JPS63501018A - Diesel lubricant and method - 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] diesel lubricant and method Background of the invention The present invention relates to a diesel lubricant, particularly when the lubricant is used in a diesel engine. A lubricant containing an additive capable of minimizing an undesirable increase in viscosity of the lubricant. Regarding. The present invention also provides basic alkali metal sulfonates, particularly basic sulfonates. A method for producing potassium chloride and a diesel engine according to the present invention during operation of a diesel engine. This invention relates to a method of operating a diesel engine, which comprises lubricating it with a lubricant.

It is well known that lubricating oils tend to degrade under the operating conditions of today's internal combustion engines. ing. This results in the formation of sludge, lacquer, carbonaceous and resinous substances, Tends to stick to various parts of the engine, especially engine rings, gloves, and skirts. be. Furthermore, under conditions such as long periods of no-load operation and stoppages, diesel When the diesel engine operates at low speeds and high torques, the lubricant becomes undesirably concentrated. Causes thickening. This undesirable thickening of the lubricating oil is caused by large amounts of insoluble substances (soot). The prior art states that this is the cause.

The types of compounds proposed for use in lubricating oils, especially diesel oil, include Patent No. A474,035;&52&917; and A70 to No.632. There are calcium salts that are overly basic. These substances are cleaning agents and It is said to act as a dispersant and also exhibit antioxidant and anti-thickening properties. In addition, About multi-purpose additives for lubricating oils with oxidation, anti-thickening, anti-corrosion and dispersion properties. This is described in US Patent No. &89Z352. Additives described in this patent There are Group 2 metal salts of nitrated alkylphenol sulfides.

As described in more detail below, the present invention comprises a particular type of carboxyl derivatized Diesel lubricants containing several types of basic alkali metal salts using body composition as a dispersant. related. This particular dispersant and detergent combination makes diesel lubricants It has the effect of minimizing the undesirable increase in viscosity that occurs when used in engines.

Lubricating oil formulations containing oil-soluble carboxylic acid derivatives, especially carboxylic acid and amine compounds The derivatives obtained by the reaction are disclosed in U.S. Pat. 5; 3.1?2,892; 31216,936; 31219,666; and 3 , 27λ746. The above patent contains such a carboxylic acid inducer. The conductor may contain ash containing basic metal salts of acidic organic substances such as sulfonic acids and carboxylic acids. There are many examples of use in lubricating oils in combination with lubricants.

The carboxylic acid derivative used as a diesel lubricant in the present invention is particularly It is a compound of the type generally described in Patent No. 4.23t435.

This patent describes the use of the carboxylic acid derivatives and other additives such as flow regulators and auxiliary detergents. , ash-forming dispersants or ash-free dispersants, antioxidants, etc. Oil compositions are also described. Carboxylic acid derivatives, basic galcium sulfonate Lubricating oil compositions containing other conventional additives are disclosed in U.S. Patent No. 4,234,435, 52 Column.

It is written on lines 1-8.

The second important diesel lubricant component in this invention has a metal ratio of at least about 2. At least one kind of basic alkali metal salt of one or more kinds of acidic organic substances. this Such compositions are commonly referred to in the prior art as metal detergents or ash detergents. stop The use of such detergents in lubricating oil formulations was proposed in many prior patents. It's here. For example, Canadian Patent No. 1. No. 055,700 includes basic sulfonic acid amines. Lucari suspension is applied to the crankcase of spark-ignition internal combustion engines and compression-ignition internal combustion engines. It states that it is used as a lubricant. This Canadian patent describes basic sulfonate Suspensions of alkali succinic acids can be used alone, and hydrocarbon-substituted succinic acids can also be used alone. Can be used with other known lubricant additives such as ashless dispersants such as esters or amides. It can also be used.

Ash-containing and ash-free detergents and dispersants are already available in diesel lubricants. Even if they are used, these lubricants contain relatively large amounts of detergents and dispersants. If not added, undesirable thickening will occur, especially in low-speed, high-torque operation. Qing Using large amounts of detergents and dispersants is generally undesirable as it increases cost. stomach.

To constitute a usable diesel lubricant, the lubricant must meet two performance criteria: must be achieved. In other words, C C’ class (Caterpillar-1-H) highly supercharged engine Operation and CD class (Caterpillar-1-G) highly supercharged engine operation, but 1-G group The standards are more stringent; When used in diesel engines, it may not be possible to prevent an undesirable increase in the viscosity of the lubricant. However, there continues to be a need for compositions that can be minimized. these If this composition is added to diesel lubricating oil, the cost of lubricating oil will significantly increase. Caterpillar-1-H and Caterpillar-1-G standard performance can be achieved without is necessary.

Summary of the invention When used in diesel engines, it is possible to minimize undesirable increases in viscosity. A diesel lubricant with improved performance is disclosed. More specifically, the data disclosed in the present invention Diesel lubricants are used in bulk oils and diesel engines with lubricating viscosity The oil contains a small amount of the composition sufficient to minimize undesirable viscosity increases in the lubricating oil. (A) at least one substituted co-phosphate lubricant; a silating agent and at least one amino compound having at least one -NH- group; The acylating agent consists of a substituent and a succinic acid group, and the substituted The group has an Mn position of at least about 1200 and an Mw/Mn of at least about 1.5 The acylating agent is derived from a polyalkene characterized by a characterized in that there is an average of at least about 1.3 succinic acid groups per equivalent of substituent. at least one carboxylic acid derivative composition, and (B) at least one acidic organic compound having a metal ratio of at least about 2; It is an alkali metal salt, a good diesel lubricant. This diesel lubrication fc) at least one oil-soluble neutral or base of at least one acidic compound; alkaline earth metal salts may also be included.

The basic alkali metal salt (B) contained in the diesel lubricant of the present invention is at least One type of sodium salt is preferred, and the sodium salt of the sulfonic acid is more preferred.

The present invention provides a method for producing basic metal salts, particularly potassium salts, and a method for producing basic metal salts, particularly potassium salts, and A method of operating a diesel engine is also disclosed that uses a lubricant to provide lubrication during engine operation.

Description of preferred embodiments The diesel lubricant of the present invention consists mostly of oil having lubricating viscosity, with a small portion consisting of Sufficient to minimize undesirable viscosity build-up of lubricants when used in diesel engines. (A) one or more carboxyl derivatives as defined in more detail below; a conductor composition, and (B) one or more basic atom(s) of at least one acidic organic compound; It consists of a composition obtained by combining at least one type of alkali metal salt.

The oils having lubricating viscosity used in the preparation of the diesel lubricants of the present invention include natural oils, Either synthetic oils or mixtures thereof may be used.

Natural oils include, for example, animal oils, vegetable oils (castor oil, lard oil), as well as liquid petroleum and petroleum oils. Solubility of roughinic, naphthenic and paraffin-naphthenic mixed mineral lubricating oils These include medium-treated products or acid-treated products. Lubricating viscosity made from coal or sierre Oils with .

Synthetic lubricants include, for example, polymerized or intercompatible olefins (polybutylene, Polypropylene, polypropylene-imbutylene copolymer, chlorinated polybutylene hydrocarbon oils and halo-substituted hydrocarbon oils such as poly(l-hexene), poly(l-octene), poly(a:+)thecene), etc. and mixtures thereof; Killbenzene (dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, etc.); polyphenyls (biphenyl, tertiary phenyl, alkylated polyphenyl, etc.); alkylated diphenyl ether, alkyl alkylated diphenyl sulfide and its derivatives, analogs and congeners. Ru.

Polymers, interpolymers and derivatives thereof of alkylene oxide, which have a terminal hydride. Compounds in which the roxyl group has been modified by esterification or etherification are another class of public compounds. It is a known synthetic lubricant and can be used. Specific examples include ethylene oxide or Oil obtained by polymerizing propylene oxide; these polyoxyalkylene glycols alkyl or aryl ether (polyisopropylene with an average molecular weight of about 100 Rene glycol methyl ether, polyethylene glycol with a molecular weight of approximately 500-1000 Cold diphenyl ether, molecule i - about 1000-1500+7) polypropylene glycol diethyl ether, etc.); or its mono- and polycarboxylic acid esters. Stel, for example, is a c13 oxo acid diester of tetraethylene glycol. .

Another suitable class of synthetic lubricants that can be used are esters of dicarboxylic acids (e.g. Talic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, aze Phleic acid, superric acid, sepacic acid, fumaric acid, adipic acid, lyluic acid dimer , malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and a large number of alcoholic acids. - alcohol (e.g. haftyl alcohol, hexyl alcohol, dodecyl alcohol, 2 -Ethylhexyl alcohol, ethylene glycol, diethylene glycol mono ethers, probile/glycols, etc.). These esters For example, dibutyl adipate, di(2-ethylhexyl) sebacate, fuma A ’-n-hexyl acid, dioctyl sepatenate, diisooctyl azelaate, Diisodecyl azelate, dioctyl phthalate, didecyl phthalate, sepasenine dieicosyl acid, di-2-ethylhexyl ester of lyluic acid dimer, sepati 1 mole of phosphoric acid was mixed with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid. It is an ester obtained by reacting with

Esters useful as synthetic oils include, for example, C5-CI2 monocarboxylic acids, glycol, trimethylolpropane, pentaerythritol, dipenta Elite rettle, retrieval pen; Which polyols and esters obtained by reacting with polyol ethers are mentioned. It will be done.

Polyalkyl-, polyaryl-, polyalkoxy-0 or polyarylox Silicone oils such as sea-siloxane oil and silicate oil are also considered synthetic lubricants. Other types of oils that are useful in Tetra(2-ethylhexyl) silicate, Tetra(4-methylhexyl) silicate, Tetra(p-tert-butylphenyl) ioate, hexyl-(4-methyl-2 -pentoxy)disiloxane, poly(methyl)siloxane, poly(methylphenylene) siloxane]. Other synthetic lubricants are liquid esters of phosphorus-containing acids ( Tricresyl phosphate, trioctyl phosphate, decanephosphonic acid diethyl ester ), tetrahydrofuran polymers, etc.

The natural or synthetic unrefined oils listed above include refined and rerefined oils (as well as mixtures of two or more) can be used in the concentrate of the present invention. Unrefined oils can be natural or synthetic The raw material is used directly without further purification.

For example, shale oil obtained directly from carbonization operations, petroleum oil obtained directly from secondary distillation, or If the ester oil obtained directly from the esterification process is used without post-treatment, it will be treated as unrefined oil. Become. Refined oil is obtained by adding 1 or more refining processes to the unrefined oil obtained in the same way. It is an improved property of a species or more. Many of these purification techniques are known to those skilled in the art. and solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. There is. Re-refined oil is obtained by processing used refined oil using the above refining technology. .

Such oils are known as recycled or reprocessed oils and are free from additive waste and oil. It is often further processed by techniques that remove decomposition products.

The component used in the diesel lubricant of the present invention is at least one substituted acyl succinate. by reaction of the oxidizing agent with at least one amine compound containing one or more -NH- groups. one or more carboxyl derivative compositions prepared, wherein the acylating agent is substituted with and a succinic acid group, and the substituents have an Mn value of at least about 1200 and a minimum of about 1.5. The acylating agent or or the presence in its structure of an average of at least about 1.3 succinic acid groups per equivalent of substituent. It is characterized by its presence.

Substituted succinic acylating agents used in the production of carboxyl derivatives contain It is characterized by the presence of two types of groups or moieties. The first group or moiety will be simplified hereinafter. For convenience, we will refer to this group as ``one substituent'', but this group is derived from polyalkenes. Ru. Polyalkenes, which are the raw materials for substituents, are characterized by their Mn (number average molecular weight) value. is 1,200 or more, generally about 1,500 to about 5,000. Also M　w　 /Mn value is greater than or equal to 1.5, and generally from about 1.5 to about 6. Abbreviation MW indicates weight average molecular weight. The number average molecular weight and weight average molecular weight of polybutene are publicly available. Known technologies such as vapor phase permeation cleansing (VPO), membrane permeation cleansing, gel permeation, and chromatog It can be measured by rough method (cpc). These techniques are well known to those skilled in the art. Therefore, the explanation will be omitted.

The second group or moiety is hereinafter referred to as the "succinate group."

The succinic acid group is a group having the following structure.

Here, X and X' are the same or different, and are replaced by at least one of X and X'. It is contemplated that the perosuccinic acylating agent can act as a carboxyl acylating agent.

That is, at least one of X and X' can form an amide or amine salt; Alternatively, it can act as a conventional carboxylic acid acylating agent. Followers in accordance with the invention of the present invention Conventional acylation reactions include transesterification and transamidation.

Therefore, X and/or X' are usually -OH, -0-hydrocarpyl, or -0 -M+. where M+ is a metal, ammonium or amine cation, -NH 2, -C1, -Br, and X and X' combine to form 10-, forming an anhydride. may be formed. Even if either X or X' is a specific group other than the above, This is not a problem as long as it does not interfere with the acylation reaction of the other group. But and X represent the two carboxyl functions of the succinic acid group (-C(0)X and -c(o)x') is preferably a group capable of causing an acylation reaction. stomach.

The valence forms a carbon-carbon bond with the carbon atom in the substituent. other vacant atoms Similar bonds can be made with substituents that have the same or different valences, but only one valence All others are usually hydrogen; bonded with -H.

Substituted succinic acylating agents have 1.3 co-units per equivalent of substituent in their structure. It is characterized by the presence of a succinic acid group (ie a group corresponding to formula I). present invention For purposes of this, the number of equivalents of a substituent is the Mn It corresponds to the quotient obtained by dividing the value by the total amount of substituents present in the substituted succinic acylating agent. It is considered as the number of

Therefore, the characteristic of the substituted succinic acylating agent is that the total number of substituents is 40,000, and If the Mn value of the polyalkylene constituting the substituent is 2000, the substituent The citric acid acylating agent has a total equivalent weight of substituents of 20 (40,000/2000-20). Characterized by Naruko and K. Therefore, the novel co-phosphate acylating agent of the present invention In order to pass one of the required properties, certain succinic acylating agents must also be present in their structure. It must be characterized by the presence of at least 26 co-phosphate groups.

Another required characteristic of the substituted succinic acylating agent of the present invention is that the substituent is Mw/ M must be derived from a polyalkene with an n value of at least 1.5. Must be.

Polyalkenes having the above-mentioned strength and strength values are known and manufactured by conventional methods. can. Some of these polyalkenes, especially polybutene, are commercially available. .

In one preferred embodiment, the succinic acid group corresponds to the conventional formula.

Here, R and R' are each a group consisting of -0H1-CI, -0-lower alkyl. and when both are combined, R and R' are 10-. In the latter case, The succinic acid group becomes a succinic anhydride group.

Although not all succinic groups in a particular succinic acylating agent need to be the same, , may be the same.

Preferably, the succinic acid group corresponds to the following formula:

and (a mixture of [[ICAL] and Cm(B)].

It is common practice to produce substituted succinic acylating agents with the same or different substituents. It is within the skill of the art and can be accomplished by conventional methods. In other words, the substitution Treatment of the acid acylating agent itself (for example, by hydrolyzing and decomposing the anhydride to form the free acid, or or converting the free acid to an anhydride using thionyl chloride) and/or as appropriate. by selecting a maleic acid or fumaric acid reactant.

As mentioned above, the minimum numerical value of the cono-phosphate group per equivalent of substituent is 1.3. most High values generally do not exceed 6.

The number of coI-phosphate groups per equivalent of substituent is preferably at least 1.4, and usually from 1.4 to about It is 6. Based on this minimum value, the range of substituted succinic acid groups is per equivalent of substituent group. A minimum of 1.5 to about 3.5, more typically about 1.5 to about 2.5.

As a result of the above, the substituted conoxylic acid acylating agent is represented by the symbol R, (R2). It's more obvious. Here, R1 is a substituent! Indicates the equivalent weight, R2 is the formula (■) 9 Formula (II) or formula (represents one cono-phosphate group corresponding to @, y is 1.3 or is a larger number. The present invention provides, for example, R7 and R2 as described in a separate section. The more preferred substituents and succinic acid groups are shown, and the y values are as described above. A more preferable embodiment can be similarly expressed by changing to .

The preference depends on the number and identity of cono-phosphate groups per equivalent of substituent. In addition to the substituted succinic acid groups, we also discuss the identity and characterization of the polyalkenes that make up the substituents. depends on your preferences.

For example, the value of Mn is preferably a minimum of about 1200 and a maximum of about 5000; A range of values of about 1300 or about 5000 is also preferred. The range of Mn values is approximately 1 500 to about 280.0 is more preferred, and about 1500 to about 2400 is most preferred. Delicious. For polybutenes, a particularly preferred minimum value for Mn is about 1700. , a particularly preferred range is from about 1700 to about 2400.

is preferred. Minimum value approx. 2. ．． More preferred is a range from 0 and about zO to about 3.4. A minimum value z5 and a range of about 25 to about 3.2 are particularly preferred.

Before proceeding further with the discussion regarding the polyalkenes that constitute the substituents, it is necessary to point out that What is not surprising is that these favorable properties of the cono-phosphate acylating agent are both independent and dependent. This does not mean having both at the same time. For example, cono・per equivalent of substituent , the preference for the lowest phosphate group to be 1.4 or 1,5 is Mn or MW/M This does not lead to a more preferable value of n. When we say that there is a dependency, for example, When the minimum value of succinic acid group is selected as 1.4 or 15, Mn and/or MW / M It means actually showing a better aspect. Therefore, the various variables are Although it is isolated for a given variable, it can be combined with another variable to generate other preferences. can.

Preferred figures, unless the contrary is clearly demonstrated or clear. This same concept for describing ranges, proportions, reactants, etc. is used in the present invention. It is expected to be.

The polyalkene constituting the substituent is a polymerizable olefin monomer having 2 to about 16 carbon atoms. It is a homopolymer or interpolymer of mer. The number of carbon atoms is usually from 2 to about 6.

Interpolymers are produced by mutually polymerizing two or more types of olefin monomers using a conventionally known method. The resulting polyalkene is a polymer obtained by combining two or more of the olefin monomers. It has units derived from each in its structure. Therefore, the term “interpolymer” used here includes dipolymers, terpolymers, quaternary polymers, etc. obvious to those skilled in the art However, the polyalkenes that make up the substituents are conventionally called "polyolefins". There were many things.

The olefin monomer that is the raw material for polyalkenes is a polymerizable olefin monomer. It is characterized by having one or more ethylenically unsaturated groups (>C=CH2).

Namely, ethyleth propylene, butene-11 butene, and octene-1 or monoolefin monomers such as butadiene-1,3 and inbrene. It is a polyolefin monomer (usually a diolefin monomer).

These olefin monomers are usually polymerizable terminal olefins; It is an olefin characterized by having a >CH=CH2 group within its structure. But that The following formula in the structure A polymerizable internal olefin monomer having the structure (in the literature, intermediate olefin (sometimes referred to as fins) can also be used in the production of polyalkenes. internal olefin When monomers are used, they are usually used with terminal olefins and polyalkenes. becomes an interpolymer. For purposes of this invention, certain polymerized olefin monomers are If they can be classified into terminal olefins and internal olefins, they are considered terminal olefins. be done. Therefore, pentagene-1,3 (piperylene) is not suitable for the purpose of the present invention. Considered a terminal olefin.

