JPH083173A - Boron-containing substituted hydroxyaromatic carboxylic acid ester derivative, method for producing the same and use of the ester derivative - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] Lubricants useful as lubricant additives (ashless detergents and antiwear agents) useful for diesel engine and methanol engine oils that comply with future emission regulations. Provided are an additive composition for a lubricant, a method for producing the same, and a lubricating oil composition containing the additive for a lubricant. [Structure] General formula (I) [In the formula, Ar ¹ is a polyvalent aromatic nucleus, R ¹ is an organic group, and p is 1
To 3 integer, n represents an integer of 1 to 4, m is an integer of 1 to 3, ^{when R 1} is more than one, a plurality of ^{R 1} may be the same or different. ] A boron-containing substituted hydroxyaromatic carboxylic acid ester derivative comprising a reaction product and / or a mixture of an ester obtained from a substituted hydroxyaromatic carboxylic acid and a hydroxy compound represented by the following, and a lubricant comprising the same Additives.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel boron-containing substituted hydroxyaromatic carboxylic acid ester derivative, a process for producing the same, a lubricant additive comprising the ester derivative, and a lubricant additive composition containing the same. And a lubricating oil composition. More specifically, the present invention is a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative useful as an ashless-type detergent excellent in high-temperature stability in place of conventional metal-type detergents, and a method for efficiently producing the same. Furthermore, for engine oils that comply with strict exhaust gas regulations in the future, especially for lubricants useful for diesel engine and methanol engine oils, lubricants including the lubricant additive and ashless dispersant The present invention relates to an additive composition and a lubricating oil composition containing the additive for a lubricant.

[0002]

2. Description of the Related Art Conventional ashless dispersants generally include succinimide type and hydroxybenzylamine type.
It is widely used as an additive for gasoline, diesel engine oil, etc. with an emphasis on its remarkable fine particle dispersing action. Further, these are recognized as synergistic effects with zinc dialkyldithiophosphate and metal type detergents, and are one of the extremely important additives for lubricants. However, in recent years, it has been frequently pointed out that the stability at high temperatures (high-temperature cleanability) is not sufficient.

Conventional lubricating oils for internal combustion engines are usually ashless dispersants such as base oil and polybutenyl succinimide, metal type detergents such as alkaline earth metal sulfonates and phenates, and zinc alkyldithiophosphates. However, there is a problem that the metal components in the additive components are generated as oxides or sulfates by combustion, which contributes to environmental pollution. In recent years, among internal combustion engines, especially diesel engines, particulates and NO _x
Environmental pollution control by exhaust gas regulations has become an important issue. Exhaust gas purifiers such as particulate traps and NO _x removal catalysts are available as countermeasures against these problems, but conventional lubricating oils for internal combustion engines have a problem of blockage due to metal oxides and sulfides produced by combustion. There is a demand for a lubricating oil for an internal combustion engine that can minimize the emission of metal oxides and sulfides.

Further, a methanol engine has been attracting attention as one means for solving future exhaust gas countermeasures. In a diesel engine, light oil is sprayed into the engine by an injection pump, but the lubrication inside the pump is self-lubrication by the light oil itself. On the other hand, in a methanol engine, since the lubricity of methanol itself is low, engine oil is usually injected into the injection pump. In that case, since the compatibility between methanol and engine oil is poor, the additive is precipitated in methanol, and particularly in the metal-type detergent, there is a problem that metal components such as calcium clog the nozzle injection port. There is a demand for a lubricating oil for an internal combustion engine that has a metal component suppressed to a minimum. As a measure against such future exhaust gas, for example, for lubricating base oil,
(3,5-di-t-butyl-4-hydroxyphenyl)
An ashless lubricating oil composition containing an alkyl carboxylic acid ester, a succinimide-based ashless dispersant and an ashless antioxidant has been proposed (JP-A-4-353598). However, this composition has a problem that the high temperature stability (high temperature detergency) cannot be sufficiently satisfied. On the other hand, U.S. Pat. No. 4,098,708 proposes esters of alkyl-substituted hydroxyaromatic carboxylic acids having at least about 10 carbon atoms and their derivatives as dispersants for lubricating oils and fuel oils.
Then, monohydric or polyhydric hydrocarbon alcohols are mentioned as suitable alcohol components of the ester, and specific examples thereof include substituted phenols such as cresol. However, also in the case of this ester, similarly, the high temperature stability is not sufficiently satisfactory.

[0005]

Under the above circumstances, the present invention is a boron-containing substituted hydroxyaromatic carvone useful as an ashless detergent having excellent stability at high temperature, which is an alternative to conventional metal detergents. An acid ester derivative, an additive for lubricants that is particularly useful for diesel engine oils and methanol engine oils, which is compatible with future emission regulations, and has excellent high-temperature stability (high-temperature detergency) and also has a fine particle dispersion action. The object of the present invention is to provide an additive composition as an ashless detergent dispersant and a lubricating oil composition containing at least the additive for a lubricant.

