JPH07500374A - Lubricating compositions and concentrates - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Lubricating compositions and concentrates Cross-reference of related applications This application is filed in U.S. Patent Application No. 07/688, filed April 19, 1991. ．． No. 195 and U.S. Patent Application No. 077 filed April 19, 1991. No. 690.179 is a continuation-in-part application. The disclosure content of the earlier application is herein is fully incorporated into.

field of invention The present invention relates to lubricating oil compositions and concentrates, and more particularly to hydrocarbyl compositions and concentrates. Relating to lubricating oil compositions containing alkali metal overbased salts of carboxylic acids Ru.

Background of the invention Power and complexity of engines, especially spark ignition and diesel engines As performance increases, the performance requirements placed on lubricants increase, including: are doing. This lubricant is less prone to deterioration under the conditions of use and therefore , wear, rust, corrosion and undesirable deposits (e.g. fez, sludge, carbon reduce the formation of carbonaceous substances and resinous substances). These precipitates are They tend to stick to engine parts and reduce engine efficiency. The lubricating oil composition Various materials may be included in lubricating oil compositions to meet different performance requirements. These substances include dispersants, detergents, friction modifiers, corrosion inhibitors, Examples include antioxidants and viscosity improvers.

Dispersants remove impurities, especially those formed during the operation of internal combustion engines, from sludge. It is used in lubricants to keep it in suspension rather than letting it settle.

Reaction of hydroxy compounds or amines with substituted succinic acids or their derivatives Dispersant additives for lubricants containing products have been described in the prior art. , typical dispersions of this type are described, for example, in US Pat. No. 3,272,746; No. 3.522.179; No. 3.219.666; and No. 4.234.43 It is disclosed in No. 5. The composition described in the '435 patent is mixed into a lubricating oil. When used, it primarily functions as a dispersant/detergent and a viscosity index improver.

Alkaline earth metal detergents are used to suspend motor oil breakdown products. included in lubricating oil compositions to neutralize acid products in engine oil. It will be done. These alkaline earth metals include calcium, magnesium, or strontium; mixtures of such metals may be used. this These alkaline earth metal detergents are generally basic. To improve cleanliness Additionally, alkali metal detergents have also been used in lubricating oil compositions.

Alkali metal salts (including basic salts) are described in the general literature and patents. Ru. For example, Canadian Patent No. 1,055,700 describes basic alkali metal sulfonate describes a phosphate dispersion and method. More specifically, this patent discloses that from about 4 to about Lithium basic sulfonates, sodium basic sulfonates with metal ratios in the range of 40 solutions and/or stable dispersions of potassium sulfonates and basic potassium sulfonates. It is listed. Methods used to prepare these oat-e-based sulfonates In this case, the reaction mixture that is brought into contact with an acidic gaseous substance (e.g. carbon dioxide) is In addition to the species or more oil-soluble sulfonic acids or derivatives thereof, one or more is one or more alkali metals or metal compounds, one or more lower aliphatic monohydric alcohol or dihydric alcohol and one or more oil-soluble Contains bonic acids or their derivatives. These carboxylic acids are monocarboxylic Includes acids and polycarboxylic acids.

U.S. Pat. No. 3,271,310 (LeSuer) discloses that alkenyl substituents include Describes metal salts of alkenylconophosphates having at least about 50 aliphatic carbon atoms are doing. These salts include acidic, neutral or basic salts; Metals include Group Ⅰ metals, Group 11 metals, aluminum, lead, tin, and and Ni-Nokel. These alkenyl succinct It can be included in the lubricating oil in an amount of about 0.1% to about 20% by weight. Jun Other additives that may be included in the lubricating oil include if, other detergents and dispersants, acids, etc. These include corrosion inhibitors, corrosion inhibitors, extreme pressure agents, etc.

U.S. Patent No. 3. 312. No. 618 (LeSuer) is an anhydrous condition and describes a method for preparing oil-soluble, highly basic metal salts of organic acids using . These organic acids include sulfonic acids, 1-non-containing acids, carboxylic acids, or mixtures thereof. It can be a compound. These carboxylic acids contain at least 12 carbon atoms fatty acids (e.g. palmitic acid), cyclic acids (e.g. benzenoid structures (e.g. (e.g., benzene), with a total of less than about 15 carbon atoms, preferably acids containing oil-soluble groups having about 15 to about 200 carbon atoms). . The metal compounds used to form this metal salt include alkali metals and and alkaline earth metals.

U.S. Patent No. 4,283,294 (Clarke) describes a lubricating oil composition useful for engines, which composition, in addition to oil, Group 1a metal overbased detergent, Group 11a metal overbased detergent and a mixture of antioxidants, provided that an overbased detergent mixture What is the weight ratio between this and this antioxidant? ．． It is between 5:1 and 50:1. these Detergent additives for Group 1a and Group 11a metals include phenol, sulfide Metals of phenols, phosphorus sulfurized polyolefins, organic sulfonic acids and carboxylic acids Salt is an example. This carboxylic acid is a long-chain monocarboxylic or dicarboxylic acid (For example, if the acid group contains at least 50 carbon atoms per molecule) bonic acid). Therefore, these metal salts include long-chain succinic acids (e.g. , succinic acid) having a molecular weight of 850 to 1200. to this patent The antioxidants listed include alkylated hindered phenols, organic amines, Includes sulfur-containing compounds, metal thiophosphates, etc. Any in this lubricating oil composition Additives include dispersants (e.g. polyisobutenyl succinic anhydride-tetraethylene pentamine reaction product).

Basic alkali metal salts of sulfonic or carboxylic acids, and substituted succinic acids. Calcium obtained by reacting a compounding agent with at least one amine compound Lubricating oil compositions containing bonic acid derivative compositions are disclosed in U.S. Pat. No. 4.904.401. No. 4.938.881; and No. 4.952.238. . These carboxylic acids can be monocarboxylic or polycarboxylic acids (substituted succinic acids) (including dicarboxylic acids such as). Useful alkali metal salts Suitable carboxylic acids from which may be prepared include aliphatic, cycloaliphatic and aromatic carboxylic acids. Monocarboxylic and polycarboxylic acids (naphthenic acid, alkenyl-substituted aromatic acids and and alkenyl-substituted succinic acids). This aliphatic acid is generally , about 8 to about 50 carbon atoms, preferably about 12 to about 25 carbon atoms. have These patents also cover basic alkali metal salts, sulfonic acids and carboxylic acids. a mixture of carboxylic acids (wherein, in this mixture, a carboxylic acid (when it is present) ) and the organic sulfonic acid is about 1:2 to about 1:20, preferably about 1:2. 2 to about 1=10). contained in these oil compositions The amount of alkali metal overbased sulfonate or carboxylate salt is about 0. 01 to about 2% by weight. These oil compositions have anti-wear properties, extremely Other desirable additives useful in improving pressure-oxidant properties (e.g., dihydro- Metal salts of carbylphosphorodithioic acids, antioxidants, friction modifiers, sulfurized phenols neutral and basic salts, sulfur-containing compounds), and neutral or basic alkali Potassium earth metal salt detergents may be included.

UK Patent Application No. 2.062.672 (Zalar) describes the use of sulfurized alkylphenols. describes additive compositions for lubricating oils containing polymers and high molecular weight dispersants. child The dispersant has a number average molecular weight of at least 1300 and has a polar group attached to it. oil-soluble carboxylic acid dispersants containing hydrocarbon-based groups (e.g. succinic acid or or their derivatives). Generally, these carboxylic acid dispersants are an acid or a derivative thereof; (a) a nitrogen-containing compound having at least one >NH group; (b) organic hydroxy compounds (e.g. phenols and alcohols) , and/or (c) is a reaction product with a reactive metal or metal-reactive compound. Ru. These carboxylic dispersants can be post-treated with various reagents. These reagents Includes sulfur and sulfur-containing compounds, urea, thiourea, aldehydes, ketones, Includes carboxylic acids, epoxides, boron-containing compounds, phosphorus-containing compounds, etc. . The carboxylic acids used in the preparation of these dispersants are called acylating agents. child The acylating agent can be used by alkylating an acid (e.g. maleic acid or its anhydride) It can be prepared as follows.

The alkylating agent contains at least one olefinic bond or halogen. It can be a polymer that The number average molecular weight of this polymer is at least 1300. and typically ranges from about 1,500 to about 5,000. The ratio of My to Mn is It is about 1.5 to about 6, usually 1.5 to about 4. This substituted co/% phosphoric acid forms depending on the amounts of reactants used to produce the dispersant and the type of dispersant desired. The molar ratio of polymer to maleic acid or anhydride in this reaction mixture is , equal to l, greater than ■, or less than l. In some applications, this amount The powder contains, on average, at least 1.3 acid moieties per polymer moiety. It is manufactured by containing the following ingredients: Reactions that can be used to make these dispersants Among the metal compounds, there are alkali metal compounds (e.g. alkali metal hydroxides, carbonates, alkoxides, oxides, etc.). This patentee claims that these lubricants The composition may also contain other additives (auxiliary detergents and dispersants, corrosion inhibitors, antioxidants). (including additives, pour point depressants, extreme pressure agents, etc.).

E-vice-dan! 1 A lubricant containing a major amount of oil of lubricating viscosity and the following (A) and (B): Lubricating oil compositions are described: (A) at least about 1% by weight of (A-1 ) and (A-2), at least one type of carvone produced by reacting Acid derivative composition: (A-1) containing at least about 50 carbon atoms in the substituent; One type of substituted conolinic acid acylating agent; (A-2) per equivalent of acylating agent (A-1) from about 0.5 equivalents to about 2 moles of at least one FIN< group in the structure. (B) at least one amine compound characterized by the presence of the at least about 0.002 equivalents of alkali metal per ioo gram of lubricating oil composition a hydrocarbyl-substituted carboxylic acid or hydrocarbyl-substituted carboxylic acid in an amount sufficient to provide at least one of a mixture of a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted sulfonic acid. Species alkali metal overbased salts: The overbased salt has a metal ratio greater than 2, wherein the the hydrocarbyl substituent of the phosphoric acid contains at least about 50 carbon atoms; , provided that the alkali metal salt is a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted carboxylic acid. When containing a mixture of overbased alkali metal salts of bir-substituted sulfonic acids , the carboxylic acid comprises more than 50% acid equivalents of the mixture, and further provided that The substituted succinic acylating agent (A-1) consists of a substituent and a succinic acid group, The silating agent contains, on average, at least 1.3 per equivalent of substituent within its structure. When the alkali metal succinate group is characterized by the presence of The metal ratio of the barbased salt (B) is greater than 1.

Awesome 1! Day Throughout this specification and claims, references to weight percentages of various ingredients refer to In the absence of instructions, it is based on chemical criteria. For example, the oil composition of the present invention is described as containing at least 2% by weight of (A), the oil composition The product contains at least 2% by weight (A) on a chemical basis.

Therefore, if component (A) is available as a 50% by weight oil solution, less At least 4% by weight oil solution is contained in this lubricating composition.

The number of equivalents of acylating agent depends on the total number of carboxylic acid functionalities present. This reed When determining the number of equivalents of the carboxylic acid acylating agent, consider Boxyl functionality is 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, 2 equivalents are present. The number of carboxyl functionalities (e.g. Conventional methods are readily available to determine the Therefore, the number of equivalents of acylating agent can be readily determined by one of ordinary skill in the art.

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; It has an equivalent weight equal to 173 of the molecular weight. Commercial blends of polyalkylene polyamines The equivalent weight of a substance is the atomic weight (14) of nitrogen contained in this polyamine. 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.

React with acylating agent to form carboxylic acid derivative (A) t6t = droxyl substitution The equivalent weight of an amine is its molecular weight divided by the total number of nitrogen groups present in the molecule. It is. For the purpose of the present invention, when preparing component (A), the hydroxyl group is Ignored when issued. Therefore, ethanolamine has an equivalent molecular weight of and jetanolamine has an equivalent weight (nitrogen-based ).

The terms "substituent J," "acylating agent," and "substituted succinic acylating 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 The term substituted succinic acylating agent or substituted succinic acylating agent refers to the compound itself; The unreacted reactant used to form the sylating agent or substituted succinic acylating agent. Contains no active ingredients.

The term "hydrocarbyl" includes hydrocarbon groups and substantive hydrocarbon groups. Ru. A substantial hydrocarbon group is primarily a non-hydrocarbon group that does not change the hydrocarbon nature of the group. Indicates a group containing an elementary substituent.

Examples of hydrocarbyl groups include; (1) hydrocarbon substituents, i.e. i.e., aliphatic substituents (e.g., aJL/-1-/L/, alkenyl), alicyclic substituents substituents (e.g. cycloalkyl or/chloroalkenyl), aromatic substituted aromatic Aromatic substituents, aliphatic-substituted aromatic substituents and alicyclic-substituted aromatic substituents groups, etc., and cyclic substituents. Here, this ring is completed by the other parts of the molecule. (i.e., if any two indicated substituents - together (can form an alicyclic group).

(2) substituted hydrocarbon substituents, i.e., these substituents are non-hydrocarbon groups; Contains. This non-hydrocarbon group, within the context of the present invention, is primarily a hydrocarbon substituted does not change the group; such groups, such as halo (particularly chloro and fluoro) ), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nito roso, sulfoxy, etc.) are known to those skilled in the art; (3) heterosubstituents, i.e., within the context of the present invention, are primarily hydrocarbon in nature; has something other than carbon present in the ring or chain, but otherwise A group composed of carbon atoms. Suitable petero atoms will be apparent to those skilled in the art. , including, for example, sulfur, oxygen and nitrogen. Such substituents include, for example , pyridyl, furyl, chenyl, imidazolyl, etc. Generally, this hydro In carbyl groups, less than about 2 non-hydrocarbon substitutions for each 10 carbon atoms Groups, preferably less than one non-hydrocarbon substituent, are present.

Often, the hydrocarbyl group has no such non-hydrocarbon substituents. , and this hydrocarbyl group is a pure hydrocarbon.

° 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) and also Mineral lubricating oils (e.g. liquid petroleum oil and paraffin type, naphthene) Solvent-treated mineral lubricating oils of the paraffin-naphthene type or mixed paraffin-naphthene type. or acid-treated mineral lubricating oil). Water derived from coal or shale Oils of lubricious viscosity are also useful. Synthetic lubricating oils include the following hydrocarbon oils: and halo-substituted hydrocarbon oils. This hydrocarbon oil and halo-substituted hydrocarbon Base oils include, for example, polymerized olefins and interpolymerized olefins. Fins (e.g. polybutylene, polypropylene, propylene-isobutylene) polymers, chlorinated polybutylene, etc.); poly(1-hexene), poly(1- octene), poly(l-decene), etc., and mixtures thereof; alkylbenzes (e.g., dodenlebenzene, tetradecylbenzene, dinonylbenzene, -(2-ethylhexyl)-benzene, etc.); polyphenyl (e.g., biphenyls); alkylated polyphenyl, terphenyl, alkylated polyphenyl, etc.); Phenyl ethers and alkylated diphenyl sulfides and their derivatives bodies, their analogs and congeners.

Alkylene oxide polymers and interpolymers and their derivatives (this In derivatives, the terminal hydroxyl group has been 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 aryl ethers of these polyoxydialkylene 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, polypropylene glyco having 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 03-C 8 fatty acid ester or CI3 oxo acid diester).

Other suitable classes of synthetic lubricating oils that may be used include dicarboxylic acids such as Ruric acid, Succinic acid, Alkyl succinic acid, Alkenyl succinic acid, Maleic acid, Azera Inic acid, superic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid timer , malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols. alcohol (e.g., butyl alcohol, alcohol, alcohol, alcohol, etc.) -Ethylhexyl alcohol, ethylene glycol, diethylene glycol mono ethers, propylene glycol, etc.). These S Specific examples of esters include dibutyl adipate, di(2-ethylhexyl sebacate) ), di-n-hexyl fumarate, dioctyl sebacate, diisoacetyl azelate Cutyl, diisodecyl azelaate, dioctyl phthalate, didecyl phthalate, Jacosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer , 1 mole of sebacic acid, 2 moles of tetraethyleneglyfur and 2-ethyl Composite esters formed by reaction with 2 moles of phosphoric acid, etc. are included.

Esters useful as synthetic oils include 05-CI2 monocarboxylic acids and polyols. and polyol ethers (e.g. neopentyl glycol, trimethylol Propane, pentaerythritol, dipentaerythritol, tripentaerythritol Also included are esters formed from (such as tritol).

silicone-based oils (e.g. polyalkyl-, polyaryl-, polyalkyl- Kogyun-1 or polyaryloxy-siloxane oil and silicate oil (1) constitute another useful class of synthetic lubricants. This includes, for example, tetra Ethyl silicate, tetraisopropyl silicate, tetosilicate, hexyl -(4-methyl-2-bento)disiloxane, poly(methyl)siloxane, Examples include poly(methylphenyl)siloxane. Other synthetic lubricants contain phosphorus. Liquid esters of acids (e.g. tricresyl phosphate, trioctyl phosphate, decane) (e.g. diethyl ester of phosphonic acid), polymerized tetrahydrofuran, etc. be done.

Unrefined oils, refined oils and re-refined oils (this includes natural oils of the types disclosed above) either two or more of these ) may be used in the concentrates of the present invention. What is unrefined oil? , obtained directly from natural or synthetic raw materials without further purification. It is il. For example, shale oil obtained directly from the retort operation, from the first stage distillation Petroleum oils obtained directly or obtained directly from an esterification process and further processed. Ester oils used without treatment are unrefined oils. Refined oil is one or more types. further processed in one or more purification steps to improve the above 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, percolation, etc. Rerefined oil is already used By applying a process similar to that used to obtain the refined oil to the refined oil ,can get. Such rerefined oils are also considered reclaimed, recyclable, or reprocessed oils. known as, consumed additives, oil impurities (e.g. water and fuel), and oil breakdown products, often by directed methods. The component (A) used in the lubricating oil of the present invention is the following (A-1) and (A -2) at least one carboxylic acid derivative produced by reacting with The composition is: (A-1> Contains at least about 50 carbon atoms in the substituent at least one substituted succinic acylating agent; (8-2) at least one ) at least one amine compound containing an IN< group. Generally, this reaction , from about 0.5 equivalents to about 2 moles of amine compound per equivalent of acylating agent. Includes responses. In a preferred embodiment, the acylating agent (A-1) has a substituent and a succinic acid group. where this substituent is derived from a polyalkene , the polyalkene has an Mn value of from about 1300' to about 5000 and from about 1.5 to about It is characterized by a Mw/Mn ratio of 4.5. The acylating agent contains each equivalent of the substituent. On average, at least about 1.3 succinic acid groups are present in the structure. It is further characterized by:

The carboxylic acid derivative (A) modifies the dispersibility and v1 properties of the oil composition. It is included in this oil composition to improve its quality. Generally from about 1% by weight to more from about 1.5% or 2% to about 10% or 15% by weight in most cases. The following components (A) may be contained in this oil composition. But this oil The composition preferably contains at least 2.5% by weight, often at least 3% by weight. % of component (A).

Substituted cono-mono-lyric acid acylating agent (used in preparing carboxylic acid derivative (A)) A-1) is characterized by the presence of two groups or moieties within its structure. It can be done. For convenience, the first group or moiety is hereinafter referred to as a "substituent". It is derived from polyalkenes. The polyalkene from which this substituent is derived is 1 embodiment contains at least about 50 carbon atoms, and about 9 00 to about 5000 or 10.000 or higher Characterized by. In one preferred embodiment, the Mn is from about 1300 to about 5000 and the 1vZin value is at least about 15 or at least 2 ．． 0 to about 4.0 or 4.5. The abbreviation My represents weight average molecular weight. This is the traditional symbol. Gel permeation chromatography (GPC) , both the weight average molecular weight and number average molecular weight of the polymer as well as the This is a method to obtain the total molecular weight distribution.

For the purposes of this invention, a series of fractionated isobutyne polymers, namely polyisobutyne is used as a calibration standard for GPC.

Methods for determining Mn and ￥Av values of polymers are well known and have been described in numerous publications. described in the references and papers. For example, determine the Mn and molecular weight distribution of a polymer The method is described by W, W, YanSJ.

rModern 5ize Ex by Kirkland, J., and Bly, D. fusion Liquid ChromatographsJ (J, W Iley & 5ons, Inc., 1979).

The second group or moiety in the acylating agent is herein referred to as a "succinic acid group." Called. The succinic acid group is a group characterized by the following structure: O II l l II X-C-C-C-C-X' (1) Here, X and Xo are the same or different, provided that at least one X and Xo indicate that the substituted succinic acylating agent is a carboxylic acylating agent. It can function as such. That is, at least one of X and Xo is Substituted decontamination agents may form amides or amine salts with amine compounds; Otherwise, this unpurifying agent may function as a conventional carboxylic acid acylating agent. It must be based on The transesterification reaction and the transamidation reaction are described in the present invention. For our purposes, it is considered a conventional acylation reaction.

Therefore, X and/or Xo are usually -0)1. -0-hydrocarbyl, -0-M'. Here, M2 is one equivalent of metal, ammonium cation or represents an amine cation, -Nl2, -CL-Br, and X and Xo are - It can be 10- such that together they form an anhydride. any of the above groups The specific identification of X or It is not important unless participation in the reaction is prevented. However, good Preferably, X and Xo each represent both carboxyl groups of the succinic acid group. ability (i.e., both -C(0)X and -C(0)X') to participate in the acylation reaction. It is something that can be involved.

One of the following incomplete valences in the group of formula to form a carbon bond: other such imperfect valences may be present in the same or different positions. may be satisfied by analogous bonds with substituents, except for one of such valences. All are normally filled with hydrogen (i.e. -H).

In one embodiment, the substituted cono-phosphate acylating agent contains less than or equal to each equivalent of substituent. At least one cono\hydric acid group (i.e., a group corresponding to formula ■) is present in the structure. Characterized by its existence. In a preferred embodiment, this substitution The acid cleaning agent contains, on average, at least 1°3 atoms per equivalent of substituent. Characterized by the presence of citric acid groups. For the purposes of this invention, the equivalent weight of a substituent is , the Mn value of the polyalkene from which the substituents are derived, in the substituted cono-phosphate acylating agent. It is believed to be the number obtained by dividing the total weight of substituents present.

Therefore, substituted cono-phosphate acylating agents are characterized by a total weight of substituents of 5000 and the Mn value of the polyalkene from which this substituent is derived is 2000. , at that time, the total ratio of this substituted cono/phosphoric acid acylating agent was 2.5 (5000/2 It is characterized by an equivalent weight of substituents of 000=2.5). Therefore, certain % phosphoric acid acylating agent is also a necessary condition in the phosphoric acid acylating agent used in the present invention. There must be at least 3.25 succinic acid groups in the structure to satisfy one of the Other requirements for O-substituted cottoriic acid acylating agents characterized by the presence of In preferred embodiments, the substituent has a molecular weight of at least about 1.5 or 2.0 / Must be derived from polyalkenes characterized by n value. Ru. The upper limit for My/'1lin is generally about 4.0 or 4.5. 1.5 Values of up to about 4.5 are useful, with ratios of 2 to about 4.5 being particularly useful.

Polyalkenes having the above Mn and My values are well known in the art. , may be prepared according to conventional methods. For example, these polyalkenes , U.S. Pat. No. 4,234,435. A port like this The disclosure of this patent relating to Rialken is incorporated herein by reference. There is. Some of these polyalkenes (especially polybutenes) are commercially available. There is.

In one preferred embodiment, the succinic acid group typically corresponds to the formula: Here, R and Ro each independently represent -OH, -CI, -0-lower atom and when taken together, R and R o is -0-. In the latter case, the succinic acid group is a co/X-anhydride group. Ru. All co/% acid groups in a particular co/% phosphoric acid acylating agent need not be the same. Although they are not, they can be identical. Preferably, the cono\hydric acid group has the following formula: Corresponding to the mixture of compounds (III(A)) and (III(B)) Correct: It is possible to obtain substituted cono-acid acylating agents in which the succinic acid groups are the same or different. , is within the ordinary skill in the art and can be accomplished 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 reaction component or fluoride. Maric acid reactive components may be selected.

As mentioned above, the minimum number of cono-acid groups for each equivalent of substituent is at least 1 and preferably 1.3. The maximum number generally does not exceed 4.5.

In other preferred embodiments, this minimum number is about 164 for each equivalent of substituent. It is an acid group. The range based on this minimum number is a small number per equivalent of substituent. from at least 1.4 to about 35 cono-lyric acid groups, and more particularly from about 1. 4 to about 2.5 cono-1-phosphate groups.

Preferred substituted succinic acid groups are those in which the preferred point is succinic acid for each equivalent of the substituent. In addition to depending on the number and type of groups, yet another preference is that this substitution It is based on the type and properties of the polyalkene from which the group 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, Mn values in the range of about 1500 to about 5 ooo are also preferred. even more preferable The Mn value ranges from about 1500 to about 2800.

The most preferred range of Mn values is about 1500 to about 2400.

Before proceeding further with the discussion of polyalkenes from which substituents are derived, it is important to These favorable properties of silating agents are both independent and pond dependent. It should be pointed out that it is intended to be understood as this et al., for example, a preference for succinic acid groups of 1.4 or 1.5 per equivalent of substituent. The preferred minimum value is not tied to any more preferred value of n or my/TAn. It is considered independent in the sense that it is independent. They are, for example, 1.4 or The preferred minimum value of succinic acid groups is 1.5 for Mn and/or My/Mn. When combined with the preferred values, this combination of preferences effectively makes the present invention may be considered dependent on each other in the sense of indicating further preferred embodiments. Ru. Therefore, the various parameters may vary with respect to the specific parameters described. Although considered isolated, other parameters can be added to confirm further favorable points. can be combined with a This same concept applies to preferred values, ranges, ratios, and reaction components. Concerning statements such as Otherwise, it is intended to apply throughout the specification.

In embodiments, the Mn of the polyalkene is at the lower end of this range (e.g., about 1300 ), in this unpurifying agent, the substituent derived from the polyalkene is The ratio of co/% phosphoric acid groups is preferably higher than the ratio when n is 1500, for example. stomach. Conversely, when the un of the polyalkene is higher (e.g. 2000), this ratio is , the Mn of the polyalkene is lower than when it is, for example, 1500.

The polyalkenes from which the substituents are derived include polymerizable olefin monomers (which , 2 to about 16 carbon atoms, usually 2 to about 6 carbon atoms) alone There are polymers and interpolymers. There are two or more types of these interpolymers. or more olefin monomers can be added to the interpolymer by well-known conventional methods. - to form the following polyalkenes: derived within its structure from each of said two or more olefin monomers. It has a unit of Therefore, as used herein, "interpolymer" includes copolymers, terpolymers, quaternary copolymers, and the like. obvious to those skilled in the art Polyalkenes from which substituents are derived, such as It is called ``in''.

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, isobutyne and octene-1) ) or polyolefin monomers (usually diolefin monomers; e.g. Gen-1,3 and isoprene).

These olefin monomers are typically polymerizable terminal olefins (i.e. Olefins characterized by the presence of >C=CH2 groups in their structure ). However, it is characterized by the presence of the following groups within its structure. Polymerizable internal olefin monomers (these are sometimes intermediate olefin monomers) medial olefin), also referred to in the literature as medial olefin. When used internal olefin monomers are used to form Rialken They are usually used with terminal olefins to form interpolymers. Produces polyalkenes. For purposes of this invention, certain polymerized olefin monomers When an olefin can be classified as both a terminal olefin and an internal olefin, This is considered a terminal olefin. Therefore, 1,3-pentanene (i.e. (i.e., piperylene) is considered to be a terminal olefin for purposes of this invention.

Substituted polyacid acylating agent (useful in preparing this carboxylic acid derivative (A)) Some of A-1) are well known in the art, e.g., U.S. Pat. No. 3,087 ．． No. 936 (LeSuer), No. 3.219.666 (Norman) and No. 4,234,435 (Meinhard t).

The disclosures thereof are incorporated herein by reference. No. 435 Special The acylating agents described therein have Mn values of about 1300 to about 5000 and about containing substituents derived from polyalkenes having an iw/'jn value of from 1.5 to about 4. Characterized as having.