The polyalkenes constituting the substituents of succinic acylating agents are generally lower alkoxy , lower alkyl mercapto, hydroxy, mercapto, keto and aldehydic Which oxo, nitro, halo, cyano, carbalkoxy (alkoxy is usually lower alkoxy), alkanoyloxy, etc. However, non-hydrocarbon water The elementary substituent is a group that does not essentially interfere with the production of the substituted fluorinated acylating agent of the present invention. be. When such non-hydrocarbon groups are present, the polyalkene accounts for approximately 10% or less is normal. Polyalkenes can have such non-hydrocarbon substituents. Therefore, the olefin monomer that is the raw material for polyalkenes also has these substituents. can have. However, from the point of view of practicality and cost, olefin monomer and polyethylene Lukene usually has no non-hydrocarbon groups other than chlorine. The chlorine group is usually used in the present invention. Promotes the production of succinic acylating agents. (As used here, we say “low grade”) using the word ``lower alkyl'' or ``lower alkoxy'' with chemical groups such as ``lower alkyl'' or ``lower alkoxy.'' (In the case of a group having 7 or less carbon atoms).

Polyalkenes contain aromatic groups (particularly phenyl groups and p-(tert-butyl) phenyl groups). lower alkyl and/or lower alkoxy substituted phenyl groups such as or a polymerizable cyclic olefin or a polymerizable acyclic olefin having an alicyclic substituent. Although it can contain alicyclic groups such as fins, it usually does not contain such groups.

However, butadiene-1,3 and styrene or p-(tert-butyl)styrene Polyalkenes using interpolymers of 5-like 1,3-dienes and styrenes are This is an exception.

Again, aromatic and alicyclic groups may be present, making polyalkenes The olefin monomers can have aromatic groups and alicyclic groups.

The diene-styrene interpolymers mentioned above are an exception, but they contain aromatic and alicyclic groups. The general preference for polyalkenes with aliphatic hydrocarbons that are The above is clear. Under this general preference, if the number of carbons is 2 or homopolymers and interpolymers of terminal olefinic hydrocarbons having about 16 There is a second preference for polyalkenes derived from the group.

This second preference indicates that a terminal-olefin interpolymer is usually preferred, but Polymer units with internal olefins of 6 or less can also be phased as required if they are less than about 40%. This is based on the premise that it may be introduced into the taupolymer.

A more preferred type of polyalkene has from 2 to about 6 carbon atoms, more preferably from 2 to about 6 carbon atoms. Polymers selected from the group consisting of homopolymers and interpolymers of 4 terminal olefins. It is an alkene. However, another preferred class of polyalkenes is Polymers using internal olefins having about 6 carbon atoms or less are the latter, more preferred polymers. Some contain less than 25 inches.

Terminal olefins and and internal olefins such as ethylene: propylene; butene-1; -2; Isobutyne: Pentene-1: Hexene=l: Heftene! :Octene-1 ; Nonene-1; Decene-1; Pentene-2; Propylene tetramer; Diisobutylene ; Inbutylene trimer: Butadiene-1,2; Butadiene-1,3; Pentaje Pen-1,2; Pentagene-1,3; Pentagene-1,4; Imprene: Hex Sadien-1,5; 2-chloro-butadiene-1゜3; 2-methyl-isothene- l; 3-cyclohexylbutene-1; 2-methyl-heptene-1; styrene; 2 ．． 4-dichlorostyrene; divinylbenzene; vinyl acetate; aryl alcohol : l-methylvinyl acetate; acrylonitrile; ethyl acrylate; methacrylic ethyl vinyl ether; and methyl vinyl ketone. child Among them, polymerizable hydrocarbon monomers are preferred, and terminal olefin monomers are particularly preferred. Particularly preferred.

Examples of polyalkenes include 1-polypropylene, polybutene, and ethylene-propylene. Ren copolymer, styrene-isobutyne copolymer, isobutyne-butadiene-1゜ 3 copolymer, propene-, isoprene copolymer, inbutene-chlorprene copolymer Copolymer, inbutene-(copolymer with p-meoctene-1, 3,3-dimethyl-1 - Copolymers of hentene and hexene-1, and isobutyne, styrene, piperi Examples include ren terpolymers.

A more detailed example of an interpolymer is 95% (by weight) isobutyne and 5% styrene. Copolymer of 1% (by weight): 98% isobutyne, 1% piperylene, 1% chloroprene Terpolymer of 95% isobutene, 12% butene, and 13% hexene Original copolymer: 60% isobutene, 120% pentene, 120% octene Original copolymer; copolymer of hexene-180%, heptene-120%; inbutene Terpolymer of 90%, 2% cyclohexene, 8% propylene; and ethylene A copolymer of 80% propylene and 20% propylene is used to convert the refinery's C4 fraction into aluminum trichloride. polyimbutane obtained by polymerization in the presence of a Lewis acid catalyst such as aluminum or boron trifluoride. preferred. These polybutenes have the repeating unit shown by the following formula as the main component. The amount of perilla exceeds about 80 units of total repeating units.

Method for producing the polyalkene that passes various standards of Mn and MW/Mn It is clear that these are within the scope of the prior art and are outside the scope of the present invention. person skilled in the art Readily known techniques include, for example, adjusting the polymerization temperature, polymerization initiators and/or These include adjusting the amount and type of catalyst, and using a polymerization terminator during polymerization. Ho Crab light end stripping (including vacuum stripping) and/or produces low molecular weight polyalkenes by oxidizing or mechanically decomposing high molecular weight polyalkenes. Conventional techniques such as building can also be used.

When producing the substituted succinic acylating agent of the present invention, one or more of the above polyalkyls selected from the group consisting of maleic acid or fumaric acid reactants with the following general formula: react with one or more acidic reactants.

X (0) C-CH=CH-C (0) X' ■Here, X and X' are as above The same is true.

The maleic acid and fumaric acid reactants are preferably one or more compounds corresponding to the following formula: .

RC(0)-CH=CH-C(0)R'(V) where R and R' are Same as above. Maleic acid and fumaric acid reactants are usually maleic acid, fumaric acid , maleic anhydride, or a mixture of two or more thereof. Maleic acid reactant are generally preferred over fumaric acid reactants. The reason is that the maleic acid reactant is available It is easy to use polyalkenes and polyalkenes when producing the substituted succinic acylating agent of the present invention. This is because it is generally easy to react with the compound and its derivatives. A particularly preferred reactant is malein. acid, maleic anhydride and mixtures thereof. Because it is easy to obtain and react with , maleic anhydride is usually used.

To prepare the substituted succinic acylating agents of the present invention, one or more polyalkenes and one Reaction of more than one maleic acid or fumaric acid reactant by any known method good. This method uses high molecular weight co-phosphoric anhydrides and a series of corresponding succinic acids. The method for producing acylating agents is basically similar. The different points are described in the prior art. The polyalkynes (or polyolefins) are converted into the above-mentioned specific polyalkenes. Alternatively, the amount of maleic acid or fumaric acid reactant may be adjusted to 5 so that the number of succinic acid groups is 1.3 or more per equivalent of substituent in the acylating agent. It is something that must be done.

For simplicity, the term "maleic acid reactant" will be often used hereinafter. Use this (V), the term also refers to Malays corresponding to formulas (V) and (V) above, as well as mixtures thereof. Comprehensive use for acidic reactants selected from acid and fumarate reactants. You need to be careful.

The method for producing substituted succinic acylating agents of the present invention is described in U.S. Pat. As a reference for producing a succinic acid acylating agent, please refer to the partial examples in No. 666. Describe it. For simplicity, this method will be referred to as the "two-stage method." using this method First, the polyalkene is chlorinated to create an average of about 1 or more chlorine in each polyalkene molecule. Add a group. (In the present invention, the molecular weight of polyalkene is expressed as a value equivalent to Mn) Chlorine The process involves contacting the polyalkene with chlorine gas until the required amount of chlorine is added to the polyalkene. Just touch it. Chlorination is generally carried out at a temperature of about 75-125°C. diluent If used, use a non-chlorinated diluent. For example polychlorinated alkanes , perchlorinated alkanes, and/or fluorinated alkanes and benzene. Ru.

In the second step of the two-stage chlorination method, the chlorinated polyalkene is treated with maleic acid in the present invention. React with the reactant at about 100-200°C. Chlorinated polyalkene and maleic acid reaction The molar ratio with the body is usually 1:1. (In the present invention, 1 mole of chlorinated polyalkene is chlorinated polyalkea) is the weight of the chlorinated polyalkene corresponding to the Mn value). death The maleic acid reactant is used in stoichiometric excess, e.g. with a molar ratio of 1=2. can do. In the chlorination process, an average of about 1 alkene is added per mole of polyalkene. If more than 1 mole of chlorine group is introduced, 1 mole per mole of chlorinated polyalkene More maleic reactants can be used. Under these conditions, chlorination It is better to express the ratio of polyalkene and maleic reactant in equivalent weights. (In the present invention , 1 equivalent of chlorinated polyalkene is equivalent to Mn present in 1 molecule of chlorinated polyalkene. is the weight divided by the average number of chlorine groups, while one equivalent of maleic acid reactant is the weight of the maleic acid reactant. molecular weight). Therefore, the ratio of chlorinated polyalkene to maleic reactant is usually The maleic acid reactant is used in excess of about 25% by weight per mole of chlorinated polyalkene. . Unreacted excess maleic acid reactant can be distilled off (usually under reduced pressure) from the reaction product. Alternatively, the reaction may be carried out in the next step as described below.

The obtained polyalkene-substituted cono-phosphate acylating agent has an insufficient number of succinic acid groups. If necessary, chlorination may be performed again. In this secondary chlorination process, excess maleic acid is added in the second step. If an acid reactant is present, the maleic reactant reacts with the introduction of chlorine. excess In the absence of reactants, the maleic acid reaction occurs during and/or after the secondary chlorination. Add body. Continue until the total number of succinic acid groups per equivalent of substituent reaches the required amount. The operation can be repeated.

Another method for making the substituted succinic acylating agents of the present invention is described in U.S. Pat. 12,764 and British Patent No. 4,440,219. Make use of it. Both patents are incorporated herein by reference. In this method, polyalkenes and The maleic acid reactant is first heated and reacted, resulting in a "direct alkylation" operation. When the killing process is completed, chlorine is introduced into the reaction solution, and if it remains, the olefin polymer is In other words, 0.3 to 2 moles or more of maleic anhydride is reacted with 1 mole of polyalkene. make them respond.

The direct alkylation step is carried out at 180-250°C. Chlorine introduction at 160-225℃ conduct. To prepare substituted succinic acylating agents in this manner, a maleic acid reactant and Use sufficient chlorine to ensure that 1.3 or more succinic acid groups per equivalent of polyalkene are present in the final product. It is necessary to make it 5 so that it is included in the product.

Currently considered to be the best method for producing the substituted succinic acylating agent of the present invention. The method depends on the efficiency, overall economics, performance of the acylating agent produced and its derivatives. Considering the performance, the so-called "one-stage method" is optimal.

This method is described in U.S. Pat. Nos. 3,215,707 and 3,231,587. It is listed. Both patents are specifically mentioned by reference to the method.

The one-step method involves preparing a mixture containing the required amounts of polyalkene and maleic acid reactant; It basically includes a method for producing the substituted succinic acylating agent of the present invention. This means that In order to have 1.3 or more succinic acid groups per equivalent of substituent, 1 mol of polyalkene is added. This means that 1.3 mol or more of the maleic acid reactant is required. Then mix While stirring the mixture, chlorine gas is introduced at a temperature of 140° C. or higher.

A variation of this method is to add the maleic acid reactant during or after the chlorine introduction. There is a law. However, U.S. Patent Nos. 3,215,707 and 3,231,587 For the reasons stated in the above issue, this method is now preferred by using polyalkenes and polymers before introducing chlorine. A method of mixing the entire amount of the leic acid reactant is preferred.

If the polyalkene completely liquefies at temperatures above 140°C, the one-stage process is essentially free. active and usually does not require the use of liquid solvents/diluents. However, as mentioned above, when a solvent/diluent is used, it is for the purpose of preventing chlorination. this eye Again, polychlorinated alkanes, perchlorinated alkanes and/or polychlorinated alkanes Using fluorinated alkanes, perfluorinated alkanes, cycloalkanes, and benzene. Ru.

In a one-stage process, chlorine is introduced continuously or continuously.

There is no particular limit to the rate of introduction of chlorine, but to maximize the utilization rate of chlorine, The consumption rate and introduction rate must be kept at a medium level for the reaction. The speed of introduction exceeds the speed of consumption. Chlorine is evolved from the reaction mixture. To prevent chlorine loss and maximize utilization For this purpose, it is often advantageous to use a 5-closed system and use pressures above atmospheric pressure. +11° The temperature at which the reaction proceeds at a suitable rate in the one-stage process is about 140°C. Therefore this method The lowest temperature at which this is carried out is around 140°C.・The preferred temperature is about 160-220 It is ℃. Although it is possible to react at high temperatures of 250°C or higher, there are few advantages. In fact, over 220℃ Problems often occur when the specific acylated cono-phosphoric acid composition of the present invention is produced as described above. . Polyalkenes may “crack” (i.e., their molecular weight decreases due to thermal decomposition). This is because the maleic acid reactant tends to decompose. Best for this Temperatures usually do not exceed about 200-210°C. Useful temperature in one-stage method The upper limit of is determined primarily by the decomposition temperature of the components of the reaction mixture, including the reactants and reaction products. It is determined as Decomposition temperature is the temperature at which the decomposition of reactants or products produces the desired product. It is a temperature that occurs in large enough quantities to cause interference.

In the one-stage method, the molar ratio of maleic acid reactant to chlorine is Approximately 1 mole or more of chlorine is required per mole of acid reactant. Furthermore, due to practical issues, An excess of chlorine, approximately 5-30% by weight, is used to limit the amount of chlorine escaping from the reaction solution.

Large excesses of chlorine can also be used without good results.

As mentioned in 5 above, the molar ratio of polyalkene and maleic acid reactant is 1 mol of polyalkene. whereas the maleic acid reactant is about 1.3 moles or more. This is substituent 1 in the product This is necessary to increase the number of succinic acid groups to 1.3 or more based on the equivalent weight. But maleic acid A method in which the reactant is used in excess is preferred. Therefore, the required number of succinic acid groups in the product The maleic acid reactant is usually used in about 5-25% excess over the amount needed to introduce the maleic acid reactant. Ru.

A preferred method of making the substituted acylated compositions of the invention is (AJ Polyalke with Mn value of about 1200-5000.Mw/Mn value of about 1.5-4 hmm, (B) One or more acidic reactants of the following formula XC(0) -CH=CH-C(0)X' where X and X are the same as above There is, and (q chlorine 1 mole of (B) reacts by heating and contacting at a temperature of about 140°C or above and below decomposition and inversion. about 0.2 mol or more (preferably 0.5 mol or more) of the substituted acylated group The composition contains on average 1.3 or more groups obtained from (B) per equivalent of substituent obtained from (N). It is characterized by having within the structure of. Substituted acyl produced by such method compositions are also part of the invention.

A description of the preferred method described above can be found in U.S. Pat. No. 3,912,764 and Direct alkylation and subsequent alkylation as described in British Patent No. 1,440.29 Chlorination Process and U.S. Pat. No. 3,215. TIO No. 7 and 3.231.5 It is clear that it encompasses both the complete one-stage method described in No. 87. Therefore In the description, the initial mixture of polyalkene and acidic reactant contains no It is not necessary to include the entire amount of acidic reactant that will ultimately be incorporated into the substituted acylating agent. . In other words, the entire amount of acidic reactant may be added initially, or a portion may be added later during the reaction. May be added. Similarly, chlorine may be introduced directly after the alkylation reaction. However, it is common practice to mix the entire amount of the polyalkene used in the first reaction solution with the acidic reaction solution. Ru. Furthermore, the amount of chlorine is determined per mole of unreacted (B) present at the beginning of introduction. It is common to use about 1 mole of chlorine. Therefore, the molar ratio (A):(B) is (A) There are 1.5 moles of door per mole, and the result of direct alkylation (B) If half of the product becomes the product, then the amount of chlorine introduced until the reaction is complete is (B) The standard value is 0.75 mol of unreacted . That is, 0.75 moles or more of chlorine (also is introduced in the above-mentioned excess amount).

In a more preferred method of making the substituted acylated compositions of the present invention, (N Mn value of about 1200-5000 and Mw/Mn of about 1.3-4 polyalkene, CB1, represented by the value one or more acidic reactants RC, represented by the formula (0) -CH=CH-C (0) R' where R and R' are the same as above. and (C) chlorine A mixture consisting of the following is heated to about 140°C or higher. here.

Molar ratio fA): (B) is about 1.3 moles or more per 1 mole of (A). , and the number of moles of particles is (the quotient of the total weight of N divided by the value of Mn, which reacts with (A) 1 mole or more of chlorine is used per 1 mole of (B), and the substituted acylating agent composition is (A) There are 13 or more groups obtained from (B) in the structure 4 for 1 equivalent of the substituent obtained from It is characterized by As mentioned above, this method is only a one-stage method. That is, ( This is a method in which the entire amount of N and (B) is present in the initial reaction solution. Manufactured using this method The substituted acylated compositions prepared are also part of the present invention.

The term "substituted succinic acylating agent" is independent of its method of manufacture. As mentioned above It is clear that there are several methods of producing sea urchin.

The term "substituted succinic acylating agents" is used regardless of the method by which they are manufactured. Used for succinic acylating agents.

Several methods are available for making substituted succinic acylating agents, as detailed below. used. On the other hand, the term "substituted acylated composition" refers to the specific The reaction mixture prepared by the preferred method is shown below. Therefore, the substituted acylation composition Identity depends on the particular manufacturing method. New material used in the present invention The type of acylating agent is best described by the unique method using this term, as described above. ・This term is particularly accurate because the origin of the invention is It is clear that the composition is a substituted succinic acylating agent as defined and discussed above. However, its structure cannot be expressed by a single specific chemical formula. Essentially there is a mixture of products. (a) a substituted succinic acylating agent, and ( b) M-! 1 value, Mw/Mn ratio, polyalkene identity (1 dentity) and composition, identity of the acidic reactants (i.e. maleic acid and or fumaric acid reactant), proportions of reactants, and reaction temperature as described above. The preferred method can also be applied to the preferred method described above. Similar preferences apply to these preferred methods The method can be similarly applied to substituted acylated compositions prepared by the above method.

For example, the reaction temperature is preferably about 160-220'C.

Similarly, as polyalkenes, homopolymers of terminal olefins having 2 to 16 carbon atoms or An interpolymer is preferred from the viewpoint of the reaction state and the resulting composition. In that case, the corresponding phase The taupolymer contains up to 409 g of polymerized units of internal olefins having about 16 carbon atoms or less. Good too. The polyalkene used in the preparation of the composition of the present invention has a terminal chain having 2 to 6 carbon atoms. It may contain up to about 25 polymerized units.