[0006]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in order to achieve the above object, and previously found that a specific substituted hydroxyaromatic carboxylic acid ester derivative is excellent in high temperature stability (high temperature detergency). It was found to be useful as an ashless detergent (Japanese Patent Application Nos. 5-143532 and 5-5
-244353, Japanese Patent Application No. 6-61260). As a result of further research, the present inventors have found that a specific boron-containing substituted hydroxyaromatic carboxylic acid ester derivative is extremely useful as an ashless-type detergent excellent in high-temperature stability in place of a conventional metal-type detergent. By adding this additive for lubricants (ashless detergent) consisting of a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative to a conventional ashless dispersant, high temperature stability (high temperature cleanability) It has been found that an additive composition for a lubricant, which is excellent as a ashless detergent dispersant having excellent fine particle dispersion action, can be obtained. The present invention has been completed based on such findings. That is, the invention has the general formula (I)

[0007]

[Chemical 4]

[Wherein, Ar ¹ is a polyvalent aromatic nucleus, R ¹ is an organic group, p is an integer of 1 to 3, n is an integer of 1 to 4, and m is 1
3 of an integer, when R ¹ is more than one, a plurality of R ¹ may be the same or different. And a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative consisting of a reaction product and / or a mixture of an ester derivative obtained from a substituted hydroxyaromatic carboxylic acid and a hydroxy compound represented by An additive for a lubricant comprising a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative, (a) the boron-containing substituted hydroxyaromatic carboxylic acid ester derivative, and (b)
Provided are an additive composition for a lubricant containing an ashless dispersant, and a lubricating oil composition containing at least the boron-containing substituted hydroxyaromatic carboxylic acid ester derivative in a lubricating base oil. It is a thing. The present invention also provides a compound represented by the general formula (I)

[0009]

Embedded image

[Wherein Ar ¹ , R ¹ , p, n and m are
Same as above. ] At least one type of substituted hydroxyaromatic carboxylic acid represented by and at least one type of hydroxy compound are reacted in the absence of a catalyst or in the presence of a catalyst to obtain an ester derivative, which is then reacted with a boron-containing compound and / or Alternatively, the present invention also provides a method for producing the above-mentioned boron-containing substituted hydroxyaromatic carboxylic acid ester derivative characterized by being mixed. Furthermore, at least one kind of the substituted hydroxyaromatic carboxylic acid represented by the general formula (I), at least one kind of the hydroxy compound and the boron-containing compound are reacted and / or mixed in the absence of a catalyst or in the presence of a catalyst. The present invention also provides a method for producing the above-mentioned boron-containing substituted hydroxyaromatic carboxylic acid ester derivative. The boron-containing substituted hydroxyaromatic carboxylic acid ester derivative of the present invention is obtained from an ester derivative of the substituted hydroxyaromatic carboxylic acid represented by the above general formula (I) and a hydroxy compound, and a boron-containing compound. Therefore, it may be a reaction product of the ester derivative and the boron-containing compound, a mixture thereof, or a mixture of the reaction product and the mixture. Furthermore, the boron-containing substituted hydroxyaromatic carboxylic acid ester derivative of the present invention may be one kind or two or more kinds. In the general formula (I), Ar ¹ represents a polyvalent aromatic nucleus. Examples of the polyvalent aromatic include those derived from benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl, and the like. Among these, those derived from benzene and naphthalene are particularly preferable. Is. In addition to the hydroxyl group, the organic group (R ¹ ), and the carboxyl group, Ar ¹ includes
In some cases, a halogen atom, a nitro group, a mercapto group or the like may be substituted.

R ¹ is an organic group, and examples thereof include a hydrocarbon group, an alkoxy group and a dialkylamino group.
Particularly, a hydrocarbon group is preferable. When there are multiple R ¹ ,
A plurality of R ¹ may be the same or different. The hydrocarbon group is not particularly limited, and is a chain hydrocarbon group such as an alkyl group or an alkenyl group, a cyclic hydrocarbon group such as a cycloalkyl group or a cycloalkenyl group, or an aromatic carbon group such as a phenyl group or a naphthyl group. It may be any of hydrogen groups, but is preferably a chain hydrocarbon group such as an alkyl group or an alkenyl group. These hydrocarbon groups may be substituted with another hydrocarbon group such as a lower alkyl group, a cycloalkyl group or a phenyl group. Further, the hydrocarbon group includes those substituted with a non-hydrocarbon group as long as it retains substantially hydrocarbon-like properties. As the non-hydrocarbon group, for example,
Examples thereof include a nitro group, an amino group, a halo group, a hydroxyl group, a lower alkoxy group, a lower alkylmercapto group, an oxo group, a thio group, and an interrupting group (eg, -NH-, -O-, -S-).