Aliphatic hydrocarbon polyalkenes containing no aromatic or cycloaliphatic groups are generally preferred. 2 to about 16 carbons of this generally preferred) polyalkene. Homopolymers and interpolymers of terminal hydrocarbon olefins with elementary atoms More preferably, polyalkenes derived from the group consisting of i. New polyalkenes are limited by the following conditions: Interpolymers of terminal olefins are preferred, but may have up to about 16 carbon atoms. Optional polymer units derived from internal olefins containing up to about 40% The interbomers which are More preferably X class of alkenes (2 to about 6 carbon atoms, preferably Homopolymers and interpolymers of terminal olefins having 2 to 4 carbon atoms) 1 selected from the group consisting of: Shijina Kadara, Bo1 No Arche Another preferred class of molecules is from internal olefins having up to about 6 carbon atoms. The latter preferred polyesters optionally contain up to about 25% derivatized polymer units. It is an alkene.

The above polyalkenes (which meet various criteria for Mn and My/Mn) It is clearly within the skill in the art and included as part of this invention. Not possible. Methods that will be readily apparent to those skilled in the art include controlling the degree of polymerization. , adjusting the amount and type of polymerization initiator and/or catalyst; and the use of chain-terminating groups.

Stripping the light end (vacuum stripping) oxidative or mechanical separation of high molecular weight polyalkenes Other conventional methods, such as producing low molecular weight polyalkenes by , can be used.

In preparing the substituted succinic acylating agents of the present invention, one or more of the above polymers may be used. Rialkenes (or their halogenated derivatives) can be substituted with maleine of the following general formula: one or more selected from the group consisting of acid-reactive components or fumaric acid-reactive components; React with the acidic reactant above: X(0)C-CH=C)l-C(0)X'(m, where X and Xo are the formula As defined above in I.

Preferably, the maleic acid and fumaric acid reactive components correspond to the formula: is one or more compounds: RC(0)-CI(=CH-C(0 ) R' (V) where R and Ro are as defined previously in Formula II herein. is the same as Typically, this maleic acid or fumaric acid reactive component is Leic acid, fumaric acid, maleic anhydride, or two or more of these It is a mixture. Generally, maleic acid reactive components are preferred over fumaric acid reactive components.

The former are readily available and are generally more easily converted to polyalkenes (also may be reacted with derivatives thereof) to prepare the substituted succinic acylating agents of the present invention. It is from. Particularly preferred reaction components are maleic acid, maleic anhydride, and It is a mixture of these. Due to availability and ease of reaction, anhydrous male Inric acid is used.

Examples of patents describing various methods of preparing useful acylating agents include U.S. Pat. No. 3.215,707 (Rense); No. 3.219.666 (Nor +aan et al.); No. 3.231.5117 (Rense); No. 3.912.7 No. 64 (Palier); No. 4.110,349 (Cohen); and No. No. 4.234.435 (Meinhardt et al.); and British Patent No. 1.440 ．． No. 219 is included. The disclosures of these patents are incorporated herein by reference. It is used as 0.

When preparing this hydrocarbyl-substituted polyalkene The proportions of the reactants and the maleic reactants are determined to provide the desired concentration in the product. The proportion of phosphoric acid groups (thus can be varied; therefore, one in each polymer molecule) Depending on whether or not more or less succinic acid groups are contained, the polymerization used For each mole of body, one or more moles of maleic acid reactive component may be used. . In general, the higher the molecular weight of this polymer, the more likely it is that the maleic reaction compound that can be used is The proportion of minutes increases. On the other hand, if a molar excess of the polymeric reactant is used, the excess The polymer simply remains in the product as a diluent, without any adverse effects. .

For convenience and brevity, the term "maleic acid reactive component" will be used hereinafter. Often used in books. When this term is used, the term refers to the formula (m and a maleic acid reactive component and a fumaric acid reactive component corresponding to formula (V). acidic reactants (including mixtures of such reactants) It should be understood that generalizations are made.

(Margin below) The above acylation reagent is used in the method for preparing the carboxylic acid derivative composition (A). It is an intermediate product. This method includes (A-1>one or more acylating reagents) and (A-2> is characterized by the presence of at least one HN< group in its structure. The method includes reacting with at least one amine compound characterized by the above characteristics.

A compound characterized by the presence of at least one HN< group in its structure Mino compound (A-2) may be a monoamine compound or a polyamine compound . Mixtures of two or more amide/compounds can be used as a mixture of one or more amino acids/compounds according to the invention. acylation reagents. Preferably, the amine compound is contains at least one primary amino group (i.e. -NH2), more preferably Preferably, the amine is a polyamine, especially one containing at least two -NH- groups. polyamine). Either or both of these -NH- groups are amine or secondary amine. This amine includes aliphatic amines, cycloaliphatic amines, amines, aromatic amines or heterocyclic amines. From this Botmin, usually , with dispersant/detergent additives compared to derivative compositions derived from monoamines. more effective carboxylic acid derivative compositions are obtained, and furthermore, these preferred From new polyamines, carboxylic acid derivative compositions exhibiting more remarkable V] improved properties. is obtained.

Among the preferred amines are alkylene polyamines, including polyalkylene polyamines. There is Min. Examples of this alkylene polyamine include those conforming to the following formula: where n is from 1 to about 10; each R3 is independently a hydrogen atom, a hydro Carbyl group or hydroxy-substituted hydrocarbyl group or amine-substituted hydrocarbyl group or hydroxy-substituted hydrocarbyl group or amine-substituted hydrocarbyl group building groups (these have up to about 30 atoms) or different nitrogen groups Two R3 groups on an atom may be joined together to form a U group, provided that at least one R group is a hydrogen atom and U has from about 2 to about 10 carbon atoms It is an alkylene group. Preferably U is ethylene or propylene. each An alkylene polyamine in which R3 is hydrogen or an amine-substituted hydrocarbyl group is , particularly preferred are ethylene polyamines and mixtures of ethylene polyamines, Most preferred. Typically, n has an average value of about 2 to about 7. Alkire like this Examples of polyamines include methylene polyamine, ethylene polyamine, and butylene polyamine. Reamin, Propylene polyamine, Bentirene podiamine, Hegylene podium and heptylene polyamine. Higher analogues of such amines and related aminoalkyl-substituted piperazines are also included.

As an alkylene polyamine useful in preparing the carboxylic acid derivative composition (A) These include ethylenediamine, triethylenetetramine, propylenediamine, and triethylenediamine. Methylene diamine, hexamethylene diamine, decamethylene diamine, octame Chylenediamine, di(heptamethylene)triamine, tripropylenetetramine Tetraethylene pentamine, trimethylene diamine, pentaethylene hexa mino, di(trimethylene)triamine, N-(2-aminoethyl)piperazine, Examples include 1,4-bis(2-aminoethyl)piperazine. 2 types or Higher homologues obtained by condensation of more than one of the above alkylene amines are Mixtures of two or more of any of the above polyamines are useful as well.

Ethylene polyamines (e.g., those mentioned above) are of special interest due to cost and effectiveness. It is useful for Such polyamines are classified under the heading "Diamines and higher amines" So, The Encylopedja of Chemical Techn. ology (2nd edition, Kirk and Othmer, vol. 7, p. 27-39, I terscience Publishers, Division of John Wiley and 5ons, 1965). , the contents of which are incorporated herein by reference for their disclosure of useful polyamines. It is being used. Such a compound is a combination of alkylene chloride and ammonia. By reaction or with ethyleneimine, open 11i! reagents (e.g. ammonia, etc.) ) is most conveniently prepared by reaction with These reactions produce alkylene complex m1xture of polyamines (in which (including cyclic condensation products such as piperazine). this mixture is particularly useful in preparing the carboxylic acid derivative (A) useful in the present invention.

On the other hand, the use of pure alkylene polyamines also gives very good results. things can be obtained.

Other useful types of polyamine mixtures include strippers of the polyamine mixtures listed above. There are things that can be gained by In this case, low molecular weight polyamines and volatile The organic impurities are removed from the alkylene polyamine mixture and A residue often referred to as ” is left behind. Generally, alkylene boria amino bottoms are , less than 2%, usually 1% (by weight) of substances that boil below about 200'C. The group 11:) may be characterized as having a lesser amount. ethyleneboso Amino bottoms (which are readily available and have proven to be extremely useful) ), the bottoms have a total weight of less than approximately 2% (by weight). amount of diethylenetriamine (DETA) or triethylenetetramine (TET Contains A). Dov Chemical Company (Freeboard, A typical sample of such ethylene polyamino bottoms is obtained from (This is called rE-100J) is heated to 15.6℃ and 1.016℃. Specific gravity of 8, 33, ts weight j 1% nitrogen percent, and 121 at 40'C The viscosity was centistokes. Gas chromatography content of such samples Analysis shows that this is approximately 0.93% of "Light Ends J ( (mostly DETA), 0.72% TETA, 21.74% Tet laethylenepentamine, and 76, 61% and more (frj1 group 1m) It was shown that it contains pentaethylene hexamino. These Algyu Shimpoji Aminobottoms include cyclic condensation products (e.g. piperazine) and , including higher congeners such as 7-triamine and triethylenetetramine. .

When this amine reaction component consists essentially of alkylene polyamine bottoms, These alkyleneboriyamino bottoms can be reacted alone with acylating agents. or they can be combined with other amines and polyamines, or alcohols or may be used with mixtures thereof. In the latter case, at least one amino The reaction component contains alkylene boria amino bottoms.

Other polyamines which can react with the acylating agent (A-1) according to the invention are, for example: As described in U.S. Patent Nos. 3.219.666 and 4.234.435. Ru. The content of these patents is that the carboxylic acid derivatives of the present invention are The disclosure of amines capable of forming body (B) is incorporated herein by reference. ing.

In other embodiments, the amine can be a hydroxyamine. Typically, These hydroxyamines can be primary, secondary or tertiary alkanolamines. or a mixture thereof. Such amines may be represented by the formula: H2N-R'-OH(Vl+) and R'+N(H)-Ro-OH(Vlll) where each R'+ is independently one a hydrocarbyl group having ~8 carbon atoms, or 2 to about 8 carbon atoms , preferably a hydroxyhydrocarbyl group having from 1 to about 4 carbon atoms. and Ro has about 2 to about 18 carbon atoms, preferably 2 to about 4 carbon atoms. is a divalent hydrocarbyl group having carbon atoms. -R' in such a formula The -OH group represents a hydroxyhydrocarbyl group. R” is an acyclic group, an alicyclic group or an aromatic group. Typically, Ro is an acyclic straight or branched chain Alkylene groups (e.g. ethylene, 1,2-propylene, 1,2-butylene, 1 ．． 2-octadecylene, etc.).

When two R'+ groups are present in the same molecule, they form a direct carbon-carbon bond. bond by or through a heteroatom (e.g. oxygen, nitrogen or sulfur) to form a 5-, 6-, 7-, or 8-membered ring structure. complex like this Examples of cyclic amines include N-(hydroxyl lower alkyl)-morpholine, -thiomo Includes luforin, -piperidine, -oxazolidine, -sonaplidine, etc. . Typically, however, each R'+ is independently a methyl group, an ethyl group, a It is a lopyl group, a butyl group, a pentyl group or a hexyl group.

Examples of these alkanolamines include monoethanolamine, jetanolamine, triethanolamine, diethylethanolamine, ethylethanolamine amine, butyljetanolamine, and the like.

These hydroxyamines are also ether N-(hydroxyhydrocarbyl) Can be an amine. These are the hydroxypoly(hydrocarbons) of the above hydroxyamines. These analogs also include hydroxyl-substituted oxy/alkyloxy) analogs. (including ren analogues). Such N-(hydroxyhydrocarbyl) Amines may be conveniently prepared by reaction of epoxides with the above amines, followed by It can be represented by the formula: H2N-(R'O)-H(IX) where X is a number from about 2 to about 15, and R+ and Ro are the same as above. It is. R’+ is also a hydroxypoly(hydrocarpyrocarbon) group obtain.

The carbon produced from the above acylation reagent (A-1> and amine compound (A-2)) The rubonic acid derivative composition (A) contains an unarylated amine. Amines include amine salts, amides, imides, amidines, amido acids (am idic acids), amidic acid salts (amidic 5 alts) and Included are imidacillin and also mixtures thereof. Acylation reagent and To prepare carboxylic acid derivatives from amino compounds, one or more /coupling reagent and one or more amino compounds, if necessary, in a normal solution. These reactions are carried out from about 80°C in the presence of a substantially inert organic solvent/diluent. at a temperature up to the decomposition point of either the active ingredient or the carboxylic acid derivative. Usually about 00°C to about 300'C (however, 300'C does not exceed this decomposition point) ). Typically, temperatures of about 25°C to about 250'C are used. It will be done. The acylation reagent and amino compound are added to approximately A sufficient amount is reacted to provide 172 equivalents up to about 2 moles of amine compound.

In this acylation reagent (A-1), a conventional high molecular weight acylating agent reacts with an amine. Because it can react with amine compound (A-2) in the same manner as U.S. Pat. No. 3.172.892; No. 3.219,666; No. 3.272.746; and No. 4.234.435 disclose that the acylation reagents and amino acids described above are With respect to methods that may be applied to react with compounds, ing.

In order to produce carboxylic acid derivative compositions that exhibit improved viscosity index performance, generally , it is necessary to react this acylation reagent with a polyfunctional amine reaction component. I know that.

For example, two or more primary amine groups and/or secondary amine groups Preferred are polyamines having However, clearly this acylation reagent and Not all reacting amino compounds need to be polyfunctional. Therefore, ■sensuality A combination of an amino compound and a polyfunctional amine compound is used.

The acylating agent may be present in an amount of about 0.5 parts to 11 to 2 moles per equivalent of unpurifying agent. React with amine compound. In other embodiments, the amount of amine is 1 equivalent of affluating agent. It can range from 0.7 equivalents to about 15 equivalents per amount.

In other embodiments, the acylating agent is present in an amount of about 0.5 equivalents per equivalent of untying agent. , often from 0.7 equivalents to less than 1 equivalent (e.g., about 0.95 equivalents M) react with an amine compound.

The lower limit of the equivalent of the amine compound is 0.75 equivalent or Furthermore, it is 0.80 equivalent, and the upper limit is about 0.90 equivalent or 0.95 equivalent. could be. Therefore, the acylating agent (A-1) for the amine compound (A-2) A narrower range of equivalents is from about 0.70 equivalents to about 0.90 equivalents, or about 0.75 equivalents. The amount can be from about 0.90 equivalents to about 0.90 equivalents, or from about 0.75 equivalents to about 0.85 equivalents. less In some situations, the equivalent of amine compound per equivalent of acylating agent is about 0°75 or less, the effect of the carboxylic acid derivative as a dispersant will decrease. is clear.

In still other embodiments, the acylating agent is about 1.0% per equivalent of acylating agent. React with 0 equivalents to 2 moles of amine. In many cases, this acylating agent is About 10 equivalents or 1.1 to 1.5 equivalents of acylating agent per equivalent of acylating agent. React with Min.

of the amine compound (A-2) to be reacted with the acylating agent (A-1) within the above range. The amount may also depend in part on the number and type of nitrogen atoms present. For example, certain In order to react with the silating agent, a port containing one or more -NH2 groups is used. Reamines have the same number of nitrogen atoms but fewer or no −NH2 groups. Less amount is needed than with no polyamine. One -NH2 group and two -Coo)I group to form an imide.

If only secondary nitrogen is present in the amine compound, each 〉NH group can contain only one can react with the -Cool group of Therefore, within the above range, the reaction with this acylating agent is The amount of polyamine that forms the carboxylic acid derivative of the present invention is determined by the amount of polyamine in this polyamine. the number and type of nitrogen atoms in (i.e. -Nl2, >NHl and 〉N-) It can be easily determined if considered.

The acylating agent used to form this carboxylic acid derivative composition (A) and In addition to the relative amounts of carboxylic acid derivatives and amine compounds used in the present invention, Other characteristics are the Mn value and it/in value of the polyalkene, and the substituent For each equivalent of The succinic acid group is present in the acylating agent. This carboxylic acid derivative composition When (A) has all these characteristics, the lubricating oil composition of the present invention is suitable for internal combustion engines. characterized by improved performance in

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

This saponification value is determined by the reaction mixture at the end of the reaction (this is generally determined by the example below). unreacted polyalkylene present in the filtrate or residue) It is corrected by taking into account the This saponification value is determined using the ASTM D-94 method. determined.

The formula for calculating the ratio from the saponification value is as follows: The corrected saponification value is the saponification value , obtained by dividing by the proportion of reacted polyalkene. For example, a 10% point If Rialken does not react and the saponification value of the filtrate or residue is Kata 95 , the corrected saponification value is the value obtained by dividing 95 by 0.90, that is, ios, s. Ru.

The preparation of this acylating agent is illustrated in Examples 1-6 below.

The preparation of carboxylic acid derivative composition (A) is illustrated in Examples A-1 to A-29 below. do. In the Examples below, and elsewhere in the specification and claims, other (f) All percentages and parts are by weight, unless explicitly indicated otherwise. Degrees are degrees Celsius and pressures are atmospheric pressure. Desired unbinding agent Cyo, time↓koha , in these examples, other substances present and their amounts are specifically determined by ζ. Example 1 Polyisobutyne (Mn=1845; Mw=5325) 510 parts (0.28 parts ) and 59 parts (0.59 mol) of maleic anhydride to 110°C. Heat. This mixture is heated to 190° C. for 7 hours. During this time, gaseous chlorine 43 parts (0.6 mol) are added subsurface. 190-192’C, additional salt 11 parts (0.16 mol) of element are added over 3.5 hours. This reaction mixture by heating at 190-193°C for 10 hours while blowing nitrogen. , to strip. This residue is converted into the desired polyisobutylene-substituted succinate. saponification agent, which has a saponification equivalent of 87 as determined by ASTM method D-94. It has a quantity number.

Example 2 Polyisobutyne (Mn=2020; Mw=6049) 1000 parts (0.49 5 mol) and 115 parts (1.17 mol) of maleic anhydride at 110° Heat to 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. 184-18 At g'C, an additional 59 parts (0,113 moles) of chlorine are added over 4 hours.

The reaction mixture was heated at 186-190°C for 26 hours with nitrogen bubbling. Stripping is done by:

This residue is the desired polyisobutyne-substituted succinic acylating agent, which is It has a saponification equivalent number of 87 as determined by ASTM method D-94.

Example 3 Polyisobutyne chloride (This is polyisobutyne (Mn・1696; gw・65 94) Add 251 parts of gaseous chlorine to 3000 parts over 4.66 hours at 80°C. (prepared by adding) and 345 parts of maleic anhydride. The mixture is heated to 200° C. for 0.5 hours. This reaction mixture was mixed with 200 to 22 maintained at 4°C for 6.33 hours, stripped at 210’C under vacuum, and Filter. This filtrate is the desired polyimbutene-substituted succinic acylating agent; It has a saponification equivalent number of 94 as determined by ASTM method D-94.

Example 4 1 mole of chlorinated polyisobutylene and 1 mole of maleic anhydride are reacted at 200°C. to prepare polyisobutenyl succinic anhydride. This polyisobutenyl group is The substituted succinic anhydride obtained has an average molecular weight of 850 and an acid value of 113. (corresponding to an equivalent weight of 500).

Example 5 Chlorinated polyisobutylene (with approximately 1050 in and 4.3% chlorine content ) and 1 mole of maleic anhydride at a temperature of about 200°C to form 105 A polyisobutenyl succinic anhydride having an acid number of 540 and an equivalent weight of 540 is prepared.

Example 6 1 mole of maleic anhydride and 1 mole of chlorinated copolymer of imbutylene and styrene A substituted succinic anhydride is prepared by reacting with This copolymer has 9 Consisting of 4 parts by weight of inbutylene units and 6 parts by weight of styrene units, approximately 120 parts by weight It has an Mn of 0 and is chlorinated to a chlorine content of 2.8% by weight.

The substituted succinic anhydride obtained has an acid number of 40.

Carbon A Example A-1 Commercial mixture of ethylene polyamine 1o, z parts (o, zs per ff1) (this is , having about 3 to 10 nitrogen atoms per molecule) was added to 113 parts of mineral oil and 1 A mixture is prepared by adding 61 parts (0.25 equivalents). This reaction mixture The mixture was heated to 150°C for 2 hours and stripped with nitrogen. ing. The reaction mixture is filtered to give the desired product as an oil solution. A liquid is obtained.

Example A-2 57 parts (1,38 parts jl) of a commercially available mixture of ethylene polyamine (this about 3 to 10 nitrogen atoms per nitrogen) in 1067 parts of mineral oil and a substituted copolymer. Huccinic acid acylating agent (which was prepared in Example 2 at 140-145°C) 8 A mixture is prepared by adding 93 parts (1,38 equivalents). This reaction mixture The mixture was stripped by heating to 155°C for 3 hours and bubbling with nitrogen. Ping. Filtering the reaction mixture yields the desired product as an oil solution. A filtrate is obtained.

Example A-3 1132 parts of mineral oil and 709 parts of the substituted succinic acylating agent prepared in Example 1 (1, 2 equivalents). 56.8 parts (1,32 equivalents) of piperazine in water 2 00 parts of the above solution from the addition funnel at 130-140°C for approximately 4 hours. Add slowly to mixture.

Continue heating to 160°C while removing water. This mixture is 160 to 165 Maintain at 1 hour and cool overnight. Reheat this mixture to 160°C After that, maintain this temperature for 4 hours. Add mineral oil (270 parts) and filter the mixture. Filter with filter aid at 150"C. The filtrate is filtered with 0.65% nitrogen (theoretical value 0 ．． 86%) of the desired product in oil (65% oil).

Example A-4 1968 parts of mineral oil and 1508 parts of the substituted succinic acid affluating agent prepared in Example 1 (2 , 5 eq.) is heated to 145°C. Then, used in Example A-1. 125.6 parts (3.0 equivalents) of a commercially available mixture of ethylene polyamines were added to the reaction temperature. Add over 2 hours while maintaining temperature at 145-150°C. This reaction mixture The mixture was stirred at 150-152°C for 5.5 hours with nitrogen bubbling. do.

The mixture is filtered at 150'C using a filter aid. This filtrate is 1.20% An oil solution of the desired product containing 1.17% of nitrogen (theoretical 1.17%). il).

Example A-5 4082 parts of mineral oil and a commercially available ethylene polyamine of the type used in Example A-1. 250.8 parts (6.24 equivalents) of the mixture is heated to 110°C. . Then, 3136 parts (52 equivalents) of the substituted succinic acylating agent prepared in Example 1 was added. ) over a period of 2 hours. During the addition, the temperature was increased to 110°C while blowing nitrogen. The mixture was heated to 160 °C when the amine was added at 0 to 120 °C. Heat to C and maintain at this temperature for about 6.5 hours while removing water.

The mixture is filtered at 140°C using a filter aid. This filtrate is 1.17% An oil solution of the desired product (55% is an oil solution containing 1.18% theoretical) il).

Example A-6 4158 parts of mineral oil and 3136 parts of the substituted succinic acylating agent prepared in Example 1 (5 , 2 eq.) is heated to 140"C. Then in Example A-1 312 parts (7.26 equivalents) of the commercially available mixture of ethylene polyamines used were Add over 1 hour while increasing to 140-1 s o'c. this mixture was maintained at 150°C for 2 hours with nitrogen bubbling, and then at 160’C for 3 hours. maintain for a while. The mixture is filtered using a filter aid at 140°C. This filtrate l, an oil solution of the desired product containing 44% nitrogen (theoretical 1.34%). liquid (55% oil).

Example A-7 Commercially available mixture 2 of 4053 parts of mineral oil and ethylene polyamine used in Example A-1 A mixture of 87 parts (7,14 parts II) is heated to 110'C. after that , 3075 parts (51 equivalents) of the substituted succinic acylating agent prepared in Example 1 was added at a temperature of is added over a period of 1 hour while maintaining the temperature at approximately 110°C. This mixture was heated for 2 hours. Heat to 160° C. and maintain at this temperature for a further 4 hours. next The reaction mixture is then filtered using a filter aid at 150°C.

This filtrate contains the desired product containing 1.33% nitrogen (theoretical 1.36%). It is an oil solution (55% oil).

Example A-8 1503 parts of mineral oil and 1220 parts of the substituted succinic acylating agent prepared in Example 1 (2 heat the mixture to 110°C. Then, used in Example A-1 120 parts (3 parts) of a commercially available mixture of ethylene polyamines of the type The reaction mixture was stirred for an additional 30 minutes at 110’C. , the temperature is then increased and maintained at about 151°C for 4 hours. Add filter aid Filter this mixture. This filtrate contained 1.44% nitrogen (theoretical value 1°49%). It is an oil solution (53.2% oil) containing the desired product.

Example A-9 Commercially available mixture of 3111 parts of mineral oil and ethylene polyamine used in Example A-1 8 44 parts (21 eq.) is heated to 140°C. Then, examples 3,885 parts (7.0 equivalents) of the substituted co/% phosphoric acid acylating agent prepared in Step 1 were added at a temperature of approx. The temperature is increased to 150°C and the mixture is added for about 1°75 hours. Blow in nitrogen The mixture was maintained at 150-155°C for about 6 hours and then heated at 130°C. Filter using a filter aid. This filtrate contains 3.5% nitrogen (theoretical value 3.78%) (40% oil) of the desired product containing.

Example A-10 18.2 parts (0,433 equivalents) of a commercially available mixture of ethylene polyamines (which contains 1 about 3 to 10 nitrogen atoms per molecule) in 392 parts of mineral oil and a substituted copolymer. 348 parts of phosphoric acid acylating agent (which was prepared at 140° C. in Example 2) A mixture is prepared by adding (0.52 eq.). This reaction mixture , by heating to 150°C for 1.8 hours and blowing nitrogen Google. The reaction mixture was filtered to give an oil solution of the desired product (55% oil). A filtrate is obtained.

Example A-11 Appropriately sized flask (this includes a stirrer, nitrogen inlet, addition funnel, and the acylating agent described in Example 3). A mixture of 2483 parts (4.2 equivalents) and 1104 parts of oil is charged. This mixture Heat the mixture to 210”C. During this time, slowly sparge the mixture with nitrogen. . At this temperature, about 1 liter of ethylene polyamine mixture (134 parts, 3.14 equivalents) Add slowly over time. The temperature was maintained at about 210°C for 3 hours, then Add 3688 parts of oil and reduce the temperature to 125°C. at 138°C After storage for 17.5 hours, the mixture was filtered through diatomaceous earth to obtain the desired acyl. A 65% oil solution of amino bottoms is obtained.

Example A-12 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 is then added with ethylene poly Commercially available mixtures of amines containing about 3 to 10 nitrogen atoms per molecule 210 parts (5.25 eq.) of Maintain at 0'C for an additional 0.5 hour. Heat at 155°C for 6 hours without removing water After that, the filtrate is added and the reaction mixture is filtered at about 150°C. This filtrate is , a solution of the desired product in oil.

Example A-13 0.8 equivalents of the substituted succinic acylating agent prepared in Example 1 was added to ethylene polyamine. The general procedure of Example A-12 was followed, except by reacting with 0.67 equivalents of a commercially available mixture of Repeat the law. The product obtained in this way is a product containing 55% diluent oil. It is an oil solution.

Example A-14 The polyamine used in this example is a mixture of equivalent amounts of the following alkylene polyamines: The general method of Example A-12 is repeated except that: This alkylene polyamide The mixture was made from ethylene polyaminocarbon obtained from Union Carbide. Toms 80% and ethylene corresponding to diethylenetriamine in the empirical formula Contains 20% of a commercial mixture of polyamines. This polyamine mixture has approximately 43 It is characterized as having an equivalent weight of 3.

Example A-15 The polyamine used in this example was ethylenebolyaminobutylene obtained from Dot. Containing a mixture of 80 parts by weight of Toms and 220 parts by weight of diethylene triamine. The general method of Example A-12 is repeated except that. This mixture of amines has approximately 4 It has an equivalent weight of 1.3.

Example A-16 444 parts (0.7 equivalents) of the substituted succinic acylating agent prepared in Example 1 and 5 parts of mineral oil. Prepare a mixture with 63 parts and heat to 140°C.

Soreka et al., ethylene polyamide corresponding to triethylenetetramine in the experimental formula 22.2 parts (0.58 eq.) of the mixture were added to the Add over time. Bubble the mixture with nitrogen while heating to 150°C. and maintain at this temperature for 4 hours, removing water. Then this mixture is filtered through a filter aid at about 135°C, the filtrate contains about 55% mineral oil. An oil solution containing the desired product.

Example A-17 422 parts (0.7 equivalents) of the substituted conolic acid acylating agent prepared in Example 1 and mineral oil Prepare a mixture with 188 parts and heat to 210°C.

