms; is a hydrocarpyl group containing an elementary atom, M is a metal, and n is the valence of M. is an integer equal to . 18. 18. The lubricating oil composition according to claim 17, wherein the R1 and R2 of (D) At least one of them is bonded to an oxygen atom via a second carbon atom. 19. 18. The lubricating oil composition of claim 17, wherein (D) is dihydrocarbyl. a mixture of metal salts of phosphorodithioic acids, wherein at least one of the metal salts of phosphorodithioic acids is In dolocarbyl phosphorodithioic acid, one of the hydrocarbyl groups (DD is iso Propyl group or secondary butyl group, other hydrocarbyl group (D-2) is small. contains at least 5 carbon atoms and all hydrocarbons present in (D) At least about 10 mole percent of the pyl groups are isopropyl groups, secondary butyl groups. or a mixture thereof. 20. 15. The lubricating oil composition of claim 14, wherein the composition also comprises the following (E ) also contains: (E) a detergent-effective amount of a neutral or basic atom of a sulfonic or carboxylic acid; At least one metal salt. 21. 21. The lubricating oil composition according to claim 20, wherein the alkali metal salt (E) is , the ratio of alkali metal equivalents to sulfonic acid or carboxylic acid equivalents is small. Both are characterized by a ratio of approximately 2:1. 22. 15. The lubricating oil composition of claim 14, wherein the composition also comprises the following (F ) also contains: (F) A small amount produced by reacting the following (F-1) and (F-2) At least one carboxylic acid ester derivative composition: (F-1) At least one carboxylic acid ester derivative composition: Transsuccinic acid acylating agent; (F-2) at least one alcohol of the following general formula :R3(OH)m(XI) Here, R3 is a monovalent or polyvalent organic group bonded to the OH group via a carbon bond. and m is an integer from 1 to about 10. 23. 23. The lubricating oil composition of claim 22, wherein m is at least 2. 24. 23. The lubricating oil composition according to claim 22, wherein the acylating agent (F-1) and The composition obtained by reacting the alcohol (F-2) with (F-2) is 3) further reaction with at least one amine containing at least one >NH group be done. 25. Lubricants for internal combustion engines containing the following (A), (B), (C) and (D) Oil composition: (A) a major amount of oil of lubricating viscosity; (B) a minor amount of at least about 1.0% by weight; At least one carboxylic acid derivative composition, the composition comprising the following (B-1): and (B-2) are produced by reacting: (B-1) at least 1 Species substituted succinic acylating agent; (B-2) at least one HN< group in the structure at least one amine compound characterized by the presence of A substituted succinic acylating agent consists of a substituent and a succinic acid group; The groups are derived from polyalkenes; the polyalkenes have a molecular weight of 1300 to about 5000 characterized by an Mn value of from about 1.5 to about 4.5; The acylating agent has an average of at least 1.3 succinic acids for each equivalent of substituent. characterized by the presence of a group in its structure; and (C) a metal; at least 1 in an amount sufficient to provide about 50 to about 300 ppm manganese. at least one overbased manganese salt of a species carboxylic acid; and D) from about 0.05% to about 5% by weight of at least one dihydride characterized by the formula: Hydrocarbyl phosphorodithioic acid metal: ▲Mathematical formulas, chemical formulas, tables, etc.▼(V III) where R1 and R2 are each independently 3 to about 13 carbons; At least one of the hydrocarbyl groups R1 and R2 containing atoms is It is bonded to an oxygen atom through an elementary atom, and M is a group II metal, aluminum, tin, Selected from the group consisting of iron, cobalt, lead, molybdenum, manganese, nickel or copper. and n is an integer equal to the valence of M. 26. 26. The lubricating oil composition of claim 25, wherein the composition also comprises the following (E ) also contains: (E) about 0.01% to about 3% by weight of a neutral or carboxylic acid or sulfonic acid; or at least one basic alkali metal salt. 27. 26. The lubricating oil composition of claim 25, wherein the composition also comprises the following (F ) also contains: (F) about 0.1% to about 10% by weight of at least one carboxylic acid ester derivative; A conductor composition, the composition reacts the following (F-1) and (F-2). produced by: (F-1) at least one substituted succinic acylating agent; (F-2) At least one alcohol of the following general formula: R3(OH)m (XI) Here, R3 is a monovalent or polyvalent organic group bonded to the OH group via a carbon bond. and m is an integer from 1 to about 10. 28. For formulating a lubricating oil composition containing the following (A), (B) and (C): Concentrate: (A) about 20% to about 90% by weight of a normally liquid, substantially inert organic diluent/ solvent; (B) about 10% to about 50% by weight of at least one carboxylic acid derivative composition; The composition is prepared by reacting the following (B-1) and (B-2). is generated: (B-1) At least one substituted succinic acylating agent; (B-2) at least one atom characterized by the presence of at least one HN< group; wherein the substituted succinic acylating agent has a substituent and a succinic acid group; wherein the substituent is derived from a polyalkene; the polyalkene is , with an Mn value of 1300 to about 5000 and a Mw/Mn value of about 1.5 to about 4.5. for each equivalent of substituent; on average, the acylating agent contains less than Both are characterized by the presence of 1.3 succinic acid groups in their structure. and (C) sufficient to provide about 10 to about 5000 ppm manganese as metal. a sufficient amount of at least one manganese compound; provided that the manganese compound is a neutral Not manganese dihydrocarbyl phosphorodithioate. 29. 29. The concentrate according to claim 28, further comprising the following (D): Contains in a proportion of 0.05% to about 15% by weight: (D) about 0.05% to about 15% by weight 5% by weight of at least one dihydrocarbyl phosphorescent compound characterized by the formula Metal thioate: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VIII) Here, R1 and and R2 are each independently a hydrocarbon containing from 3 to about 13 carbon atoms. is a building group, M is a metal, and n is an integer equal to the valency of M. 30. 29. The concentrate according to claim 28, further comprising the following (E): Contains in a proportion of about 1% to about 20% by weight: (E) sulfonic acid or carboxylic acid At least one neutral or basic alkali metal salt of an acid.