Particularly preferred polyalkynes include polybutene, ethylene-propylene copolymer, polyalkylene Propylene, with polybutene being particularly preferred.

The succinic acid group content of the substituted acylated composition thus obtained is also It is preferable that the composition be the same as that of the coating agent. Therefore, substituted acylated compositions 1.4 or more succinic acid groups obtained from B) per equivalent of substituent obtained from (A) in the structure. It is characterized by the fact that it has the same amount of More preferably, it has from 1.4 to about 3.5 phosphoric acid groups. Similarly these substitutions The acylated composition has within its structure (B for each equivalent of substituent obtained from N) It is more preferable to have 1.5 or more cono-phosphate groups, but 1 equivalent of the substituent obtained from (4) The amount of succinic acid groups obtained from B) is 1. It is particularly preferable if it has s or more.

Finally, for the substituted succinic acylating agent, the succinic acid group obtained from (B) has the following formula: and mixtures thereof by the preferred method of preparation. It is preferable to manufacture the same.

A particularly preferred method of producing substituted acylated compositions includes (A) a Mn value of about 1700; -2400, Mw/Mn value approximately Z5-3.2, derived from butene Polybutene derived from isobutyne in which 50 or more of the total units are derived from isobutene, (B) One or more acidic reactants of the following formula: RC(o) -CH=CH-C(o) R' Here, R and R' are each -OH, and when bonded to each other, - is 0-, and (C) Chlorine The process involves heating the mixture to a temperature of about 160-220°C. mole here The ratio (A): (B) is (B to AJt mol) 1.5 mol or more, ( The number of moles of A) is the quotient of the total weight of (A) divided by the excitation value, and the amount of chlorine used is (N and The acylation composition is about 1 mole or more per mole of reacting (B), and the acylation composition has a structure Substituents obtained from (A) within! Having an average of 1.5 or more groups obtained from B) per equivalent amount It is characterized by Substituted acylated compositions prepared by such methods are also preferred. It is one of the most desirable compositions.

For brevity, the term "6-acylating agent" is used herein to refer to substituted succinic acylating agents. The term is often used hereinafter to encompass both types of substituted acylation compositions used.

The acylating agent of the present invention has one or more acylating agents having one or more groups within its structure. A carboxylic acid derivative composition (A) characterized in that it is reacted with an amino compound that It is an intermediate during manufacturing.

Amine compounds that have one or more -NH- groups in their structure are also monoamine compounds. A polyamine compound may also be used.

In the present invention, hydrazine and hydrazine having 3 or less substituents are carboxylic acids. It is an amine compound suitable for producing derivative compositions. Two or more amine compounds can be reacted with one or more acylating agents of the present invention. Amination Preferably, the compound contains one or more primary amine groups (-NH2), especially two or more. Particularly preferred are polyamines containing the above -NH- groups. The amine group may be primary or 2nd grade is fine. Polyamines form carboxylic acid derivatives derived from monoamines. In addition, these preferred polyamines include V, 1. Even better features with improved properties A rubonic acid derivative composition is formed.

Monoamines and polyamines must have one or more -NH- groups in their structure. not; therefore has one or more primary (H2N-) or secondary (H-N=) groups . Amines can be aliphatic, cycloaliphatic, aromatic, or heterocyclic; Cyclic, aliphatic, group-substituted aromatic, aliphatic-substituted heterocyclic, alicyclic-substituted aliphatic, alicyclic Substituted - Terocyclic, aromatic substituted aliphatic, aromatic substituted alicyclic, aromatic substituted heterocyclic heterocyclic-substituted aliphatic, heterocyclic-substituted acyclic, and heterocyclic-substituted aromatic Also includes group amines. Further, it may be a saturated amine or an unsaturated amine. For unsaturated amines Contains no acetylenic unsaturation. Although the amine may contain non-hydrocarbon substituents, These substituents do not interfere with the reaction between the amine and the substituted acylating agent of the present invention. is necessary. Examples of non-hydrocarbons include lower alkoxy, lower alkyl, and metal. Interrupt groups such as lucapto, nitro, -0- or -8- ng group) (-CH2CH2-X-CH2CH2-, etc., where X is 10 - or -8-).

Branched polyalkylene polyamines, polyoxyalkylene polyamines, and the following Except for the high molecular weight hydrocarbyl-substituted amines detailed in It contains less than about 40 carbon atoms in amount, and usually less than about 20 carbon atoms.

Aliphatic monoamines are mono- and di-aliphatic substituted amines, including aliphatic The group may be saturated or unsaturated, and may be linear or branched. like that Amines include, for example, mono- and di-alkyl substituted amines, mono- and di-alkyl substituted amines, alkenyl-substituted amines, and N-alkyl substitution with one of the N-alkenyl substituents There are amines each having one group. As mentioned above, these aliphatic monomers The total number of carbon atoms in the amine is generally less than about 40, and usually less than about 20.

Examples of monoamines include ethylamine, diethylamine, n-butylamine. , di-n-butylamine, allylamine, isobutylamine, cocoamine, Allylamine, laurylamine, methyllaurylamine, oleylamine, N- Methyl-octylamine, dodecylamine, octadecylamine, etc. Ru. Alicyclic substituted aliphatic amines, aromatic substituted aliphatic amines and heterocyclic substituted aliphatic amines Examples of aliphatic amines include 2-(cyclohexyl)ethylamine and benzylamine. amine, phenylethylamine, and 3-(furylglobyl)amine.

Alicyclic monoamines have a single carbon atom in the cyclic structure that converts the alicyclic group into an amine nitrogen. It is a directly bonded monoamine. Examples include cyclohexylamine, Cyclopentylamine, N-ethylcyclohexylamine, dicyclohexylamine There are min etc. Cycloaliphatic monoamines substituted with aliphatic, aromatic or heterocyclic groups - for example, propyl-substituted cyclohexylamine, phenyl-substituted cyclopentyl amines, and pyranyl-substituted cyclohexylamines.

Aromatic amines are monoamines in which one of the carbon atoms in the aromatic ring is directly bonded to the amine nitrogen. There is a problem. Aromatic rings are usually monocyclic (benzene-based), but especially naphthalene-based A fused aromatic ring may also be used. Aromatic monoamines include aniline, di(p-methylphenylphenyl) amine, naphthylamine, N-(n-butyl)aniline, etc. fat is p-ethoxyaniline, p-dodecylaniline, cyclohexyl-substituted naphthyl There are amine and chenyl substituted anilines.

Polyamines are aliphatic, cycloaliphatic and aromatic polyamines that have different It is the same as the monoamine described above except that amine nitrogen is present. Another amine nitrogen may be a primary, secondary or tertiary amino nitrogen. such polyamines N-(aminopropyl)cyclohexylamine, N,N'-di-n-butyl -p-phenylenediamine, bis(p-aminophenyl)methane, 1,4-dia Minocyclohexane and the like can be used to prepare the bonic acid derivative composition. used here The term "6-heterocyclic mono- and poly-amines" refers to one or more primary or is a secondary amino group and a compound containing one or more nitrogen atoms as heteroatoms in the heterocycle. It refers to terocyclic amines. However, in heterocyclic mono- and polyamines, If one or more primary or secondary amine groups are present, the heteronitrogen atom in the ring Tertiary amine nitrogen may also be used. In other words, hydrogen does not need to be directly bonded to the ring nitrogen. stomach. Heterocyclic amines can be saturated or unsaturated, including nitro, alkoxy, alkyl Mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkyl There may be substituents.

Generally, the number of carbon atoms in the substituents is about 20 or less. Heterophase liquid amines are non-nitrogen It may also contain heteroatoms, especially oxygen and sulfur. one or more nitrogen heteroatoms It is clear that it may include. 5-membered heterocycle or 6-membered heterocycle is preferred stomach.

Suitable peterocyclic compounds include atiridine, azetidine, azolidine, tetra-or and dihydropyridine, virol, indole, piperidine, imidazole, G and tetrahydroimidazole, piperazine, kilpiperazine, N, N'-diaminoalkylpiperazine, azepine, azocine, azonine, aze ion, their tetra-, di- and perhydro derivatives, and their heterolayer liquids. There are mixtures of two or more amines.

Some heterocyclic amines contain only nitrogen, oxygen and/or sulfur within the heterocycle 5- and 6-membered saturated heterocycles are preferred, especially piperidines, piperazines, Thiomorpholines, morpholines, pyrrolidines and the like are preferred. Among these Particularly preferred are piperidine/, aminoalkyl-substituted piperidines, and piperazine. , aminoalkyl-substituted morpholines, pyrrolidine, and aminoalkyl-substituted morpholines, It is a loridine. Aminoalkyl substituents are usually attached to the nitrogen atom forming the heterocycle. Join. As such a heterolayer amine, for example, N-aminopropyl mol. Holin, N-aminoethylpiperazine, and N,N'-di-aminoethylpiperazine There's perazine.

Hydroxyamines can also be used as monomers if they have one or more primary or secondary amine groups. Both noamine and polyamine (a> can be used in the same manner as above. Trihydride Hydroxy-substituted amines with only tertiary amine nitrogen, such as loxethylamine, Mines are excluded as (a). [However, it can be used as (b) below]. With expectations Hydroxy-substituted amines in which the hydroxy substituent group is a carbon atom other than a carbonyl carbon atom These are amines that are directly bonded to atoms.

That is, these hydroxyl groups can act as alkyl groups. This is so nice Doro-oxy substituted amines include, for example, ethanolamine, di(3-hydroxypropylene), lopylamine, 3-hydroxybutylamine, 4-hydroxybutylamine diethanolamic, di(2-hydroxypropyl)amine, N-(hydroxy propyl)propylamide 7, N-(2-hydroxyethyl)cyclohexylamide 3-hydroxycyclopentylamine, p-hydroxyaniline, N-hydro Examples include roxyethylpiperazine.

Hydrazine and substituted hydrazines can also be used. One or more nitrogens in hydrazine requires that hydrogen be directly bonded. directly bonded to hydrazine nitrogen It is preferable that there are two or more hydrogens, and if two hydrogens are bonded to the same nitrogen, More preferred. Examples of substituents for hydrazi/ include alkyl, alkenyl, 71J-#, aralkyl, alkaryl, etc.

Substituents are commonly alkyl, especially lower alkyl, phenyl and lower alkoxy substituted groups. Substituted phenyl such as phenyl and lower alkyl substituted phenyl.

Substituted hydrazines include, for example, methylhydrazine, N.

N-dimethylhydrazine, N,N'-dimethylhydrazine, N,N'-di (p-chlorophenol)hydrazine, N-phenyl-N'-cyclohexylhydrazine High molecular weight hydrocarbylamines that can be used as dorazine (a) are Both amines and polyamines are generally chlorinated polyolefins with a molecular weight of about 400 or more. It is produced by reacting fins with ammonia or amines. These amines are known and, for example, U.S. Pat. Nos. 3,275,554 and 3,428,757. I would like to mention what is described in this article as reference material for the amine production method. These a All that is required for the amine is to have one or more primary or secondary amine groups. .

Another class of suitable amines include polyalkylene polyamines with branched . Branched polyalkylene polyamine is a polyalkylene polyamine in which branched groups form side chains. It is kylene polyamine. The side chain is an aminoalkylene bonded to nitrogen as shown in the following formula. an average of one or more amino groups for every nine amino units present in the main chain, e.g. There are 1 to 4 branches for every 9 units on the main chain unit. Therefore these polyamide The ion contains three or more primary amine groups and one or more tertiary amino groups.

Also suitable amines include polyoxyalkylene polyamines, i.e. polyoxy There are alkylene diamines and polyoxyalkylene triamines. the average amount The molecular weight is in the range of about 200-4000, preferably 400-2000. these The polyoxyalkylene polyamine can be represented by the following formula, for example.

N) (2-alkylene-〇〇-alkylene%NH2(Vl) where m is 3-70 , preferably 10-35.

R-! = Fullylene - ÷ 0 - Alkylene 1 τX Chi] 3-6 (To) The value is approximately 3- 70. Generally it will be about 6-35. In addition, R is a polyvalent saturated compound having a valence of 3-6. It is a Japanese hydrocarbon group and the number of carbon atoms is 1O or less. Alkylene groups can be separated even in straight chains. It may be branched and contains 1-7, usually 1-4 carbon atoms. Expression (b) and (to) ) may be the same or different.

Preferred polyoxyalkylene polyamines include polyoxyethylene diamine, There are polyoxypropylene diamines and polyoxypropylene triamines.

Its average molecular weight is about 200-2000. polyoxyalkylene polyamine Similar products are available on the market. For example, Jeffern Chemical Company Product name of Ni Co., Ltd. “Diefermin D-230, D-400, D-1000, D- 2000, T-403'', etc.

Discloses an amine and a method for acylating the same using a carboxylic acid acylating agent. There is. The method can be used for affylation reactions using the acylating agents of the present invention.

The most preferred amines are alkylene polyamides such as polyalkylenepo'J7mine. This is explained in detail below. alkylene polyamine The class corresponds to the following formula.

Here, n is 1-10, and ≦R3 is a hydrogen atom, a hydrocarpyl group, or a hydroxy-substituted hydrocarbyl group having up to about 30 atoms, one or more R3 is a hydrogen atom, and U is an alkylene group having 2-IO carbon atoms. U is ethylene Or propylene is preferred.

Alkylene polyamines in which all R3s are hydrogen are particularly preferred, and ethylene polyamines Most preferred are min and mixtures thereof. n is usually on average 2-7. Like that Examples of alkylene polyamines include methylene polyamine, ethylene polyamine, and methane polyamine. Ren polyamine, propylene polyamine, pentylene polyamine, hexylene polyamine These include lyamine, hexylene polyamine, etc. Higher homologues of these amines and related aminoalkyl-substituted piperazines are also included.

Alkylene polyamines useful in the preparation of carboxylic acid derivative compositions include ethylenedia triethylenetetramine, propylene diamine, triethylene diamine, Hexamethylene diamine, decamethylene diamine, octamethylene diamine, diamine (heptamethylene)triamine, tripropylenetetramine, tetraethylenepetramine tamamine, trimethylenediamine, pentaethylenehexamine, di(trimethylenediamine) /) triamine, N-(2-aminoethyl)piperazi/, 1,4-bis(2-aminoethyl) (minoethyl) piperazine, etc. Two or more of the above alkylene polyamines A mixture of two or more of the higher homologs obtained by condensation and the above polyamines is also referred to as (a). It can be used as

The ethylene polyamines are particularly useful for reasons of cost and availability. this Such polyamines are described in Kirk and Osmer, The Encyclopedia Op. Chemical Technology, Volume 7, pp. 27-39 (Interscience, The The Division Option (Wiley & Sons 1965) For your information, please refer to the detailed description under the heading “Amines and Higher Amines”. state These compounds are produced by the reaction of alkylene chloride with ammonia or by the reaction of ethylene chloride with ammonia. It is most conveniently prepared by the reaction of lenimine with a ring-opening agent such as ammonia. be. The reaction results in an alkylene polyamide containing a cyclic condensation product such as piperazine. A rather complex mixture of components is formed. The mixture produces a new type of sulfur-containing composition of the present invention. This is particularly useful when On the other hand, if pure alkyl-lembolyamine is used, A completely satisfactory product is obtained.

Another useful type of polyamine mixture is the stripping of the polyamine mixtures described above. You can get good results. In this case, low molecular weight polyamines and volatile impurities are replaced by alkylene polymers. A residue, often referred to as ``polyamine bottoms,'' is removed from the polyamine mixture. remain. Generally, fullkylene polyamine bottoms contain substances that boil below about 200°C. It is characterized by an amount of 2% by weight, usually less than 1% by weight. ethylene polyamide Nobottom is readily available and extremely useful; diethylenetriamine ( DETA),! :,) The total amount of diethylenetetramine (TETA) is approximately 2 times It is less than a quantum. Dow Chemical Company, Freeboard, Texas The external sample of ethylene polyamine bottom obtained as “E-100” from The weight is 1.0168 at 15.6℃, the nitrogen content is 33.15% by weight, the viscosity is The temperature is 120 cst at 40°C. According to gas chromatography analysis, Itto end (DETA) 0.93chi, TETA O, 72nd person, Tetra ethire 21.74% for benpentamine, 76.61% for benphtaethylenehexamine ( Both contain weight). Alkylene polyamine bottoms are piperazine and di- Cyclic condensates of higher homologs such as ethylenetriamine and triethylenetetramine are also available. include.

These alkylene polyamines react only with acylating agents. In that case, amine anti- The reactant may consist essentially of alkylene polyamine bottoms or may include other amino acids. Can also be used in combination with alcohols and polyamines, or alcohols or mixtures thereof. can. In the latter case, one or more hydroxyalkyl substituents are attached to the nitrogen atom. The hydroxyalkyl alkylene polyamines also serve as olefin carboxylic acid derivatives. Useful for manufacturing conductors. Preferred hydroxyalkyl-substituted alkylene polyamides The hydroxyalkyl group is a lower hydroxyalkyl group, that is, a carbon number of 8 or more. This is the group below. Such hydroxyalkyl-substituted polyamines include N-(2- hydroxyethyl) ethylenediamine, N,N-bis(2-hydroxyethyl) Ethylenediamine, 1-(2-hydroxyethyl)hyperazine, monohydroxy Propyl-substituted diethylenetriamine, dihydroxypropyl-substituted tetraethylene Pentamine, N-(2-hydroxybutyl)tetramethylenediamine, etc. . The above-mentioned hydroxyalkylene polyamine is converted into an amine group or a hydroxyl group. Higher condensed homologs are also useful as (a). Condensation with amine groups In this case, ammonia is removed and becomes a higher amine, and in condensation with hydroxyl group, Water is removed to form an ether bond.

A carboxylic acid derivative composition (A) produced from an acylating agent and the amino compound Acylated amines obtained using amine salts, amides, imides, imidacillins and There's a mixture of that. Produce carboxylic acid derivatives from acylating agents and amino compounds In this step, one or more acylating agents and one or more amine compounds are heated. heating is necessary Usually in the presence of a liquid, essentially inert organic liquid solvent/diluent. heating The temperature is between approximately 80℃ and the decomposition point (the decomposition temperature is measured in advance). If the decomposition point is 300°C or higher, heat to a temperature in the range of about 100-300°C. Approximately 1 Temperatures of 25-250"C are usually used. The acylating agent and the amino compound are Approximately 1/z equivalent - 2 moles of the amino compound is reacted with respect to 1 equivalent of the binding agent.

In the present invention, one equivalent of an amine compound is calculated by dividing its total weight by the total number of nitrogen atoms present. This is the value. Therefore, the equivalent weight of octylamine is equal to its molecular weight; The equivalent weight of aminopiperazine is 1/2 of its molecular weight; /3.

The number of equivalents of an acylating agent refers to the number of carboxylic acid functional groups present in the acylating agent [i.e. C(0)X, -C(0)X', -C(0)R.

and -C(0)R- where X, X', R and R' are the same as above). Exists. Therefore, the number of equivalents of the acylating agent depends on the number of succinic groups present in it. Change.