Then, a commercial mixture of ethylene polyamino bottoms obtained from Dot Company 2 Add 2.1 parts (0.53 parts) 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. mineral oil (625 parts) and the mixture is maintained at 135°C for about 17 hours. Or is it? When this mixture is filtered, the filtrate is an oil solution (65%) of the desired product. is oil).

Example A-18 The polyamine used in this example has about 3 to 10 nitrogen atoms per molecule. Example 1, except that it is a commercially available mixture of ethylene polyamines (equivalent weight is 42). Repeat the general method of F-17.

Example A-19 414 parts (0.71 equivalents) of the substituted phosphoric acid unlying agent prepared in Example 1 and the mineral A mixture with 183 parts of oil is prepared. Heat this mixture to 210°C or commercially available mixtures of ethylene polyamines, containing about 3 to 10 polyamines per molecule. 20.5 parts (0.4 g equivalent) of nitrogen atoms) at a temperature of 210-217 Add over approximately 1 hour while increasing the temperature. This reaction mixture was sparged with nitrogen. Maintain this temperature for 3 hours while watching and then add 612 parts of mineral oil. this mixture is maintained at 145°C to 135°C for about 1 hour and at 135°C for 17 hours. . This mixture is filtered while hot and the filtrate contains an oil solution of the desired product. liquid (65% oil).

Example A-20 414 parts (0.71 equivalents) of the substituted succinic acylating agent prepared in Example 1 and mineral oil Prepare a mixture with 184 parts. Heat this mixture to about 80°C and then , 22.4 parts (0,534 equivalents) of melamine are added. Mix this mixture for about 2 hours. Heat to 160° C. and maintain at this temperature for 5 hours. - After cooling overnight, this mixture The material was heated to 170°C for 2°5 hours and heated to 21°C for 15 hours. Heat to 5°C. This mixture was maintained at about 215°C for about 4 hours and about Maintain at 220°C for 6 hours. - After cooling overnight, the reaction mixture was filtered at 150°C. Filter with supernatant. This filtrate is a solution of the desired product in oil (30% mineral oil). ).

Example A-21 414 parts (0.71 equivalents) of the substituted acylating agent prepared in Example 1 and 184 parts mineral oil Heat the mixture to 210°C. Then, in the empirical formula, tetraethyl 21 parts of a commercially available mixture of ethylene polyamines corresponding to lempentamine (0,53 equivalent amount) for 0.5 hour while maintaining the temperature at about 210-217°C. I can do it. Once the polyamine addition was complete, the mixture was blown with nitrogen. Maintain at 217°C for 3 hours. Add mineral oil (613 parts) and heat the mixture to approximately 135° Maintain at C for 17 hours and filter. This filtrate is an oil solution of the desired product. (65% mineral oil).

Example A-22 414 parts (0.71 equivalents) of the substituted acylating agent prepared in Example 1 and 183 parts mineral oil Prepare a mixture with and heat to 210°C. Then, ethyleneamine potum While blowing nitrogen, 18.3 parts (0.44 equivalents) of Add over time. This mixture was heated to about 210-217°C for about 15 minutes. Heat and maintain at this temperature for 3 hours. An additional 608 parts of mineral oil was added and the mixture was Maintain at approximately 135°C for 17 hours. This mixture was filtered through a filter aid at 135°C. Upon filtration, the filtrate is an oil solution (65% oil) of the desired product.

Example A-23 Ethyleneamine Potatomus is mixed with an equivalent amount of ethylenepolyamine (this is per molecule with about 3 to 10 nitrogen atoms). Repeat the general method of Example A-22.

Example A-24 422 parts (0.70 equivalents) of the substituted acylating agent prepared in Example 1 and 190 parts mineral oil Heat the mixture to 210'C. Then, ethyleneamine bottoms ( Dot) 26.75 parts (0,636 equivalents) for 1 hour while blowing nitrogen. Add over. After all of the ethylene amine has been added, the mixture is 215°C for approximately 4 hours and to this mixture, with stirring, 632 parts of mineral oil. Add. The mixture was maintained at 135°C for 17 hours and filtered with filter aid. do. The filtrate is an oil solution (65% oil) of the desired product.

Example A-25 468 parts (08 equivalents) of the substituted succinic acylating agent prepared in Example 1 and 90 parts of mineral oil. Heat the mixture with 81 parts to 142°C. Then, ethyleneamine bottom Mus (Dot) 28.63 parts (0.7 equivalents) over 1.5 to 2 hours Add. The mixture is stirred for an additional 4 hours at about 142°C and filtered. child The filtrate is an oil solution (65% oil) of the desired product.

Example A-26 A mixture of 2653 parts of the substituted acylating agent prepared in Example 1 and 1186 parts of mineral oil was , heat to 210°C. Then maintain the temperature between 210°C and 215°C. Shinaga murmured 154 parts of ethyleneamine bottoms (Dot) over 1.5 hours. Add. This mixture is maintained at 215-220°C for about 6 hours. 210°C mineral oil (3953 parts) was added and the mixture was sparged with nitrogen at 135-128°C. Stir for 17 hours while watching the heat. Once filtered, the filtrate is an oil solution (65%) of the desired product. It is.

Example A-27 Soo part (1 equivalent) of polyisobutenyl succinic anhydride prepared in Example 4 and 35 parts (1 equivalent) of diethylenetriamine was added to a mixture with 160 parts of ene at room temperature. Add. This addition should be done in portions over 15 minutes to allow for an initial exothermic reaction. The temperature rises to about 50°C. Heat this mixture to remove water-tol from the mixture. Distill the ene azeotrope. Once no more water is distilled, the mixture is depressurized. Heat to 150'C below to remove toluene. This residue was mixed with 300 parts of mineral oil. The solution is found to have a nitrogen content of 1.6%.

Example A-28 300 parts by weight of polyisobutenyl succinic anhydride prepared in Example 5 and 160 parts by weight of mineral oil. At 65-95°C, an equivalent amount (25 parts by weight) of Polyami neH (this is an ethyl alcohol with an average composition corresponding to tetraethylenepentamine) Add renamine mixture). This mixture was then heated to 150"C The water formed in this reaction is then distilled. Blow nitrogen into the mixture at this temperature Make sure to remove any remaining water. This residue was mixed with 79 parts by weight of mineral oil. When diluted, the oil solution is found to have a nitrogen content of 1.6%.

Example A-29 710 parts (0.51 equivalents) of the substituted succinic anhydride prepared in Example 6 were added to 5 parts of toluene. Add 22 parts (051 parts) of Polyamine H little by little to 00 parts. . This mixture was heated at reflux temperature for 3 hours to remove the azeotropic distillation of the Remove any water that may be present. The mixture was then heated to 150°C/20mm and Remove luene.

This residue contains 1.1% by weight of nitrogen.

The lubricating oil compositions of the present invention also include (B) a hydrocarbyl-substituted carboxylic acid or a hydrocarbyl-substituted carboxylic acid; of a mixture of locarbyl-substituted carboxylic acids and hydrocarbyl-substituted succinic acids. contains a remetal overbased salt, with the proviso that the carboxylic acid in the mixture is Contains more than 50% of the acid equivalents of this mixture. The hydrocarbyl position of this carboxylic acid Substituents generally contain at least 50 carbon atoms.

a hydrocarbyl-substituted carboxylic acid contained in the lubricating oil composition of the present invention, or The amount of alkali metal overbased salt in the mixture of carboxylic acid and sulfonic acid is , at least about 0.002 equivalents of alkali per 100 grams of the lubricating oil composition. The amount is sufficient to provide remetallization. In other embodiments, this lubricating oil composition 1 at least about 0.003 equivalents per 00 grams, and even at least Sufficient alkali metal overbase to provide about 0.005 equivalents of alkali metal A salt is included in the lubricating oil composition.

This alkali metal overbased salt (B) reacts with the metal and the metal in excess of the amount present according to the stoichiometry of a particular hydrocarbyl-substituted carboxylic acid It is characterized by its metal content. The amount of excess metal is usually expressed by the metal ratio. , which is the ratio of the total equivalents of metal to the equivalents of acidic organic compound. For example, positive A salt that has 4.5 times as many metals as there are in the salt has a metal ratio of 4.5. It is characterized by In the present invention, the alkali metal overbased salt comprises 1 A metal ratio of greater than, preferably at least about 1.5 or at least about 2 or has a metal ratio of 3 to about 30 or even about 40. Further pond implementation In embodiments, the metal ratio is at least about 6.5.

In one embodiment of the invention, the alkali metal oil used in the lubricating oil composition of the invention The metal ratio of the barbased salt (B) is per equivalent of substituent in the acylating agent (A-1). is related to the ratio of succinic acid groups. For example, if the acylating agent Contains on average from at least 1 to less than 1.3 succinic acid groups, relative to the amount containing a carboxylic acid derivative (A) prepared from such an acylating agent. The metal ratio of the alkali metal overbased salt used in lubricating oil compositions at least 2 or 3, and in preferred embodiments at least about 6.5 .

This carboxylic acid derivative (A) has at least 1.3 on average in its structure. derived from an acylating agent characterized by the presence of a succinic acid group of and the alkali metal overbase used in combination with such acylating agents. The metal ratio of the sulphide salt (B) is greater than 1, preferably at least about 1.5. Ru.

The alkali metal overbased composition contains an acidic substance (which is typically carbon dioxide) and a carboxylic acid or a mixture of a carboxylic acid and a sulfonic acid, Alkali metal compounds (typically metal oxides or metal hydroxides), promoters, and at least one inert organic diluent for the carboxylic acid compound. It is prepared by reacting a mixture with.

The hydrocarbyl-substituted carboxylic acid has at least about 50 hydrocarbyl groups. may be characterized as containing up to about 300 or 400 carbon atoms. derived from polyalkenes. In one embodiment, the polyalkene is at least from about 900 or 1000 to about 2500 or even about 5000 , Mn value. This hydrocarbylsulfonic acid hydrocarbyl The group contains at least about 8 carbon atoms, and in other embodiments at least Contains about 20 or even 50 carbon atoms.

The polyalkenes from which the hydrocarbyl substituents of this acid are derived include 2 to about 1 6 carbon atoms, usually 2 to about 6 carbon atoms, preferably 2 to about 4 carbon atoms Homopolymers and interpolymers of polymerizable olefin monomers having carbon atoms Rimmer is an example. These olefins are monoolefins (e.g. ethylene polyethylene, propylene, 1-butene, isobutene and 1-octene), or polyol Lefinic monomers (preferably diolefinic monomers (e.g. 1,3- butadiene and isoprene)). These polyalkenes are prepared by the method. The hydrocarbyl substituents of conohydric and sulfonic acids are Still other examples of polyalkenes that can be derived include: Any of the above related polyalkenes is included and such polyalkenes are Certain contents of the described specification are incorporated herein by reference.

Hydrocarbyl-substituted compounds useful in preparing the alkali metal salts used in this invention When preparing rubonic acids, one or more of the polyalkenes described above are one or more α,β-unsaturated monocarbons by methods well known in the art. React with acid reagent or dicarboxylic acid reagent. For example, polyisobutyne and ・The halogenated hydrocarbon obtained from the halogenating agent is heated to an appropriate temperature (for example, 80° C or higher), by mixing these reaction components, α, β-unsaturated can be reacted with carboxylic acid reagents. This reaction requires the presence of an inert solvent or diluent. It can be done below.

This α,β-unsaturated monocarboxylic acid reagent is suitable for acids, esters, amides, imides, It can be an ammonium salt, or a halide. It is preferably about 12 Contains fewer carbon atoms. Examples of such monocarboxylic acids include, for example: Acrylic acid, methacrylic acid (α-methylacrylic acid), crotonic acid , cinnamic acid, α-ethyl acrylic acid, α-phenylacrylic acid, α-octyl acrylic acid Acrylic acid, β-brobyl acrylic acid, β-octyl acrylic acid, β-cyclohexyl Silacrylic acid, α-cyclopentyl acrylic acid, β-decyl acrylic acid, α- Methyl-β-pentylacrylic acid, α-propyl-β-phenylacrylic acid, α -chloroacrylic acid, α-bromoacrylic acid, β-chloroacrylic acid, α-chloroacrylic acid Rocrotonic acid, incrotonic acid, α-methylcrotonic acid, α-methylisocrotonic acid Examples include phosphoric acid, β, β-dichloroacrylic acid, and the like.

Esters of such α,β-unsaturated carboxylic acids, especially those in which the ester group is a lower alkyl derived from canols (i.e., those having less than about 8 carbon atoms) Esters are also useful in the present invention. Specific examples of such esters include , methyl acrylate, methyl methacrylate, ethyl acrylate, acrylic acid lohexyl, cyclopentyl methacrylate, neopentyl α-phenylacrylate Hexyl α-propyl-β-propylacrylate, β-decyl acrylate This includes cutyl and the like. Other alcohols (e.g., decyl alcohol, shrimp) Lorohydrin, β-chloroethanol, dodecyl alcohol, and 4-bromo Other esters are also considered, such as those derived from -1-decanol). be done.

Still other esters useful in the present invention are those derived from phenolic compounds. exemplified by Le. These phenolic compounds include phenol, naphthol, Talesol, 0-butylphenol, m-butylphenol, tertiary butylphenol Lefe/-le, 0. p-; isopropylphenol, α-decyl-β-naphthol p-dodecylphenol, and other alkylphenols and alkylphenols. phthol (where the alkyl substituent preferably has less than about 12 carbon atoms) ) are included.

The halides of this α,β-unsaturated monocarboxylic acid are mainly chlorides and It is a bromide. These are acrylyl chloride, methacrylyl bromide , α-phenylacrylyl chloride, β-decyl acrylicyl chloride and , further exemplified by the chlorides and bromides of the acids exemplified above. α, β -Amides and ammonia salts of unsaturated monocarboxylic acids mainly include derived from monoamines or monoamines (e.g. aliphatic or arylamines). Here are some things that led to this. Such amines include monoalkylamines, dialkylamines, arylamine, trialkylamine or arylamine; these may be e.g. For example, methylamine, dimethylamine, trimethylamine, diethylamine, Phosphorus, toluidine, cyclohexylamine, dicyclohexylamine, Torie Thylamine, melamine, piperazine, pyridine, N-methyloctylamine, N , N-diethylcyclohexylamine, 0-butylaniline, p-decylaniline It includes such things as Additionally, amide and ammonium salts of the above amines are derived. The unsaturated acids include 0 ammonia or primary ammonia, which can be the unsaturated acids exemplified above. Imides of such acids derived from amines are also useful in the present invention; These imides convert two hydrogen atoms of ammonia or primary amine into this α, It is formed by substituting a β-unsaturated monocarboxylic acid with a carboxy group. child Anhydrides of monocarboxylic acids such as Also useful are those formed by dehydration).

α, β-unsaturated monocarboxylic acids can be obtained using the above acids and toners. , for convenience, these are referred to as "α,β-unsaturated monocarphonic acid reagents" or "α,β-unsaturated monocarphonic acid reagents" or "α,β- Note that the general expression “unsaturated monocarboxylic acid-forming compounds” I want to be understood.

Hydrocarbon substitution useful in preparing this alkali metal overbased salt (B) Methods for preparing monocarboxylic acid reagents are described, for example, in U.S. Pat. No. 3,454,607 ( LeSuer et al.), such methods, and the use of such reagents. The descriptions of other examples are incorporated herein by reference.

(Margin below) The examples below illustrate such methods and reagents.

Example 7 Chlorinated polyisobutyne (6 300 grams, 8 equivalents of chlorine) with acrylic acid (940 grams, 13 equivalents) Mix and heat the mixture to 235°C. During this time, hydrogen chloride is generated. Next This is an acid with a chlorine content of 130-2% and an acid number of 63.

Example 8 Acrylic acid (720 grams, 10 equivalents) with a molecular weight of 1000 and 4.3% Chlorinated polyisobutyne with chlorine content (6536 grams, 8 equivalents of chlorine) The mixture was heated at 170-225 °C for 12 hours, then at 200 °C/io m Heat at m. This residue was filtered at 140"C and the filtrate was o, 36% The desired acid has a chlorine content of and an acid number of 6o.

Example 9 Chlorinated isobutyne was combined with isobutyne (98% by weight) and isobutyne on a halogen equivalent basis. A brominated copolymer with Ren (2% by weight), which has a molecular weight of 50,000 and a molecular weight of 2.5 bromine content) and the acrylic acid used was The method of Example 7 is repeated except that phenyl lylate is substituted.

Example 10 Crotonic acid (2 equivalents) and chlorine with a molecular weight of 2500 and a chlorine content of 5% of polypropene (0.5 equivalents of chlorine) at 180-220°C for 5 hours. Heat and then heat to 200°C/1+am. When this residue is filtered, it The filtrate is the desired acid.

Example 11 Chlorinated polyisobutyne with a molecular weight of 1000 and a chlorine content of 4.7% by weight and methyl methacrylate at 140 to 220°C. The methyl ester of a high molecular weight monocarboxylic acid is prepared by:

Hydrocarbyl-substituted radicals useful in preparing alkali metal salts used in the present invention When producing hydrogenated acid, one or more of the above polyalkenes (or halogens) polyalkenes) are maleic acid-reactive components or fumaric acid-reactive components of the following general formula: Reacts with one or more acidic reagents selected from the group consisting of: X(0)C-CH=CH-C(0)X' (X11) Here, X and Xo are are the same or different, provided that at least one of X and Xo is each independently is OH,O-lower hydrocarbyl, 0-M5CISBr, or and Xo can both be -0- to form an anhydride. Usually these The maleic acid reactive component or the fumaric acid reactive component is maleic acid, fumaric acid, anhydrous Leic acid, or a mixture of two or more thereof. These Malays A fumaric acid reactive component is generally preferred over a fumaric acid reactive component. The former is easily available , generally reacts readily with polyalkenes to form the desired hydrocarbyl-substituted succinic acids. This is because it prepares.

The hydrocarbon used to prepare this alkali metal overbased salt (B) The carbyl-substituted succinic acid reagent is a carbyl-substituted succinic acid reagent used as the acylating agent (A-], ). Similar to hydrocarbyl-substituted succinic acid, in which case this hydrocarbyl-substituted Succinic acid contains at least about one succinic acid group for each equivalent of substituent. . Therefore, in one embodiment, the hydrocarbyl-substituted succinic acid is about 1 mole ( and 1 mole (or 2 equivalents) of the maleic acid reaction component. Alternatively, it is prepared by reacting with a fluoric acid reaction component.

Hydrocarbyl substitutions useful in preparing this alkali metal overbased salt Methods for preparing dicarboxylic acid reagents are described, for example, in U.S. Pat. No. 3,087,936 (L eSuer) and No. 3.219.666 (Norman); The disclosure is incorporated herein by reference. This alkali metal salt (B ) Examples of hydrocarbyl-substituted succinic reagents useful in preparing The succinic acylating agents exemplified above at No. 6 are included.

(Margin below) In one embodiment, the carboxylic acid is an aromatic carboxylic acid. useful aromatic cal The group of bonic acids includes those with the following formula: Here, R1 is preferably an aliphatic hydrocarbon derived from the above polyalkene. is a building group, a is a number ranging from 1 to about 4, usually 1 or 2, and A r is an aromatic group and each X is independently sulfur or oxygen, preferably oxygen , b is a number ranging from 1 to about 4, usually 1 or 2, and C is 0 to about 4. The number ranges from 1 to 2, but the sum of a, b and C is the source of Ar. Does not exceed child valence. Examples of aromatic carboxylic acids include substituted benzoic acids, phthalic acids and salicylic acid.

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

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

Examples of aromatic groups useful here include benzene, naphthalene, anthracene, etc. Preferably, polyvalent aromatic groups derived from benzene) are included. Specification of Ar group Examples include phenylene and naphthalene, such as methylphenylene, Phenylene, isopropylphenylene, hydrobovine diphenylene, dipropoxynaf Examples include taren.

Among this group of aromatic acids, the most useful carboxylic acids include those of the formula: where R1 is as defined above and a is a number ranging from 1 to about 4, preferably , a number ranging from 1 to about 3; b is a number ranging from 1 to about 4, preferably 1 to about 3; C is a number in the range of about 2, C is a number in the range of 0 to about 4, preferably 1 to about 2. The number of circles, more preferably l; provided that the sum of a, b and C exceeds 6. No. Preferably b and C are each 1 and the carboxylic acid is It is salicylic acid.

Overbased salts prepared from salicylic acid are particularly useful: In salicylic acid, the aliphatic hydrocarbon substituent (R1) is the polyalkene mentioned above, in particular: Polymerized lower 1-monoolefins (e.g. polyethylene, polypropylene, polymers) (isobutylene, ethylene/propylene copolymer, etc.), and is a carbon precursor. It has an average carbon content of about 50 to about 400 carbons.

The above aromatic carboxylic acids are well known or can be prepared according to methods well known in the art. It can be prepared by Carboxylic acids of the types exemplified by these formulas, and those Methods for preparing neutral and basic metal salts are well known, e.g., U.S. Pat. No. 97.832; No. 2.197.1135; No. 2.252.662; No. 2. No. 252.664; No. 2.714.092; No. 3.410.798; and No. 3.595.7'H. These contents are carboxylic acids, herein incorporated by reference for their disclosure of basic salts and methods for their production. It is being used.

As mentioned earlier, this alkali metal overbased hydrocarbyl substituted carbon Bonic acid is a combination of hydrocarbyl-substituted carboxylic acid and hydrocarbyl-substituted sulfonic acid. may be derived from a mixture. The hydrocarbyl-substituted carboxylic acid in this mixture is containing at least about 50 carbon atoms in the drocarbyl substituent; Carbyl substituents are also specifically defined as having a number average molecular weight of at least about 900. can be marked. Sulfonic acids useful in this mixture include sulfonic acids and thiosulfonic acids. Examples include sulfonic acid. Generally these are salts of sulfonic acids. these Sulfonic acids include l-nuclear or polynuclear aromatic compounds or cycloaliphatic compounds. Included. Oil-soluble sulfonic acids can in most cases be represented by one of the following formulas: :R2T (SO3)aH and R3-(SO3)bH; where T is the cyclic nucleus (e.g., benzene, naphthalene, anthracene, diphenylene oxide, diphenyl phenylene sulfide, petroleum naphthalene, etc.). R2 and R3 are generally , a hydrocarbon group containing from about 4 to about 60 or more aliphatic carbon atoms; a qualitative hydrocarbon group (preferably one that does not contain acetylenic unsaturation); , preferably an aliphatic hydrocarbon group (e.g. alkyl or alkenyl) . When R3 is aliphatic, it usually contains at least about 15 carbons; In the case of an aliphatic-substituted cycloaliphatic group, the number of aliphatic substituents is usually small (at least Contains about 12 carbon atoms. Specific examples of R2 and R3 include petrolatum , derived from saturated and unsaturated paraffin waxes and polyalkenes mentioned above. There is a base. These groups T, R2 and R3 of the above formula can also be those listed above. in addition to other inorganic or organic substituents (e.g. hydroxy, mercap halogens, nitro, amines, nitrones, sulfides, disulfides, etc.) May contain. In the above formula, a and b are at least l.

Specific examples of such sulfonic acids include mahogany sulfonic acid, brightstock Cusulfonic acid, petroleum sulfonic acid, mono- and polywax-substituted naphthalene sulfur Fonic acid, cetylchlorobenzenesulfonic acid, cetylphenolsulfonic acid, cetyl phenol disulfide sulfonic acid, cetoxylic brylbenzene sulfonic acid, Dicetylthianthrene sulfonic acid, dilauryl-β-naphthol sulfonic acid, Caprylic nitronaphthalene sulfonic acid, saturated paraffin wax sulfonic acid, unsaturated Saturated halaffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid acid, tetraisobutylene sulfonic acid, tetraamylene sulfonic acid, tetra-substituted paraffin wax, sulfonic acid, nitroso-substituted paraffin wax sulfonic acid, Petroleum naphthalene sulfonic acid, cetylcyclopentylsulfonic acid, laurylcyclo Hexylsulfonic acid, mono- and polywax-substituted cyclohexylsulfonic acid , dodecylbenzene sulfonic acid, “dimer alkylate” sulfonic acid, etc. Included.

Alkyl-substituted benzenesulfonic acid, where the alkyl group has at least 8 carbon atoms), including dodecylbenzene "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 C14 substituents are introduced. dodecyl benzene bottle Mus (primarily a mixture of mono- and didodecylbenzenes) is commonly used in household detergents. It is available as a by-product of manufacturing.

Alkylated bottoms formed during the production of linear alkyl sulfonates (LAS) Similar products obtained from Useful.

In other embodiments, the substituted sulfonic acid also has at least 50 carbon atoms. May contain. Illustrative examples of these sulfonic acids include polybutene or polypropylene. Pyrene-substituted naphthalene sulfonic acid, ranging from 700 to 5000, preferably 70 A number average molecular weight (Mn) in the range of 0 to 1200, more preferably about 1500. Sitasulfonic acid derived by treating polybutene with chlorosulfonic acid , halafine wax sulfonic acid, polyethylene (Mn is about 900 to 2000 , preferably about 900-1500, more preferably about 900-1200 or is equal to 1300)) and sulfonic acids. Preferred sulfonic acids are No-, di- and tri-alkylated benzenes (including their hydrogenated forms) ) It is a sulfonic acid.

Accelerators, i.e. substances that promote the incorporation of excess metal into the overbased material, are , this acidic substance and a carboxylic acid or a mixture of carboxylic acid and sulfonic acid (or (bar-based substrate). Generally, this accelerator is It is a substance that is acidic and can form salts with basic metal compounds. This accelerator is The acid must be weak enough to be replaced by an acidic substance (usually carbon dioxide). No. Generally, the promoter has a pKa ranging from about 7 to about 10. suitable A particularly extensive discussion of such accelerators can be found in U.S. Pat. No. 2,777,874; , No. 695.910; No. 2.616.904; No. 3.384.586; and and No. 3.492.231. The content of these patents is The disclosure is hereby incorporated by reference. On the promoting side, phenol substances (e.g. phenol and naphthol); amines (e.g. aniline, phenylenediamine, dodecylamine), etc. In one embodiment, the preferred Preferred accelerators include phenolic accelerators. There are various types of phenolic accelerators. hydroxy-substituted benzenes and naphthalenes. Particularly useful Phenol is an alkylated phenol of the type listed in U.S. Pat. No. 2,777,874. phenols, such as heptylphenol, octylphenol, nonylphenol and tetrapropenyl-substituted phenols.

Mixtures of various promoters are sometimes used.

Mixture of promoter, basic metal compound, reaction medium and hydrocarbyl-substituted carboxylic acid Inorganic or lower carboxylic acids that react with compounds are also described in the patents cited above, For example, it is disclosed in US Patent No. 2.616.904. useful acidic substances The well-known group includes low carbon atoms having from 1 to about 8 carbon atoms, preferably from 1 to about 4 carbon atoms. carboxylic acids. Examples of these acids include formic acid, acetic acid, and propionic acid. Among them, acetic acid is preferably included. Useful inorganic acidic compounds include HCI, S Examples include O2, SO3, CO2, H2S, N2O3, etc., which are commonly known as acidic substances. commonly used. Preferred acidic substances are carbon dioxide and acetic acid; Preferably, it is carbon dioxide.

The alkali metals present in the alkali metal overbased salts are primarily Among these are sodium, sodium and potassium amides, with sodium being preferred. this <-base metal salts are prepared using basic alkali metal compounds. Ru.

Exemplary basic alkali metal compounds include alkali metal hydroxides, oxides, koxide (typically the alkoxy group has up to 10 carbon atoms, preferably (containing up to 7 carbon atoms), hydrides and amides. therefore , useful basic alkali metal compounds include sodium oxide, potassium oxide, Lithium, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium salt Ropoxide, lithium methoxide, potassium ethoxide, sodium butoxide , lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium Mention may be made of lithium amide and potassium amide. Sodium hydroxide and nat Lium lower alkoxides (i.e. containing up to 7 carbon atoms) are Particularly preferred.

Alkali metal overbased materials useful in the present invention can be prepared by methods well known to those skilled in the art. can be prepared. This method generally involves hydrocarbyl-substituted carboxylic acids or A mixture of carboxylic and sulfonic acids, accelerators and basic alkali metal compounds and adding an acidic substance to the reaction mixture containing the acidic substance. These methods are: Described in U.S. Patents: U.S. Patent No. 2.616.904; No. 905; No. 2.616.906; No. 3.242.080; No. 3.250. No. 710: No. 3.256.186; No. 3.274.135; No. 3, 49, 2 ．． No. 231: and No. 4.230.5116. The contents of these patents are , the disclosure of which is incorporated herein by reference.

In the present invention, preferred hydrocarbyl-substituted carboxylic acids have relatively high molecular weights. do. Generally, the relationship between this acidic substance, the acid, and the basic alkali metal compound is Elevated temperatures are used to promote contact. High temperatures also cause at least some of the water to Removal promotes the formation of weakly acidic promoter salts.

Water is removed from the reaction system when preparing the overbased metal salts useful in this invention. must be removed.

The reaction is generally carried out from about 100°C to The process proceeds at temperatures up to the decomposition temperature of each component. This reaction will occur if a vacuum is applied. temperature below 100°C (e.g. 60°C or higher) ). Generally, this reaction is carried out at about 110°C to about 200°C5. more preferably from about 120'C to about 175°C1, more preferably from about 110'C to about 15°C. Occurs at a temperature of 0°C. Preferably, the reaction is carried out using naphtha, mineral oil, quinceline, In the present invention, water is Apply a vacuum, bubble a gas (e.g. nitrogen) through the reaction mixture, or By removing water as a boiling mixture (e.g., ky/lene-water azeotrope), can be removed. Generally, in the present invention, this acidic substance is a gas (usually carbon dioxide). ) is provided as. This carbon dioxide is also involved in the overbasing process. Also, carbon dioxide is released at a rate that exceeds the rate of carbon dioxide consumed in the reaction system. Remove water if added.

The alkali metal overbased metal salts used in the present invention may be applied incrementally (batch-wise). ) or by a continuous method. The incremental method includes the following steps = (A) Hydrocarbyl-substituted carboxylic acids (or mixtures of carboxylic acids and sulfonic acids) A basic alkali metal compound is added to the reaction mixture containing a compound) and a promoter; remove free water from the reaction mixture to form the alkali metal salt of this acidic organic compound. (B) further adding a basic alkali metal compound to this reaction mixture; , removing free water from the reaction mixture; and (C) while removing water; Introducing the acidic substance into the reaction mixture. A product with the desired metal ratio is obtained. Repeat steps (B) and (C) until

Other methods of preparing this alkali metal overbased salt include this alkali metal overbased salt. There are semi-continuous methods for preparing genus overbased salts. This method consists of (A) hydro Alkaline carbyl-substituted carboxylic acids (or mixtures of carboxylic acids and sulfonic acids) At least one basic alkali metal compound is added to the reaction mixture containing the metal salt. (B) then simultaneously removing free water from the reaction mixture; , (1) adding a basic alkali metal compound to the reaction mixture; (2) adding a basic alkali metal compound to the reaction mixture; adding an inorganic or lower carboxylic acidic substance to the reaction mixture; and (3 ) removing water from the reaction mixture. This inorganic or lower carb Basic alkali metallization carried out continuously with removal of water, together with acidic substances. The addition of compounds shortens the processing time of the reaction system.

The term "free water" refers to the amount of water that is readily removed from the reaction mixture.

This water is typically removed by azeotropic distillation. remaining in this reaction mixture Water that is present is considered to be coordinated, associated, or solvated. This water , can be in the form of water of hydration. Certain basic alkali metal compounds are can be fed to the reaction mixture.

The excess or free water added, together with the basic alkali metal compound, and is usually removed by azeotropic distillation or vacuum stripping.

The water generated during this overbasing step is preferably an oil-insoluble metal carbonate. Removed in situ to minimize or eliminate salt formation.

Addition of inorganic or lower carboxylic acids during this overbasing step as described above. The amount of water present before addition (steps (B) and (B-1) above) is less than about 30%, preferably less than 20%, more preferably less than about 30% by weight of the compound. Preferably less than 10% by weight.

Generally, the amount of water present after addition of the inorganic or lower carboxylic acidic material is Up to about 4%, more preferably up to about 2% by weight of the reaction mixture.

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

Borated overbased metal salts are suitable for use with boron-containing compounds and basic alkalis. It is prepared by reacting with metal salts. Boron-containing compounds include Boron, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, trisalt Boron chloride, boron-containing acids (e.g. boronic acid, boric acid, tetraboric acid and boronic acid) taboric acid), borohydrides, boron amides and various esters of boron-containing acids can be mentioned. The boron-containing ester is preferably a lower alkyl boric acid. (1 to 7 carbon atoms) ester. Preferably, the boron-containing compound is boric acid. Generally, the overbased metal salt is heated to about 0°C to about 250°C. C., preferably from 100'C to about 200C.

This reaction is carried out in a solvent (e.g. mineral oil, naphtha, solvent oil, toluene or xylene). It can occur in the presence of The overbased metal salt adds less to the composition. from at least about 0.5% by weight, preferably from about 1% to about 5% by weight. Preferably, up to about 4% by weight boron is provided, more preferably up to about 3% by weight. Reacts with boron-containing compounds in amounts that

The following examples illustrate: - Alkali metal overbased salts (B) useful in the present invention; The following is an example of the manufacturing method.

Example B-1 In a reaction vessel, polybutenyl-substituted succinic anhydride derived from polybutene (Mn= 1000, the ratio of polybutene to maleic acid is 1:1) 1122 crumbs (2 per serving, 105 grams (0.4 equivalents) of tetrapropenylphenol, 11 22 grams, and 1000 grams of 100 neutral mineral oil. This mixture The mixture was stirred and heated to 80°C under nitrogen, and 1 Add 580 grams of 50% aqueous sodium hydroxide solution over 0 minutes. this The mixture is heated from 80°C to 120°C for 1.3 hours. azeotropic reflux The water is removed by and the temperature is increased to 150° C. over a period of 6 hours. During this time , collect 300 grams of water.

(1) Cool the reaction mixture to about 80'C, then add 50% Add 540 grams of aqueous sodium hydroxide solution. (2) This reaction mixture was mixed into 1. Heat to 140° C. for 7 hours and remove water at reflux. (3) This of carbonate at a rate of 1 standard cubic foot per hour (scfh). become During this time, water is removed for 5 hours. Sodium hydroxide aqueous solution 560 Repeat steps (1) to (3) using grams. Sodium hydroxide aqueous solution 64 Repeat steps (1)-(3) using 0 grams. Then 50% sodium hydroxide Repeat steps (1)-(3) using another 640 grams of the aqueous solution. child Cool the reaction mixture and add 10% neutral mineral oil to the reaction mixture. Add 00 grams. The reaction mixture was heated to 115°C and about 30 mmHg under vacuum. Stripping. This residue is filtered through diatomaceous earth. This filtrate is 361 total base number, 43.4% sulfate ash, 16.0% sodium, 39.4% oil, and having a specific gravity of 1.11, this overbased metal salt has a specific gravity of about 13 It has a metal ratio of

Example B-2 The overbased salt obtained in Example B-1 was diluted with mineral oil to give 1375% nat. 320, and 45% oil.

Example B-3 In a reaction vessel, 700 grams of 100 neutral mineral oil, anhydrous amber of Example B-1 700 grams of acid (1,25 equivalents) and 200 grams of 50% aqueous sodium hydroxide gram (2,5 equivalents). The reaction mixture was stirred and heated to 80°C. Heat. Then, add 66 grams of tetrapropenylphenol to this reaction vessel. (o, per zs is added.) The reaction mixture is sparged with nitrogen and 40 g of water is added. Heat from 80°C to 140°C for 2.5 hours while removing the rum. 140-16 Carbon dioxide (28 grams, 1.25 equivalent amount). The reaction mixture was charged at 2 standard cubic feet per hour (scf. Blow nitrogen at a rate of h) and remove a total of 112 grams of water. reaction The temperature is lowered to 115°C and the reaction mixture is filtered through diatomaceous earth. This filtrate is 4.06% sodium, total base number of 89, specific gravity of 0.948, 44.5% of oil and this overbased salt has a metal ratio of about 2.

Example B-4 In a reaction vessel, 281 grams (0.5 equivalents) of phosphoric acid anhydride of Example B-1, 281 grams of phenol, 26 grams of tetrapropenyl-substituted phenol and 100 grams of tetrapropenyl-substituted phenol. Fill with 250 grams of Utral mineral oil. Heat this mixture to 80°C, Then, 272 grams (3.4 equivalents) of sodium hydroxide aqueous solution was added to this reaction mixture. Add. This mixture was blown with nitrogen at a rate of 15 cfh, and the reaction temperature Raise the temperature to 148°C. This reaction mixture was then added at a rate of 1 s + Jh. Bubble carbon dioxide for 1 hour and 25 minutes. During this time, collect 150 grams of water. Melt. The reaction mixture was cooled to 80"C, then the reaction mixture was Add 272 grams (3.4 equivalents) of an aqueous sodium hydroxide solution of Blow nitrogen at a rate of 1.5efh. Raise the reaction temperature to 140°C, then , carbon dioxide was added to the reaction mixture at a rate of 15 cfh for 1 hour and 25 minutes. Infuse the essence. During this time, collect 150 grams of water. Lower the reaction temperature to 100℃ , and add 272 grams (3.4 equivalents) of the above aqueous sodium hydroxide solution. child During this time, the mixture is sparged with nitrogen at a rate of 15 cfh. Reaction temperature to 148 °C and the reaction mixture was heated to 1 h 40 min at a rate of and blow in carbon dioxide. During this time, collect 160 grams of water. This reaction mixture was cooled to 90°C, whereupon the reaction mixture was treated with 1 (10% neutral mineral oil). Add 250 grams. The reaction mixture was vacuum stripped at 70°C and the remaining Filter the distillate through diatomaceous earth. This filtrate was rated at 50% by ASTM D-814. 0% sodium sulfate ash, total base number of 408, specific gravity of 1.18, 37.1% Containing oil, this salt has a metal ratio of approximately 15.8.

Example B-5 Charge the reaction mixture with 700 grams of the product of Example B-4 into a reaction vessel. to 75°C and then add 340 grams of boric acid (5, 5 equivalents). The reaction mixture was heated to 110° C. for 45 minutes, This reaction temperature is maintained for 2 hours. This reaction mixture was added with 100% neutral mineral oil ( 80 grams). Add 160'C to this reaction mixture at a rate of 15cfh. Bubble with nitrogen for 30 minutes. During this time, collect 95 grams of water. This anti Add xylene (200 grams) to the reaction mixture and adjust the reaction temperature to 130-140"C. Maintain for 3 hours. The reaction mixture was heated under vacuum at 150"C and 20+amHg. Empty stripping. This residue is filtered through diatomaceous earth. This filtrate is 5. Contains 84% boron and 33.1% oil. This residue is 309 It has a total base number.

Example B-6 In a reaction vessel, 224 grams (0.4 equivalents) of succinic anhydride of Example B-1, tetra 21 grams of propenylphenol (appropriate amount of o, og, 224 grams of t-silene) and 224 grams of 100 neutral mineral oil. heat this mixture , and into this reaction vessel, 212 grams (2,6 grams) of 50% aqueous sodium hydroxide solution 5 equivalents). Raise the reaction temperature to 130 °C and the rate of l 5 cfh 41 grams of water are removed by bubbling nitrogen at . This reaction mixture then The material is blown with carbon dioxide at a rate of 15 cfh for 1.25 hours. ( Bubbling carbon dioxide at a rate of 1,55 cfh at 130°C for 4 hours. Add additional sodium hydroxide solution (432 grams, 5.4 equivalents). this During the addition, 301 grams of water is removed from the reaction vessel. Reaction temperature 150'C and increase the carbon dioxide blowing rate to 1.55 cfh for 1 hour. Hold for 15 minutes. The reaction mixture was cooled to 150°C and 15 cfh Blow nitrogen at a rate of . During this time, add 176 grams of oil to the reaction mixture. Ru. The reaction mixture was sparged with nitrogen at 1.85 cfh for 2.5 hours. and the mixture is then filtered through a diatomaceous filter. This lI@ liquid is Contains 157% sodium and 39% oil. This filtrate contains 380 It has a total base number and a metal ratio of about 145.

Example B-7 In a reaction vessel, 561 grams (1 equivalent) of succinic anhydride from Example B-1 and tetrapropylene were added. 52.5 grams of penylphenol (0.2 equivalents), 561 grams of xylene and and 500 grams of 100 neutral mineral oil. This mixture was prepared under nitrogen. Heat to 50°C and add to this mixture 373.8 grams of potassium hydroxide ( Add 6,8 parts I and 299 grams of water. The reaction mixture was heated to 135°C. Heat.

During this opening, 145 grams of water is removed. The azeotropic distillate is clear. This reaction mixture Carbon dioxide is added to the mixture at a rate of 15 cfh over 2 hours. During this time, 195 grams of water are removed azeotropically.

The reaction mixture was cooled to 75°C and then a second portion was added to the reaction vessel. Add 373.8 grams of potassium hydroxide and 150 grams of water. 70 grams of water The reaction mixture is heated to 150°C with azeotropic removal of. Carbon dioxide (1 5cfh) over 2.5 hours. During this time, add 115 grams of water azeotropically. Remove. The reaction system was cooled to 100'C, whereupon a third part was added to the vessel. 373.8 grams of potassium hydroxide and 150 grams of water are added.

Heat the reaction mixture to 150'C. During this time, remove 70 grams of water. . The reaction mixture was blown with carbon dioxide at a rate of 15 cfh for 1 hour. It's crowded. During this time, remove 30 grams of water.

Reduce reaction temperature to 70'C. The reaction mixture was heated to 150'C under nitrogen. Reheat. 15 (at 1'c) for 2 hours at a rate of 15 crh. Bubble carbon dioxide into the reaction mixture. During this time, 80 grams of water are removed. this diacid The carbon is replaced with a nitrogen purge and 60 grams of water is removed. this reaction system, then at a rate of 15 crh for 3 hours while removing 64 grams of water. and blow in carbon dioxide. The reaction mixture was cooled to 75°C, where the Add 500 grams of 100 neutral mineral oil to the reaction mixture. This reaction system is Vacuum strip to 115° C. and 25 mdg. Diatomize this residue Filter through soil.

This filtrate contains 35% oil, a base number of 322 and a metal of about 13.6. has a ratio.

Example B-8 562 grams (1 equivalent) of succinic anhydride from Example B-1, and polybutene (Mn 720 grams of polybutenyl-substituted sulfonic acid (0,8 eq. ), and 1632 grams (20.4 equivalents) of 50% aqueous sodium hydroxide solution. and overbased sodium sulfonate by the method described in Example B-1. 2. Prepare a rum/sodium succinate mixture.

Example B-9 1 equivalent of the high molecular weight monocarboxylic acid of Example 8 and a total of 15 equivalents of sodium hydroxide. By the general method of Example B-1, sodium or Prepare the barbased monocarboxylic acid salt.

The lubricating oil composition of the present invention comprises a major amount of oil of lubricating viscosity, at least 1% by weight. The above carboxylic acid derivative composition (A), and a certain amount of the above carboxylic acid or carboxylic acid derivative composition (A). at least one alkali metal overbase of a mixture of rubonic and sulfonic acids; Contains sulfide salt (B). In many cases, the lubricating compositions of the present invention will contain at least 70% % or 80% oil. The carboxylic acid derivative contained in this lubricating oil composition The amount of conductor (A) can vary within a wide range, provided that the oil composition at least about 1% by weight (oil-free chemical groups) of a carboxylic acid derivative composition; Contains (A). In other embodiments, the oil compositions of the present invention contain at least about 2% or 2.5% or even at least about 3% by weight of carboxylic acid derivatives It may contain composition (A). This carboxylic acid derivative composition (A) is the moisturizer of the present invention. Provides the lubricating oil composition with desirable Vl and dispersant properties.

As mentioned above, the lubricating oil compositions of the present invention also have a or at least about 0.002 equivalents of alkali metal. In other embodiments The lubricating oil composition has at least about 0.05 g of lubricating oil composition per 100 grams of lubricating oil composition. 003 equivalents or about o, oos equivalents of alkali metal. This lubricating oil composition The maximum amount of alkali metal present in the lubricating oil composition will depend on the nature of the other components of the lubricating oil composition. It can vary widely depending on the oil composition and the intended use of the lubricating oil composition. but However, in general, the lubricating oil compositions of the present invention contain, per 100 grams of lubricating oil composition, Contains up to about 0.008 equivalents or up to 0.01 equivalents of alkali metal.

(C) Dihydrocarbyldithioline.

The carboxylic acid dispersant (A) and the alkali metal overbased metal salt (B) In addition, the lubricating oil compositions of the present invention may contain other additive ingredients and generally contain do. Other additive components include antiwear agents (e.g. dihydrocarbyldithiophosphate metal salts).

Metal phosphates are characterized by the following formula: where R1 and R2 are each are independently hydrocarbyl groups containing from 3 to about 13 carbon atoms; is a metal, and n is an integer equal to the valence of M.

Generally, the oil compositions of the present invention have different compositions, based on the weight of the total oil composition. (e.g., from about 0.01% to about 2% or 5% by weight) and generally from about 0.01% to about 1% by weight) of one or more Contains the metal dithiophosphate identified in . This metal dithiophosphate is The lubricating oil compositions of the present invention are used to improve the antiwear and antioxidant properties of the compositions. added to things.

Hydrocarbyl groups R1 and R2 in this dithiophosphate are alkyl groups, Substances of cycloalkyl, aralkyl or alkaryl groups, or similar structures It can be a typical hydrocarbon group. "Substantial hydrocarbon" means that the hydrocarbon character of the group is Substituents that do not significantly change (e.g. ether, ester, nitro or halogen) means a hydrocarbon containing

Exemplary alkyl groups include isopropyl, isobutyl, n-butyl, 5ec-butyl, various amyl groups, n-hexyl, methylisobutyl, carbinyl, heptyl , 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl Examples include dodecyl, dodecyl, and tridecyl. Examples of lower alkylphenyl Examples include phenyl. Cycloalkyl groups are also useful and these Mainly includes cycloalkyl group and lower alkyl-cyclohexyl group. It will be done. Polysubstituted hydrocarbon groups may also be used, e.g. chloropentyl, di-substituted There are chlorophenyl and dichlorodecyl.

In other embodiments, at least one of R1 and R2 of formula It is a pyr group or a secondary butyl group. In yet other embodiments, R1 and R2 Both are secondary alkyls.

The phosphorodithioic acids C from which metal salts useful in the present invention are prepared are well known. Dihydro locarbyl phosphorodithioic acids and their metal salts, and such acids and Examples of methods for preparing salts are, for example, U.S. Pat. No. 4,263. No. 150; No. 4, 289, No. 635; No. 4, 308.

No. 154; and No. 4,417,990. of these patents The contents are incorporated herein by reference for such disclosure.

This phosphorodithioic acid is a combination of phosphorus trisulfide and alcohol or phenol or alcohol. It is prepared by reacting a mixture of coles. This reaction is based on trisulfide per mole of alcohol or phenol, and approximately 0 It may be carried out at temperatures ranging from 0.degree. C. to about 200.degree. Therefore, o. o-jin-to beef The preparation of phosphorodithioic acid consists of phosphorus trisulfide and 4 moles of n-hexyl alcohol. and for about 2 hours at a temperature of about 100°C. Hydrogen sulfide is liberated and its residue is an acid as defined. Metal salts of this acid are formed by reaction with metal oxides. can be prepared. To initiate a reaction, simply mix these two reactants and heat them. It is enough just to do so. The product obtained is sufficiently pure for the purposes of the present invention. .

Metal salts of dihydrocarbyl dithiophosphoric acid useful in the present invention include Group I metals, Group I metals, Group 1 metals, aluminum, lead, tin, molybdenum, manganese, cobalt and nitrogen. Included are salts containing nickel. Number 1 and Group 1+ (la, Ib, Ila and and Ilb) are listed in the Merck Index, 9th edition (1976) of elements. Defined on the periodic table. Group 1+ metals such as aluminum, tin, iron, and cobal metal, lead, molybdenum, manganese, nickel and copper are among the preferred metals. Ru. Zinc and copper are particularly useful metals. In one embodiment, the lubrication assembly of the present invention The compositions are zinc dihydrocarbyl dithiophosphate and dihydrocarbyl dithiophosphate. Contains acid copper. Examples of metal compounds that can react with this acid include lithium oxide, lithium hydroxide, tium, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, Silver oxide, magnesium oxide, magnesium hydroxide, calcium oxide, zinc hydroxide , strontium hydroxide, cadmium oxide, cadmium hydroxide, barium oxide, Aluminum oxide, iron carbonate, copper hydroxide, lead hydroxide, tin butyrate, cobalt hydroxide, Di-ethyl hydroxide, nickel carbonate, etc. are included.

In some cases, certain ingredients (e.g. small amounts of metal salts of acetic acid or acetic acid) may be By mixing together with the metal reactive components, the reaction is accelerated and improved production is achieved. You can get things. For example, up to about 5% zinc acetate in combination with the required amount of zinc oxide. By using lead, the formation power of zinc phosphorodithioate is promoted.

In a preferred embodiment, the alkyl groups R1 and R2 are secondary alcohols. (e.g. isopropyl alcohol, secondary butyl alcohol, 2-pentanoyl alcohol, 2-methyl-4-pentanol, 2-hexanol, 3-hexanol, etc. ) is derived from

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 mixture The use of an inexpensive alkali that cannot produce oil-soluble phosphorodithioic acids by itself It is now possible to use Lucor.

Useful mixtures of metal salts of dihydrocarbyl dithiophosphoric acids include phosphorus trisulfide and (a ) isopropyl alcohol or secondary butyl alcohol; and (b) at least 5 a mixture with an alcohol containing carbon atoms (where the alcohol in this mixture at least 10 mole percent, preferably 20 or 25 mole percent of the The solvent is isopropyl alcohol, sec-butyl alcohol or a mixture thereof. It can be obtained by reacting

Therefore, a mixture of isopropyl alcohol and hexyl alcohol is very It can be used to produce effective oil-soluble metal phosphorodithioates. same For reasons, mixtures of phosphorodithioic acids are preferred because they form cheaper oil-soluble salts. can react with this metal compound.

This alcohol mixture is a mixture of different primary alcohols, different secondary alcohols, It is a mixture of coles, or a mixture of primary and secondary alcohols. obtain. Examples of useful mixtures include: n-butanol and n-ol. Kutatool; n-pentanol and 2-ethyl-1-hexanol; isobutanol; alcohol and n-hexanol; isobutanol and isoamyl alcohol; Isopropanol and 2-methyl-4-pentanol; Isopropanol and and secondary butyl alcohol degree. Particularly useful alcohol mixtures include small amounts (about 20 liters per cent. Propyl alcohol, in a preferred embodiment, at least 40 mole percent is a mixture of secondary alcohols with isopropyl alcohol.

(Margin below) The following examples demonstrate the preparation of metal phosphorodithioates prepared from alcohol mixtures. Illustrate.

Example C-1 Alcohol mixture (this consists of 6 moles of 4-methyl-2-pentanol and 4 moles of (containing isopropyl alcohol) and phosphorus trisulfide. A phosphorodithioic acid is prepared from This phosphorodithioic acid is then treated with oxidized nitrogen. React with lead oil slurry. The amount of zinc oxide in this slurry is This is approximately 1.08 times the theoretical amount required to completely neutralize phorodithioic acid. This person The oil solution (10% oil) of zinc phosphorodithioate obtained by the method was 9.5% Contains phosphorus, 20.0% sulfur and 10.5% zinc.

Example C-2 Finely powdered phosphorus trisulfide and an alcohol mixture (this is isopropyl alcohol 11. 53 moles (692 parts by weight) and Inoctatool 7, 69 moles (1000 parts by weight) The phosphorodithioic acid is prepared by reacting the phosphorodithioic acid with the following:

The phosphorodithioic acid obtained in this way has an acid number of about 178-186 and has a phosphorus 10 ．． 0% and 21.0% sulfur. This phosphorodithioic acid is then React with zinc oxide oil slurry. Oxidation contained in this oil slurry The amount of zinc is 1.10 times the theoretical equivalent of the acid value of the phosphorodithioic acid. this method The zinc salt oil solution prepared in 12% oil, 8.6% phosphorus, 18.5 % sulfur and 9.5% zinc.

Example C-3 1560 parts (12 moles) of inoctyl alcohol and isopropyl alcohol 180 parts (3 mol) of the mixture was reacted with 56 parts (3.4 mol) of trisulfide phosphorus. The phosphorodithioic acid is prepared by: This reaction The mixture is heated to about 55°C and then heated while maintaining the reaction temperature at about 60-75°C. , by adding phosphorus trisulfide for 1°5 hours.

After all the phosphorus pentoxide 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 & 6゜28 mol) was added for 30 minutes. When filled with zinc oxide slurry, heat generation of up to 60°C is observed. . The mixture is then heated to 80° C. and maintained at this temperature for 3 hours. 100 ℃ and 6 mm, Hg, the mixture was filtered with filter aid. Filter twice. This filtrate is the desired oil solution of the zinc salt. This solution is 1 0% oil, 7.97% zinc (theoretical value 7°40%); 7.21% phosphorus (theoretical value 7.06%); and 15.64% sulfur (theoretical value 14.57%). contains.

Example C-4 Isopropyl alcohol (396 parts, 6.6 moles) and inoctyl alcohol 1,287 parts (9.9 moles) of 1,287 parts (9.9 moles) were charged into a reactor and heated to 59°C without stirring. heat. Then, phosphorus trisulfide (833 parts, 3.75 mol) was added without blowing nitrogen. Add it. The addition of phosphorus trisulfide is approximately 2 It will be completed in time. This mixture was then stirred at 45-63°C for about 1.45 hours. , and filter. This filtrate is the desired phosphorodithioic acid.

The reactor is charged with 312 parts (7,7 equivalents) of zinc oxide and 580 parts of mineral oil. room While stirring at room temperature, add the phosphorodithioic acid prepared above (2287 parts, 6.97 eq. ) is added over a period of approximately 1.26 hours, an exotherm of up to 54°C is observed.

The mixture is heated to 78°C and maintained at 78-85°C for 3 hours. This reaction mixture Vacuum strip the compound to 100" C119 mm Hg. This residue , filtered through a filter aid, the filtrate is a solution of the desired zinc salt in oil (19.2% is oil). This solution contains 7.86% zinc, 7.76% phosphorus and 1 Contains 4.8% sulfur.

Example C-S The molar ratio of isopropyl alcohol to inoctyl alcohol is 1:1. The general method of Example C-4 is repeated except as follows. The product obtained by this method is , oil solution 1 of zinc phosphorodithioate (10% oil). This solution is , containing 11.96% zinc, 8.49% phosphorus and 18.05% sulfur. Ru.

Example C-6 Alcohol mixture (this consists of 520 parts (4 moles) of inoctyl alcohol and containing 360 parts (6 moles) of isopropyl alcohol), phosphorus trisulfide 504 (2.21 mol) to form a phosphorase according to the general method of Example C-4. Prepare dithioic acid.

Oil slurry of 116.3 parts of mineral oil and 141.5 parts (3.44 moles) of zinc oxide and 950.8 parts (3.20 mol) of bosporodithioic acid prepared above were reacted. The zinc salt is prepared by: The product prepared in this way A lead salt solution in oil (10% mineral oil). This oil solution contains 9.36% zinc Contains lead, 8.81% phosphorus and 18.65% sulfur.

Example C-F Inoctyl alcohol 520 parts (4 moles) Toisopropyl alcohol 559. A mixture of 8 parts (9.33 mol) is prepared and heated to 60'C. at this point , While stirring, 672.5 parts (3.03 moles) of phosphorus trisulfide is added little by little.

The reaction is then maintained at 60-65°C for about 1 hour and filtered. this The filtrate is the desired phosphorodithioic acid.

Prepare an oil slurry of 188.6 parts (4 moles) of zinc oxide and 144.2 parts of mineral oil. Then, 1145 parts of the phosphorodithioic acid prepared above are added little by little. During this time, The mixture is maintained at about 70"C. After charging all the acids, the mixture is Maintain at ’c for 3 hours.

The reaction mixture is then stripped of water to 110°C. This residue The distillate is filtered through a filter aid, and the filtrate contains a solution of the desired product in oil (10 % is mineral oil). This oil solution contains 9.99% zinc and 19.55% iron. Contains sulfur and 9.33% phosphorus.

Example C-8 Isooctyl alcohol 26ON (2 mol), isopropyl alcohol 480 parts (8 mol) and 504 parts (2.27 mol) of phosphorus trisulfide, Bosphorodithioic acid is prepared by the general method of This phosphorodithioic acid (10 94 parts, 3.84 moles) was added to the oil slurry (which was 181 parts (441 moles) of zinc oxide and 135 parts of mineral oil). this The mixture is heated to 80°C and maintained at this temperature for 3 hours. 100”C and After stripping to 19+nmHg, the mixture was filtered twice with filter aid. Upon filtration, the filtrate is a solution of zinc salt in oil (10% mineral oil). This oil The solution contained 10.0 parts % zinc, 904% phosphorus and 19.2% sulfur. have

Further identification of metal phosphorodithioates as component (C) in the lubricating oil of the present invention Examples are given in the table below. Examples C-9 to C-14 are from a single alcohol. and Examples c-15 to C-19 were prepared according to the general method of Example C-1. It is prepared from an alcohol mixture.