When determining the number of equivalents of the acylating agent, consider that it will react as a carboxylic acid acylating agent. Carboxyl functional groups that cannot be removed are excluded. However, in general, succinic acid in the acylating agent The amount of acylating agent is 2 equivalents per group. In other words, (B); First, the components in the acylating agent produced using the maleic acid reactant, which is the raw material for the acylating agent. The amount is 2 equivalents per 1 succinic acid group. The number of carboxyl functional groups (i.e. acid value and (saponification value and saponification value), therefore the number of equivalents of acylating agent used in the reaction with the amine is It can be easily quantified by the method.

The acylating agent is prepared in a manner similar to that of the high molecular weight acylating agents of the present invention. Production of acylated amines suitable for use as component (A) in diesel lubricants It can be used for. U.S. Patent No. 3,172,892゜3.219,66 No. 6.3,272,746 and No. 4,234,435 disclose an acylating agent and the amino acid Methods that can be used for reactions with compounds are shown for reference. Disclosure of these patents When applied to hair acylating agents, the same equivalent amount of acylating agent is disclosed in these patents. It can be used as a substitute for the high molecular weight carboxylic acid acylating agent. i.e. , using one equivalent of the high molecular weight carboxylic acid acylating agents disclosed in these patents. Sometimes one equivalent of the acylating agent of the present invention can be used.

In order to produce a carboxylic acid derivative composition having the ability to improve the viscosity index, acyl It has been found that it is generally necessary to react the curing agent with a polyfunctional reactant. For example 2 Polyamines having 7 or more primary and/or secondary amide groups are preferred.

The polyfunctional reactants create “bridges” in the carboxylic acid derivative composition, i.e., create crosslinks. It is thought that it acts as a cheat. On the contrary, this point is difficult because the main mechanism of the viscosity index is unknown. There is no point in combining it with theory.

However, it is not necessary that all amino compounds that react with the acylating agent be polyfunctional. is clear. Mixtures of mono- and polyamino compounds are therefore used.

Although the variables have not yet been completely determined, the acylating agents of the present invention have a sufficient amount of polyfunctionality. By reacting with an amino compound containing a reactant (i.e. polyamine), a cono-phosphate group is formed. or the total number of carboxy and ru groups derived from groups using maleic acid reactants as raw materials. It must be ensured that 25 or more reactants react with the polyfunctional reactant. carboxylic acid As far as the viscosity index improving property of the derivative is concerned, more than 50% of the carboxyl groups are polyfunctional. It appears that better results can be obtained by reacting with a reactive reactant. in most cases is an amount sufficient for the acylating agent of the present invention to react with 75 or more carboxyl groups. It appears that the best viscosity index improving properties can be achieved by reacting with a polyamine of . The above percentages are "theoretical" and the carboxyl functional groups in the above percentages are It must be understood that there is no need to actually react with the valence reactant. Rather these The percentage of the acylating agent that can be reacted with the acylating agent to achieve the desired viscosity index improving properties. was used to characterize the amount of polyfunctional reactant desired.

Another optional aspect of the invention includes post-treatment of carboxylic acid derivative composition (A). mosquito Post-treatment methods for carboxylic acid derivative compositions have also been proposed for high molecular weight carboxylic acids in the prior art. Work-up methods are similar to those carried out on similar derivatives of acylating agents. Therefore The same reaction conditions, reactant ratios, etc. can be used.

An acylated nitrogen composition obtained by reacting an acylating agent and an amino compound as described above can also be used. , the acylated nitrogen composition thus produced (i.e. the carboxylic acid derivative composition Post-treatment is carried out by contacting the product) with one or more post-treatment agents. Post-treatment agent is acid Boron oxide, boron oxide hydrate, boron halide, boric acid, boric acid ester, Carbon sulfide, sulfur, sulfur chloride, alkeny cyanide, carboxylic acid acylating agent, alkali Dehyde, ketone, urea, thiourea, guanidine, dicyandiamide, phosphoric acid hydrocarbyl, hydrocarbyl phosphite, hydrocarbyl thiophosphate, thiolite Hydrocarbyl phosphate, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiosia nate, hydrocarbyl thiocyanate, hydrocarbyl inthiocyanate, Epoxide, episulfide, formaldehyde or formaldehyde formation selected from the group consisting of compounds and phenols, and sulfur and phenols.

Post-treatment methods using these post-treatment agents are based on prior art high molecular weight carboxylic acid acylating agents. and amino and/or alcohol. There is no need to elaborate on these methods. The method of the prior art is combined with the carboxylic acid derivatives of the present invention. All that is required for application to the composition is the reaction conditions and reactants described in the prior art. ratios, etc. are only applicable to carbo/acid derivative compositions (Al).

Especially for post-treatment methods and post-treatment reagents applicable to carboxylic acid derivative composition (A). A related disclosure example is U.S. Pat. No. 4,234,435. Next candy The Rica patent also covers carboxylic acid derivative compositions (post-treatment methods and post-treatment tests applicable to Al). It describes medicines. American patent: 3,200,107; 3,254,0 25; 3,256,185; 3.2a 2,955; 3,284,410 ;3,366,569;3.403,102;3,428,561 ; 3,502,677; 3.639,242; 3,70 s, s 22 ;3,8　s　s,s　t　3　;3.865,740　;　3,9　s 4,639 Acylating agent, carboxylic acid derivative composition (Shu production method and carboxylic acid derivative composition) A method for post-processing the derivative composition is illustrated in the following example. These examples are currently This shows a preferred embodiment. The following examples, other parts of the specification, and In the claims, unless otherwise specified, "s", "percentages" and "parts" indicate weight. vinegar.

Example A-1 Polyisobutyne (Mn = 1845; Mw = 5325) 510u (0 , 28 moles) and maleic anhydride (59 parts (9 moles)) at 110°C. Heat to. This mixture was heated to 190°C and 43 parts (0.6 mol) of chlorine gas was added. Conduct subsurface for 7 hours. Furthermore, [11 parts (0.16 mmol) of chlorine gas] The solution is heated at 190-192° C. for 3.5 hours. The reaction solution is 190-19 It is heated to 3° C. and stripped for 10 hours using nitrogen gas. The residue is the target Polyisobutyne-substituted succinic acylating agent, measured according to ASTM D-94 The determined saponification value is 87.

Example A-2 Polyisobutylene y (Mn=2020; MW=6049) 1000 parts (0,4 A mixture of 95 mol) and 115 parts (1.17 mol) of maleic anhydride was heated at 110°C. Heat to. This mixture was heated to 184°C and 85 parts (1.2 moles) of chlorine gas was added. Conduct subsurface for 6 hours. An additional 59 parts (o, s) at 184-189°C 3 mol) of chlorine is passed in for 4 hours. Bring the reaction mixture to 186-190℃ Heat and strip with nitrogen gas for 26 hours.

The residue is the target polyinobutene-substituted acylating agent, and it meets ASTM D-94. The saponification value is 87.

Example A-3 Polyimbutyl: y (Mn=1696; Mw=6594) 3000 parts with chlorine gas 3251 parts of chlorinated polyisobutyne obtained by passing 251 parts at 80°C for 4.66 hours was Mix with 345 parts of maleic anhydride and heat to 200° C. for 30 minutes.

The reaction mixture was kept at 200-224°C for 6.33 hours and then vacuum-stripped at 210°C. After ripping, it is filtered.

The filtrate is the target polyisobutyne-substituted cono-phosphoric acid acylating agent, and the ASTM The saponification value according to D-94 is 94.

Example A-4 3000 parts (1,63 mol) of polyisobutylene 7 (Mn=1845; Mw=5225) ) with 344 parts (3.51 mol) of maleic anhydride and heated to 140°C.

This mixture was heated to 201°C and 312 parts (4.39 moles) of chlorine gas was added under the surface. Conduct for 5.5 hours. The reaction solution was heated to 201-236°C and nitrogen was added for 2 hours. After injecting for a while, perform IJ tubing at 203°C under reduced pressure. Filter the reaction mixture If so, the target material for filtration is polyisobutyne-substituted succinic acylating agent. ASTM The saponification value according to D-94 is 92.

Example A-5 Polyimbutene (Mn=2020; Mw=6049) 3000 parts (1,49 mol ) Wow! Water-Vleic acid 364 ffls (3,71 mol) and heated to 220°C for 8 hours do. Cool the reaction mixture to 170°C. 105 parts of chlorine gas at 170-190℃ (1.4 s mol) is passed under the surface for 8 hours. 190 while passing nitrogen into the reaction solution. ℃ for 2 hours, then vacuum stripping at 190℃ and filtration. The liquid is the target polyisobutyne-substituted co-phosphate acylating agent.

Example A-6 800 parts of polybutene falling within the scope of the claims of the invention and having an Mn of about 2000; 646 parts of oil and 87 parts of maleic anhydride were mixed and heated to 179°C over 13 hours. Heat it up. At 176-180°C, 100 parts of chlorine gas was applied under the surface for 19 hours. conduct. The reaction solution was stripped with nitrogen gas at 180°C for 0.5 hours. Line 5゜Residue is the target oil-containing polyisobutyne-substituted succinic acylating agent. Ru.

Example A-7 Polyisobutyne (Mn = 1845; MW = 5325) was replaced by the same mole of polyin. Same as Example A-1 except that butene (Mn-1457; MW Engineering 5808) was used. I did exactly the same thing.

Example A-8 Polyisobutyne (Mn = 1845; Mw = 5325) was replaced by the same mole of polyin. Same as Example A-1 except that butene (Mn=2510; Mw=5793) was used. I did the same thing.

Example A-9 The same molar amount of polyisobutyne (Mn=1845; Mw=5325) Example except that Inbuchi 7 (Mn=3220; Mw=5660) was used It was carried out in exactly the same manner as A-1.

Example A-10 Commercial product 1 of ethylene polyamine mixture having about 3-10 nitrogen atoms in one molecule 0.2 parts (0.2s equivalent) of 113 parts of mineral oil and the substituted chloride obtained in Example A-1. It was added to 161 parts (0.2 s equivalent) of citric acid acylating agent at 138°C. reaction mixture After heating to 150℃ for 2 hours, stripping was carried out by passing nitrogen through. went.

When the reaction solution is filtered, the filtrate is an oil solution of the target product.

Example A-11 Commercial mixture of ethylene polyamines having about 3-10 nitrogen atoms in one molecule 57 (1,38 equivalents) in 1067 parts of mineral oil and the substituted succinic acid obtained in Example A-2. Added to 893 parts (1,38 equivalents) of acylating agent at 140-145°C. reaction mixture It takes 3 hours to heat the material to 155℃ and strip it by blowing nitrogen gas. It was. The reaction mixture was filtered to obtain the desired product as an oil solution.

Example A-12 Commercial mixtures of ethylene polyamines having about 3-10 nitrogen atoms in one molecule18. 2 parts (0,433 equivalents) of the substituted succinate obtained in Example A-2 and 392 parts of mineral oil. Add to 348 parts (o, 52 equivalents) of acid acylating agent at 140°C. reaction mixture After heating to 150℃ for 1.8 hours, stripping by blowing nitrogen gas. The filtrate obtained by filtering the reaction solution for 5 degrees is an oil solution of the target product.

Example A-13 5500 parts of the substituted cono-phosphate acylating agent obtained in Example A-7 was mixed with 3000 parts of mineral oil and 3000 parts of mineral oil. and commercially available mixtures of ethylene polyamines having an average of 3-10 nitrogen atoms per molecule. The mixture was added to 236 parts of the product at 150° C. over 1 hour. The reaction solution was heated to 155-165°C. After heating for 2 hours, stripping is performed by blowing nitrogen gas at 165℃ for 1 hour. .

When the reaction solution is filtered, the desired nitrogen-containing product is obtained as a filtrate.

Examples A-14 to A-27 were carried out according to the general method shown in Example A-10. I went.

Examples Reactants °Substituted succinic acid acylation Diluent agent: Reactant ratio (%) A-15) Lis(2-amino 2:1 mol), 50A-17 hexamethylene 1 :2 mol 40 diamine A-181-(2-aminoe l:l equivalent 40A-192-aminopropyl l:l mole 40 pyrrolidone Examples Reactant Substituted succinic acid acylation Diluent A-20N, N'-dimethyl- 1,1:1 equivalent 403-propanediamine A-21 ethylenediamine l:l equivalent weight 4゜A-221,3-propa7　1 :1 Mo# 4Q diamine A-232-pyrrolidinoy 1:1.1moy 20A-249 rare 1:0 ．． 625 mol 50A-25 diethylenetriamine<b> 1: 1 mol 5゜ A-26) Liethyleneamine (c)l: 0.5 mol 5゜A-27 Ethanol amine Nl: 1 mole 45(a) The empirical formula corresponds to pentaethylenehexamine Ethylene polyamine mixture.

(b) Commercially available ethylene polyamine mixture whose empirical formula corresponds to diethylene triamine thing.

(C) Commercially available ethylene polyamine mixture whose empirical formula corresponds to triethylenetetramine Compound.

Example A-28 31 parts of carbon disulfide was added to 853 parts of the oil solution obtained in Example A-14 at 113-145°C. The addition took 1.66 hours. The reaction solution was kept at 145-152°C for 3.5 hours. After filtration, an oil solution of the target product was obtained.

Example A-29 A mixture of 62 parts of boric acid and 272 parts of the oil solution obtained in Example A-10 was heated in a nitrogen stream for 1 hour. Heated at 50°C for 6 hours.

The reaction solution was filtered to obtain an oil solution of the desired boron-containing product as a filtrate.

Example A-30 Equimolar amounts of oleyl alcohol and boric acid are refluxed in toluene, and the water is evaporated azeotropically. is removed to produce oleyl ester of boric acid. The reaction solution was heated to 150°C under the following reduced pressure. The residue obtained by heating to be. 344 parts of this heater and 2720 parts of the oil solution obtained in Example A-10 were mixed. , heated to 150° C. for 6 hours, and then filtered. The filtrate contains the desired boron-containing product. It is an oil solution.

Example A-31 34 parts of boron trifluoride was added to 12,190 parts of the oil solution obtained in Example A-11 at 80°C for 3 hours. Infuse within a short time. Nitrogen was blown into the reaction solution at 70-80°C for 2 hours, and the resulting residue The substance is an oil solution of the target substance.

Example A-32 53 parts of acrylonitrile were mixed with 3420 parts of the oil solution of the product obtained in Example A-12. After boiling and refluxing at 125-145°C for 1.25 hours, then at 145°C for 3 hours, Vacuum stripping is carried out at 125°C. The resulting residue is an oil solution of the target product .

Example A-33 44 parts of ethylene oxide was added to 1460 parts of the oil solution obtained in Example A-11 at 150°C. Add it over an hour.

The reaction mixture was kept at 150°C for 1 hour and then filtered. The filtrate obtained was an oil solution of the target product. Ru.

Example A-34 73 parts of terephthalic acid was mixed with 1160 parts of an oil solution of the product of Example A-10, and 1 The filtrate obtained by heating to 50-160°C and filtration is an oil solution of the target product.

Example A-35 After adding 1 mole of phosphorus pentoxide to 3 moles of decyl alcohol at 32-35°C, the reaction was completed. The mixture was heated to 60-63° C. until the temperature reached 60-63° C. to obtain phosphoric acid decyl ester. The product is phosphorus It is a mixture of acid decyl esters, has a phosphorus content of 9.9%, and an acid value of 250 (phenol). - ゛Sulphthalene indicator). Oil solution of the product obtained in Example A-10 1750 and 112 parts of the above decyl ester were mixed and heated at 145-150°C for 1 hour. do. The filtrate obtained by filtering the reaction solution is the desired oil solution.

Example A-36 2920 parts of the oil solution of the product obtained in Example A-11 was mixed with 69 parts of Thioclea; It was heated to 80'C and kept at the same temperature for 2 hours. The reaction mixture was then heated to 150-155°C for 4 hours. It was heated for a while and nitrogen was blown into it at the end. The filtrate obtained by filtering the reaction solution is the target oil. It is a solution.

Example A-37 146 parts of the oil solution of the product obtained in Example A-11 was dissolved in 37% thiformaldehyde in water. The mixture was mixed with 81 parts of liquid and boiled and refluxed for 3 hours. Vacuum stripping of reaction solution at 150℃ The residue is an oil solution of the target product.

Example A-38 1160 parts of an oil solution of the product obtained in Example A-10 are mixed with 67 parts of sulfur monochloride; The mixture was heated at 150° C. for 1 hour in a nitrogen stream. The filtrate obtained by filtering the reaction solution is used for the purpose It is an oil solution of the sulfur-containing product.

Example A-39 11.5 parts of formic acid were mixed with 1000 parts of the oil solution of the product obtained in Example A-11 at 60°C. match. Heat the reaction solution at 60-100°C for 2 hours and at 92-100°C for 1.75 hours. After that, it was filtered to obtain an oil solution of the target product.

Example A-40 Equipped with stirrer, nitrogen inlet tube, addition funnel and Dean-Stark trap condenser 2483 parts of the acylating agent described in Example A-3 (4, 2 equivalents) and 1104 parts of oil. Mixture while gradually blowing nitrogen gas Heat to 210°C. At this temperature, 134 parts of ethylenediamine bottoms (3,t 4 equivalents) was cleaved for about 1 hour and added slowly. After keeping the temperature at 210℃ for 3 hours , 3688 parts of oil are added and the temperature is lowered to 125°C. 17.5 hours at 138℃ After retention, if filtered through diatomaceous earth, the desired acylated amine bottom 6 A 5% oil solution was obtained.

Component (B) of the diesel lubricant of the present invention is one or more of one or more acidic organic compounds. It is a basic alkali metal salt of This component is a metal-containing composition known in the prior art. ``monobasic'', ``overbasic'', or ``overbase'' salts Or called a complex. The method of preparation is commonly referred to as "overbasing."゛Money The term "metallic ratio" refers to the amount of gold relative to the amount of organic ions in these salts or complexes. It is often used to define the ratio of metallic quantities. and the usual chemistry of the compounds it contains. Based on stoichiometry, it is defined as the equivalent ratio existing in the positive salt.

The main alkali metals present in basic alkali metal salts are lithium and sodium. potassium and potassium, with potassium being preferred. The most useful acidic organic compounds are sulfur acids, carboxylic acids, organic phosphoric acids and phenols.

Sulfur acids include sulfonic acid, sulfamic acid, thiosulfonic acid, sulfinic acid, Includes sulfenic acid and partial esters of sulfuric acid, sulfuric acid and thiosulfuric acid. . Sulfur acids are generally sulfonic acids.

Sulfonic acid is preferred as component (B) of the diesel lubricant of the present invention. these is the general formula: R'(S03H)', and (R2)xT(SO2F).

It is indicated by.