(Margin below) table Component C: Metal phosphorodithioate Tianfeng■　Wang and Yu C-9n-nonyl n-nonyl Ba 2C-10 cyclohexyl cyclohexyl Sil Zn 2C-11 butyl isobutyl Zn 2C-12 hexyl Xyl Ca 2C-13n-decyl n-decyl Zn 2C-144-methy Ru-2-butyl 4-methyl-2-butyl Cu 2C-15(n- 7'chill + Tochicil) (1:1) v Zn 2C-16 (isopropyl) + isooctyl) (ni 1) w Ba 2C-17 (isopropyl + 4-methane) Chini-2-to' 7 chill) (40:60) m Cu 2C-18 (iso 7' chill + Iso 1 mil) (65:35)m Zn 2C-19 (Isopropyl + 5ec-7゛fl) (40:60) III Zn 2 Used in the lubricating composition of the present invention Other classes of phosphorodithioate additives that may be considered include the phosphorodithioate additives listed above. Included are adducts of metal oxides and epoxides. When preparing such adducts The metal phosphorodithioates useful in most cases are zinc phosphorodithioates. be. This epoxide is an alkylene oxide or aryl alkylene oxy I can get it tomorrow. This aryl alkylene oxide is styrene oxide, p-ethyl oxide, Tylstyrene oxide, α-methylstyrene oxide, 3-β-naphthyl-1, 1,3-butylene oxide, enteric-dodecylstyrene oxide and p-chloros Illustrated by tyrene oxide. This alkylene oxide mainly includes: lower alkyleneoxy in which the alkylene group contains 8 or fewer carbon atoms One example is de. Examples of such lower alkylene oxides include ethylene oxy propylene oxide, 1,2-butene oxide, trimethylene oxide, Tramethylene oxide, butadiene monoepoxide, ■, 2-hexene oxide , and shrimp chlorohydrin. Other epoxides useful here include e.g. , 9.10-epoxybutyl stearate, epoxidized soybean oil, epoxy tung oil and epoxidized copolymers of styrene and butadiene. It will be done.

This adduct is produced by simply mixing the metal phosphorodithioate and the epoxide. , can be obtained. This reaction is usually exothermic and has a wide temperature range of about 0°C to about 300°C. It can be carried out within the limits of the temperature range. This reaction is exothermic, so the reaction temperature should be carefully controlled. To manipulate, one reactant (usually an epoxide) is added in small amounts to the other reactant. This is best done by adding it to

The reaction is carried out in a solvent (e.g. benzene, mineral oil, naphtha or n-hexene). , can be done.

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

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

Example C-20 2365 parts (3.33 mol) of zinc phosphorodithioate prepared in Example C-2, Fill the reactor. While stirring at room temperature, add 38.6 parts of propylene oxide (0.6 parts). 7 mol), an exotherm of 24-31°C is observed. Add this mixture to 80~ Hold at 90°C for 3 hours, then vacuum strip to 101°C 17BHg do. When this residue is filtered using a filter aid, the IR fluid contains the desired salt. Oil solution (11.8% oil). This solution contains 17.1% sulfur, Contains 8.17% zinc and 7.44% phosphorus.

In one embodiment, the dihydrocarbon used as component (C) in the lubricating oil compositions of the present invention Metal carbyl dithiophosphates are small groups of carbyl dithiophosphates bonded to an oxygen atom through a secondary carbon atom. Characterized by having at least one hydrocarbyl group (R' or R2) I get kicked. In a further preferred embodiment, the hydrocarbyl groups R1 and R2 Both are bonded to the dithiophosphate oxygen atom via a secondary carbon atom.

In still other embodiments, the dihydrocarbyldithin used in the preparation of the metal salt is Ophosphoric acid is a mixture of phosphorus trisulfide and an aliphatic alcohol (where this mixture is at least 20 mole percent is isopropyl alcohol). It can be obtained by More generally, such mixtures contain at least Also contains 40 mole percent isopropyl alcohol. Others in this mixture The alcohol can be either a primary alcohol or a secondary alcohol. Ru. In some applications (e.g. passenger car crankcase oil), isopropyl alcohol mixing alcohol with other secondary alcohols (e.g. 2-methyl-4-pentanol). Metal phosphorodithioates derived from compounds appear to give improved results. . An engine designed for use with both compression ignition and spark ignition engines. For this phosphorodithioic acid, isopropyl alcohol and a primary When prepared from a mixture with alcohol (e.g. inoctyl alcohol), Often improved results are obtained.

Other classes of phosphorodithioic acids contemplated as useful in the lubricating compositions of the present invention The salt additive (C) is at least one phosphorescent compound as defined and exemplified above in (a). (b) at least one aliphatic or cycloaliphatic carboxylic acid; , containing mixed metal salts of . This carboxylic acid usually has 1 to about 3 carboxylic acids. a monocarboxylic acid or a polycarboxylic acid containing only one carboxy group, preferably only one carboxy group. Can be a recarboxylic acid. The carboxylic acid has about 2 to about 40 carbon atoms, preferably Preferably from about 2 to about 20 carbon atoms, advantageously from about 5 to about 20 carbon atoms. may contain children. Preferred carboxylic acids are those having the formula R3COOH; Here, R3 is preferably an aliphatic or fatty acid containing no acetylenic unsaturation. It is a cyclic hydrocarbon-based group. Suitable acids include butanoic acid, pentanoic acid, hexyl sananoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, octadecanoic acid and arachidic acid, as well as olefinic acids (e.g., oleic acid, linoleic acid, and lyllonic acid and lyllonic acid dimer). In most cases R3 is saturated aliphatic groups, and especially branched alkyl groups (e.g. isopropyl groups or -heptyl group). Exemplary polycarboxylic acids include succinic acid, alkyl- and and alkenylsuccinic acid, adipic acid, sebacic acid and citric acid.

Simply combine the metal salt of phosphorodithioic acid and the metal salt of carboxylic acid in the desired ratio. By this, mixed metal salts can be prepared. Phosphorodithioates and carboxylates The equivalent ratio of is between about 0.5:1 and about 400:1. Preferably, this ratio is It is between about 0°5:l and about 200:l. Advantageously, this ratio is approximately 0°5:l to about 100:1, preferably from about 0.5:1 to about 50:1. Even more preferably , about 0.5:1 to about 20:1. Additionally, this ratio may range from about 0.5:1 to about 4.5:L is preferably about 2.5:1 to about 4.25:1. this For this purpose, the equivalent weight of a phosphorodithioic acid is defined as its molecular weight, the -PSSH in it. It is the value divided by the number of groups, and the equivalent weight of a carboxylic acid is the molecular weight divided by the number of carboxylic acids in it. It is the value divided by the number of xy groups.

A second preferred method of preparing the mixed metal salts useful in the present invention is to prepare the desired mixture of acids. and reacting this acid mixture with a suitable metal base. . When this method of preparation is used, an excess of metal with respect to the number of equivalents of acid present is used. It is often possible to prepare salts containing; therefore, per equivalent of acid , mixed metal salts containing as much as 2 equivalents of metal, especially up to about 1.5 equivalents of metal, are prepared. can be manufactured. The equivalent weight of a metal for this purpose is its atomic weight divided by its valence It is a value.

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

Suitable metal bases for preparing mixed metal salts include the free metals listed above, and and their oxides, hydroxides, alkoxides and basic salts.

Examples include sodium hydroxide, potassium hydroxide, magnesium oxide, calcium hydroxide. These include aluminum, zinc oxide, lead oxide, and nickel oxide.

The temperature at which the mixed metal salt is prepared is generally between about 30°C and about 150'C. , preferably up to about 125°C. This mixed salt is a mixture of acids and metal bases. If prepared by neutralization, temperatures above about 50°C, especially above about 75°C. Preferably, high temperatures are used. Substantially inert, normally liquid organic diluents (e.g. For example, performing the reaction in the presence of naphtha, benzene, xylene, mineral oil, etc. Often advantageous. This diluent is mineral oil or has physical and chemical properties with mineral oil. If chemically similar, this mixed metal can be used as an additive in lubricants or functional fluids. There is no need to remove the salt before using it.

U.S. Patent Nos. 4.308.154 and 4.417.970 address these describes a method for preparing mixed metal salts and discloses many examples of such mixed salts. Ru. The disclosures of these patents are incorporated herein by reference.

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

Example C-21 A mixture of 67 parts (1,63 equivalents) of zinc oxide and 48 parts of mineral oil was stirred at room temperature; 401 parts (1 equivalent) of di(2-ethylhexyl)phosphorodithioic acid and 2-ethylhexyl Add a mixture of 36 parts (025 equivalents) of bovine acid to the chill over a period of 10 minutes. . During this addition, the temperature is increased to 40°C. Once the addition is complete, reduce this temperature to Raise to go'c in 3 hours. This mixture was then vacuum strung at 100°C. Popping yields the desired mixed metal salt as a 91% solution in mineral oil.

QJH Hi Swimming - 10,000 The lubricating oil compositions of the present invention may also contain an antioxidant (D), with the proviso that (D) The antioxidant and (C) metal dithiophosphate are not the same. For example, (C) and (D) are both metal dithiophosphates, provided that the metal (C) is (D) is not the same as metal.

In one embodiment, the antioxidant is present in a sulfur-containing composition, an alkylated aromatic amino acid, phenol, and an oil-soluble transition metal-containing compound.

When antioxidants are present, the lubricating oil compositions contain from about 0.01 to about 2% or 5% % of at least one antioxidant.

The antioxidant can be one or more sulfur-containing compositions. sulfided Substances that can be combined to form the sulfurized organic compositions of the present invention include oils, fatty acids, or esters. olefins or polyolefins produced therefrom, or diels -alda-adducts are included.

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

Fatty acids generally contain about 8 to about 30 carbon atoms.

In general, unsaturated fatty acids contained in naturally occurring vegetable or animal fats and oils include: Includes palmitoleic acid, oleic acid, linoleic acid, lylunic acid and erucic acid. It will be done. This fatty acid is a mixture of acids, such as naturally occurring animal and vegetable oils ( This includes beef tallow, stored fat, lard oil, tall oil, peanut oil, and corn. oil, safflower oil, sesame oil, poppy seed oil, soybean oil, cottonseed oil, sunflower seed oil or wheat (including bud oil). Tall oil is made from rosin acids (mainly abietic acid). A mixture of unsaturated fatty acids (mainly oleic acid and linoleic acid) be. Tall oil is a byproduct of the sulfate process for the manufacture of wood valves.

The fatty acid esters are also derived from the above types of aliphatic olefinic acids. They can be prepared by reacting with either alcohols or polyols. fat Examples of group alcohols include -hydric alcohols (e.g. methanol, ethanol, n - Propanol or isopropanol; n-butanol, isobutinol, (such as secondary butanol or tertiary butanol); and polyhydric alcohol (such as contains ethylene glycol, propylene glycol, trimethylene glycol, (including opentyl glycol, glycerol, etc.).

The olefinic compounds that can be sulfurized are virtually diverse.

These compounds contain at least one olefin, defined as a non-aromatic double bond. Lefinic double bonds; i.e., those containing two aliphatic carbon atoms Ru. Broadly speaking, this olefin is defined by the formula R"R"2C=CR"3R"4 where each R1, R°2, R°3 and v4 are hydrogen or an organic group. Ru.

Generally, in the above formula, the R° group that is not hydrogen is -C(R")3, -C0OR"5, -C0N(R”)2, -C00N(R°5)4, -COOM, -CN, -X, -YR''5 or -Ar, where each R.5 is independently , hydrogen, alkyl, alkenyl, aryl, substituted alkyl, substituted alkyl rukenyl or substituted aryl, provided that any two R.5 groups are , alkylene or substituted alkylene, whereby up to about 12 carbons A ring is formed with atoms; M is one equivalent of a metal cation (preferably Group 1 or Group 1, such as sodium, potassium, barium, calcium); X is halogen (e.g. chlorine, bromine or iodine); Y is oxygen or divalent ion cormorant; Ar is an aryl group or substituted aryl group having up to about 12 carbon atoms It is the basis.

Any two of Rol, R°2, R゛3 and R-4 are also - together, It may form an alkylene group or a substituted alkylene group. In other words, this Olef The phosphoric compound may be cycloaliphatic.

In this olefinic compound, each non-hydrogen R group is usually independently an alkyl group. , an alkenyl group or an aryl group. Monoolefinic compounds and diolefinic compounds, especially the former are preferred, especially monoolefinic terminal Hydrocarbon; ie R°3 and R°4 are hydrogen and R.

1 and R°2 have 1 to about 30 carbon atoms, preferably 1 to about 16 carbon atoms carbon atoms, more preferably 1 to about 8 carbon atoms, even more preferably 1 Alkyl or aryl having from 5 to about 4 carbon atoms, especially alkyl (i.e. In other words, the olefin is aliphatic). Approximately 3 to 30 pieces of carbon atoms, especially about 3 to 16 (in most cases less than 9) carbon atoms Olefinic compounds having atoms are particularly desirable.

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

In other embodiments, the sulfurized organic compound is a sulfurized terpene compound. "Tell" As used herein and in the claims, the term "pen compound" refers to the actual Various isomeric terpene hydrocarbons (e.g. terpene ), and various synthetic and natural It is intended to include the resulting oxygen-containing derivatives. These various compounds The mixture of Matsuura and turpentine is particularly useful when natural products such as turpentine are used. and generally used. For example, Matsuura has α-terpineol, β-terpineol, Neol, α-fenchol, fencol, borneol/ Isoborneol, fenchone, estragole, dihi Mixture of dolo-alpha-terpineol, anethole and other monoterpene hydrocarbons Things are included. The specific ratios and amounts of the various components in a given Matsuura are and depends on the degree of purification. A group of products derived from Matsuura include Hercule Commercially available from S Incorporated.

Chillbear 7/L commercially available from Hercules Incorporated The Matsuura product, commonly known as :ff-le, is the sulfurized product of the present invention. It has been found to be particularly useful in the preparation of Matsuura product is alpha-Te rpineol, Terpineol 318 Prime, Yarmor 302, Herco pine oil, Yarmor 302W, Ya With names like rmor F and Yarn+or 60, Hercules It is commercially available from the company.

In other embodiments, the sulfurized organic composition comprises a sulfur source and at least one diacetate. at least one sulfur-containing substance containing a reaction product with a Ruth-Alder adduct; be. Generally, the molar ratio of sulfur source to Diels-Alder adduct is about 0. ．． 75 to about 4.0, preferably about 1 to about 3.0, and More preferably, it is in the range of about 1 to about 2.5.

This Diels-Alder adduct can be used for diene synthesis or Diels-Alder reaction. is a well-known and art-recognized class of compounds prepared by chemical reactions. child A summary of the prior art for the class of compounds is given in A.S.Onischenko. Russian monograph by Dienov i 5 intes, Izdatels Found in two Akademii Nauk (SSSR, 1963) . (L, Mandel, A, S, 0nischenko, Dien e　S　nthesis　N, Y,, Daniel Davey andCo , Inc., translated into English in 1964). This monograph, and the references cited herein, the contents of which are incorporated herein by reference. .

Basically, this diene synthesis (Diels-Alder reaction) requires at least one conjugated diene and at least one ethylenically or acetylenically unsaturated compound these latter compounds include reactions with dienophyl les). piperylene, isoprene, methyl isoprene, chloro Lovrene and 1,3-butadiene prepared this Diels-Alder adduct. Among the preferred dienes used in Examples of cyclic dienes include /clopene Tagene, fulvenes, 1.3-ink O hexadiene, 1. 3-cyclohebutadiene, 1.3.5-cyclohebutatriene, cyclooctate tolyene, and 1,3.5-7 chrononatriene.

Preferred classes of genophiles include formyl, cyano, nitro, carboquine, carbonate. at least one electron selected from groups such as rubohydrocarbyloxy, etc. It has an acceptor group. Typically, this hydrocarbyl group and substituted hydrocarbyl groups Bill groups, if present, each contain no more than 10 carbon atoms .

One preferred class of genophiles has few (at least one carboxylic acid ester group) -C(0)OR11, where Re represents up to about 40 carbon atoms. is the residue of a saturated aliphatic alcohol with ~R[+ derived from the aliphatic alcohol The alcohol can be any of the monohydric or polyhydric alcohols mentioned above.

Preferably, the alcohol is a lower aliphatic alcohol, more preferably is methanol, ethanol, bronomol or butanol.

In addition to this ethylenically unsaturated genophile, there are many useful acetyls such as: Renically unsaturated genophiles are present: propiolaldehyde, methylethini ketone, propylethynyl ketone, propenylethynyl ketone, propiolic acid , furopiolic acid nitrile, ethyl propionate, tetrolic acid, propargyl acetate aldehyde, acetylene dicarboxylic acid, dimethyl ester of acetylene dicarboxylic acid dibenzoylacetylene, etc.

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

Into this reaction mixture, substances useful as sulfurization promoters are often mixed. It's advantageous. These substances can be acidic, basic or neutral. useful neutral Substances and acidic substances include acidified clays (e.g. rsuper Filtrol J (diatomaceous earth treated with sulfuric acid), p-) luenesulfonic acid, phosphorus-containing reagent ( For example, phosphorus-containing acids (e.g., dialkylphosphorodithioic acids), phosphorus-containing acids, etc. esters (e.g. triphenyl phosphate), phosphorus sulfides (e.g. phosphorus trisulfide), and surfactants (eg lecithin).

Preferred promoters are basic substances. These include inorganic oxides and salts (e.g. , sodium hydroxide, calcium oxide and sodium sulfide). deer However, the most desirable basic promoters are nitrogen salts containing ammonia and amines. It is the basis.

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

promoter or diluent for one or more of the promoters listed above. In any event, water is also present in the reaction mixture. when water is present , the amount is usually about 1-25% by weight of the olefinic compound. but However, the presence of water is not essential and may be practical when certain types of reactors are used. It may be advantageous to carry out this reaction under qualitatively anhydrous conditions.

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

a sulfur source used to prepare any of the sulfur-containing materials of the invention; The reagent may be, for example, sulfur, I\sulfur chloride (for example - sulfur chloride or sulfur chloride), mixtures of hydrogen sulfide and sulfur or sulfur dioxide, etc. Zero sulfur or a mixture of sulfur and hydrogen sulfide is often preferred. but However, it is understood that other sulfiding reagents may be substituted for it, if appropriate. It will be done. Commercially available sources of all sulfiding reagents are commonly used for the purposes of this invention; Impurities normally associated with commercial products of It can exist.

When this sulfidation reaction occurs by using only sulfur, the reaction is approximately This reagent is applied at a temperature of 50 to 250°C, typically about 150 to about 210°C. This occurs simply by heating with sulfur. The weight of the substance to be sulfurized and sulfur The quantity ratio is between about 5:1 and about 15:1, generally between about 5:1 and about 10:1. It is. This sulfidation reaction is generally carried out efficiently under an inert atmosphere (e.g. nitrogen). This is done with constant stirring. Either the components or reagents are significantly volatile at the reaction temperature If necessary, the reaction vessel may be sealed and maintained under pressure. Sulfur is mixed with other ingredients. It is often advantageous to add it to the mixture in portions.

When a mixture of sulfur and hydrogen sulfide is used in the method of the invention, sulfurized The amounts of sulfur and hydrogen sulfide per mole of component are each typically from about 0.3 to about 3 gram atoms, and about 0.1 to about 1.5 moles. The preferred range is that about 0.5 to about 20 gram atoms and about 0.4 to about 1.25 moles, respectively; Also desirable ranges are about 0.8 to about 1.8 gram atoms and about 0.4 to about 1.8 grams, respectively. It is about 0.8 mole. In this reaction mixture operation, these components are within these ranges. It is introduced at a level that provides a

In semi-continuous operation, these components can be mixed in any ratio, but with variations in mass. present, to be consumed in amounts within these ratios, based on the that Thus, for example, if the reaction vessel is initially filled with only sulfur, terpenes and /or the olefinic compound and hydrogen sulfide are mixed in proportions such that the desired ratio is obtained. is added incrementally.

If a mixture of sulfur and hydrogen sulfide is used in this sulfidation reaction, The corresponding temperature range is generally from about 50°C to about 350°C. A preferred range is about 1 00°C to about 200°C, with temperatures of about 120°C to about 180°C being particularly suitable.

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

It is generally preferred that the reaction mixture consist primarily of the components and reagents described above. Although difficult, this reaction also requires an inert solvent that is liquid within the temperature range used ( For example, alcohols, ethers, esters, aliphatic hydrocarbons, ), rogenated aromas This can occur in the presence of hydrocarbons (e.g. group hydrocarbons). This reaction temperature is relatively high (for example 200° C.), sulfur may be evolved from the product. The occurrence of this sulfur is , if low reaction temperatures (e.g., about 150-170°C) are used, avoid It will be done.

In some cases, according to the methods described herein to reduce active sulfur, It is desirable to treat the resulting sulfurized product. The term "active sulfur" includes copper Sulfur in a form capable of staining and similar substances is included and determines sulfur activity. Standard tests are available to determine the Alternative treatment methods to reduce active sulfur As a method, metal deactivators can be used with lubricants containing sulfurized compositions. .

The following examples relate to sulfurized compositions useful in the present invention.

Example D-1 In a reaction vessel, 780 parts of inpropyl alcohol, 752 parts of water, 50% by weight hydroxide 35 parts of sodium aqueous solution, diatomaceous earth treated with sulfuric acid (Engelhard C) organization (Menlo Park, New Jersey) and 23 parts of sodium sulfide. Fill 9 parts. The mixture is stirred and heated to 77-80'C. this The reaction temperature is maintained for 2 hours. The mixture was cooled to 71°C and then Lefin (which consists of 337 parts of -sulfur chloride, 733 parts of 1-dodecene and Neod ene 1618 (This is C+6 obtained from Shell Chemica1) - 1000 parts of a mixture of +e olefins) ) was added to this mixture. This reaction mixture was Heat to 7-80°C and maintain this temperature until the chlorine content reaches a maximum of 0.5. Ru. The reaction mixture was vacuum stripped to 80°C and 20+amHg. Ru. This residue is filtered through diatomaceous filter. This filtrate contains 19.0% sulfur. and has a specific gravity of 0.95.

Example D-2 A mixture of 100 parts of soybean oil and 50 parts of a commercially available C+6 α-olefin was prepared under nitrogen. When heated to 175°C and slowly added 17.4 parts of sulfur, an exothermic reaction occurred. The temperature rises to 205°C. This mixture was heated at 188°C to 200°C for 5 After heating for an hour, gradually cooling to 90°C, and filtering, 10.13% of the iodine The desired product containing corrugated iron is produced.

Example D-3 100 parts of soybean oil, 3.7 parts of tall oil acid, and a commercially available α-olefin of C+s-+a. The mixture with 463 parts of sulfur was heated to 165°C under nitrogen and heated to 17 ．． Add 4 parts. The temperature of this mixture rises to 191°C. Temperature from 165℃ Maintain at 200°C for 7 hours, then cool to 90°C and filter. This generation The material contains 10.13% sulfur.

Example D-4 In a reaction vessel equipped with a condenser, thermometer and stirrer, 93 parts of Matsuura (0.5 equivalents) and A mixture with 48 parts of sulfur (1,5 equivalents) is charged. Blow this mixture with nitrogen. Heat to about 140°C while stirring and maintain at this temperature for about 28 hours. cooling Then add C+s α-olefin (this is Gulf Oil) through the addition funnel. Generic trade name of Gulftene 16 from Chemicals company Add 111 copies (available under the name ). After the addition is complete, drain this addition funnel with nitrogen. Replaced by immigration. The reaction mixture was heated to 170'C while blowing nitrogen. Heat and maintain at this temperature for about 5 hours. Cool the mixture and filter with filter aid. Filter with agent. This filtrate has a sulfur content of 19.01% (theoretical value 1904%). is the desired product with.

Example D-5 (a) Contains 400 grams of toluene and 66.7 grams of aluminum chloride The mixture was cooled with a stirrer, nitrogen inlet tube, and solid carbon dioxide in a reflux condenser. Fill a 2 liter flask with a 640 grams of butyl acrylate (5 mo ) and 240.8 grams of toluene over a period of 0.25 hours. Add to AlCl3 slurry. During this time, maintain the temperature in the range 37-58°C . Then, over 2.75 hours, 313 grams (5.8 mol) of butadiene Add to this slurry. During this time, the temperature of the reaction mass was increased to 60°C by external cooling. Maintain at ~61°C. The reaction mass was sparged with nitrogen for about 0.33 hours; Then transfer to a 4 liter branch funnel and add 150 grams of concentrated hydrochloric acid to 1100 grams of water. Wash with gram solution. The product is then washed two more times with water. child For the water washes, 1000 ml of water is used for each wash. This washed reaction product is Continuous distillation removes unreacted butyl acrylate and toluene. This first The residue of one distillation step is further distilled at a pressure of 9-10 mmHg and then Collect 785 grams of the desired adduct at a temperature of 105-115°C.

(b) Diels-Alder addition of butadiene-butyl acrylate prepared above (4550 grams, 25 moles), and 1600 grams (50 moles) of sulfur into a 12 liter flask equipped with a stirrer, reflux condenser and nitrogen inlet tube. do. The reaction mixture is heated at a temperature in the range 150-155°C for 7 hours. child During this time, nitrogen is passed through it at a rate of about 0.5 cubic feet per hour.

After heating, the mass is cooled to room temperature and filtered, leaving the sulfur-containing product in the filtrate. It is.

(Margin below) The antioxidant (D) can also be an alkylated aromatic amine. Alkylation Aromatic amines include compounds represented by the following formula: where Ar3 and Ar' are independently mononuclear or polynuclear substituted or unsubstituted aromatic group; and R6 is hydrogen, halogen, OH, Nl2, SH, NO A hydrocarbyl group having 2, or 1 to about 50 carbon atoms. Ar3 and Ar' can be any of the above aromatic groups. Ar' and/or A When r' is a substituted aromatic group, Ar3 and/or the substituent on Ar' The number independently refers to the number of positions available for substitution on Ar' and/or Ar'. This is the range. These substituents are independently halogens (e.g. chlorine, bromine). etc.), OH, Nl2.5HSNO2, *t:-Hax to about 50 carbon atoms selected from the group consisting of hydrocarbyl groups having

In a preferred embodiment, the antioxidant (D) is represented by the formula: where R7 and R9 are independently hydrogen or 1 to about 50 carbon atoms. hydrocarbyl groups having from about 4 to about 20 carbon atoms, preferably from about 4 to about 20 carbon atoms. It is a drocarbyl group. Examples of aromatic amines include p,p-dioctyldiphenyl Amine; octylphenyl-β-naphthylamine; octylphenyl-α-naph Thylamine; Phenyl-α-naphthylamine; Phenyl-β-naphthylamine; p-octylphenyl-α-naphthylamine and 4-octylphenyl-1- Includes octyl-β-naphthylamine and di(nonylphenyl)amine, Di(/nylphenyl)amine is preferred.

U.S. Patent Nos. 2.558.285; 3.601.632; 3.368.9 No. 75; and No. 3.505.225 is a diaryl group within component (D). Disclosing Min. The contents of these patents are incorporated herein by reference. ing.

The antioxidant (D) used in the present invention is one of several types of phenolic compounds. or more. These phenolic compounds do not contain metals It can be a phenolic compound.

In one embodiment, the antioxidants of the invention include at least one metal-free Hindered phenols may be mentioned. Fring derivatives may also be used. Hindered phenol is and in the claims), defined as containing a sterically hindered hydroxyl group. These include dihydroxy 7-aryls in which the hydroxyl groups are in the 0- or p-position relative to each other. derivatives of the compound.

This metal-free hindered phenol has the following formulas xv1XVI and XVI + can be represented by: sulfalkyl group, each RI[l is hydrogen or alkyl is a kill group, and R1+ is hydrogen or an alkyl group containing from 1 to about 9 carbon atoms. and each RI2 is independently hydrogen or a methyl group. preferred In some embodiments, Rle has about 3 to about 50 carbon atoms, preferably about 6 carbon atoms. Contains ~20 carbon atoms, more preferably about 6 to about 12 carbon atoms It is an alkyl group. Examples of such groups include hexyl, heptyl, octyl , decyl, dodecyl, tripropenyl, tetrapropenyl, and the like. R Examples of groups RI9 and R11 include propyl, isopropyl, butyl, Included are secondary butyl, tertiary butyl, heptyl, octyl and nonyl. good Preferably, each R9 and R1+ is a tertiary group (e.g., tert-butyl, tertiary atom). mill, etc.). Phenolic compounds of the type represented by formula xv include the species In one embodiment, such a phenol can be prepared by first The para-substituted alkylphenol is prepared and then desirably By alkylating this partially substituted phenol at the 6- or 6-position, stepwise It can be prepared by various methods. of the type represented by formula xv1 and formula XVI + When it is desired to prepare a hardened phenol, a second stage alkyl The alkylation is carried out under conditions in which only one position ortho to the hydroxyl group is alkylated. be exposed.

Examples of useful phenolic substances of the type represented by formula xv include: =2-t-butyl-4-heptylphenol: 2-t-phthyl-4-octyl Phenol; 2-t-butyl-4-dodecylphenol; 2,6-di-t-butyl 2,6-dibutyl-4-butylphenol ;2.6-di-t-butifure 4-dode/luphenol;2-methyl-6-di t-Butyl-4-heptylphenol; 2,4-dimethyl-6-t-butylphenol 2.6-t-butyl-4-ethylphenol; 4-t-butylcatechol 2,4-di-butyl-p-cresol; 2,6-di-t-butyl-4- Methylphenol; and 2-methyl-6-di-t-butyl-4-dotesylphene Nord.

Examples of ortho-coupled phenols of the type represented by formula xv1 include: Included: 2.2-bis(6-t-butyl-4-hebutylphenol);2. 2-bis(6-t-butyl-4-octylphenol); 2.6-bis(1°- methylcyclohexyl)-4-methylphenol; and 2,2-bis(6-t -butyl-4-dodecylphenol).

Phenolization of the type represented by formula XVI+ with alkylene coupling The compound is a phenolic compound derived from a phenol represented by formula xv in which R1+ is hydrogen. compounds and aldehydes (e.g. formaldehyde, acetaldehyde, etc.) or It can be prepared by reaction with a ketone (eg acetone). phenolic compounds and aldehydes and ketones are well known in the art. , and this method does not need to be described in detail herein. Illustrate this method phenolic compounds of the type of formula Xv in which R1+ is hydrogen is a base or acid (e.g. , sulfuric acid) and this mixture is then contacted with an aldehyde or ketone. Let me touch it. After this opening, the mixture is heated to reflux and as the reaction progresses. to remove water.

Example 1 of a phenolic compound of the type represented by formula XV11 2.2'-methylene-bis(6-1-butyl-4-heptylphenol) ); 2,2'-methylene-bis(6-1-butyl-4-octylphenol ); 2.2°-methylene-bis-(4-dodenyl-6-t-butylphenol) ;2,2°-methylene-bis-(4-octyl-6-t-butylphenol); 2.2-methylene-bis-(4-octylphenol); 2,2°-methylene- Bis-(4-dodecylphenol; 2,2-methylene-bis-(4-hebutylphenol) 2,2-methylene-bis(6-t-butyl-4-dodecylphenol); 2,2-methylene-bis(6-t-butyl-4-dodecylphenol) 2,2°-methylene-bis(6-t-phthyl-4-tetrapropenyl); phenol; and 2,2°-methylene-bis(6-t-butyl-4-butylphenylene); Nol This alkylene-coupled phenol (ma, phenol (2 equivalents) ) with 1 equivalent of aldehyde or ketone. Ru. Examples of low molecular weight aldehydes (preferred and particularly preferred of useful aldehydes) Nagi formaldehyde, their reversible polymers (e.g. formaldehyde) ), trioxane, acetaldehyde, etc.

As used herein and in the claims, the term "formaldehyde" is believed to include such reversible polymers. This alkylene is powerful derived from phenols (or phenols or substituted alkylphenols). Preferred are substituted alkylphenols which can be derived from t'I0. , must have an ortho or (yobara) position available for reaction with the aldehyde. do not have.

In one embodiment, the phenol is a compound capable of producing sterically hindered hydroxyl groups. Contains one or more alkyl groups that cannot occur or occur. This alkylene Examples of hindered phenols that can be used in the formation of coupled phenols includes = 2,4-dimethylphenol; 2,4-sheet t-butyl Thylphenol, 2,6-di-t-butylphenol; 4-octyl-6-t- butylphenol etc.

In one preferred embodiment, the alkylene-coupled phenol is prepared by The phenols containing at least 6 carbon atoms in the rose position are defined as It is a phenol substituted with an aliphatic group. Generally, this alkyl group has 6 to Contains 12 carbon atoms. Preferred alkyl groups are ethylene, propylene, i1 combination of l-butene and isobutyne, preferably propylene tetramer or or derived from trimmers.

The reaction between phenol and aldehydes, their polymers or ketones is usually carried out indoors. and about 150°C, preferably about 50-125°C. This anti The reaction is preferably an acidic or basic substance (e.g. hydrochloric acid, acetic acid, sulfuric acid, water ammonium oxide, sodium hydroxide or potassium hydroxide) Ru. The relative amounts of reagents used are not critical, but generally formaldehyde or from about 0.3 to about 2.0 moles of phenol per equivalent of or other aldehyde. The following examples are of the type represented by formula xv and formula XVI+. The preparation of phenolic compounds is illustrated.

Example D-6 A reaction vessel was charged with 3192 parts (12 moles) of 4-tetrapropenylphenol. Ru. Heat this phenol to 80°C for 30 minutes, and add 93% sulfuric acid solution to this container. Add 21 parts (0.2 mol) of liquid. Heat this mixture to 85 °C and 1344 parts (24 moles) of isobutylene are added over time. This temperature is 85 Maintain between °C and 91 °C. After introducing isobutylene, the reaction system was heated at 85° Blow nitrogen at a rate of 2 standard cubic feet per hour at C for 30 minutes. It's crowded. Calcium hydroxide (6 parts, 0.2 moles) was added to the reaction vessel along with 12 parts of water. Add to. Heat this mixture to 130'C under nitrogen for 1.5 hours. do. The reaction system was heated under vacuum at 130°C and 20IIIHg for 30 minutes. Stripping. The residue was cooled to 90°C and filtered through a diatomaceous filter. The desired product is obtained. This desired product, the filtrate, is 0°90 It has a specific gravity of 1 and a hydroxy percentage (Grinard method) of 4.25 (theoretical value). 4.49).

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

Heat the phenol to 95°C to 100°C and then add 9 Add 5 parts of 3% sulfuric acid solution. This container was incubated at 100°C for 17 hours. Add butylene (168 parts, 3 moles). After introducing isobutylene, this reaction system , at a rate of 2 standard cubic feet per hour at 100°C for 172 hours. Insert nitrogen. Add 890 parts (2,98 mole) of the above phenol to the reaction vessel. ) and heat to 34-40°C. Add 37% formal Add aqueous dehyde solution (137 grams, 1.7 moles). Remove the water from this mixture While heating, heat to 135°C. At a rate of 1.55 cfh at 105-110℃ and start blowing nitrogen. The reaction mixture was heated at 120 °C under nitrogen for 3 Hold for an hour, cool to 83°C, then add 50% sodium hydroxide to the container. 4 parts (0.05 mol) of an aqueous solution of aluminum are added. The reaction mixture was heated under nitrogen for 13 Heat to 5°C. The reaction mixture was heated to 135°C and Vacuum stripped to 20 mmHg, cooled to 95°C, and the residue Filter through sawdust. This product has a hydroxypere of 5.47 (theoretical value 5.5). Cent (Grinard method) and 682 (theoretical value 6 is also 7) molecule! ! (vapor phase immersion (permeability method).

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

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

Example D-9 Except that the phenol of Example D-6 was replaced with the phenol of Example D-8. , repeat the general method of Example D-7. In this method, [1] The ringed phenol contains 5.74% hydroxyl groups.

In other embodiments, the lubricating compositions of the present invention are metal-free (i.e., ashless). ) may contain alkylphenol sulfides. A method for preparing this sulfide Rukylphenol is represented by formula XV as described above, where R1+ is hydrogen. ) types of phenols. For example, alkylphenol sulfide Alkylphenols that can be converted to include 2-t-butyl-4-hebutylphenol. 2-t-butyl-4-octylphenol; and 2-t-butyl-4- Examples include dode/luphenol.

The term [alkylphenol sulfide] refers to di(alkylphenol) moiety. Nosulfides, disulfides, polysulfides, and alkylphenols Sulfur chloride, sulfur dichloride or other products obtained by reaction with elemental sulfur It means to include. 1 mole of phenol is about 0.5 to 1.5 moles or Reacts with higher amounts of sulfur compounds. For example, alkylphenol sulfide , 1 mole of alkylphenol and 0.5 to 10 moles of sulfur dichloride are mixed. It can be easily obtained by The reaction mixture is typically about 150-160' It is maintained at F for about 2 to 5 hours. The resulting sulfide is then dried and filtered. . When elemental sulfur is used, 1 mole of alkylphenol is 0.5-2. reacts with 0 moles of elemental sulfur and at temperatures of about 150-250°C or higher Temperature is typically used. Drying operation under nitrogen or similar inert gas It is also desirable to do so.

Suitable basic alkylphenol sulfides are described by Eba, U.S. Pat. No. 3,372. ．． No. 116, No. 3.410.79'8 and No. 4.021.419. , the contents of which are incorporated herein by reference.

These sulfur-containing phenols described in U.S. Pat. No. 4.021.419 The composition is made by sulfurizing a substituted phenol with sulfur or a sulfur halide. Afterwards, this sulfurized phenol is reacted with formaldehyde or their reversible polymers. It can be obtained by making it correspond. On the other hand, substituted phenols are first treated with formaldehyde. reaction with sulfur or sulfur halides to form the desired alkyl can produce phenol sulfide. Disclosure of U.S. Patent No. 4.021.419 Contains disclosures of such compounds and methods of preparing such compounds. , incorporated herein by reference. Synthetic oils of the types described below are , in place of the mineral or natural oil used in preparing the salts used in this invention. used. .

In other embodiments, the antioxidant (D) is a phenothiazine, a substituted phenothiazine, or a derivative of formula XVI, where RIA is a higher alkyl Kyl group, or alkenyl, aryl, alkaryl, or aralkyl group and RI3 is selected from the group consisting of (and mixtures thereof), and RI3 is an alkylene group, lukenylene group or aralkylene group, or a mixture thereof; each RI5 is , independently, alkyl, alkaryl, arylalkyl,! -rogen, hydrogen Roxy, alkoxy, alkylthio, arylthio, and (ma-fused aromatic rings) , or a mixture thereof; a and b (y, each independently O or In other embodiments, the phenothiazine derivative (of formula Can be represented by X: Cocote, R13, Rld, RI5, a and b + t, defined for formula XVIIIE It is the same as what was defined.

The above phenothiazine derivatives and methods for their preparation (U.S. Pat. No. 4,78 No. 5,095, the disclosure of this patent describes such methods and compounds. the teachings of which are incorporated herein by reference. In one embodiment, di Alkyldiphenylamines can be , treated with sulfur for a time sufficient to complete the reaction. It's iodine Such catalysts can be used to establish sulfur bridges.

Phenothiazine and its various derivatives are phenothiazines containing free NH groups. gin compound with the formula R14SR+30)! (Here, R1' and R13 are the formula by contacting with a thioalcohol (as defined for XVII+) , can be converted to a compound of formula XVI. This thioalcohol under basic conditions can be obtained by reacting mercaptan R''SH with alkylene oxide.

On the other hand, this thioalcohol can melt with terminal olefins under free radical conditions. It can be obtained by reacting with captoethanol. This thioalcohol The reaction between the compound and the phenothiazine compound is generally carried out in an inert solvent (e.g. benzene, etc.). Strong acid catalysts (e.g. sulfuric acid or Latoluenesulfonic acid) is about 1 part to about 50 parts per 1000 parts of phenothiazine. A catalytic amount of is preferred.

This reaction is generally carried out at reflux temperature with removal of the water formed. convenient The reaction temperature may be maintained between 80°C and 170°C.

Tas represented by formulas XVII+ and XIX (where X is 1 or 2) It is desirable to prepare compounds of the same type, i.e., sulfones or sulfoxides. When the derivative prepared by the reaction with the thioalcohol is under a lancet in a solvent such as glacial acetic acid or ethanol, such as hydrogen peroxide. Oxidized by oxidizing agents such as Conveniently, the partial oxidation occurs at about 20°C to about 150°C. happen. The following examples demonstrate the use of non-phenolic antioxidants ( Figure 2 illustrates the preparation of phenothiazines that can be used as D).

Example D-10 1 mole of phenothiazine was added to 1 liter of round bottom flask along with 300 ml of toluene. Put it in Lasco. A nitrogen blanket is maintained in the reactor. Phenothiazi 0.05 mol of sulfuric acid catalyst is added to the mixture of chlorine and toluene. This mixture is and heated to reflux temperature for approximately 90 minutes. Add 11 moles of nol dropwise. As water is formed during the reaction process, Remove continuously.

The reaction mixture was continuously heated under reflux until substantially no further water was evolved. Stir. The reaction mixture is then cooled to 90°C. This sulfuric acid catalyst is neutralized with sodium hydroxide. This solvent was then heated to 2 KP at 110°C. Remove under vacuum at a. This residue was filtered to give the desired product in 95% yield. You can get things.

In other embodiments, the antioxidant (D) is a transition metal-containing composition. this Transition metal-containing antioxidants are oil-soluble. The composition generally includes titanium, Manganese, cobalt, nickel, copper, and zinc (preferably manganese, copper, and at least one transition metal selected from zinc, more preferably copper). Contains. These metals include nitrates, nitrites, halides, and oxyhalides. ionides, carboxylates, borates, phosphates, phosphites, sulfates, sulfites, Can be in carbonate and oxide forms. The transition metal-containing composition generally contains gold. This is the form of a genus-organic compound complex. This organic compound includes carboxylic acids and esters, monothiophosphoric acids and dithiophosphoric acids, dithiocarbamic acids, and dispersants. can be mentioned. Generally, the transition metal-containing composition renders the composition oil-soluble. Therefore, it contains at least about 5 carbon atoms.

In one embodiment, the organic compound is a carboxylic acid. This carboxylic acid is one ~ about 10 carboxylic groups, and 2 to about 75 carbon atoms, preferably Containing 2 to about 30 carbon atoms, more preferably 2 to about 24 carbon atoms. It can be a monocarboxylic acid or a polycarboxylic acid with. An example of monocarboxylic acid is 2-ethyl bovine acid, octanoic acid, decanoic acid, oleic acid, linoleic acid, Included are stearic acid and gluconic acid. Examples of polycarboxylic acids include Kono 1 Includes phosphoric acid, malonic acid, citraconic acid, and substituted forms of these acids. . This carboxylic acid is one of the above hydrocarbyl-substituted carboxylic acid acylating agents. can be obtained.

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

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

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

In Example D-1 50 parts of copper acetate hydrate, 283 parts of 100 nitral mineral oil, 250 ml of xylene 507 parts of Little and acylated nitrogen intermediate were heated at 160"C for 32 hours, Further add 3240 parts of 100 22-toral mineral oil and heat at 130°C to 240’C. A metal complex is obtained by heating for 3.5 hours.

Here, this acylated nitrogen intermediate is polybutene-substituted succinic anhydride (which is t a chlorinated polybutene having a number average molecular weight of ooo and a chlorine content of 4.3%; 4,392 parts (prepared by reaction with 20 mol% excess of maleic anhydride) and , Al+ of 3 parts by weight of triethylenetetramine and 1 part by weight of diethylenetriamine Prepared by reacting with 540 parts of L/7 amine polyamine mixture . The reaction system is vacuum stripped to 110'C and 5 mmHg.

When this reaction system was filtered through diatomaceous earth, 59% by weight of oil and 0.3% by weight of copper were obtained. and a filtrate with 1.2% by weight of nitrogen is produced.

Example D-12 (a) 420 parts (7 moles) of isopropyl alcohol and 51 parts of n-butyl alcohol 8 parts (7 moles) and heated to 60°C under nitrogen atmosphere. heat. Phosphorus disulfide (647 parts, 2.9 1 mol) over 1 hour. This mixture was allowed to cool for an additional hour. Stir.

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

(b) Prepare a mixture of 69 parts (0.97 equivalents) of cuprous oxide and 38 parts of mineral oil, 239 parts (0.88 equivalents) of the phosphorodithioic acid prepared in a) was added over a period of about 2 hours. I add. The reaction is slightly exothermic during the addition, after which the temperature is reduced to ca. The mixture is stirred for an additional 3 hours while maintaining the temperature at 706C. 10% of this mixture Strip to 5°C/10+u+FIg and filter. This filtrate is a dark green liquid containing 17.3% copper.

Example D-13 A mixture of 285 parts of 100 neutral mineral oil and 260 parts (1,8 equivalents) of copper oxide (1). Prepare the compound and heat to 93°C. While maintaining the temperature at 95℃, Propylmethylamyldithiophosphoric acid (which contains phosphorus disulfide, and methylamyl dithiophosphoric acid) prepared from a 60:40 molar mixture of alcohol and isopropyl alcohol) (1000 parts, 3.3 eq.) is added to this mixture over a period of 3 hours.

Steam is bubbled through the reaction mixture at 105-110°C for 3 hours. Next The reaction mixture is then sparged with nitrogen for 1 hour at 82-88°C.

This residue is filtered through diatomaceous earth.

This filtrate is the desired product and contains 20% oil and 15.35% copper. have

(E) and alkali 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 , commonly referred to as ash-containing cleaning agents. This acidic organic compound is at least or one sulfur-containing acid, carboxylic acid, phosphorus-containing acid, or phenol or It can be a mixture of these.

The carboxylates, magnesium, barium and strontium are the preferred alkaline salts. Magnesium is a potassium earth metal and is preferred in certain lubricating oil compositions. child Salts containing mixtures of two or more ions of these alkaline earth metals are , can be used.

Salts useful as component (E) can be neutral or basic.

These neutral salts are nearly sufficient to neutralize the acidic groups present in this salt anion. and this basic salt contains an excess of alkaline earth metal. Contains similar metal cations. Generally, this basic or overbased salt is preferable. This basic or overbased salt has a metal ratio (M R), more particularly having a metal ratio of about 2 to about 30 or 4 degrees.

Methods commonly used to prepare this basic (or overbased) salt The mineral oil solution of the acid is treated with a stoichiometric excess of the metal neutralizing agent (e.g. metal oxidation substances, hydroxides, carbonates, bicarbonates, sulfides, etc.) at temperatures above about 50°C. This includes heating. Additionally, to aid in mixing large excess metals, neutralization Various accelerators may be used in the process. These accelerators include compounds such as: These include: phenolic substances (e.g. phenol and naphthol); Alcohols (e.g. methanol, 2-propanol, octyl alcohol and amines (e.g. aniline, phenylene diamide); and dodecylamine). Particularly effective method of preparing basic barium salts In the presence of a phenolic accelerator and a small amount of water, acid and excess 17) barium and heating the mixture to a high temperature (e.g., 60°C to about 200°C). °C).

As stated above, the acidic organic compound from which the salt of component (E) is derived is at least one sulfur-containing acid, carboxylic acid, phosphorus-containing acid, or phenol; or It can be a mixture of

Sulfur-containing acids include sulfonic, thiosulfonic, sulfinic, and sulfenic acids. , partially esterified sulfuric acid, sulfite and thiosulfuric acid.

Sulfonic acids useful in preparing component (E) include the following formulas (XX) and (X XI): R-T (5 oil) y (XX ) In these formulas, Ro is an aliphatic hydrocarbon group or an aliphatic substituted cyclic aliphatic group. Aliphatic or essentially hydrocarbon groups (these contain acetylenic unsaturation) First, it contains up to about 60 carbon atoms). When Ro is aliphatic, it are usually small (both containing about 15 carbon atoms; Ro is substituted with an aliphatic When cycloaliphatic, the aliphatic substituents usually have a total of at least about 12 Contains carbon atoms. Examples of Ro include alkyl groups, alkenyl groups and alkoxy groups. sialkyl groups, and aliphatic-substituted cycloaliphatic groups (where the aliphatic substitution The groups are alkyl, alkenyl, alkoxy, alkoxyalkyl, carboxy (such as Lukiru). Generally, this cycloaliphatic prokaryote is a cycloalkane or is a cycloalkene (e.g., cyclopentane, cyclohexane, cyclohexene) or cyclopentene). Specific examples of Ro include cetylcyclohe xyl, laurylcyclohexyl, cetyl-diethyl, octadecenyl, and and groups derived from: petroleum, saturated and unsaturated paraffin waxes, and olefinic polymers (which contain about 2 ml per olefinic monomer unit) Polymerized monoolefin containing ~8 carbon atoms and 1 monomer unit (includes diolefins containing 4 to 8 carbon atoms per portion). Ro is also Other substituents (e.g. phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, ni Toroso, lower alkoxy, lower alkyl mercapto, carboxy, carbalco quin, oxo or thio), or interrupting gro ups) (for example, -NH-1-0- or -5-).

R in formula xx is generally a hydrocarbon group or an essentially hydrocarbon group, preferably or contains about 4 to about 60 aliphatic carbon atoms without acetylenic unsaturation. A hydrocarbon group or an essentially hydrocarbon group, preferably an aliphatic hydrocarbon group ( for example, alkyl or alkenyl). However, R is also essentially substituents or interrupting groups (e.g., (listed). Generally, any non-carbon present in Ro or R Elementary atoms also do not account for more than 10% of their total weight.

■ Aromatic hydrocarbons (e.g. benzene, naphthalene, anthracene or bicarbonate) cyclic nuclei from which phenyl) can be derived, or heterocyclic compounds (e.g. pyridine, It is a cyclic nucleus from which indole or isoindole) can be derived. Usually, T is Aromatic hydrocarbon nuclei, especially benzene or naphthalene nuclei.

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 generally also 1.

The sulfonic acid is generally a petroleum sulfonic acid or a synthetically prepared alkali is sulfonic acid. The most useful products of this petroleum sulfonic acid include acid Sulfonation of suitable petroleum fractions using continuous sludge removal and refining There are some products prepared by Synthetic alkaryl sulfonic acids are usually benzene (e.g., a mixture of benzene and a polymer such as tetrapropylene) der-Kraf reaction product). The following prepares salt (E) A specific example of a particularly useful sulfonic acid is Such embodiments also include component (E) It should be understood that this serves to illustrate salts of sulfonic acids useful as Ru. In other words, for each sulfonic acid listed, their corresponding base It is intended to be understood that alkali metal salts are also exemplified. (same applies to the list of other acids listed below). Such sulfonic acids Contains mahogany sulfonic acid, pritestock sulfonic acid, and petrolatum sulfonic acid. Pontic acid, mono- and polywax-substituted naphthalene sulfonic acid, cetyl chloro Benzene sulfonic acid, cetylphenol sulfonic acid, cetylphenol disulfonate acid sulfonic acid, cetoxylic prylbenzenesulfonic acid, dicetylthianthrene Sulfonic acid, dilauryl-β-naphthol sulfonic acid, capril nitronaphtha Rensulfonic acid, saturated paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid, tetraisobutylene Rensulfonic acid, tetraamylenesulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitroso-substituted paraffin wax sulfonic acid, petroleum naphthene sulfone acid, cetylcyclopentylsulfonic acid, laurylcyclohexylsulfonic acid, Nor- and polywax-substituted cyclohexyl sulfonic acid, dodecylbenzenesulfonate Included are phonic acids, "gweimer alkylate" sulfonic acids, and the like.

Alkyl-substituted benzenesulfonic acid, where the alkyl group has at least 8 carbon atoms), including dodecylbenzene "bottoms" sulfonic acids , is particularly useful.

The latter is an acid derived from benzene, which is similar to propylene tetramer or is alkylated with isobutyne trimer to form 1, 2, and 3 molecules on the benzene ring. One or more branched C12 substituents are introduced. dodecylbenzene bottom (primarily mixtures of mono- and didodecylbenzenes) are commonly used in household cleaning products. It is available as a by-product of manufacturing.

Alkylated bottoms formed during the production of linear alkyl sulfonates (LAS) Similar products obtained from It is useful.

For example, sulfonate salts are produced from by-products of the manufacture of detergents by reaction with SO3. It is well known to those skilled in the art. For example, the rE of Kirk-Otbn+er ncyclopedia of Chemical Technology J ( 2nd edition, volume 19, p. 291 et seq.; This is from John Wiley & 5o ns (N, Y, ) published in 1969). See.

Basic sulfonate salts, which are mixed into the lubricating oil compositions of the present invention as component (E). ) and other descriptions of their method of manufacture may be found in the following U.S. patents: U.S. Patent No. 2.174°110; No. 2.202.781; No. 2.239 ．． No. 974; No. 2.319.121; No. 2, 337.552; No. 3.488 ．． No. 284; No. 3.595.790; and No. 3.7911.012, which et al., the contents of which are incorporated herein by reference for their disclosure in this regard. ing.

Suitable carboxylic acids from which useful alkaline earth metal salts (E) can be prepared include: , aliphatic carboxylic acids, cycloaliphatic carboxylic acids, and aromatic monobasic carboxylic acids Acids and polybasic carboxylic acids include naphthenic acid, alkyl m or alkenyl-substituted cyclopentanoic acid, alkyl-substituted or alkenyl-substituted cyclohexanoic acid, and alkyl- or alkenyl-substituted aromatic carbs. Contains bonic acid. The aliphatic acid generally has about 8 to about 50 carbon atoms, preferably Preferably, it contains about 1z to about 25 carbon atoms. Cycloaliphatic carboxylic acids and and aliphatic carboxylic acids are preferred; they may be saturated or unsaturated. identification Examples include 2-ethylhexanoic acid, lylunic acid, propylene tetramer-substituted male Inic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitole Inic acid, linoleic acid, lauric acid, oleic acid, linoleic acid, undecylic acid, Dioctylcyclopencune carboxylic acid, myristic acid, dilauryl decahydrona Phthalenecarboxylic acid, stearyl octahydroindenecarboxylic acid, valmitine acids, alkylsuccinic acids and alkenylsuccinic acids, petrolatum or hydrocarbons Acids formed by oxidation of wax, and acids such as tall oil acids, rosin acids, etc. Commercially available mixtures of two or more carboxylic acids are included.

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 carboxylic acid groups.

Trivalent phosphorus-containing acids useful in the preparation of component (E) include organophosphoric acids, phosphoric acids or phosphoric acids. sphinic acids, or thio analogs of these (zero shear force).

Component (E) also includes phenol (i.e., containing a hydroxyl group directly bonded to the aromatic ring ζ). can be prepared from compounds with The term "phenol" used here is a compound with more than one hydroxyl group attached to an aromatic ring (e.g. catechol , resorcinol and hydroquinone). That's it↓This is my turn again, Al Kylphenol (e.g. I!, Fre//-l and ethylphenol), and alkaline Lucenil Fenorca (included).

at least about 3 to 100 carbon atoms, especially about 6 to 50 carbon atoms Pheno-#(fileva, heptylphenol) containing one alkyl substituent , octylphenolphenol, tetrapropenealkyl Decylphenol and polybutenylphenol. More than one alkyl substitution Phenyl groups containing phenol groups can also be used, but availability and ease of production Monoalkylphenol is preferred because of its properties.

Condensation product of the above phenol and at least one lower aldehyde or ketone objects are also useful. The term "lower" refers to carbon atoms containing 7 or fewer carbon atoms. Indicates Rudehydoton. 1 to the appropriate aldehyde, formaldehyde, cetaldehyde There are a number of forces such as hydrogen, propionaldehyde, etc.

The equivalent weight of this acidic organic compound is the molecular weight of the acidic organic compound. That is, it is the value divided by the number of sulfonic acid groups (or more luboquine groups).

The amount of component (E) contained in the lubricants of the invention may also vary over a wide range. The amount obtained and useful in the present invention ranges from about 0% or about 0.01% to about 5% or less. The above can be changed. Generally, component (E) is present in an amount of about 0.1 to about 2%. .

The following examples illustrate neutral and basic alkaline earth metals useful as component (E). Illustrating the preparation of salts.

Example E-1 Alkylphenyl sulfonic acid has an average molecular weight of 450; vapor phase 906 grams of oil solution (osmotic pressure method), 564 grams of mineral oil, and 600 grams of toluene. gram, 98.7 grams of magnesium oxide, and 120 grams of water, at a rate of about 3 cubic feet per hour for 7 hours at a temperature of 78-85°C. or inject carbon dioxide. The reaction mixture is constantly stirred during carbonation.