In this formula, R1 is an aliphatic or aliphatic substituted alicyclic hydrocarbon, or an acetylene bond. It is essentially a hydrocarbon group having about 60 or less carbon atoms. When R1 is aliphatic usually has about 15 or more carbon atoms; in the case of an aliphatic substituted alicyclic group, an aliphatic substituent The total number of carbon atoms is about 12 or more. R1 is, for example, alkyl, alkenyl and and alkoxyalkyl groups, as well as alkyl, alkenyl, alkoxy, alkoxy It is an aliphatic substituted alicyclic residue substituted with sialkyl, carboxyalkyl, etc. one Generally aliphatic mGi cyclopentane, cyclohexane, cyclohexene, or Derived from cycloalkanes or cycloalkenes such as cyclopentene. R' Examples include cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl , octadecenyl and petroleum, saturated paraffin wax, unsaturated paraffin wax The monoolefin or olefin monomer has about 2-8 carbon atoms. There are also groups derived from olefin polymers obtained by polymerizing diolefins. R1 may also contain other substituents such as phenyl, cycloalkyl, hydroxy, mercapto. , halo, nitro, amino, nitroso, lower alkoxy, lower alkyl mercapto , carboxy, carbalkoxy, oxo or thio, or -NH-1-〇- or -8-, etc., unless its essential hydrocarbon character is destroyed. But it doesn't matter.

, R2 is generally a hydrocarbon group or a C4-60 group without acetylenically unsaturated bonds. It is essentially a hydrocarbon group containing an aliphatic carbon atom. alkyl or alkur Such aliphatic hydrocarbon groups are preferred. However, if the hydrocarbon character is preserved, The substituents or intervening non-carbon atoms as described above account for no more than 10% of the total weight.

T is a cyclic group, such as benzene, naphthalene, anthracene or biphenyl aromatic hydrocarbons or heterocycles such as pyridine, indole, isoindole, etc. Can be derived from compounds. T is usually an aromatic hydrocarbon group, especially benzene or naph It is a talen ring.

The subscript X must be greater than or equal to 1, typically 1-3.

The subscripts r and y average l-4 per molecule, typically l.

Examples of sulfonic acids that can be used in producing salt (B) are shown below. This example completes It also serves to illustrate sulfonate salts useful as component (B). In other words, It is understood that all sulfonic acids also exemplify the corresponding basic alkali metal salts. Should. (The same applies to the following acidic raw materials, i.e. carboxylic acids, phosphoric acids and The same can be said of phenols. ) Such sulfonic acids include mahogany sulfonate. Fonic acid, bright stock sulfonic acid, petroleum sulfonic acid, mono and polywax substituted naphthalenesulfonic acid, cetylchlorobenzenesulfonic acid, cetylphenol sulfonic acid, cetylphenol disulfide sulfonic acid, cetoxylic acid Benzene sulfonic acid, dicetylthianthrene sulfonic acid, silacryl-β-naph Tolsulfonic acid, cicapril nitronaphthalenesulfonic acid, saturated paraffin wax wax sulfonic acid, unsaturated halafine wax sulfonic acid, hydroxy-substituted halafine wax sulfonic acid, Fin wax sulfonic acid, tetraisobutylene sulfonic acid, tetraamylene Sulfonic acid, chlorine-substituted halaffin wax sulfonic acid, nitrone-substituted paraffin wax ox sulfonic acid, petroleum naphthalene sulfonic acid, cetyl cyclopentyl sulfone Acid, laurylcyclohexylsulfonic acid, mono- and polywax substituted cyclo Hexyl sulfonic acid, post-dodecylbenzenesulfonic acid, ``Temmar'' L/-)" sulfonic acid, etc.

Acids of 8 or more carbon atoms such as dodecylbenzene “bottom” sulfonic acid Alkyl-substituted benzenesulfonic acids containing alkyl groups are particularly useful. The latter is Ben Acid derived from zene, using propylene tetramer or isobutyne trimer Alkylated and containing 12 carbon substituents with 1.2°3 or more branches. introduced into the benzene ring. Dodecylbenzene bottoms are mainly mono- and di- A mixture of decylbenzene, commonly used as a by-product in the production of household detergents. It can be used to produce sulfonate salts used in the invention.

Disulfonate is produced from a byproduct during surfactant production by reaction with S03. Methods are known to those skilled in the art.

For example, Kirk Othmer, “Encyclopedia op Chemical Tech.” Nology” 2nd edition, Volume 19.

Pages 291 et seq. (John Wiley & Sons, New York, 196 9) under the heading of 6-sulfonate salts. − In addition, basic sulfonate salts and their manufacturing methods are described in the following U.S. patents: has been done. 2,174,1 lo; 2.202,781; 2,239, 974; 2,319,121; 2.337,552; 3,488,2 84　;　3,595,790　;3.798,012゜These are the These disclosures are incorporated herein by reference.

Suitable carboxylic acids include aliphatic, cycloaliphatic and aromatic acids without acetylenic unsaturation. There are many mono- and polybasic carboxylic acids. Specific examples include naphthenic acid, Alkyl or alkenyl substituted cyclopencunic acid, alkyl or alkenyl substituted substituted cyclohexanoic acids, and alkyl- or alkenyl-substituted aromatic carboxylic acids. Can be mentioned. Aliphatic acids generally have about 8-50 carbon atoms, preferably about 12-25 carbon atoms. be. Alicyclic or aliphatic carboxylic acids are preferred and may be saturated or unsaturated. So Examples include tetramer-substituted maleic acid, behenic acid, instearic acid, pelargonic acid, carbonic acid, Puric acid, palmitoleic acid, lysyl Inic acid, lauric acid, oleic acid, lysyllic acid, undecylenic acid, dioctyl Cyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalenka Rubonic acid, stearyl octahydroindene carboxylic acid, palmitic acid, alkyl and alkenyl succinic acids, acids oxidized from petroleum or hydrocarbon waxes, and Examples include commercially available mixtures of two or more acids, such as rosin acid, rosin acid, and rosin acid.

Pentavalent phosphoric acid used in the production of component (B) is represented by the following formula.

Here, R3 and R4 are each hydrogen, hydrocarbon or preferably carbon number 4-2. 5 is essentially a hydrocarbon group, and at least one of R3 and R4 is a hydrocarbon or is essentially hydrocarbon; X: X2. X3 and Hiro are oxygen or sulfur. R: a and b are each 0 or l. In other words, phosphoric acid is an organic phosphoric acid, Sulfonic acid, phosphinic acid or their thio analogs.

Phosphoric acid is also represented by the formula:

Here, R3 is a phenyl group or (preferably) an alkyl group having 18 or less carbon atoms. and R4 is hydrogen or a similar phenyl or alkyl group. phosphoric acid formulation is often preferred because it is easy to manufacture.

Component (B) is a phenol, that is, a compound in which a hydroxyl group is directly bonded to an aromatic ring. It can also be produced from a compound. Here, the word "1 phenol" is catechol, Two or more hydroxyl groups are bonded to an aromatic ring, such as resorcinol and hydroquinone. Contains compounds such as Also cresol, ethylphenol and alkenylphenol Also includes alkylphenols such as Phenol has about 3-100 carbon atoms, especially Those with about 6-50 alkyl substituents are preferred. For example, heptylphenol, Cutylphenol, dodecylphenol, tetrapropene alkylated phenol , octadecylphenol, and polybutenylphenols. 2 or more Phenols having alkyl substituents of Monoalkylphenols are preferred in terms of ease.

Condensates of the above phenols and one or more lower aldehydes or ketones are also preferred. Yes. "Lower" refers to aldehydes or ketones having 7 or fewer carbon atoms.

Suitable aldehydes include formaldehyde, acetaldehyde, and propionaldehyde. Hyde, butyraldehyde, valeraldehyde and benzaldehyde. Ba Raaldehyde, trioxane, methylol, methylformsel and valalde Reagents that release aldehydes, such as hydrides, are also preferred. Particularly preferred is formua divided by the number of acidic groups (i.e. sulfonic acid, carboxylic acid or acidic hydroxyl groups) This is the value.

In one preferred embodiment, an alkali metal salt (Bl is an alkaline alkali gold It is a genus salt. The metal ratio is about 2 or more, generally about 4-40, preferably about 6- 30, especially about 8-25.

In another preferred embodiment, the basic salt (B) is sufficient to form a stable dispersion. The following (B-t) and This is an oil-soluble dispersion produced by contacting (B-2).

(B-1) One species selected from the group consisting of carbon dioxide, hydrogen sulfide, and sulfur dioxide or more acidic gaseous substances.

(B-2) A reaction mixture consisting of the following components.

(B-2-a) One or more oil-soluble sulfonic acids, or those that tend to become excessively basic. derivative (B-2-b) One or more alkali metal compounds or basic alkali metal compounds ; (B-2-c) One or more aliphatic alcohols, alkylphenols, or sulfides Alkylphenol; and (B-2-d) one or more oil-soluble carboxylic acids or its functional derivatives.

When (B-2-c) is an alkylphenol or a sulfurized alkylphenol, (B-2-d) may not be used. Satisfactory basic sulfonate mixture It can be produced with or without carboxylic acid in (B-2).

The reactant (B-1) is one or more acidic gaseous substances such as carbon dioxide, hydrogen sulfide, or Or use sulfur dioxide. A mixture of these gases may also be used. carbon dioxide is preferred Better~1° The above-mentioned permeability reactant (B-2) is generally a mixture containing at least four components. component ('B-2-a) is one or more oil-soluble sulfonic acids as specified above, or is a derivative thereof that tends to become excessively basic. Mixture of sulfonic acids and their derivatives You can also use objects. Sulfonic acid derivatives that tend to become excessively basic should be treated with their metal salts, especially their alkyl salts. Zinc and lead salts as alkaline earth metals: ammonium salts and ermine salts (such as ethylamine, butylamine and ethylene polyamine salts); and ethyl , butyl and glycerin esters.

Component (B-2-b) is one or more alkali metals or basic compounds thereof.

Examples of basic alkali metal compounds include hydroxides and alkoxides (with a carbon number of 10 or less). (typically an alkoxy group, preferably 7 or less carbon atoms), hydrides, and alkoxy groups. There is mido. Therefore, the basic alkali metal compound used is sodium hydroxide. potassium hydroxide, lithium hydroxide, sodium propoxide, lithium meth oxide, potassium ethoxide, sodium chloride, lithium hydride, hydrogenation Sodium, potassium hydride, lithium amide, sodium amide, and potassium Examples include umamide.

Particularly preferred compounds are sodium hydroxide and sodium lower alkoxide (carbon prime number 7 or less). Since the alkali metal is monovalent, in the present invention, the component (B The equivalent weight of -2-b) is equal to the molecular weight.

Component (B-2-c) is one or more lower aliphatic alcohols, monovalent or divalent. Alcohol is preferred. Examples include methanol, ethanol,! −Property tools , l-hexanol, isopropanol, inbutanol, 2-pentanol, 2.2-Dimethyl-1-propatol, ethylene glycol, I, 3-7' donkey diol, and 1,5-bentanediol. Like methylselonlupe Glycol ethers can also be used. Among these, methanol, ethanol, and propatool are preferred, particularly methanol).

Component (B-2-c) is one or more alkylphenols or sulfurized alkylphenols. It can also be a rule. %K (B-2-b) is potassium or a salt such as potassium hydroxide In the case of basic compounds, sulfurized alkylphenols are preferred. “ used here The word ``phenol'' refers to a compound in which a hydroxyl group is bonded to an aromatic ring with two or more valences. and may be benzyl or naphthyl compounds. "Alkylphenol" The term 5 includes monoalkyl and dialkylphenols, and each alkyl substituent The number of carbon atoms is about 6-Zoo, preferably about 6-50.

Examples of alkylphenols include hebutylphenol, octylphenol, and dodecylphenol. polyphenol, polypropylene (molecular weight approximately 150) substituted phenol, polyimbu There is ten (molecular weight approximately 1200) substituted phenol and cyclohexylphenol. .

Condensates of the above phenols and one or more lower aldehydes or ketones can also be used. Ru. "Lower" refers to aldehydes or ketones having 7 or fewer carbon atoms. suitable alde Hyde includes formaldehyde, acetaldehyde, propionaldehyde, butyl Aldehydes, including realaldehyde and benzaldehyde. paraaldehyde such as trioxane, methylol, methylformsel and paraldehyde. Aldehyde releasing agents can also be used. Formaldehyde and formaldehyde emissions Particularly preferred are agents.

Sulfurized alkylphenols include phenol sulfides, disulfides, and polysulfides. Ru. Sulfurized phenol can be produced from a suitable alkylphenol by a known method. There are many sulfurized phenols available commercially.

Sulfurized alkylphenols are alkylphenols and elemental sulfur and/or sulfur. It is produced by reacting with a monohalide (i.e. - sulfur chloride). This reaction is excessive It is carried out in the presence of a base, and depending on the reaction conditions polysulfide, disulfide or polysulfide It is also possible to produce salts of the mixture. In the present invention, in the production of component (B-2), using the reaction product of U.S. Patents 2,971,940 and 4,309 ．． No. 293 discloses various sulfurized phenols as examples of component (B-2-c). There is.

The following non-limiting examples include alkylphenols that can be used as component (B-2-c). and a method for producing sulfurized alkylphenol.

Example 1 The reactor equipped with a stirrer, condenser, thermometer, and gas inlet tube below the liquid surface was heated to 55°C. 100 parts of phenol and sulfonated polystyrene catalyst (Roam and 15) 68 parts of Anno ζ-Lis (manufactured by Haas) were charged.

The mixture is heated to 120°C and sparged with nitrogen for 2 hours. Propylene tetramer! 232 copies After addition, the mixture was stirred at 120°C for 4 hours. Stop stirring and let stand for 0.5 hour. anti The reaction solution was filtered, the filtrate was stripped under reduced pressure, and the propylene 4 in the residue was removed. Concentrate until the mass is at most 0.5%.

Example 2 Add 217 parts of Hensen to 324 parts (3.45 moles) of phenol at 38°C and mix. Warm the mixture to 47°C. 38 boron trifluoride (8.8 parts, 0.13 mol) Blowing takes 1.5 hours at -52°C. C4 monomer whose main component is isobutylene Polyimbutene (loo.

1.0 mol) is added to this mixture over a period of 3.5 hours at 52-58°C.

The reaction was kept at 52°C for an additional hour. Add 15 parts of 26thiammonia water and heat to 70°C. Heat for 2 hours. The filtrate obtained by filtering the reaction mixture is the desired crude polyisobutylene. It is a chin-substituted phenol. 1465 parts of this intermediate was heated to 167°C and As the temperature rose to 218°C in 5°6 hours, the pressure decreased to 10 parts m. It dropped to . Stripped polyisobutyne-substituted phenol (Mn=s 85 ) was obtained as a residue in a yield of 64 cm.

Example 3 The raw material obtained in Example 1 was placed in a reactor equipped with a stirrer, a condenser, a thermometer and a subsurface addition tube. 1000 parts of the product were charged and the temperature was adjusted to 48-49'C. Sulfur dichloride 319 part was added while keeping the temperature below 260°C. heating the mixture to 88-93°C; Blow nitrogen until the acid value is 4.0 or less (bromophenol blue indicator). continued. Add 400 parts of diluent oil and mix thoroughly.

Example 4 In the same manner as in Example 3, 1000 parts of the reaction product of Example 1 was mixed with 175 parts of sulfur dichloride. React, react. The reaction product is diluted with 400 parts of diluent oil.

Example 5 In the same manner as in Example 3, 1000 parts of the reaction product obtained in Example 1 was added to 319 parts of sulfur dichloride. react with the part. Add 788 parts of diluent oil and mix thoroughly.

Example 6 In the same manner as in Example 4, 1000 parts of the reaction product of Example 2 was reacted with 44 parts of sulfur dichloride. to produce sulfurized phenol.

Example 7 In the same manner as in Example 5, 1000 parts of the reaction product of Example 2 was mixed with 80 parts of sulfur dichloride. Make it react.

The equivalent weight of component (B-2-c) is the value obtained by dividing the molecular weight by the number of hydroxyl groups in one molecule. It is.

Component (B-2-d) is one or more of the above-mentioned oil-soluble carboxylic acids or functional groups thereof. It is a derivative. A particularly suitable carboxylic acid is designated 2R5(COOH). here where n is an integer of 1-6, preferably 1 or 2. R5 is saturated or substantial It is preferably an aliphatic group with a saturated carbon content and a hydrocarbon group, preferably an aliphatic carbon group. A prime number is 8 or more. Depending on the value of n, it becomes a monovalent to hexavalent group of R5.

R5 may contain non-hydrocarbon substituents provided their hydrocarbon character is not substantially altered. stomach. Such substituents are the non-hydrocarbon groups described above with respect to 2° (B-2-a). . R5 contains up to 5 olefinically unsaturated bonds relative to the total number of carbon-carbon covalent bonds, preferably Preferably, it may contain 2 or less.

The number of carbon atoms in R5 varies depending on the raw material, usually 8-. It becomes 700.

Preferred groups of carboxylic acids and derivatives thereof, olefin polymers or is a halogenated olefin polymer with acrylic acid, methacrylic acid, maleic acid or is an α, β-unsaturated acid such as fumaric acid or maleic anhydride or its anhydride. to form the corresponding substituted acid or derivative thereof. .

The number average molecular weight of the R5 group in these products was measured using gel permeation chromatography. Then it will be about 150-10,000, usually 700-5000.

The monocarboxylic acid used as component (B-2-d) is represented by the formula R5C0OH. Ru. Examples include caprylic acid, capric acid, palmitic acid, stearic acid, These include tearic acid, liluic acid and behenic acid. A particularly preferred group of monocarbo Phosphoric acid is produced by reacting chlorinated polybutene with methacrylic acid.

Suitable dicarboxylic acids include substituted succinic acids of the formula:

R6’LCH-C0OH CH2-C0OH Here, R6 is the same as R5. R6 is ethylene, propylene, l-butene , imbutene, 2-pentene, l-hexene and 3-,hexene. It is a group of olefin polymer systems obtained by polymerization of olefins. R6 is essentially a saturated high It can also be derived from molecular weight petroleum fractions. Hydrocarbon-substituted succinic acid and its derivatives Conductors are the most preferred group of carboxylic acids used as component (B-2-d). be.

The aforementioned carboxylic acid groups obtained from olefin polymers and their derivatives are well known to those skilled in the art. It is knowledge. There are numerous representative examples of methods of manufacture and types suitable for use in the present invention. Described in detail in the US patent.

The functional derivatives of the aforementioned acids used as component CB-2-d) include anhydrides, esters, etc. metal salts, amides, imides, amidines, metal salts and ammonium salts. Orefi Polymers substituted with succinic acid and mono- or polyamines, especially polyamines with less than 10 amine nitrogen. Reaction products with alkylene polyamines are particularly preferred. These reaction products are commonly It is usually a mixture of one or more amides, imides, and amidines. Nitrogen below about IO Polyethyleneamine and polybutene groups containing elementary atoms are mainly composed of imbutene units. Particularly preferred are the reaction products with polybutene-substituted succinic anhydride. Functional group of ζ゛ Among the derivative groups, the reaction products of amines and anhydrides include carbon disulfide and boron compounds. , nitrile, urea, thiofrea, guanidine, alkylene oxide, etc. It also includes compositions obtained by post-treatment. Substituted succinic acid semi-amide, semimetallic clay Esters and metalloid salt derivatives can also be used.

Substituted acids or anhydrides and mono- or Esters prepared by reaction with polyhydroxy compounds can also be used. me Fin polymer substituted succinic acid or anhydride with 2-10 hydroxyl groups and fat Esters with polyhydric aliphatic alcohols containing up to about 40 group carbon atoms are preferred.