After carbonation, the reaction mixture was stripped to 165°C/20 torr. and filter the residue. This filtrate contains the desired overbased sulfonic acid polymer. Gnesium (which has a metal ratio of approximately 3) in oil (34% oil) It is.

Example E-2 Chlorinated poly(isobutyne), which has an average chlorine content of 4.3% and 1 mole of maleic anhydride (containing 82 carbon atoms) and 1 mole of maleic anhydride Polyisobutenyl succinic anhydride is prepared by reacting at 0°C. Obtained The obtained polyisobutenyl succinic anhydride has a saponification number of 90. This anhydrous Koha At 25°C for a mixture of 1246 grams of citric acid and 1000 grams of toluene. , add 76.6 grams of barium oxide. Heat this mixture to 115°C, Add 125 grams of water dropwise over an hour. This mixture is then completely Reflux at 150°C until all barium oxide has reacted. Stripping and filtration to obtain a liquid containing the desired product.

Example E-3 160 grams of U oil and polyisobutenyl (number average Mw=950) succinic anhydride 111 grams, 52 grams of n-butyl alcohol, 11 grams of water, and Pe1 adov (DotC identified as containing 94-97% CaCl2) mixture of 1.98 grams of hemica1 product) and 90 grams of hydrated lime are mixed together. Additional hydrated lime to neutralize the subsequently added sulfonic acid Add. The amount of additional lime depends on the acid number of the sulfonic acid. straight chain dial Killbenzenesulfonic acid (MW=430) in oil solution (1078 grams; 58 % oil) is added, but the temperature of the reaction mixture does not exceed 79°C.

The temperature is adjusted to 60°C. heptylphenol, lime, and formaldehy (64.5 grams) and 217 grams of methyl alcohol were added. I can do it. Add to this reaction mixture up to a base number of 20-30 (bromophenol blue). , inject carbon dioxide. Hydrated lime (112 grams) was added to the reaction mixture; Add carbon dioxide to this mixture to a base number of 45-60 (bromophenol blue). Infuse the essence. During this time, the temperature of the reaction mixture is maintained at 46-52°C. water The latter step of adding Japanese lime followed by blowing in carbon dioxide was repeated three times, but the final repeat, the reaction mixture has a base number of 45 to 55 (bromophenol It is carbonated to roux). The reaction mixture was flash dried at 93-104°C. (flash dried), kettle dry at 149-160℃ dried>, filtered, and adjusted with oil to a Ca level of 12.0%. Ru. This product has a base number of 300 (bromophenol blue), 12.0% Metal content, metal ratio of 12, sulfate ash content of 40.7% by weight and 1.5% by weight is an overbased calcium sulfonate with a sulfur content of . That oi The content is 53% by weight.

Example E-4 Ore m　135　crumb, xylene 330g, alkylphenyl sulfonic acid ( 200 grams (0,235 equivalents) of mineral oil solution (average molecular weight 425), tall oil acid 19 grams (0,068 equivalents), 60 grams of magnesium oxide (approximately 2.75 equivalents) ), a reaction mixture containing 83 grams of methanol and 62 grams of water was at the reflux temperature of the bottle at a rate of 15 grams of carbon dioxide per hour for about 2 hours. It crosses over and becomes carbonated. Next, the introduction rate of this carbon dioxide was set to about 7 per hour. methane by reducing the temperature to about 98°C for 3 hours. Remove the nols. Add water (47 grams) and add another 3.5 grams at a temperature of approximately 95°C. Continue carbonation over time. This carbonated mixture was then heated to 140°C. Strip by heating to a temperature of ~145°C for 2.5 hours.

This results in a basic magnesium salt oil characterized by a metal ratio of about 10. le solution force (obtained).

This carbonated mixture was cooled to about 60°C to 65'C, and then 208 grams of magnesium oxide, 60 grams of magnesium oxide, 83 grams of methanol and water Add 62 grams. At the reflux temperature of methanol, at a rate of 15 grams per hour 2 hours with a counter iron (if it breaks, restart carbonation. Addition rate of carbon dioxide to 1 Reduce the temperature by 7 grams per hour and increase the temperature to approximately 95°C for 3 hours (over 3 hours). Methanol is removed by removing the methanol. Add additional calories;+l<41.5 grams 3.5 at a rate of 7 rams per hour at a temperature of about 906°C to 95°C. Continue carbonating for 35 hours. (Heat to about 150″C to 160°C, then 20 minutes at this temperature. Reduce the pressure to 1 mm, (Hg-), then strip further. Ru. When this carbonated reaction product is filtered, the filtrate has a metal specific gravity of 20. A solution of the desired basic magnesium salt in oil is further characterized.

Example E-5 o) 118 grams of 5ifm anhydrous phosphoric acid, and 2-butyl alcohol and acetic acid. 140 grams of a 65:35 molar mixture of mill alcohol and 15% calcium chloride A mixture of 43.2 grams of aqueous solution and 86.4 grams of lime is prepared. Temperature 8 While maintaining the temperature below 0°C, add the first m bright stock monoalkyl to this mixture. 85% solution of rubenscens sulfonate (molecular weight approximately 480, molecular weight 110) Add 100 grams of 100 g .

The mixture is dried at 150°C to a water content of approximately 0.7%. Add this mixture to 4 Cool to 6-52°C, whereupon the mixture is added with isobutyl alcohol as described above. - 127 grams of amyl alcohol mixture, 277 grams of methanol, and Heptylphenol fused with Si overbased cyformaldehyde A 31% solution of mol (which has a metal ratio of 8 and 2.2% calcium) Add 87.6 grams. Add 3 increments of 171 grams of lime separately, 50 Carbonate to a neutral base number in the range of ~60. Add the fourth increment of lime, 171 grams. Carbonate to a neutral base number of 45-55. Approximately 331 grams of carbon dioxide Use. This mixture is dried at 150°C to approximately 0.5% water content. . The reaction mixture is filtered and the filtrate is the desired product. This product is , contains 41% oil, 12% calcium and has a metal ratio of 11.

(Margin below) (F) Magic 1st Creation The lubricating oil compositions of the present invention also provide friction modifiers that provide the lubricating oil with more desirable friction properties. May contain stimulants. Generally, to improve performance, from about 001 to about 2 or 3 A weight percent amount of friction modifier is considered sufficient. Various amides and amines, especially Tertiary amines) are effective friction modifiers. Examples of tertiary amine friction modifiers include , N-fatty alkyl N, N-jetanolamine, u-fatty alkyl N, N -Jetoxyethanolamine and the like. Such tertiary amines are By reacting a fatty alkylamine with an appropriate number of moles of ethylene oxide. It can be prepared from Naturally occurring substances (e.g. coconut oil and oleoamines) Tertiary amines derived from Armor Chemical Company 0 specific examples available under the product name ``[:tomeenJ'' include Etho There are meen-C and ethomeen-0 series.

Amide includes fatty acid amides where the fatty acid contains 8 to 22 carbon atoms. It will be done. Examples include oleylamide, stearylamide, laurylamide, etc. be done.

Partial fatty acid esters of polyhydric alcohols are also useful as friction modifiers. child These fatty acids generally contain from about 8 to about 22 carbon atoms and their esters is a dihydric or polyhydric alcohol containing 2 to about 8 or 10 hydroxyl groups Obtained by reaction with Suitable fatty acid esters include norpitane monool. leate, sorbitane dioleate, guIJ cerol monooleate, glycero and mixtures thereof (Emerest 2421 (Em including commercially available mixtures such as Ery Industries Inc.). Can be mentioned. Other examples of partial fatty acid esters of polyhydric alcohols include K, S, Ma rkley, ed., "Fatty Ac1dsJ" (2nd edition, parts 1 and 7, In terscience Publishers (196B)) .

Sulfurized C+2-2a fats, alkyl sulfides and polysulfides (where , the alkyl group containing 1 to 8 carbon atoms), and sulfurized polyolefins. Sulfur-containing compounds, such as fins, function as friction modifiers in the lubricating oil compositions of the present invention. It can function as

The lubricating compositions of the present invention may contain other additives (e.g., supplemental dispersants, antiwear agents, extreme pressure agents). , emulsifiers, demulsifiers, rust inhibitors, corrosion inhibitors, viscosity modifiers, pour point depressants, dyes, and antifoaming agents). These additives depend on the needs of the final product. may be present in varying amounts.

This supplemental dispersant may be any of the following (a), (b), (c), (d), and (e). (a) an amine component other than the above carboxylic acid derivative (A); Powder; (b) Ester dispersant; (C) Mannich dispersant; (d) Dispersant-viscosity modified Good agents; (e) mixtures thereof; In one embodiment, these dispersants are as follows: Can be post-treated with reagents such as: urea, thiourea, carbon disulfide, aldehydes, ketones, Carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron containing compounds, phosphorus-containing compounds, etc.

Amine dispersants include hydrocarbyl substituted amines. These hydrocarbyls Substituted amines are well known to those skilled in the art.

These amines are described in U.S. Pat. No. 3.275.554; : No. 3.454.555; No. 3.565.804; No. 3.755.433 : and No. 3,822.289. The contents of these patents are Reference is made herein for the disclosure of dolocarbylamines and methods of making them. It is used as.

Typically, amine dispersants are used for olefins and olefin polymers (polyalkylene prepared by reacting amines (monoamines or polyamines) with amines (monoamines or polyamines) be done. The polyalkene can be any of the polyalkenes described above. these The amine of can be any of the above amines. Examples of amine dispersants include poly( propylene)amine; N,N-dimethyl-N-poly(ethylene/propylene)amine; amine (monomer molar ratio 50:50); polybutenamine; N,N-di( hydroxyethyl)-N-polybutenamine; N-(2-hydroxypropyl) -N-polybuteneamine; N-polybutene-aniline: N-polybutene morpholy N-poly(butene)ethylenediamine; N-poly(propylene) trimethylene Ndiamine; N-poly(butene)diethylenetriamine; N', N'-poly (butene)tetraethylenepentamine 1, N-dimethyl-N-poly(propylene) )-1,3-propylene diamine and the like.

In other embodiments, the supplemental dispersant may also be an ester dispersant. this The ester dispersant contains at least one of the above hydrocarbyl groups as (A-1). acyl carboxylate (tJI), at least one organic hydroxy compound, and It is prepared by reacting with an amine as necessary. In other embodiments, The ester dispersant comprises the acylating agent and at least one of the hydroxyl It is prepared by reacting with amine.

Examples of this organic hydroxy compound include compounds of the general formula R''(OH). , where R'' 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, where the hydrocarbyl The group contains at least about 8 aliphatic carbon atoms. This hydroxy compound is , aliphatic compounds (e.g. -hydric and polyhydric alcohols), or aromatic compounds ( for example, phenol and naphthol). This ester can be derived Aromatic hydroxy compounds are exemplified by the following specific examples: phenols, β-naphthol, α-naphthol, cresol, resol/nol, catechol, p, p'-dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutyl Phenolnato.

The alcohol from which this ester can be derived preferably has up to about 40 aliphatic carbon atoms, preferably from 2 to about 30 carbon atoms, more preferably from 2 to about 30 carbon atoms; Contains about 10 carbon atoms. These are -hydric alcohols (e.g. methanol ethanol, isooctyl, dodecanol, cyclohexamer, etc.) It can be. In embodiments, these hydroxy compounds are polyhydric alcohols ( For example, alkylene polyol). Preferably, these polyhydric alcohols has from 2 to about 40 carbon atoms, more preferably from 2 to about 20 carbon atoms. and preferably contains from 2 to about 10 hydroxyl groups, more preferably 2 to about 10 hydroxyl groups. 2 to about 6 hydroxyl groups.

Polyhydric alcohols include ethylene glycol (which includes g-, tri-, and (including tetraethylene glycol); brobylene glycol (which includes glycerol; Tanediol; Hexanediol; Sorbitol; Arabitol; Mannitol ; Sucrose; Fructose; Glucose; Cyclohexanediol; Elythyl ritol; and pentaerythritol (which includes gee and tribentaerythritol); diethylene glycol, triglycerol, etc.), preferably diethylene glycol, Ethylene glycol, glycerol, sorbitol, pentaerythritol and and dipentaerythritol.

The polyhydric alcohol has from 2 to about 30 carbon atoms, preferably from about 8 to about] Can be esterified with monocarboxylic acids having 8 carbon atoms, provided that less than In both cases, one hydroxyl group remains unesterified. Examples of monocarboxylic acids include vinegar Acids include propionic acid, butyric acid and fatty carboxylic acids. This fat monocal Bonic acids have about 8 to about 30 carbon atoms and include octanoic acid, oleic acid, stenoic acid, Includes arilic acid, sonolic acid, dodecanoic acid and tall oil acid. These S. Specific examples of esterified polyhydric alcohols include sorbitol oleate (mo/- and dioleates), nrubitol stearates (mono- and dioleates) glycerol oleate (including glycerol mono-, di- and trioleate), and erythritol octanoate.

This carboxylic ester dispersant is prepared by any of several well-known methods. can be done. Preferred due to convenience and superior properties of the esters produced. The method includes the above carboxylic acylating agent and one or more alcohols or Hydroxylation of about 0.5 to about 4 equivalents per equivalent of unlying agent with phenol This includes reacting at the ratio of the compounds. This esterification is usually carried out at approximately 100°C. It is carried out at temperatures exceeding 150°C and 300°C. by-product The water formed as a product is removed by distillation as the esterification progresses. ．． No. 522.179 and No. 4,234,435.

The carboxylic acid ester dispersant is further combined with at least one of the above amines, preferably Alternatively, it may be reacted with at least one of the above polyamines. This amine is It is added in an amount sufficient to neutralize the non-tellated carboxyl groups. Like In a new embodiment, the nitrogen-containing carboxylic ester dispersant comprises acylating agent 1 per equivalent, about 1.0 equivalents to 2.0 equivalents, preferably about 1.0 equivalents to 1.8 equivalents equivalents of hydroxy compound and up to about 0.3 equivalents, preferably from about 0.02 equivalents to It is prepared by reacting with about 0.25 equivalents of polyamine.

In other embodiments, the carboxylic acid alkating agent is a combination of the alcohol and the amine. Both can be reacted simultaneously. The total number of equivalents of this formulation is should be at least about 0.5 equivalents, but generally at least about 0.0. There is 1 equivalent of alcohol and at least 0.01 equivalent of amine.

These nitrogen-containing carboxylic ester dispersant compositions are known in the art. and the preparation of many of these derivatives is described, for example, in U.S. Pat. No. 3,957,854. and No. 4.234.435, the contents of which are hereby incorporated by reference. It has been used as a reference.

This carboxylic ester dispersant and its manufacturing method are known in the art. U.S. Patent Nos. 3,219,666; 3,381,022; 3,522 ．． No. 179; and No. 4.234.435, the contents of which are Disclosure of the preparation of rubonic acid ester dispersants is incorporated herein by reference. It is.

The following example illustrates this ester dispersant and how to prepare such an ester. Show.

Example 5D-1 Chlorinated polybutene with number average molecular weight of 1000 and chlorine content of 4.5% Then, at a temperature of 150 to 220°C, the chlorinated polybutene was heated to 1.2 Substantially replaced by hydrocarbons by heating with a molar proportion of maleic anhydride Prepare succinic anhydride. 874 grams (1 mole) of succinic anhydride and neo A mixture with 104 grams (1 mole) of pentyl glycol was heated at 240-250°C. /30m+n for 12 hours. This residue consists of one of these glycols and It is a mixture of esters obtained from the esterification of both hydroxyl groups.

Example 5D-2 3225 parts (5,0 equivalents) of the polybutene-substituted succinic acylating agent prepared in Example II amount), 289 parts (8,5 equivalents) of pentaerythritol, and 5204 parts of mineral oil. The mixture is heated at 224-235°C for 5.5 hours.

The reaction mixture was filtered at 130'C to obtain an oil solution of the desired product. Ru.

Acylating agents and hydroxy-containing compounds (e.g. alcohols or phenols) The above carboxylic acid ester derivative obtained from the reaction with nitrogen-containing dispersant is and further with any of the above amines (especially polyamines) in the manner described above. Can be reacted.

In other embodiments, the carboxylic acylating agent is a combination of the alcohol and the amine. Both can be reacted simultaneously. The total number of equivalents of this formulation is per equivalent of acylating agent. should be at least about 0.5 equivalents, but generally at least about 0.5 equivalents. There are 0.01 equivalents of alcohol and at least 0.01 equivalents of amine. this carboxylic acid ester derivative compositions are known in the art and these Many preparations of derivatives are described, for example, in U.S. Pat. Nos. 3.957.854 and 4. No. 234.435, the contents of which are incorporated herein by reference. The specific example below σ shows that both the alcohol and the amine are Figure 2 illustrates the preparation of esters that react with cleaning agents.

Example 5D-3 1000 parts of polybutene having a number average molecular weight of about 1000 and 1 part of maleic anhydride. 011 parts (1.1 mol) was heated to about 190"C and the temperature 100 parts (1,43 moles) of chlorine was added to about 4 Add from below the surface over a period of time. This mixture is then stirred at this temperature for several hours. The residue is converted into the desired polybutenyl-substituted acyl succinate by blowing with nitrogen. It is a chemical agent.

A solution of too many parts of the acylating agent prepared as above in 857 parts of mineral oil was stirred. Heat with stirring to about 150'C and, with stirring, add pentaerythritol. Add 109 parts (3,2 parts). This mixture is sparged with nitrogen and approx. About z over 14 hours.

Heat to 0°C to form an oil solution of the desired carboxylic ester intermediate. Ru. This intermediate product has an average of about 3 to about 10 nitrogen atoms per molecule. 19.25 parts (0.46 equivalents) of a commercially available mixture of ethylene polyamines are added. . The reaction mixture is heated at 205°C for 3 hours with nitrogen bubbling. and filter. This filtrate contains 0.35% nitrogen. An oil solution of the desired amine-modified carboxylic ester with (45% is 100% neutral mineral oil).

This supplemental dispersant may also be a Mannich dispersant.

Mannich dispersants generally contain at least one aldehyde and at least one of the above amine and at least one alkyl-substituted hydroxyaromatic compound. formed by reaction.

This reaction is carried out at room temperature to 225°C, typically so'c to about 200'C (75°C to 1sO °C (most preferably). The amount of this reagent is The molar ratio of formaldehyde to amine is from about (1:1:<1) to about (1:3 :3).

This first reagent is an alkyl-substituted hydroxyaromatic compound. This term includes , phenol (preferred), carbon-1 oxygen-, sulfur- and nitrogen cross-linked In addition, phenols bound directly through covalent bonds (e.g. For example, 4,4-bis(hydroxy)biphenyl), derived from fused ring hydrocarbons Hydroxy compounds (e.g. naphthol etc.); and polyhydroxy compounds ( For example, catechol, resorcinol and hydroquinone). 1 [or a mixture of more hydroxyaromatic compounds as this first reagent] can be used.

The hydroxyaromatic compound has at least about 6 carbon atoms (usually at least (also about 30 carbon atoms, more preferably at least 50 carbon atoms) up to about 400 carbon atoms, preferably up to 300 carbon atoms, and Preferably at least one, preferably having up to 200 carbon atoms, Substituted with no more than two aliphatic or cycloaliphatic groups. These groups are , can be derived from the above polyalkenes.

In one embodiment, the hydroxyaromatic compound has a molecular weight of about 420 to about to, ooo Phenols substituted with aliphatic or cycloaliphatic hydrocarbon-based groups having Mn of It is.

The second reagent is a hydrocarbon-based aldehyde, preferably a lower aliphatic aldehyde. It is de. Suitable aldehydes include formaldehyde, benzaldehyde, acetic acid, Toaldehyde, butyraldehyde, hydroxybutyraldehyde and heptana and also aldehyde precursors that react as aldehydes under the reaction conditions (e.g. (e.g. paraformaldehyde, paraldehyde, formalin and metal) and is included. Formaldehyde and its precursors (e.g. rose formaldehyde) Hydroxane, trioxane) are preferred. A mixture of aldehydes as the second reagent can be used.

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

Mannich dispersants are described in the following patents: U.S. Patent No. 3.980.5 No. 69; U.S. Patent No. 3,877.899; and U.S. Patent No. 4.454.05 No. 9 (the content of these patents is incorporated herein by reference for the disclosure of Mannich dispersants). (Incorporated as a reference).

This supplemental dispersant may also be a dispersant-viscosity modifier.

The dispersant-viscosity modifier is a polymer that is functionalized by reaction with an amine source. One example is the skeleton. True or regular block copolymers, or random block copolymers copolymers, or a combination of both. These are, in fact, stoppers. It is hydrogenated before use in the present invention to remove olefinic double bonds. this Methods of carrying out hydrogenation are well known to those skilled in the art. Briefly, hydrogenation is a metal catalyzed (e.g. colloidal nickel, palladium supported on charcoal, etc.) is carried out by contacting this copolymer with hydrogen at pressures above atmospheric pressure. .

Generally, these block copolymers have a low carbon content in the average molecule for reasons of oxidative stability. Up to about 5%, preferably about 0.5%, based on the total number of elementary-carbon covalent bonds Contains the following residual olefinic unsaturation: Such unsaturation is well known to those skilled in the art. It can be measured by many known methods (eg, infrared, NMR, etc.).

Most preferably, these copolymers are identifiable as determined by the analytical method described above. Contains no functional unsaturation.

The block copolymer typically ranges from about to, ooo to about SOO.

000 range, preferably about 30.000 to about Zoo, 000 range It has an average molecular weight of 11 (in). The weight average molecular weight (Mw) of these copolymers is generally ranges from about so, ooo to about 500.00017), preferably about 3 It ranges from 0.000 to about 300.000.

This amine source is an unsaturated amine compound or an unsaturated carboxyl compound capable of reacting with the amine. Can be an acid reagent. This unsaturated carboxylic acid reagent and amine are described above. ing.

Examples of saturated amine compounds include N-(3,6-dioxahebutyl)maleimide, N -(3-dimethylaminopropyl)maleimide, and N-(2-methoxyethyl) xyethyl)maleimide. Preferred amines are ammonia, and It is a primary amine-containing compound. Examples of such primary amine-containing compounds include: Ammonia, N,N-dimethylhydrazine, methylamine, ethylamine, butylene Lamine, 2-methoxyethylamine, N.

N-dimethyl-1,3-propanediamine, N-ethyl-tomethyl-1,3-propanediamine Lopanediamine, N-methyl-1,3-propanediamine, N-(3-aminopanediamine) morpholine, 3-methoxypropylamine, 3-imbutquinpropyl Amine and 4,7-di-oxyoctylamine, N-(3-aminopropyl) -N-1-methylpiperazine, N-(2-aminoethyl)piperazine, (2-aminoethyl)piperazine, (minoethyl)pyridine, aminopyridine, 2-aminoethylpyridine, 2-aminoethylpyridine Nomethylfuran, 3-Amino-2-O-Beef Sotetrahydrofuran, N-(2-Aminofuran) Noethyl)pyrrolidine, 2-aminomethylpyrrolidine, 1-methyl-2-amino Methylpyrrolidine, 1-amino-pyrrolidine, 1-(3-aminopropyl)-2 -Methylpiperidine, 4-aminomethylpiperidine, N-(2-aminoethyl) Morpholine, 1-ethyl-3-aminopiperidine, 1-aminopiperidine, N- Ami-7morpholine and the like are included. Among these compounds, N-(3-amino propyl)morpholine and N-ethyl-N-methyl-1,3-propanediami N,N-dimethyl-1,3-propanediamine is highly preferred. .

Another group of primary amine-containing compounds include various amine-terminated polyethers. be. This amine-terminated polyether has the common trade name Jeffa mina@J, commercially available from Texas Cheatcal Company. It is. Specific examples of these materials include Jeffamine' M-600; M-1000; M-2005; and M-20707 Mino are included.

Examples of dispersants-viscosity improvers are, for example, EP 171.167; No. 3, 687. No. 849; No. 3.756.954; and No. 4.320. (As shown in No. 119) These contents are incorporated herein with respect to the disclosure of dispersant-viscosity modifiers. It is used as a reference.

The above dispersant may be one or more post-treatment agents selected from the group consisting of: Can be post-treated with drugs = boron-containing compounds (mentioned above), carbon disulfide, hydrogen sulfide , sulfur, sulfur chloride, alkenyl cyanide, carboxylic acid acylating agent, aldehyde de, ketones, urea, thiourea, guanidine, dicyanodiamide, phosphate hydrocarbons Rubil, Hydrocarbyl Phosphite, Hydrocarbyl Thiophosphate, Hydrocarbyl Thiophosphite Drocarbyl, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, Hydrocarbyl incyanate, hydrocarbyl incyanate, epoxy formaldehyde, episulfide, formaldehyde or formaldehyde-generating compounds and di/-ol, and sulfur and phenol.

The following U.S. patents disclose post-treatments that can be applied to the carboxylic acid derivative compositions of the present invention. Disclosures of methods and post-treatment reagents are expressly incorporated herein by reference. U.S. Pat. No. 3,087,936; No. 3,254. 025 No. 3. 256, No. 185; No. 3.278, No. 550: No. 3. 282 , No. 955; No. 3. 284. No. 410; No. 3, 338. No. 832; No. 3, 533, 945; No. 3. 639, No. 242; No. 3, 708.　 No. 522; No. 3, 859, 318; No. 3,865,813; No. 4. 2 34, 435 etc. British Patent Nos. 1.085, 903 and 1. 16 2. No. 436 also describes such a method.

In one embodiment, these dispersants are post-treated with at least one boron-containing compound. be managed. The reaction of this dispersant with a boron-containing compound is a process in which these reactive components are This can occur by simply mixing at a temperature of . Typically this temperature is around so’c. It is between about 250°C. In some cases, this temperature is 25°C or higher. It can be low. This upper temperature limit is determined by the specific reaction mixture and/or product fraction. This is the solution.

The amount of boron-containing compound reacted with this dispersant is determined for each mole of dispersant (i.e. The atomic ratio of nitrogen or hydroxyl groups contained in this dispersant is approximately 0.1 ˜10 atomic percent of boron. Preferred reaction components The amount provides from about 0.5 atomic percent to about 2 atomic percent boron for each mole of dispersant. The amount is such that For illustration purposes, an amino acid with 5 nitrogen atoms per molecule Boron having one boron atom per molecule used with one mole of dispersant The amount of element-containing compound is within the range of about 0.1 mole to about 50 mole, preferably about 0, It is within the range of 5 moles to about 10 moles.

Corrosion inhibitors, extreme pressure agents and anti-wear agents include, but are not limited to: Not determined: metal salts of phosphorus-containing acids, chlorinated aliphatic hydrocarbons; (This includes dihydrocarbyl and trihydrocarbyl phosphites) boron-containing compounds including boric acid esters; dimercaptothiadiazole Derivatives; benzotriazole derivatives; aminomercaptothiadiazole derivatives; and molybdenum compounds.

Viscosity modifiers include, but are not limited to: polyisobutylene Ten, polymethacrylate ester, polyacrylate ester, diene polymer, polymer Realkylstyrene, alkenylaryl conjugated diene copolymer (preferably (tyrene-maleic anhydride copolymer ester), polyolefins and polyfunctional Viscosity improver.

Pour point depressants are particularly useful agents often included in the lubricating oils described herein. type of additive. For example, C. V.

Smalheer and R. rLubrica by Kennedy Smith nt AdditivesJ (Lesius-Hiles Company P Publishers, Cleveland, Ohio, 1967), page 8. Shine on.

/l! used to reduce or prevent stable foam formation. 17II Agents include silicones or organic polymers. These and further An example of an antifoam composition is rFoam Control Agents J (Henr y T. Kerner, Noyes Data Corporation, I), 125-162 (1976).

These and other additives are described in U.S. Pat. No. 4,582. No. 618 (1 4, line 52 to column 17, line 16, inclusive). The content includes disclosures of other additives that may be used in combination with the present invention. is incorporated herein by reference.

The lubricating composition of the present invention combines the above components (A) and (B) with an oil having lubricating viscosity. Including any additional additives (e.g. components (C) to (F) and other components listed above). ) or without these additives. many , one or more of the chemical components of the invention are substantially inert and normally liquid. of an organic diluent/solvent (eg mineral oil) to form an additive concentrate.