This group of alcohols includes ethylene glycol, glycerol, sorbitol, Erythritol, polyethylene glycol, jetanolamine, trieta Nolamine, N, N'-di(hydroxyethyl)ethylenediamine, etc. There is. If the alcohol contains a reactive amine group, the reaction product is The product is obtained by reacting with both the roxyl group and the amine group. Therefore this reaction Products include half-esters, half-amides, esters, amides, and imides.

The equivalent ratios of the components of reactant (B-2) vary widely. General: Two components (B-2-b) and (B-2-a) is at least 4:1, usually 40:1, and preferably preferably between 6:1 and 30:1, most preferably between 8:1 and 25:1.

This ratio may exceed 40:I, but there is usually no advantage in doing so.

The equivalent ratio of components (B-2-c) and (B-2-a) is between about 1:20 and 80:l and preferably between 2:1 and 50:1. Maeko, Shitayo Ingredients (B-2-c ) is an alkylphenol or a sulfurized alkylphenol, a carboxylic acid (B-2-d) is not essential. When using this, component (B-2-d) and The equivalent ratio with (B-2-a) is generally about 1:1-1:20, about 1:2-t: to is preferred.

Generally, the reaction between reactants (B-1) and (B-2) will no longer proceed between them. contact until the reaction essentially stops. reaction becomes too basic It is usually preferred to continue until no more product is produced. Contact between both reactants The amount of CB-t) required to reach the "end point" at which the reaction stops is 70 samples. A good quality dispersion can be obtained if the reaction is continued for a sufficient period of time.

The point at which the reaction is complete or essentially stopped can be determined by any of a number of conventional methods. You can also check it. One method is to determine the amount of gas [reactant (B-1)] entering the mixture and the amount of gas coming out. Measure the amount of gas. If the amount of gas coming out is 90-100% of the amount entering, the reaction will stop. I think it has essentially stopped.

This amount can be easily measured by applying instrumentation pulp to the outlet and inlet.

When (B-2-c) is an alcohol, the reaction temperature is not by weight. The reaction temperature is one Generally, there is a difference between the solidification temperature and the decomposition temperature (the lowest decomposition temperature of each component) of the reaction mixture. Ru. The temperature is usually about 25-200°C, preferably about 50-150°C. . Reactants (B-1) and (B-2) are conveniently brought into contact at the reflux temperature of the mixture. Ru. It is clear that this temperature depends on the boiling point of each component.

Therefore, when methanol is used as component (B-2-c), the contact temperature is The temperature will be at or below the reflux temperature of the bottle.

When component (B-2-C) is alkylphenol or sulfurized alkylphenol In order to remove the water produced, the reaction temperature is at or near the azeotropic point of the water-diluent mixture. We must do more than that. Therefore, in such cases the diluent is generally aliphatic or become volatile organic liquids such as aromatic hydrocarbons. Examples include hebutane, de Can, toluene, and quincearum.

The reaction is often accelerated if it is carried out under pressure, increasing the utilization rate of reactant (B-1). However, the reaction is usually carried out at normal pressure. The reaction can also be carried out under reduced pressure. However, this is rarely done for practical reasons.

The reaction is usually carried out in the presence of an essentially liquid organic diluent, which is usually liquid. Ru. The diluent serves as the dispersion medium and reaction medium. This diluent is the total weight of the reaction mixture. However, it does not exceed 80%. About 30-70 inches is preferred.

Although there are many types of diluents that can be used, diluents that are soluble in lubricating oil are preferred. diluent itself The body usually consists of a low viscosity lubricating oil.

Other organic diluents can be used alone or in combination with the lubricating oil. this eye Preferred diluents include aromatic hydrocarbons such as benzene, toluene, and xylene. ; Halogenated aromatic hydrocarbons such as chlorobenzene; Petroleum ether, various naphthas Low-boiling petroleum fractions such as: hexane, heptane, hexene, cyclohexene, cyclohexene, etc. lopentane, cyclohexane and ethylcyclohexane, and their There are aliphatic and alicyclic hydrocarbons that are normally liquid, such as rogogenated derivatives. gigro Dialkyl ketones such as pirketone and ethyl butyl ketone; acenofunino Alkylarylketones such as n-propylphenyl, n-propylphenyl, n-butyl ether, (n-butyl)methyl ether, isoamyl ether, etc. Ethers can also be used.

When using a combination of lubricating oil and other diluent, the weight ratio of lubricating oil and diluent is Generally about 1:20-20:1. Especially when the product is used as a lubricating oil additive. In such cases, it is usually preferred to use at least about 50% by weight of the diluent, which is a mineral lubricating oil. Rare Since the diluent is inert, its amount is not critical. However, diluents are usually There is about 1 o-so weight percent of the reaction mixture, preferably about 30-70 weight percent.

After the reaction is complete, it is preferable to remove the solid koji in the mixture by filtration or other convenient method. Delicious. Easily removed diluents, alcoholic promoters and those formed during the reaction Water may be removed by any suitable method, such as distillation.

The presence of water makes filtration difficult and emulsifies fuel and lubricants, which is undesirable. It is usually desirable to remove substantially the entire amount from the reaction mixture. Such moisture is always It can be easily removed by pressure or vacuum heating or azeotropic distillation. As component (B) In one preferred embodiment when basic potassium sulfonate is required, carbon dioxide Sooo! Potassium using sulfurized alkylphenol as the component (B-2-C) Manufacture salt. If sulfurized phenol is used, a basic salt with a high metal ratio can be made, and the salt Uniformity and stability are increased. The reaction is generally carried out in an aromatic diluent such as xylene. During the reaction, water is removed as a xylene-water azeotrope.

is considered a stable dispersion. Separately, component (B) is an acidic substance, excessively basic. Considered as ``polymerizable salts'' produced by the reaction of oil-soluble acids and metal compounds. It will be done.

In view of the above, these compositions are best defined according to the method by which they are produced. is also convenient.

In the above method, a sulfonic acid alkali having a metal ratio of about 2 or more, preferably about 4-40 is used. Alcohol is used as component (B-2-c) when producing a metal salt. this The method is described in Canadian Patent No. 1,055,700 and corresponding British Patent No. No. 1,481,553 provides further details. These patents disclose methods It is listed as a reference. Aluminum using component (B) of the diesel lubricant of the present invention A method for preparing an oil-soluble dispersion of potassium metal sulfonate is illustrated in the following example. .

Example B-1 790 parts (1 equivalent) of alkylbenzenesulfonic acid and primarily isobutyne units 71 parts of polybutenyl succinic anhydride (equivalent weight: about 560) was dissolved in 176 parts of mineral oil. To the dissolved solution, add 320 parts (8 equivalents) of sodium hydroxide and 640 parts of methanol. (20 equivalents) is added. The temperature of the mixture rises to 89°C in pto minutes due to exotherm and returns to cause a flow During this time, carbon dioxide is introduced at a rate of 4 cfh (ft3/hr). Ru. After approximately 30 minutes of carbonation, the temperature gradually decreases to 74°C. carbonated Pass nitrogen through the mixture at a rate of 2 cfh and bring it to 150'C in 90 minutes. Gradually raise the temperature and strip methanol and other volatiles. Striptease After pinging, keep at 155-165℃ for another 30 minutes and filter to obtain the desired product. An oil solution of basic sulfonic acid IJ is obtained. Metal ratio is 7.75, oil content The quantity is 1259J.

Example B-2 In the same manner as in Example B-1, 780 parts of alkylbenzenesulfonic acid (1 equivalent) 780 parts (1 equivalent) of polybutenylsuccinic acid were dissolved in 442 parts of mineral oil. To the solution were added sodium hydroxide SOO parts (20 equivalents) and 704 parts of hismethanol (22 equivalent amount). Pass carbon dioxide through this mixture at a rate of 7 cfh for 11 minutes. Then, the temperature gradually decreases to 97°C. The conduction rate of carbon dioxide is 6 cfh decreases to The temperature gradually decreases to 88°C in about 40 minutes. Next, increase the speed to 5c fh and conduct for 300 minutes. The temperature gradually decreases to 73°C. carbonated mixture It took 105 minutes to raise the temperature to 160°C while passing nitrogen at a rate of 2 cfh. Raise the temperature gradually and strip the volatiles. After stripping, increase the temperature to 160℃. ℃ for another 45 minutes and filtered to obtain the target basic salt with a metal ratio of 19.75. Obtain an oil solution of sodium luponate. The oil content of this solution is 18.7%.

Example B-3 3120 parts (4 equivalents) of alkylbenzenesulfonic acid in the same manner as in Example B-t. and hydroxyl into a solution of 284 parts of polybutenyl succinic anhydride dissolved in 704 parts of mineral oil. 1280 parts (32 equivalents) of sodium chloride and 2560 parts (80 equivalents) of methanol Mix. When carbon dioxide is passed through the mixture at a rate of 10 cfh for 65 minutes, the temperature 70. after rising to 90°C. Gradually descend to 'C. “Nitrogen is passed through at a rate of 2 cfh. Gradually raise the temperature to 160'C while guiding and strip the volatiles. cormorant. An oil solution of basic sodium sulfonate with a metal ratio of about 775 that is strippin get. The oil content of this solution is 1135%.

Example B-4 In the same manner as in Example B-1, 3200 parts (4 equivalents) of alkylbenzenesulfonic acid and 284 parts of polybutenyl succinic anhydride dissolved in 623 parts of mineral oil. 1280 parts (32 equivalents) of sodium chloride and 2560 parts of methanol (SO equivalents) Mix. When carbon dioxide is passed through the mixture at a rate of 10 cfh for 77 minutes, The temperature rises to 92°C and then gradually decreases to 73°C.

While passing nitrogen gas at a rate of 2ft3/hr, the temperature was gradually raised to 160'C. Elevate and strip volatiles. Strain the last traces of volatiles under reduced pressure. If the residue is kept at 170℃ and filtered, the target substance with a metal ratio of 7.72 can be obtained. Obtain a clear oil solution of thorium salt.

The oil content is 11 inches.

Example B-5 In the same manner as in Example B-1, 780 parts (1 equivalent) of alkylbenzenesulfonic acid and Add sodium hydroxide to a solution of 86 parts of polybutenyl succinic anhydride and 254 parts of mineral oil. Mix 480 parts (12 equivalents) of thorium and 640 parts (20 equivalents) of methanol. Ru. Passing carbon dioxide through the mixture at a rate of 6 cfh for 45 minutes brings the temperature to 95 After rising to 74°C, the temperature gradually decreases to 74°C. Flow nitrogen gas at a rate of 2 cfh Gradually increase the temperature to 160'C and strip the volatiles. strike After ripping, keep the temperature of the mixture at 160’C for 30 minutes and filter it. An oil solution of the sodium salt with a target metal ratio of 11.80 is obtained. The oil content of this solution is This is Section 14 and 7.

Example B-6 In the same manner as in Example B-1, 3120 parts (4 equivalents) of alkylbenzenesulfonic acid and and 344 parts of polybutenyl succinic anhydride dissolved in 1016 parts of mineral oil, 1,920 parts of sodium oxide (48 equivalents) and 2,560 parts of methanol (SO equivalents) Mix. By passing carbon dioxide through the mixture at a rate of 10 cfh for 2 hours, the temperature The temperature rises to 96°C and then gradually decreases to 74°C. Pass nitrogen at a rate of 2 cfh. It takes about 2 hours to raise the temperature from 74℃ to 160'C by heating from the outside while guiding. Elevate and strip volatiles. After stripping the mixture, 16 Keep at 0°C for 1 hour and filter. Filtration involves vacuum stripping to remove small amounts of water. By removing the solution and filtering again, a solution of the target sodium salt with a metal ratio of 11.8 is obtained. child The oil content of the solution is 14.7%.

Example B-7 In the same manner as in Example B-1, 2800 parts (3,5 equivalents) of alkylbenzenesulfonic acid was added. amount) and 302 parts of polybutenyl succinic anhydride dissolved in 818 parts of mineral oil. 1,680 parts of sodium hydroxide (42 equivalents) and 2,240 parts of methanol (70 equivalents) amount). If carbon dioxide is passed through the mixture at a rate of 10 cfh for 90 minutes, , the temperature rises to 96°C and then gradually decreases to 76°C. 2 c of “nitrogen gas” The temperature was gradually increased from 76°C to 165°C by heating from the outside while conducting at a rate of fh. Bring to a boil and strip off volatiles. Water is removed by vacuum stripping. filter If the reaction mixture is filtrated, an oil bath of a basic sodium salt having a metal ratio of 10.8 of the target product can be obtained. this The oil content of the solution is 13.6 inches.

Example B-8 In the same manner as in Example B-1, 780 parts (1 equivalent) of alkylbenzenesulfonic acid and and 103 parts of polybutenyl succinic anhydride dissolved in 350 parts of mineral oil. Mix 640 parts of sodium and 640 parts of methanol (20 equivalents). blend When carbon dioxide is passed through the water at a rate of 6 cfh for 1 hour, the temperature rises to 95°C. Afterwards, the temperature gradually drops to 75℃. Pass nitrogen through and strip volatiles. that time , the temperature drops to 70°C in the first 30 minutes and gradually rises to 78°C in the next 15 minutes. . The mixture is then heated and raised to 155°C over a period of 80 minutes. strippin' After finishing the heating, the mixture was further heated to 155,160°C for 30 minutes and filtered. The obtained filtrate is used for the purpose This is an oil solution of basic sodium sulfonate with a metal-to-metal ratio of 15.2. of this solution Oil content was 17.1%.

Example B-9 511 parts In the same manner as in Example B-1, 2400 parts (3 equivalents) of alkylbenzenesulfonic acid were added. amount) and 308 parts of polybutenyl succinic anhydride dissolved in 991 parts of mineral oil. 1920 parts of sodium hydroxide (48 equivalents) and 1920 parts of methanol (60 equivalents) amount). Carbon dioxide was passed through this mixture at a rate of 10 cfh for 110 minutes. When the temperature was introduced, the temperature rose to 98°C, and then gradually decreased to 76°C in 95 minutes. nitrogen Methanol was introduced at a rate of 2 cfh, and the temperature was gradually raised to 165°C. Perform water and water stripping. Strip the last traces of volatiles under vacuum Then, by filtration, an oil solution of the target sodium salt with a metal ratio of 15.1 is obtained. This melt The oil content of the liquid is 16.1 inches.

Example B-10 780 parts (1 equivalent) and 119 parts of polybutenyl co-phosphoric anhydride dissolved in 442 parts of mineral oil. Add 800 parts (20 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol to the liquid. amount). Pass carbon dioxide through this mixture at a rate of 8 cfh for 55 minutes. Then, the temperature rises to 95°C and then gradually decreases to 67°C. 2 cfh of nitrogen conduction for 40 minutes at a rate of Strip.

After stripping, the temperature of the mixture is maintained at 160-168°C for about 30 minutes. this is filtered to obtain a solution of the corresponding sodium sulfonate with a metal ratio of 16.8. . The oil content of this solution is 187 inches.

Example B-11 Sodium petroleum sulfonate (''petronate'') was prepared in the same manner as in Example B-1. 836 parts (1 equivalent) of 48 parts of oil and 63 parts of polybutenyl phosphoric anhydride After mixing with a solution consisting of 280 parts of sodium hydroxide ( 7 eq.) and 320 parts (10 eq.) of methanol are added. Dioxide in the reaction mixture When carbon is passed through at a rate of 4 cfh for about 45 minutes, the temperature rises to 85°C and then The temperature gradually drops to 74°C. While passing nitrogen gas at a rate of 2 cfh, the temperature was increased to 160 °C. Gradually raise to °C and strip volatiles. After stripping, mix the Further heating to 160° C. for 30 minutes and filtration yields the sodium salt as a solution.

The metal ratio of this product is 8. The O1 oil content is 22.2%.

Example B-12 In the same manner as in Example B-11, 1256 parts (1,5 equivalents) of sodium petroleum sulfonate was added. amount) was added to a solution consisting of 48% oil and 95 parts of polybutenylconophosphoric anhydride. After heating to 60°C, 420 parts of sodium hydroxide (!O,S equivalent) and methano, - mix 960 parts (30 equivalents). Add carbon dioxide to the mixture at a rate of 4 cfh When conduction is conducted for 60 minutes, the temperature rises to 90°C and then gradually decreases to 70°C. nitrogen The volatiles were stripped by passing through the element and gradually increasing the temperature to 160°C. Do a After stripping, leave it at 160℃ for 30 minutes and filter it to remove the metal. An oil solution of sodium sulfonate with a ratio of 80 is obtained. The oil content of this solution is 22.2 It is 4.

Example B-13 584 parts (0.75 mol) of a commercially available aromatic sulfonic acid, tetyl sulfide obtained in Example 3 Lapropenylphenol 144 parts (0.37 mol), same as used in Example B-1 93 parts of polybutenyl succinic anhydride, 500 parts of xylene and 549 parts of oil After mixing the parts, heat to 70'C with stirring. Add 97 parts of potassium hydroxide Then, heat to 145°C to azeotrope water and xylene and remove them. potassium hydroxide 36 8 parts were added over a period of 10 minutes, followed by heating to about 145-150°C and carbon dioxide was conducted for 110 minutes at a rate of 1.5 cfh. Next, the temperature was increased to 160°C while passing nitrogen through the temperature. 1 L, strip off volatiles. After stripping, filter the reaction solution. By passing through the solution, an oil solution of potassium sulfonate having a metal ratio of 10 is obtained. to this Add lubricating oil to bring the oil content to 39%.

Example B-14 Commercial mixtures of linear and branched alkyl aromatic sulfonic acids 705 parts (0.7 s mol) of tetrapropenylphenol produced in Example 1 Mix 133 parts of 98 oil, heat to 50°C with stirring, and add 65 parts of sodium hydroxide. A solution of 100 parts of water is added. Heat the mixture to 145’C and add water Removed by azeotrope with xylene. After cooling the reaction solution overnight, add sodium hydroxide. Add 279 parts, heat to 145°C, and add carbon dioxide at a rate of 2 cfh for 1.5 hours. to communicate. It is removed by azeotroping with water and xylene. 179 parts of sodium hydroxide was further added with stirring, and at 145°C, carbon dioxide was again added at a rate of about 2 cfh. Continuously conducts for 2 hours. 133 parts of oil were added after 20 minutes to form an azeotrope of xylene and water. The residue was evaporated and the residue was poured into an IJ tube at 170°C and 5ωkHf. Filter the reaction solution The filtrate obtained by Ru.

Example B-15 386 parts (0.75 mol) of commercially available primary branched monoalkyl aromatic sulfonic acid, 58 parts (O, IS mol) of sulfurized tetrapropenylphenol obtained in Example 3, 92 parts oil After mixing 6 grams and 700 grams of xylene and heating to 70'C, hydroxide 97 parts of potassium are added over 15 minutes. Heat the mixture to 145°C and remove the water. leave Add 368 parts of potassium hydroxide over 10 minutes, stirring the mixture. Heat to 145° C. and pass in carbon dioxide at a rate of 1.5 cfh for 2 hours. mixture Heat the item to 150℃ while stripping it, and finally heat it to 150'C150C15 O? Perform stripping. The filtrate obtained by filtering the residue is the desired product.

The diesel lubricant of the present invention comprising the above composition diagram and (B) also contains sulfate ash. It is characterized by containing about O, S or more, usually about 1% or more. Diesel of the invention It is understood by those skilled in the art that the amounts of the components (N and (B)) contained in lubricants can vary over a wide range. can be measured. Generally, however, the diesel lubricants of the present invention will be about 1.0-10 wt. % of component (A) and about 0.05-5% by weight, more typically 0.05-1% by weight. Contains component (B).

In another preferred embodiment, the diesel lubricant of the invention also comprises as (C) at least one oil-soluble neutral or basic alkali of one or more acidic organic compounds; Contains lithium metal salts. Such salt compounds are commonly referred to as ash-containing detergents.

Acidic organic compounds include one or more sulfur acids, carboxylic acids, phosphoric acids, or phenols or or a mixture thereof.

Calcium, magnesium and barium are the preferred alkaline earth metals . Salts containing ion mixtures of two or more of these alkaline earth metals can be used.

These salts used as component (q) are neutral or basic. Neutral salts are Contains just enough alkaline earth metal to neutralize the acidic groups present in the ion, and is a base. The salt contains an excess of alkaline earth metal cations.

A commonly used method for making basic salts is to add a solution of the acid in mineral oil to a stoichiometric excess. Heat to 50°C or above with a metal neutralizer. Neutralizing agents include metal oxides, hydroxides, and carbonates. Furthermore, a promoter can be used for neutralization to assist the reaction of a large excess of metal. this These accelerators are known, for example, phenol, naphthol, alkylphenol. phenols, thiophenols, sulfurized alkylphenols and formaldehyde and phenols. Phenols such as various condensates with alcoholic substances, such as methyl, 2-propanol, etc. Ropatool, octyl alcohol, selonlubucarpitol, ethylene glycol alcohol, stearyl alcohol, and cyclohexyl alcohol Class: hinianiline, phenylene diamine, phenothiazine, phenyl-β-na There are amines such as phthylamine and dodecylamine. manufacture basic salts A particularly effective method is to combine the acid and excess basic alkaline earth metal with a phenolic accelerator. and a small amount of water and heat the mixture to 60-200' (, charcoal). This is a method of oxidizing.

As mentioned above, the acidic organic compounds that serve as raw materials for the salt of component (C) include sulfuric acids, carboxyl acids, etc. At least one type of acid, phosphoric acid, or phenol, or a mixture thereof. this The acidic organic compounds mentioned above in connection with the production of the alkali metal salt [component (B)] Ta. All of the above acidic organic compounds are converted into silicone molecules c) by known methods. It can be used to produce alkaline earth metal salts used in Diesel lubricant of the present invention The amount of component (C) contained therein will also vary widely, but one skilled in the art will readily determine the amount used. can be determined. Component (C) acts as an auxiliary detergent.

The amount of component (C) contained in the diesel lubricant of the present invention ranges from 0% to about 5% or more. fluctuates even more than that. Ingredients (neutral and basic alkali used as q A method for producing a lithium metal salt will be exemplified below.

Example C-1 Oil solution 9 of alkylphenyl sulfonic acid having an average molecular weight of 450 by vapor phase permeation method 06 parts, mineral oil 564 parts, toluene 600 parts, magnesium oxide 987 parts, and After mixing 120 parts of water and heating it to 1.78-85℃, add 3 cfh of carbon dioxide. conduction for 7 hours at a speed of The reaction solution is carbonated while continuing to be stirred. Carbonation finished Afterwards, the reaction solution is stripped at 165° C. and 20 Torr, and the residue is filtered. The filtrate is The target metal ratio is an overbased magnesium sulfonate solution in oil with a metal ratio of about 3.

Example C-2 Polyisobutenyl succinic anhydride is chlorinated polyisobutyne (average chlorine content 4.3 %, average carbon number 82) and maleic anhydride at about 200℃. Ru.

The obtained polyimbutenyl phosphoric anhydride has a saponification value of 90. - Mix 1246 parts of phosphoric acid with 1000 parts of toluene and add 76.6 parts of ζ Add at 25°C. The mixture was heated to 115°C and 125 parts of water was added dropwise over 1 hour. After cooling, heat to 150℃ to react the entire amount of nitric oxide. The filtrate obtained after the washing and filtration has a Noterium content of 4.71%.

Example C-3 Basic calcium sulfonate with a metal ratio of about 15 is mixed with calcium hydroxide and neutral petroleum salt. Sodium sulfonate, calcium chloride, methanol, and alkylphenols It was prepared by carbonating a mixture of

Example C-4 323 parts mineral oil, 48 parts water, 0.74 parts calcium chloride, 79 parts lime, and meth 128 parts of Nord was mixed and heated to 50°C. This mixture has an average molecular weight of 500 ( Gas phase G pressure? Add 1000 parts of alkylphenyl sulfone e from 1) to the mixture. Add. Carbon dioxide was poured into this at a rate of about 5.4 cfh for about 25 hours. Conductive at temperatures of °C.

After carbonation, add 102 parts of mineral oil and volatilize at 150-155°C under reduced pressure of 55 m. Strip things. The filtrate obtained by filtering the residue has a calcium content of 3.7 H. It is an overbasified calcium sulfonate with a metal ratio of about 27.

In the present invention, other additives may be added to the diesel lubricant composition. these Additives include antioxidants, extreme pressure additives, rust inhibitors, pour point depressants, color stabilizers, Traditionally used additives such as anti-foaming agents, which are commonly used in diesel lubricant formulations. is known to those skilled in the art.

Examples of extreme pressure additives, rust inhibitors and antioxidants include chlorinated waxes, etc. Chlorinated aliphatic hydrocarbons; benzyl disulfide, bis(chlorobenzyl) disulfide dibutyltetrasulfide, sulfurized methyl ester of oleic acid, sulfurized acetic acid Organic sulfides and polysulfides such as lukyphenol, dipentene sulfide, and terpene sulfide phosphorus compounds, such as the reaction products of phosphorus sulfide and turpentine or methyl oleate. Sulfurized hydrocarbons; diptyl phosphite, dihebutyl phosphite, dicyclohexyl phosphite sil, pentylphenyl phosphite, tridecyl phosphite, distearyl phosphite , dimethylnaphthyl phosphite, oleyl phosphite, 4-pentylphenyl, poly Propylene (molecular weight 500) substituted phenyl phosphite, diisobutyl substituted phosphorous acid Lithium whose main components are phosphite dihydrocarbons and phosphite trihydrocarbons such as phenyl. acid esters; zinc dioctyl dithiocarnogmate, thiocarbamate metal salts such as luphenyldithiocarpa “mate; Cyclohexyl phosphorodithioate, zinc, dioctyl phosphorodithioate , ζ-li-di(heptylphenyl) phosphorodithioate, cadmium-di(heptylphenyl) phosphorodithioate, Nonylphosphorodithioate, phosphorus trisulfide, isopropyl alcohol and n-hexyl Zinc salt of phosphorodithionic acid obtained by reaction with equimolar mixture with silalcohol Examples include Group I metal salts of phosphorodithionic acid such as phosphorodithionic acid.

Many of the extreme pressure additives and anti-rust/oxidant agents also act as anti-wear agents. zinc di Alkyl phosphorodithioates are known examples.

Pour point depressants are particularly effective additives and are frequently used in the lubricating oils of this invention.

It is known that these pour point depressants can be used in oil-based compositions to improve their low-temperature properties. For example, C.B. Smolheer and Earl Kennedy Smith, “Lubrication Oil “Additives”, page 8 (Retius Hires Co., Creepland, Ohio) (published in 1967).

Examples of pour point depressants include polymethacrylates; polyacrylates; Acrylamide; condensation product of haloparaffin wax and aromatic compound; bicarboxylic acid and dialkyl fumarates, fatty acid vinyl esters and alkyl polymers; Three elements of rubinyl ether! There is a union. Pour point depressants used in the present invention and their The method of manufacturing and use of is disclosed in U.S. Patent Nos. 2,387,501; 2,015.748; 2.655,479; 1,815.022; 2.191,498; 2,6 s 6,746; 2,72 l, s 77; 2.721.878 ; 3,250,715; and are incorporated by reference in their appropriate disclosures. It is incorporated into the specification.

Antifoam agents are used to reduce or prevent the formation of stable foam. representative Antifoam agents include silicones and organic polymers. Do not use other anti-foam agents. ``Foam Control Agents'' by N.T. Karner, pages 125-162 (Fiba Data) ・Corporation Company.

(published in 1976).

The invention may be better understood by the following examples, which are merely illustrative of the invention. Other aspects of this embodiment will be obvious to those skilled in the art.

Weight part Product of Example A-11 2 Product of Example B-2 0.5 Lubricating oil 97.5 Lubricant■ Product of Example A-12 1,0 Product of Example B-2 0.4 Product of Example C-3 0.25 Lubricating oil 98.35 Weight part Product of Example B-2, 45. 33-Product of Example C-3-,1 2' Product of Example B-13 --, , 25-Hydrogenated in-plane styrene 7.60. 60. 60/60 copolymer Maleic anhydride-styrene co, 08. 08. 08. 08 Polymer and Alco and a Min reaction product Polybutenyl succinic anhydride-1,971,971,971,97-ethyleneboria min reaction product Sulfurized tetrapropenylphenol 1.18 1.18 1.12 1.11-ol basic calcium salt Isobutyl and primary amino, 39. 39. 39. 39 Phosphorosis onic acid mixture zinc salt of Octyl phosphorodithio 1.04 1.04 1.04 1.04 phosphoric acid mixture compound zinc salt Alkylated arylamine, 08. 08. 06. 06 petroleum sulfonic acid Basicity, 50. 50. 49-49 magnesium salt Basicity of petroleum sulfonic acid, 27. 27. 25. 2f magnesium feces 1 Silicone antifoam agent 10P 1011118 101) PI IOP mineral oil 　Remainder The diesel lubricant of the present invention can be used in the operation of diesel engines. The present invention Diesel lubricants can be used to clean diesel engines without undesirable viscosity build-up. Seki can be operated for a longer period of time. Furthermore, the lubricant of the present invention is manufactured by Caterpillar Co., Ltd. can pass the I-G-2 and l-H-2 exams.

The diesel lubricant of the present invention is characterized by the diesel lubricant described in Lubricant Examples nr-v. Mack T-7 dated August 31, 1984 using lubricant: Diesel Mack with the title 5 “Viscosity Evaluation of Sekisui Oil”) Rack Technical Service Standard Test Method/ This can be verified by performing %5GT57. This test method correlates with practical experience. Designed.

In this test, the Mack EM6-285 engine was operated at low speed, high torque, and steady state. do. This engine is a direct injection, in-line, 6-cylinder, 4-stroke, turbocharged engine. It is an air-cooled compression ignition engine with a keystone ring.

The rated horsepower is 283 fhp at an adjustment speed of 2300r11m.

Test runs include an initial break-in period (performed only after major reassembly), test oil flushing 150 hours at 1200 revolutions and 80 ft/lb torque Consists of steady operation. No oil changes or additions, but testing for analysis Periodically take an oil sample from the drain valve of the oil pan. Sample 8 times. The drain pipe is Drain 16 oz of oil from the drain valve before taking the sample. This purge sample After collecting the material, return it to the organization. No supplementary oil will be added to the engine to replace the 4a7.0 sample.

The kinematic viscosity at 210″F was measured 100 hours and 150 hours after the start of the test, Calculate the "viscosity slope".

The "viscosity slope" is the difference in viscosity between 100 hours and 150 hours divided by 50. sticky The degree slope reflects the final increase in viscosity as the test progresses, so the number is The smaller the better.

Kinematic viscosity at 210″F can be measured using two methods. Pass it through a No. 200 sieve before loading it into a Canon reverse flow viscometer. ASTM D-44 For method 5, select a viscometer with a flow time of 200 seconds or more. Set. In the Mack T-7 standard method, a Canon 300 type viscometer is used for all viscosities. Used for degree measurement. In the latter method, the flow time is 15W-40 days for a fully formulated For diesel lubricants, 5O-100 seconds is typical.

The following are the results of the MackT-7 test conducted on three types of diesel lubricants of the present invention. Shown in the table.

MackT-7 test results ■ Sodium 0.33 0.01 ■ Sodium + 0.33 0.02 calcium ■ Potassium 0.09 0.11 Given the specification and practice of the invention disclosed herein, one skilled in the art will be able to understand the invention. Other aspects will also be apparent. The specification and examples are merely examples; The true scope and spirit of the invention will be indicated in the following claims.

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Claims (1)