These concentrates usually contain about 20-90%, preferably 10-50% of the components ( A), 20-80%, preferably 0.1-20% of component (B), and optionally Accordingly, it contains one or more of components (C) to (F). 15%, 20 %, 30% or 50% or more may be used. for example, The concentrate contains, on a chemical basis, from about lθ to about 50% by weight of the carboxylic acid derivative composition (A). and 0.1 to about 10% by weight of (B). These concentrates also have approx. 0.001 to about 15% (C), o, oot to about 15% (D) and/or It may contain from about 1 to about 20% (E).

The formulation is carried out at temperatures ranging from room temperature to the decomposition temperature of this mixture or the individual components. This is done by mixing (usually by stirring) the ingredients. in general, These ingredients are heated at a temperature of about 25°C to about 250°C, preferably about Z ( Temperatures of up to 10°C, more preferably temperatures of up to about 150°C, even more Preferably, it is compounded at a temperature up to about 100°C.

The following examples illustrate concentrates and lubricants of the present invention.

[Ba1. J or "residual amount" refers to the balance or remaining amount of this composition. Indicates that it is oil. Unless otherwise indicated, the amounts of each ingredient in these examples are: , volume percent, and the amount of oil-containing product used in the lubricant. It reflects.

Dark IJu11 doctor Dark 1st grade 1st grade Product of Example A-13 45 Product of Example B-1 12 Mineral oil 43 1 supervision and Product of Example A-28 40 Product of Example B-1 15 Mineral oil 45 1 box top Product of Example A-21 60 Product of Example B-2 15 Product of Example C-t 5 Mineral oil 20 Dark 101■ Product of Example A-21 40 Product of Example B-2 10 Product of Example C-2 5 Product of Example No. 5 5 Mineral oil 40 1 red tV Product of Example A-21 40 Product of Example 13-2 10 Product of Example C-2 5 Product of Example Kano 7 5 Product of Example E-1 5 Mineral oil 35 11th Rebellion Jun 1b A Product of Example A-13 6°0 Product of Example B-2 1.2 100 New Trano (Rough-in oil remaining amount (margin below) Jun 1st To Example-13 Product 6,2 Product of Example B-2 1.2 Product of example c-i 0.5 100 = Neetra JLt Halafin Oil Remaining amount 1 脣5工 Product of Example A-21 '5.8 Product of Example B-1 1.0 Product of Example C-2 O,S Product of Example D-5 0.5 100 neutral paraffin oil residual layer Product of Example A-20 5.0 Product of Example B-1 0.8 Product of Example C-2 0.4 Product of Example D-5 0.5 Product of Example E-1 0.4 100 neutral paraffin oil remaining amount (margin below) table two Example 11 different size XL 1st generation FGIU B-10,820,820,750,80C-I Q, 85 0.85 1, I Q, 90D-130,130,13--0,10 di(/nylphenyl)ami -------0,5--oleylamine 0.01 0.01 0.01 0.01100 in neutral mineral oil 8% hydrogenated styrene Butadiene copolymer 8.5 6.5 6.5 6.5 Silicone antifoaming agent 80 ppm 80ppm 80ppm 80ppm oil Ba1. Ba1. B a1. Bal.

The lubricating oil compositions of the present invention exhibit a tendency to reduce degradation under conditions of use, thereby reduce wear, corrosion, rust, and the formation of undesirable deposits such as: : Varnishes, sludge, carbonaceous substances and resinous substances (this applies to various engine parts) (which tend to adhere to the engine and reduce the efficiency of the engine).

A lubricating oil may also be formulated according to the present invention for use in the crankcase of a passenger car. Fuel economy is improved when the vehicle is used.

Although the invention has been described with respect to preferred embodiments thereof, various modifications thereof may be made. will be obvious to those skilled in the art after reading this specification. follow Thus, the invention disclosed herein encompasses such claims as come within the scope of the appended claims. It should be understood that all modifications are intended to be included.

Copy and translation of written amendment) Submission (Article 184-7, Paragraph 1 of the Patent Act) Small

Claims (72)

[Claims] 1. Containing a major amount of oil of lubricating viscosity and the following (A) and (B): Lubricating oil composition: (A) React at least about 1% by weight of the following (A-1) and (A-2): At least one carboxylic acid derivative composition produced by: (A-1) containing at least about 50 carbon atoms in the substituent; One type of substituted succinic acylating agent; (A-2) per equivalent of acylating agent (A-1) , at least one HN< group is present in the structure, from about 0.5 equivalents to about 2 moles (B) at least one amine compound characterized by: Provides at least about 0.002 equivalents of alkali metal per 100 grams of oil composition a hydrocarbyl-substituted carboxylic acid or a hydrocarbyl-substituted carboxylic acid in an amount sufficient to at least one atom of a mixture of carboxylic acids and hydrocarbyl-substituted sulfonic acids; alkali metal overbased salt; The overbased salt has a metal ratio greater than 2, where the carboxylic acid The hydrocarbyl substituent contains at least about 50 carbon atoms, with the proviso that The alkali metal salt is a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted carboxylic acid. When containing a mixture of overbased alkali metal salts of sulfonic acids, the The acid contains more than 50% of the acid equivalents of the mixture, with the proviso that the substituted hydrogen The citric acid acylating agent (A-1) consists of a substituent and a succinic acid group, and the acylating agent has an average of at least 1.3 chains per equivalent of substituent in its structure. When characterized by the presence of citric acid groups, the alkali metal overbase The metal ratio of the sulfide salt (B) is greater than 1. 2. The substituent of the acylating agent (A-1) is derived from a polyalkene, The polyalkene has an Mn value of from 1300 to about 5000 and from about 1.5 to about 4.5. Oil composition according to claim 1, characterized by Mw/Mn value. 3. the acylating agent contains less than 1.3 succinic acid groups for each equivalent of substituent; When the metal ratio of the alkali metal salt (B) is at least about 6. 5. The oil composition according to claim 1, wherein the oil composition is 4. containing at least about 1.5% by weight of the carboxylic acid derivative composition (A); The oil composition according to claim 1. 5. The substituent in (A) is derived from polybutene, and in the polybutene, , at least about 50% of the total units derived from butene are derived from isobutene. The oil composition according to claim 1. 6. The carboxylic acid derivative composition (A) contains 1 equivalent of the acylating agent (A-1). or by reacting about 0.7 to about 1.5 equivalents of the amine (A-2). The oil composition according to claim 1. 7. The amine (A-2) is an aliphatic polyamine, a cycloaliphatic polyamine, or The oil composition according to claim 1, which is an aromatic polyamine. 8. The succinic acylating agent (A-1) has a structure in which the succinic acid acylating agent (A-1) has a and by the presence of at least about 1.5 to about 2.5 succinic acid groups. The oil composition according to claim 1, characterized in that: 9. The above (B) hydrocarbon-substituted carboxylic acid is hydrocarbon-substituted succinic acid, The oil composition according to claim 1. 10. The alkali metal overbased salt (B) is a hydrocarbyl substituted alkali metal overbased salt (B). a salt of citric acid, wherein the number average molecular weight of the hydrocarbyl substituent is about 900. 5. The oil composition of claim 1, wherein the oil composition is from about 5000 to about 5000. 11. The hydrocarbyl substituent of the hydrocarbyl-substituted carboxylic acid (B) is It is derived from polybutene, in which all the monomers derived from butene are 2. The oil of claim 1, wherein at least about 50% of the oil is derived from isobutene. le composition. 12. Claim wherein the alkali metal (B) is sodium or potassium. 1. The oil composition according to 1. 13. The alkali metal overbased salt (B) is an equivalent of succinic acid, or The ratio of equivalents of alkali metal to equivalents of mixture of succinic acid and sulfonic acid is small. 10. The oil set of claim 9, characterized in that the oil set is at least about 1.5. A product. 14. (C) further contains at least one metal dihydrocarbyldithiophosphate The oil composition according to claim 1. 15. The metal of the dihydrocarbyl dithiophosphate metal (C) is a Group II metal, Aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel or 15. The oil composition of claim 14, wherein is copper. 16. The metal of the dihydrocarbyl dithiophosphate metal (C) is zinc, copper, or 15. The oil composition of claim 14, wherein is a mixture thereof. 17. (D) further comprising at least one antioxidant. Oil composition: However, the antioxidant (D) and the dithiophosphate (C) are not the same. 18. The antioxidant (D) is present in at least one sulfur-containing composition, at least also one alkylated aromatic amine, at least one phenol, at least one Claim 1: an oil-soluble transition metal-containing antioxidant, or a mixture thereof. 7. The oil composition according to 7. 19. at least one alkaline earth metal neutral salt or overbase of an organic acid The oil composition according to claim 1, further comprising a salt. 20. Contains a major amount of oil of lubricating viscosity and the following (A) and (B): A lubricating oil composition comprising: (A) at least about 1.5% by weight of (A-1); At least one carboxylic acid derivative produced by reacting with (A-2) Conductor composition: (A-1) containing at least about 50 carbon atoms in the substituent; One type of substituted succinic acylating agent; (A-2) per equivalent of acylating agent (A-1) , at least one HN< group is present in the structure, from about 0.5 equivalents to about 2 moles (B) at least one amine compound characterized by: Provides at least about 0.002 equivalents of alkali metal per 100 grams of oil composition. hydrocarbyl-substituted succinic acid or hydrocarbyl-substituted succinic acid in an amount sufficient to provide At least one alkali of a mixture of succinic acid and hydrocarbyl-substituted sulfonic acid Potassium metal overbased salt; The overbased salt has a metal ratio of at least about 6.5, wherein the overbased salt has a metal ratio of at least about 6.5; The hydrocarbyl substituent of citric acid contains at least about 50 carbon atoms, However, the alkali metal mass is hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic acid. When containing a mixture of overbased alkali metal salts of substituted sulfonic acids, the Succinic acid comprises more than 50% of the acid equivalents of the mixture. 21. Contains a major amount of oil of lubricating viscosity and the following (A) and (B): A lubricating oil composition comprising: (A) at least about 1% by weight of (A-1) and (A -2) at least one carboxylic acid derivative produced by reacting with Composition: (A-1) At least one substituted succinic acylating agent; (A-2) Acylating agent 1 from about 0.5 equivalents to about 2 moles per equivalent of at least one HN in the structure <at least one amine compound characterized by the presence of a group; Here, the substituted succinic acylating agent consists of a substituent and a succinic acid group, where , the substituent is derived from a polyalkene, and the polyalkene is 1300 Characterized by an Mn value of ~5000 and a Mw/Mn value of about 1.5 to about 4.5 and the acylating agent has, on average, less for each equivalent of substituent in its structure. Both are characterized by the presence of 1.3 succinic acid groups; (B) at least about 0.002 equivalents of aluminum per 100 grams of the lubricating oil composition; a hydrocarbyl-substituted carboxylic acid or hydroxide in an amount sufficient to provide the potassium metal; of a mixture of locarbyl-substituted carboxylic acids and hydrocarbyl-substituted sulfonic acids. At least one alkali metal scrap overbased salt; wherein the hydrocarbyl substituent of the succinic acid has at least about 50 carbon atoms. with the proviso that the alkali metal salt is a hydrocarbyl-substituted carboxylic acid and and overbased alkali metal salts of hydrocarbyl-substituted sulfonic acids. When included, the carboxylic acid comprises more than 50% of the acid equivalents of the mixture. 22. Contains at least about 1.5% by weight of the carboxylic acid derivative composition (A) 22. The oil composition of claim 21. 23. 22. The Mn value of (A-2) is at least about 1500. The oil composition described. 24. The substituent in (A) above is derived from polybutene, and in the polybutene, is such that at least about 50% of the total units derived from butene are derived from isobutene. 22. The oil composition according to claim 21. 25. The carboxylic acid derivative composition (A) contains 1 equivalent of the acylating agent (A-1) By reacting about 0.7 to about 1.5 equivalents of the amine (A-2) per An oil composition according to claim 21 obtained. 26. The carboxylic acid derivative composition (A) contains 1 equivalent of the acylating agent (A-1). and reacting about 0.5 equivalent to less than 1 equivalent of the amine (A-2). The oil composition according to claim 21, obtained from. 27. The amine (A-2) is an aliphatic polyamine, a cycloaliphatic polyamine or 22. The oil composition of claim 21, wherein is an aromatic polyamine. 28. The succinic acylating agent (A-1) has a structure in which each equivalent of a substituent has On the other hand, there are at least about 1.5 to about 2.5 succinic acid groups present. 22. Oil composition according to claim 21, characterized by: 29. The hydrocarbon-substituted carboxylic acid of (B) is hydrocarbon-substituted succinic acid, The oil composition according to claim 21. 30. The alkali gold scrap overbased salt (B) is a hydrocarbyl-substituted alkali metal a salt of citric acid, wherein the number average molecular weight of the hydrocarbyl substituent is about 900. 22. The oil composition of claim 21, wherein the oil composition is about 5000. 31. Number average of hydrocarbyl substituents in the hydrocarbyl-substituted succinic acid (B) 31. The oil composition of claim 30, wherein the molecular weight ranges from about 900 to about 2500. thing. 32. The hydrocarbyl substituent of the hydrocarbyl-substituted carboxylic acid (B) is It is derived from butene, in which all units derived from butene 22. The oil of claim 21, wherein at least about 50% of the oil is derived from isobutene. le composition. 33. Claim wherein the alkali metal of (B) is sodium or potassium. 22. The oil composition according to 21. 34. The alkali gold scrap overbased salt (B) is an equivalent of succinic acid, or The ratio of the equivalent of the alkali metal to the equivalent of the mixture of succinic acid and sulfonic acid is 30. The oil of claim 29, characterized in that the oil is at least about 1.5. le composition. 35. 35. The oil composition of claim 34, wherein the ratio is from about 2 to about 40. 36. (C) further contains at least one metal dihydrocarbyldithiophosphate The oil composition according to claim 21. 37. The metal of the dihydrocarbyl dithiophosphate metal (C) is a Group II metal, Aluminum, tin, iron, cobalt, lead, molybdenum, anganese, nickel or 37. The oil composition of claim 36, wherein is copper. 38. The hydrocarbyl group of the metal dihydrocarbyl dithiophosphate (C) is each independently a hydrocarbyl group containing from 3 to about 13 carbon atoms; , and is bonded to the oxygen atom of the dithiophosphate via a secondary carbon atom. 37. The oil composition of claim 36. 39. The metal of the dihydrocarbyl dithiophosphate metal (C) is zinc, copper, or 37. The oil composition of claim 36, wherein is a mixture thereof. 40. The dithiophosphate (C) is a metal salt of dihydrocarbyl phosphorodioic acid. of the dihydrocarbyl phosphorodithioic acids, wherein at least In one type, one of the hydrocarbyl groups (C-1) is an isopropyl group or a secondary butyl group, and the other hydrocarbyl group (C-2) has at least 5 carbon atoms. and of all hydrocarbyl groups present in (C) 10 mole percent isopropyl groups, secondary butyl groups or mixtures thereof 37. The lubricating oil composition of claim 36. 41. (D) further comprising at least one antioxidant. Oil composition: However, the antioxidant (D) and the dithiophosphate (C) are not the same. 42. The antioxidant (D) is present in at least one sulfur-containing composition, at least also one alkylated aromatic amine, at least one phenol, at least one 4. A type of oil-soluble transition metal-containing antioxidant, or a mixture thereof. 1. The oil composition according to 1. 43. The antioxidant (D) is alkylene-coupled phenol. 4. wherein the alkylene group contains from 1 to about 8 carbon atoms. 1. The oil composition according to 1. 44. Claim wherein the antioxidant (D) is an alkylated hindered phenol. The lubricating oil composition according to item 41. 45. The antioxidant (D) is an antioxidant containing at least one transition metal. 42. The oil composition of claim 41. 46. A major amount of oil of lubricating viscosity, and the following (A), (B), (C) and and (D): (A) at least about 1% by weight of: At least one kind produced by reacting (A-1) and (A-2) Carboxylic acid derivative composition: (A-1) At least one substituted succinic acylating agent; (A-2) about 0.5 equivalent by the presence of at least one HN< group in the structure, up to about 2 moles from At least one amine compound characterized by: Here, the substituted succinic acid acylating agent consists of a substituent and a succinic acid group, and here , the substituent is derived from a polyalkene, and the polyalkene is 130 Characterized by an Mn value of 0 to about 5000 and a Mw/Mn value of about 1.5 to about 4.5 and the acylating agent has, on average, less for each equivalent of substituent in its structure. Both are characterized by the presence of 1.3 succinic acid groups; (B) at least about 0.002 equivalents of aluminum per 100 grams of the lubricating oil composition; a hydrocarbyl-substituted succinic acid or hydrocarbyl-substituted succinic acid in an amount sufficient to provide the potassium metal; of a mixture of a carbyl-substituted succinic acid and a hydrocarbyl-substituted sulfonic acid; also an alkali metal overbased salt; wherein the hydrocarbyl substituent on the succinic acid has at least about 50 carbon atoms. with the proviso that the alkali metal salt is a hydrocarbyl-substituted succinic acid and and overbased alkali metal salts of hydrocarbyl-substituted sulfonic acids. when containing, the succinic acid comprises more than 50% of the acid equivalents of the mixture; (C) at least one metal dihydrocarbyl dithiophosphate; (D) at least One type of antioxidant: However, the antioxidant (D) and the dithiophosphate (C) are not the same. 47. A major amount of oil of lubricating viscosity, and (A), (B), (C), Lubricating oil compositions containing (D) and (E): (A) at least about 1% by weight; Produced by reacting the following (A-1) and (A-2), at least One type of carboxylic acid derivative composition: (A-1) At least one substituted succinic acylating agent; (A-2) Acylating agent ( A-1) from about 0.5 equivalents to about 2 moles per equivalent of at least at least one amine characterized by the presence of one HN< group compound; wherein the substituted succinic acylating agent consists of a substituent and a succinic group; , wherein the substituent is derived from a polyalkene, and the polyalkene is , by an Mn value of 1300 to about 5000 and a Mw/Mn value of about 1.5 to about 4.5 characterized, the acylating agent has, on average, for each equivalent of substituent within its structure characterized by the presence of at least 1.3 succinic acid groups; (B) at least about 0.002 equivalents of aluminum per 100 grams of the lubricating oil composition; a hydrocarbyl-substituted carboxylic acid or hydroxide in an amount sufficient to provide the potassium metal; of a mixture of locarbyl-substituted carboxylic acids and hydrocarbyl-substituted sulfonic acids. at least one alkali metal overbased salt; wherein the hydrocarbyl substituent of the carboxylic acid has at least 50 carbon atoms. with the proviso that the alkali metal salt is a hydrocarbyl-substituted carboxylic acid or and a mixture of overbased alkali metal salts of hydrocarbyl-substituted sulfonic acids. when the carboxylic acid contains more than 50% of the acid equivalents of the mixture; (C) at least one metal dihydrocarbyl dithiophosphate; (D) at least One type of antioxidant: However, the antioxidant (D) and the dithiophosphate (C) are not the same; (E) at least one alkaline earth metal overbased salt of an acidic organic compound; . 48. Contains at least about 1.5% by weight of the carboxylic acid derivative composition (A) 48. The oil composition of claim 47. 49. The substituent in (A) above is derived from polybutene, and in the polybutene, is such that at least about 50% of the total units derived from butene are derived from isobutene. 48. The oil composition of claim 47. 50. The carboxylic acid derivative composition (A) contains 1 equivalent of the acylating agent (A-1) About 0.5 equivalent to less than 1 equivalent of the amine (A-2) may be reacted per amine (A-2). The oil composition according to claim 47, obtained by. 51. The amine (A-2) is an aliphatic polyamine, a cycloaliphatic polyamine or 48. The oil composition of claim 47, wherein is an aromatic polyamine. 52. The acylating agent (A-1) contains a small amount of Characterized by the presence of at least about 1.5 to about 2.5 succinic acid groups 48. The oil composition of claim 47. 53. The alkali metal overbased salt (B) is a hydrocarbyl substituted alkali metal overbased salt (B). a salt of citric acid, wherein the number average molecular weight of the hydrocarbyl substituent is about 900. 48. The oil composition of claim 47, wherein the oil composition is about 5000. 54. Claim wherein the alkali metal (B) is sodium or potassium. 47. The oil composition according to 47. 55. The alkali metal overbased salt (B) has an equivalent amount of carboxylic acid, and is the ratio of the equivalents of the alkali metal to the equivalents of the mixture of carboxylic and sulfonic acids is at least about 1.5. oil composition. 56. The metal of the dihydrocarbyl dithiophosphate metal (C) is a Group II metal, Aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel or 48. The oil composition of claim 47, wherein is copper. 57. The hydrocarbyl group of the metal dihydrocarbyl dithiophosphate (C) is each independently a hydrocarbyl group containing from 3 to about 13 carbon atoms; , and is bonded to the oxygen atom of the dithiophosphate via a secondary carbon atom. 48. The oil composition of claim 47. 58. The metal of the dihydrocarbyl dithiophosphate metal (C) is zinc, copper, or 48. The oil composition of claim 47, wherein is a mixture thereof. 59. Claim 4, comprising about 0.05 to about 2% by weight of the dithiophosphate (C). 7. The oil composition according to 7. 60. The antioxidant (D) is present in at least one sulfur-containing composition, at least also one alkylated aromatic amine, at least one phenol, at least one 4. A type of oil-soluble transition metal-containing antioxidant, or a mixture thereof. 7. The oil composition according to 7. 61. The antioxidant (D) is an alkylene-coupled phenol. , wherein the alkylene group contains from 1 to about 8 carbon atoms. 47. The oil composition according to 47. 62. 47. The antioxidant is an alkylated hindered phenol. The oil composition described in . 63. The antioxidant (D) is an antioxidant containing at least one transition metal. 48. The oil composition of claim 47. 64. containing at least one magnesium overbased salt of an acidic organic compound. 48. The oil composition of claim 47, comprising: 65. Contains at least one calcium overbased salt of an acidic organic compound 48. The oil composition of claim 47. 66. A major amount of oil with lubricating viscosity and the following (A) and (B) are blended. A lubricating oil composition prepared by: (A) at least about 1% by weight of: At least one type produced by reacting (A-1) and (A-2) of Carboxylic acid derivative composition of: (A-1) At least one substituted succinic acylating agent; (A-2) Acylating agent 1 from about 0.5 equivalents to about 2 moles per equivalent of at least one HN in the structure <at least one amine compound characterized by the presence of a group: Here, the substituted succinic acylating agent consists of a substituent and a succinic acid group, where , the substituent is derived from a polyalkene, and the polyalkene is 1300 Characterized by an Mn value of ~5000 and a Mw/Mn value of about 1.5 to about 4.5 and the acylating agent has, on average, less for each equivalent of substituent in its structure. Both are characterized by the presence of 1.3 succinic acid groups; (B) at least about 0.002 equivalents of aluminum per 100 grams of the lubricating oil composition; a hydrocarbyl-substituted carboxylic acid or hydroxide in an amount sufficient to provide the potassium metal; of a mixture of locarbyl-substituted carboxylic acids and hydrocarbyl-substituted sulfonic acids. at least one alkali metal overbased salt; wherein the hydrocarbyl substituent of the carboxylic acid has at least about 50 carbon atoms. containing atoms, provided that the overbased alkali metal salt is a hydrocarbyl When containing a mixture of substituted carboxylic acids and hydrocarbyl substituted sulfonic acids, The carboxylic acid contains more than 50% of the acid equivalents of the mixture. 67. A major amount of lubricating viscous oil and the following (A), (B), (C), (D ) and (E), a lubricating oil composition prepared by blending: (A) React at least about 1% by weight of the following (A-1) and (A-2): At least one carboxylic acid derivative composition produced by: (A-1) At least one substituted succinic acylating agent; (A-2) Acylating agent 1 from about 0.5 equivalents to about 2 moles per equivalent of at least one HN in the structure <at least one amine compound characterized by the presence of a group: Here, the substituted succinic acylating agent consists of a substituent and a succinic acid group, where , the substituent is derived from a polyalkene, the polyalkene having a molecular weight of 1300 to about 5 characterized by an Mn value of 000 and a Mw/Mn value of about 1.5 to about 4.5, The acylating agent has an average of at least 1 for each equivalent of substituent in its structure. ．． characterized by the presence of three succinic acid groups; (B) the lubricating oil composition; provides at least about 0.002 equivalents of alkali metal per 100 grams of a sufficient amount of hydrocarbyl-substituted carboxylic acid or hydrocarbyl-substituted carboxylic acid to at least one alkali of a mixture of a bonic acid and a hydrocarbyl-substituted sulfonic acid. remetal overbased salt; wherein the hydrocarbyl substituent of the carboxylic acid has at least about 50 carbon atoms. containing atoms, provided that the overbased alkali metal salt is a hydrocarbyl Overbased Alkaline Substituted Carboxylic and Hydrocarbyl Substituted Sulfonic Acids When containing a mixture of metal salts, the carboxylic acid is greater than 50% of the mixture. Contains acid equivalent; (C) at least one metal dihydrocarbyl dithiophosphate; (D) at least One type of antioxidant: However, the antioxidant (D) and the dithiophosphate (C) are not the same; (E) at least one alkaline earth metal overbased salt of an acidic organic compound; . 68. At least about 0.002 equivalents of alkali per 100 grams of lubricating oil composition Concentrate for preparing lubricating oil compositions containing remetallics, the concentrate comprising about 20% by weight ~90% by weight normally liquid, substantially inert organic diluent/solvent, and the following: Concentrate containing (A) and (B): (A) React about 20% to about 80% by weight of the following (A-1) and (A-2) At least one carboxylic acid derivative composition produced by: (A-1) containing at least about 50 carbon atoms in the substituent; One type of substituted succinic acylating agent; (A-2) per equivalent of acylating agent (A-1) , at least one HN< group is present in the structure, from about 0.5 equivalents to about 2 moles (B) at least one amine compound characterized by: Provides at least about 0.002 equivalents of alkali metal per 100 grams of oil composition. from about 0.1 to about 20% by weight sufficient to provide a hydrocarbyl-substituted carboxylic acid. or a mixture of a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted sulfonic acid. at least one alkali metal overbased salt of The hydrocarbyl substituent contains at least about 50 carbon atoms, with the proviso that , the alkali metal salt is a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted carboxylic acid. When containing a mixture of overbased alkali metal salts of converted sulfonic acids, the The carboxylic acid contains more than 50% of the acid equivalents of the mixture, with the proviso that the substituted The succinic acid acylating agent (A-1) consists of a substituent and a succinic acid group, and the acylating agent (A-1) The agent has an average of at least 1.3 copolymer(s) in its structure for each equivalent of substituent. When characterized by the presence of succinic acid groups, the alkali metal overbase The metal ratio of the salt (B) is greater than 1. 69. At least about 0.002 equivalents of alkali per 100 grams of lubricating oil composition Concentrate for preparing lubricating oil compositions containing remetallics, the concentrate comprising about 20% by weight ~90% by weight normally liquid, substantially inert organic diluent/solvent, and the following: Concentrate containing (A) and (B): (A) React about 20% to about 80% by weight of the following (A-1) and (A-2) At least one carboxylic acid derivative composition produced by: (A-1) At least one substituted succinic acylating agent; (A-2) Acylating agent 1 from about 0.5 equivalents to about 2 moles per equivalent of at least one HN in the structure <at least one amine compound characterized by the presence of a group; Here, the substituted succinic acylating agent consists of a substituent and a succinic acid group, where , the substituent is derived from a polyalkene, the polyalkene having a molecular weight of 1300 to about 5 characterized by an Mn value of 000 and a Mw/Mn value of about 1.5 to about 4.5, The acylating agent has an average of at least 1 for each equivalent of substituent in its structure. ．． characterized by the presence of three succinic acid groups; (B) the lubricating oil composition; provides at least about 0.002 equivalents of alkali metal per 100 grams of from about 0.1 to about 20% by weight of a hydrocarbyl-substituted carboxylic acid or of a mixture of a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted sulfonic acid, at least one alkali metal overbased salt; The hydrocarbyl substituent contains at least about 50 carbon atoms, with the proviso that The alkali metal salt is a hydrocarbyl-substituted carboxylic acid and a hydrocarbyl-substituted carboxylic acid. When containing a mixture of overbased alkali metal salts of sulfonic acids, the Bonic acids contain more than 50% acid equivalents of the mixture. 70. Using the oil composition according to claim 1, spark ignition engines or compression point A method involving lubricating a fire engine. 71. Using the oil composition according to claim 21, a spark ignition engine or a compressor A method comprising lubricating an ignition engine. 72. Using the oil composition of claim 47, a spark ignition engine or a compressor A method comprising lubricating an ignition engine.