[Claims] 1. Preference for lubricants when used in primarily oil and diesel engines with lubricating viscosity. A diesel lubricant comprising: (A) at least one substituted succinic acylating agent and at least one - Has NH- group and at least one amino compound in which the acylating agent is placed. a substituent and a succinic acid group, the substituent having an Mn value of at least about 1200 and a succinic acid group. The acylating agent is derived from a polyalkene characterized by a Mw/Mn ratio of at least about 1.5, and the acylating agent has an average of at least about 1.3 succinic acid groups per equivalent of substituent in its structure. (B) at least one basic alkali metal salt of at least one acidic organic compound having a metal ratio of at least about 2; Diesel lubricant. 2. A lubricant according to claim 1 containing at least 0.8% sulfated ash. 3. The lubricant of claim 1 containing at least about 1% sulfated ash. 4(A) is characterized by an Mn value of from about 1300 to about 5000. The lubricant according to item 1. 5. The lubricant of claim 1, wherein the substituent (A) is characterized by a Mw/Mn value of from about 1.5 to about 1.6. 6. The succinic acid group corresponds to the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R and R' are each independently -OH, -Cl, -O-lower atom. or R and R' together are -O-, provided that all 2. The lubricant of claim 1, wherein all succinic acid groups need not be the same. 7. These are homopolymers and interpolymers of terminal olefins having from 2 to about 16 carbon atoms, but these interpolymers may optionally contain internal olefins having up to about 16 carbon atoms. at least one polyester selected from the group containing up to about 40% of polymerized units derived from The lubricant according to claim 1, wherein the substituent is derived from an alkene. 8. 8. The lubricant of claim 7, wherein the Mn value is at least about 1500. 9. 8. The lubricant of claim 7, wherein the Mw/Mn value is at least about 1.8. 10. Homopolymers or interpolymers of terminal olefins having from 2 to about 16 carbon atoms, but the interpolymers may optionally contain internal olefins having up to about 16 carbon atoms. 2. The lubricant of claim 1, wherein the substituents are derived from at least one polyalkene selected from the group which may contain up to about 25% of polymerized units derived from polyalkenes. 11. Polybutene, ethylene-propylene copolymer, polypropylene and The lubricant according to claim 1, wherein the substituent is derived from a polymer selected from the group consisting of a mixture of two or more of the following. 12. The acylating agent has an average of at least 1.0% per equivalent of substituent within its structure. 4. A lubricant according to claim 1, characterized by the presence of succinic acid groups. 13. 2. The lubricant of claim 1, wherein the lubricant has an Mn value of about 1,500 to about 2,800. 14. 2. The lubricant of claim 1, wherein the Mw/Mn value is greater than about 20 and about 3.4. 15. 2. The lubricant of claim 1, wherein the acylating agent is characterized by the presence of at least 1.5 to about 2.5 succinic acid groups per equivalent of substituent in its structure. 16. The substituent is derived from polybutene and comprises at least 50% of its total units isobutene. 12. A lubricant according to claim 11, which is derived from ten. 17. The lubricant according to claim 1, which corresponds to a succinic acid group, a formula ▲a mathematical formula, a chemical formula, a table, etc.▼ and a mixture thereof. 18. 2. The lubricant according to claim 1, wherein the basic alkali metal salt (B) is at least one sulfur acid, phosphoric acid, carboxylic acid or phenol, or a mixture thereof. 19. The lubricant according to claim 1, wherein the alkali metal salt is a salt of an organic sulfonic acid. 20. A sulfonic acid is represented by the formula R1(SO3H)r or (R2)xT(SO3H)y, R1 and R2 are each an aliphatic group without acetylenically unsaturated bonds and containing up to 60 carbon atoms, and T is an aromatic hydrocarbon ring group, x is a number from 1 to 3, and r and 20. The lubricant of claim 19, wherein y and y are numbers from 1 to 4. 21. The lubricant according to claim 20, wherein the sulfonic acid is an alkylbenzene sulfonic acid. 22. The basic sulfonate (B) contains (B-1) at least one acidic gaseous substance selected from the group consisting of carbon dioxide, hydrogen sulfide, sulfur dioxide, and mixtures thereof; and (B-2) A mixture of the following, (B-2-a) at least one oil-soluble sulfonic acid that is susceptible to excessive basicization, and (B-2-b) At least one alkali metal selected from the group consisting of lithium, sodium, or potassium, or selected from the group consisting of hydroxide, alkoxide, hydride, or amide. At least one basic compound of these metals, (B-2-C) At least one lower aliphatic alcohol selected from monohydric alcohols or dihydric alcohols, or at least one alkylphenol or sulfur an oil-soluble alkylphenol, and (B-2-d) at least one oil-soluble carboxylic acid or a functional derivative thereof at a temperature between the coagulation temperature and the decomposition temperature of the reaction mixture. The lubricant according to claim 19, which is a dispersion. 23. The lubricant according to claim 22, wherein the acidic gaseous substance (B-1) is carbon dioxide. 24. Sulfonic acid (B-2-a) is represented by the formula R1(SO3H)r or (R2)xT(SO3H)y, and R1 and R2 are each an aliphatic group without an acetylenically unsaturated bond. 23. The lubricant of claim 22, wherein T is an aromatic hydrocarbon ring group, X is a number from 1 to 3, and r and y are numbers from 1 to 4. agent. 25. 23. The lubricant of claim 22, wherein the functional derivative of component (B-2-d) is selected from the group consisting of anhydrides, esters, amides, imides, amidines and metal salts. 26. Each component of B-2 has the following equivalent ratio: (B-2-b)/(B-2-a) 4 :1 or more (B-2-c)/(B-2-a) between about 1:1 and about 80:1 (B-2-d)/(B-2-a) between about 1:1 and about 23. The lubricant of claim 22, wherein the lubricant is between 1:20 and 1:20. 27. 23. The lubricant of claim 22, wherein the basic salt (B) has a metal ratio of about 6 to about 30. 28. Component (B-2-d) is at least one hydrocarbon-substituted succinic acid or functional derivative. 23. The lubricant of claim 22, which is a conductor and has a reaction temperature in the range of about 25-200<0>C. 29. The lubricant according to claim 22, wherein component (B-2-a) is an alkylbenzenesulfonic acid. 30. Claims in which component (B-2-b) is sodium or a sodium compound The lubricant according to item 22. 31. Ingredients (B-2-C) are methanol, ethanol, propanol, butanol Component (B-2-d) is at least one of polyptenol and pentanol. 23. The polyptenyl succinic acid and polyptenyl succinic anhydride group consisting primarily of isobutene units and having a number average molecular weight between about 700 and about 10,000. lubricant. 32. The lubricant according to claim 1, further comprising (C) at least one oil-soluble alkaline earth metal salt of at least one acidic organic compound. 33. 33. The lubricant of claim 32, wherein the alkaline earth metal salt is at least one sulfuric acid, carboxylic acid, phosphoric acid or phenol, or a mixture thereof. 34. The amino compound in (A) is an alkylene polyamine corresponding to the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where U is an alkylene group having 2 to about 10 carbon atoms, and each R3 is independently a hydrogen Atom, lower alkyl group or lower hydrogen The lubricant according to claim 1, wherein the lubricant is a loxyalkyl group, at least one of R3 is a hydrogen atom, and n is from 1 to about 10. 35. Component (A) is a carboxylic acid derivative composition obtained by reacting a carboxylic acid derivative with at least one type of post-treatment agent and subjected to at least one type of post-treatment, and this post-treatment agent is boron oxide, boron oxide, etc. Hydrates, boron halides, boric acids, boric acid esters carbon disulfide, hydrogen sulfide, sulfur, sulfur chloride, alkenyl cyanide, carboxylic acid acylating agent, aldehyde, ketone, wallea, thiourea, guanidine, dicya diamide, hydrocarbyl phosphate, hydrocarbyl phosphite, hydride thiophosphate locarbyl, hydrocarbyl thiophosphite, phosphorus sulfide, phosphorus oxide, phosphoric acid, isocarbyl Hydrocarbyl cyanate, Hydrocarbyl isothiocyanate, Epoxide, Epi The lubricant of claim 1 selected from the group consisting of sulfides, formaldehyde or mixtures of formaldehyde-releasing compounds and phenols, and mixtures of sulfur and phenols. 36. A diesel lubricant consisting of a major amount of oil of lubricating viscosity and a minor amount of a composition sufficient to minimize undesirable viscosity build-up of the lubricant when used in diesel engines. In the lubricant, the composition comprises (A) at least one substituted succinic acylating agent and at least one -NH- group; and at least one amino compound in which the acylating agent is placed. a substituent and a succinic acid group, the substituent having an Mn value of at least about 1200 and a succinic acid group. Derived from polyalkenes characterized by a Mw/Mn ratio of at least about 1.5, the alkylating agent is characterized by the presence of an average of at least about 1.3 succinic acid groups per equivalent of substituent within its structure. At least one characterized carboxylic acid derivative (B) at least one basic sodium or potassium salt of at least one acidic organic compound having a metal ratio of at least about 2. 37. 37. The lubricant of claim 36, comprising at least about 0.8% sulfated ash. 38. 37. The lubricant of claim 36, comprising at least 1% sulfated ash. 39. 37. The lubricant of claim 36, wherein the substituent (A) is characterized by an Mn value of from about 1,300 to about 5,000. 40. (A) is characterized by a Mw/Mn value of from about 1.5 to about 6.0; The lubricant according to claim 36. 41. The succinic acid group corresponds to the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R and R' are each independently -OH, -Cl, -O-lower atom. 37. The lubricant of claim 36, wherein R and R' together are -O-, but not all succinic groups need to be the same. 42. Homopolymers and interpolymers of terminal olefins having from 2 to about 16 carbon atoms, but the interpolymers may optionally contain internal olefins having up to about 16 carbon atoms. 37. The lubricant of claim 36, wherein the substituents are derived from at least one polyalkene selected from the group which may contain up to about 40% of polymerized units derived from polyalkenes. 43. 43. The lubricant of claim 42, wherein the Mn value is at least about 1500. 44. 43. The lubricant of claim 42, wherein the Mw/Mn value is at least about 1.8. 45. Homopolymers or interpolymers of terminal olefins having from 2 to about 16 carbon atoms, but the interpolymers may optionally contain internal olefins having up to about 16 carbon atoms. 37. The lubricant of claim 36, wherein the substituents are derived from at least one polyalkylene selected from the group which may contain up to about 25% polymerized units derived from. 46. Polybutene, ethylene-propylene copolymer, polypropylene and 37. The lubricant according to claim 36, wherein the substituent is derived from a polymer selected from the group consisting of a mixture of two or more of the above. 47. The acylating agent has an average of at least 1.0% per equivalent of substituent within its structure. 37. The lubricant according to claim 36, characterized by the presence of succinic acid groups of No. 4. 48. 37. The lubricant of claim 36, wherein the Mn value is from about 1,500 to about 2,800. 49. 37. The lubricant of claim 36, wherein the Mw/Mn value is from about 20 to about 34. 50. 37. The lubricant of claim 36, wherein the acylating agent is characterized by the presence of at least 1.5 to about 25 succinic acid groups per equivalent of substituent within its structure. 51. The substituents are derived from polybutene and at least 50% of the total units are isobutene. 47. The lubricant according to claim 46, comprising ten. 52. The lubricant according to claim 36, wherein the succinic acid group has the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and mixtures thereof. 53. 37. The water absorbent according to claim 36, wherein the basic sodium salt (B) is at least one sulfuric acid, phosphoric acid, carboxylic acid, or phenol, or a mixture thereof. lubricant. 54. The basic salt (B) is a sodium salt or carbonate of at least one organic sulfonic acid. 37. The lubricant according to claim 36, which is a lithium salt. 55. the sulfonic acid has the formula R1(SO3H)r, or (R2) T is an aromatic hydrocarbon ring group, and x is a number from 1 to 3. 55. The lubricant of claim 54, wherein r and y are numbers from 1 to 4. 56. benzenes in which the sulfonic acid is substituted with an alkyl group containing at least 8 carbon atoms; 55. The lubricant according to claim 54, which is sulfonic acid. 57. The basic salt (B) contains (B-1) at least one acidic gaseous substance selected from the group consisting of carbon dioxide, hydrogen sulfide, sulfur dioxide, and mixtures thereof; (B-2) the following: mixture, (B-2-a) at least one oil-soluble sulfonic acid or a derivative thereof that is susceptible to excessive basicization, (B-2-b) sodium or potassium, or a hydroxide, an alkali At least one of these basic compounds selected from the group consisting of coxide, hydride, or amide; (B-2-c) At least one lower aliphatic compound selected from monohydric alcohol or dihydric alcohol. Alcohol, or alkylphenol or sulfurized alkylphenol (B-2-d) at least one oil-soluble carboxylic acid or functional derivative thereof selected from the group consisting of anhydrides, esters, amides, imides, amidines, and metal salts; and about 25-200°C. produced by a method of reacting for a sufficient period of time to form a dispersion in 37. The lubricant according to claim 36, which is an oil-soluble dispersion of a basic sodium salt or potassium salt of a sulfonic acid. 58. Each component of B-2 has the following equivalent ratio (B-2-b)/(B-2-a) 4:1 or more (B-2-c)/(B-2-a) approximately 1:1. 58. The lubricant of claim 57, wherein (B-2-d)/(B-2-a) is between about 80:1 and between about 1:1 and about 1:20. 59. 58. The lubricant according to claim 57, wherein the acidic gaseous substance (B-1) is carbon dioxide. 60. Sulfonic acid (B-2-a) is represented by the formula R1(SO3H)r or (R2)xT(SO2H)y, where R1 and R2 are each an aliphatic group without acetylenic unsaturation and up to 60 contains carbon of 58. The lubricant of claim 57, wherein T is an aromatic hydrocarbon ring group, x is a number from 1 to 3, and r and y are numbers from 1 to 4. 61. 61. The lubricant according to claim 60, wherein the sulfonic acid is an alkylbenzenesulfonic acid. 62. Claim 57, wherein the alcohol (B-2-b) is a monohydric alcohol. lubricant. 63. Alcohol is methanol, ethanol, propanol and mixtures thereof 63. The lubricant of claim 62 selected from the group consisting of: 64. 64. The lubricant of claim 63, wherein the alcohol is methanol. 65. The moisturizer according to claim 64, wherein (B-2-C) is an alkylphenol. lubricant. 66. 65. The lubricant of claim 64, wherein (B-2-c) is a sulfurized alkylphenol having an alkyl group having from about 6 to about 100 carbon atoms. 67. Claims in which (B-2-b) is potassium or a basic compound of potassium The lubricant according to paragraph 66. 68. 58. The lubricant according to claim 57, wherein the carboxylic acid (B-2-d) is a dicarboxylic acid or an anhydride thereof. 69. Dicarboxylic acids and their anhydrides are hydrocarbon-substituted succinic acid, hydrocarbon-substituted non-substituted succinic acid, 69. The lubricant of claim 68 selected from hydrosuccinic acid or mixtures thereof. 70. The hydrocarbon substituent of succinic acid or its anhydride is The lubricant according to claim 69, obtained by polymerization of monomers selected from thene and isobutene. 71. Claims in which the hydrocarbon substituent of succinic acid or its anhydride is a polyptenyl group consisting primarily of isobutene units and having an Mn value of about 700 to about 10,000. The lubricant according to item 70. 72. 58. The lubricant of claim 57, wherein the basic sodium or potassium sulfonate (B) metal ratio is from about 6 to about 30. 73. 37. The lubricant of claim 36, comprising from about 1 to about 10% by weight of (A). 74. 58. The lubricant of claim 57, comprising from about 0.05 to about 1% by weight of dispersion (B). 75. (C) at least one oil-soluble neutral or at least one acidic organic compound; 37. The lubricant of claim 36, wherein also comprises a basic alkaline earth metal salt. 76. The acidic organic compound contains at least one sulfuric acid, carboxylic acid, phosphoric acid, or 76. The lubricant according to claim 75, which is an enol or a mixture thereof. 77. Alkyl-substituted benzenes in which the sulfuric acid has an alkyl group of at least 8 carbon atoms 77. The lubricant of claim 76, which is sulfonic acid. 78. An amino compound is an alkylene polyamine represented by the formula ▲Mathematical formula, chemical formula, table, etc.▼, where U is an alkylene group having 2 to about 10 carbon atoms, and each R3 is independently a hydrogen atom, a lower alkyl group or lower 37. The lubricant according to claim 36, which is a droxyalkyl group, in which at least one R3 is a hydrogen atom, and n is from 1 to about 10. 79. In a diesel lubricant comprising a major amount of oil having lubricating viscosity and a minor amount of the composition sufficient to minimize undesirable viscosity build-up of the lubricant when used in a diesel engine, the composition comprises (A) at least one substituted succinic acylating agent and at least one -NH- group; and at least one amino compound in which the acylating agent is placed. It consists of a substituent and a succinic acid group, and the substituent has an Mn value of about 1300 to about 5000. and polyalkenes characterized by Mw/Mn values of about 1.5 to about 4. The acylating agent has on average less than at least one carboxylic acid derivative composition characterized by the presence of succinic acid groups of about 1.3; and (B) having a metal ratio of at least about 4; , (B-2) a mixture of the following components, (B-2-a) at least one oil-soluble alkylbenzene sulfonic acid or derivative thereof that is susceptible to excessive basicization, (B-2-b) sodium hydroxide, (B-2-C) Monohydric alcohol, alkylphenol, or sulfurized alkylphenol (B-2-d) a copolymer having a polybutenyl substituent with a number average molecular weight of 700-5000; succinic acid and its derivatives, and each component of (B-2) in the following equivalent ratio (B-2-b)/(B-2-a) between about 6:1 and 30:1 (B-2-b)/(B-2-a). 2-c)/(B-2-a) between about 2:1 and 50:1 (B-2-d)/(B-2-a) between about 1:2 and 1:10, about A diesel lubricant comprising at least one basic sodium sulfonate dispersion obtained by reacting at 25-200C for a period sufficient to form a dispersion. 80. 80. The lubricant of claim 79, comprising at least about 0.8% sulfated ash. 81. 80. The lubricant of claim 79, comprising at least about 1.0% sulfated ash. 82. The amino compound in (A) is an alkylene polyamine represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where U is an alkylene group having 2 to about 10 carbon atoms, and each R3 is independently hydrogen atom, lower alkyl group, or lower hydroxyalkyl group, at least one of R3 is a hydrogen atom, and n is 1 or 80. The lubricant of claim 79, wherein the lubricant is about 10. 83. (A) in which the amino compound contains at least about 2 to about 8 amino groups; 80. The lubricant of claim 79, which is a ethylene polyamine, a propylene polyamine or a trimethylene polyamine or a mixture thereof. 84. 80. The lubricant of claim 79, wherein the polyalkene in (A) has an Mn value of about 1,500 to about 2,800. 85. 80. The lubricant of claim 79, wherein the polyalkene in (A) has a Mw/Mn value of about 20 to about 34. 86. 80. The lubricant of claim 79, wherein the acylating agent in (A) is characterized by the presence of at least about 1.5 to about 25 succinic acid groups per equivalent of substituent within its structure. 87. Homopolymers or interpolymers of terminal olefins having from 2 to about 16 carbon atoms, optionally containing up to about 40% polymerized units derived from internal olefins having up to about 16 carbon atoms. At least one type of pot selected from the group obtained. 80. The lubricant according to claim 79, wherein the substituent in (A) is derived from Rialken. 88. 88. The lubricant of claim 87, wherein the polyalkene substituent in (A) is derived from polybutene and at least 50 of its total units are derived from isobutene. 89. (C) at least one acidic organic compound and at least one neutral or basic atom; 88. The lubricant of claim 87, also comprising a alkaline earth metal. 90. The acidic organic substance is at least one sulfur acid, carboxylic acid, phosphoric acid or phenol 90. The lubricant of claim 89, wherein the lubricant is a lubricant or a mixture thereof. 91. The acidic substance is a benzene sulfonate substituted with an alkyl group having at least 8 carbon atoms. 90. The lubricant according to claim 89, which is a phosphoric acid. 92. 80. The lubricant of claim 79, wherein the sulfonate (B) has a metal ratio of about 6 to about 30. 93. A minor amount of oil of lubricating viscosity and a preference for lubricants used in tasel engines. A diesel lubricating oil comprising (A) at least one substituted succinic acylating agent and at least one -NH - has a group and at least one amino compound in which the acylating agent is placed. It consists of a substituent and a succinic acid group, and the substituent has an Mn value of about 1300 to about 5000. and polyalkenes characterized by a Mn/MW ratio of about 1.5 to about 4. The acylating agent is derived from at least one carboxylic acid derivative characterized by the presence of at least about 1.3 succinic acid groups per equivalent of substituent within its structure. (B) having a metal ratio of at least about 4; (B-1) carbon dioxide; (B-2) a mixture of the following components; (B-2-a) overbasic; (B-2-b) Potassium hydroxide; (B-2-c) Alkylphenol or sulfurized alkylphenol; (B-2-d) Number average molecular weight 700 −5000 polyptenyl substituents Huccinic acid and its derivatives, and each component of (B-2) in the following equivalent ratio (B-2-b)/(B-2-a) between about 6:1 and about 30:1 (B-2-b)/(B-2-a) between about 6:1 and about 30:1. -2-c)/(B-2-a) between about 2:1 and about 50:1 (B-2-d)/(B-2-a) between about 1:2 and about 1:10 The resulting small amount is reacted at about 25-200°C for a time sufficient to form a dispersion. A diesel lubricant comprising at least one basic potassium sulfonate dispersion. 94. 94. The lubricant according to claim 93, wherein (B-2-c) is a sulfurized alkylphenol. 95. A method for operating a diesel engine, which comprises lubricating the engine with the diesel lubricant according to claim 1 while the diesel engine is in operation. 96. While the diesel engine is in operation, the diesel engine is A method of operating a diesel engine that consists of lubricating it with a lubricant. 97. While the diesel engine is in operation, the diesel engine is A method of operating a diesel engine that consists of lubricating it with a lubricant. 98. While the diesel engine is in operation, the diesel engine is operated as described in claim 36. A method of operating a diesel engine that consists of lubricating it with a lubricant. 99. While the diesel engine is in operation, the diesel engine is operated as described in claim 57. A method of operating a diesel engine that consists of lubricating it with a lubricant. 100. While the diesel engine is in operation, the diesel engine is operated as described in claim 75. A method of operating a diesel engine consisting of lubrication with a gel lubricant. 101. While the diesel engine is in operation, the diesel engine is operated as described in claim 79. A method of operating a diesel engine consisting of lubrication with a gel lubricant. 102. While the diesel engine is in operation, the diesel engine is operated as described in claim 89. A method of operating a diesel engine consisting of lubrication with a diesel lubricant. 103. While the diesel engine is in operation, the diesel engine is operated as described in claim 93. A method of operating a diesel engine consisting of lubrication with a gel lubricant. 104. (B-1) one type of acidic gaseous substance selected from the group consisting of carbon dioxide, hydrogen sulfide, sulfur dioxide, and mixtures thereof; (B-2) a mixture of the following; (B-2-a) At least one oil-soluble sulfonic acid or (B-2-b) At least one alkali, hydroxide, alkoxide, water At least one of these selected from the group consisting of basic compounds or amides (B-2-c) at least one alkylphenol or sulfurized alkylphenol and optionally (B-2-d) at least one oil-soluble carboxylic acid or a functional derivative of, at a temperature between the solidification temperature and the decomposition temperature of the reaction mixture. A method for producing an oil-soluble basic alkali metal sulfonate having a metal ratio of at least about 2. 105. Claim 104, wherein the acidic gaseous substance (B-1) is carbon dioxide. How to put it on. 106. The mixture (B-2) contains at least some carboxylic acids (B-2-d). The method according to item 104. 107. Sulfonic acid (B-2-a) is represented by the formula R1(SO3H)r or (R2)xT (SO3H)y, where R1 and R2 are each an acetylenically unsaturated bond. an aliphatic group containing up to 60 carbon atoms, T is an aromatic hydrocarbon ring group, x is a number from 1 to 3, and r and y are numbers from 1 to 4. Section 104. The method described in paragraph 104. 108. The method according to claim 104, wherein the functional derivative of component (B-2-d) is selected from the group consisting of anhydrides, esters, amides, imides, amidines and metal salts. Law. 109. The components of (B-2) have the following equivalent ratio (B-2-b)/(B-2-a) at least 4:1 (B-2-c)/(B-2-a) 1:20 and 80:1 (B-2-d) / (B-2-a) between 1:1 and 1:20. 110. 105. The method according to claim 104, wherein (B-2-c) is an alkylphenol or a sulfurized alkylphenol. 111. 105. The method of claim 104, wherein the basic salt (B) has a metal ratio of about 6 to about 30. 112. (B-2-b) is potassium or at least one basic compound thereof; 109. The method of claim 109. 113. 105. The process of claim 104, wherein component (B-2-d) is at least one hydrocarbon-substituted succinic acid or functional derivative thereof and the reaction temperature is in the range of about 25-200<0>C. 114. 105. The method according to claim 104, wherein component (B-2-a) is an alkylbenzenesulfonic acid. 115. 105. The method of claim 104, wherein component (B-2) also includes at least one hydrocarbon diluent. 116. 116. The method of claim 115, wherein the diluent is a volatile organic solvent. 117. Component (B-2-c) is alkylphenol or sulfurized alkylphenol 117. The method according to claim 116, wherein the temperature is at or above the water-solvent azeotropic temperature.