Examples of the above-mentioned hydrocarbon group include propyl group, butyl group, isobutyl group, pentyl group, hexyl group, 1-methylhexyl group, 2,3,5-trimethylheptyl group, octyl group, 3-ethyloctyl group. Group, 4-ethyl-5-methyloctyl group, nonyl group, decyl group, dodecyl group, 2-methyl-4-ethyldodecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, tetracontyl group, 4-hexenyl group , 2-ethyl-4-hexenyl group, 6-octenyl group, 3-cyclohexyloctyl group, phenylnonyl group, nitrododecyl group, 3-aminononyl group, chlorohexadecyl group, (2
-Nitroethyl) octyl group, (3-aminocyclohexyl) nonyl group, 4- (p-chlorophenyl) octyl group, 4-butoxyhexadecyl group, and further olefin polymer (for example, polyethylene, polypropylene, polyisobutylene, ethylene- Hydrocarbon groups derived from propylene copolymer, polychloroprene, chlorinated olefin polymer, oxidized ethylene-propylene copolymer, etc.). Among the above-mentioned hydrocarbon groups, preferred is a linear or branched alkyl group, preferably 6 to 7,000 carbon atoms, more preferably 8 to 225 carbon atoms.
The hydrocarbon group can be mentioned.

Specific examples of preferred alkyl groups include hexyl group, 1-methylhexyl group, 2,3,5-trimethylheptyl group, octyl group, 3-ethyloctyl group,
4-ethyl-5-methyloctyl group, nonyl group, decyl group, dodecyl group, 2-methyl-4-ethyldodecyl group,
A straight-chain or branched alkyl group such as hexadecyl group, octadecyl group, eicosyl group, docosyl group, tetracontyl group, or a derivative derived from an olefin polymer (eg, polyethylene, polypropylene, polyisobutylene, ethylene-propylene copolymer, etc.) Examples thereof include a chain or branched alkyl group. When a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative having a low viscosity is desired, the hydrocarbon group is preferably a linear hydrocarbon group. In the general formula (I), p and m are each an integer of 1 to 3, and n is 1
Is an integer of ~ 4. The boron-containing substituted hydroxyaromatic carboxylic acid ester derivative of the present invention having such a structure is useful as a detergent excellent in high-temperature stability (high-temperature detergent) that replaces the conventional metal-type detergent, and will be used in severe exhaust gas in the future. It is suitable for use as an additive for engine oil lubricants that comply with gas regulations.

Next, the boron-containing substituted hydroxyaromatic carboxylic acid ester derivative of the present invention has the general formula (I) according to the method of the present invention.

[0015]

[Chemical 6]

[Wherein Ar ¹ , R ¹ , p, m and n are
Same as above. ] At least one of the substituted hydroxyaromatic carboxylic acids represented by and at least one of the hydroxy compounds are reacted in the absence of a catalyst or in the presence of a catalyst to obtain an ester derivative, which is then reacted with a boron-containing compound and / or Alternatively, it can be produced by mixing. Preferred examples of the hydroxy compound include aliphatic or aromatic monohydric or polyhydric alcohols and mixtures thereof. Further, these alcohols may be primary alcohols or secondary alcohols. Further, the aliphatic alcohol or aromatic alcohol may be, for example, a non-hydrocarbon group such as a nitro group, an amino group, a halo group or a hydroxyl group as long as the organic group portion retains the property of being substantially a hydrocarbon group. , A lower alkoxy group, a lower alkylmercapto group,
Oxo group, thio group, interrupting group (for example, -NH-, -O
-, -S-) and the like.

Examples of monohydric aliphatic alcohols include hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, oleyl alcohol, linolenyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol. , Stearyl alcohol, behenyl alcohol, etc., a relatively higher-grade synthetic monohydric alcohol (eg, 2-ethylhexyl alcohol) produced by the oxo process, a type formed by aldol condensation, and α-catalyzed by an organoaluminum catalyst. Relatively higher synthetic monohydric alcohols of the type formed by the oligomerization of olefins (eg ethylene, propylene, etc.) and their subsequent oxidation, as well as cyclopentanol, cyclohexa Lumpur, such as cycloalkyl alcohols such as cyclododecanol the like.

Examples of the polyhydric aliphatic alcohol include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, 2-ethyl-1,3.
-Trimethylene glycol, neopentyl glycol,
Diethylene glycol, relatively high-grade polyethylene glycol, tripropylene glycol, dibutylene glycol, dipentylene glycol, dihexylene glycol, diheptylene glycol, and further the general formula HOC
H ₂ (CHOH) _n CH ₂ OH (eg glycerol,
Examples thereof include sugars such as sorbitol and mannitol, pentaerythritol and oligomers thereof (for example, dipentaerythritol and tripentaerythritol), and methylol polyols such as trimethylolethane and trimethylolpropane.

Preferred hydroxy compounds include, for example, general formula (II) (OH) _q -Ar ^2- (R ² ) _k (II) [wherein Ar ² is a polyvalent aromatic nucleus, R ² Is an organic group, q is an integer of 1 to 3, and k is an integer of 1 to 4. ] The aromatic alcohol represented by these can be mentioned. In the general formula (II), Ar ² and R ² are the same as those described for Ar ¹ and R ¹ in the general formula (I). q is an integer of 1 to 3, and k is an integer of 1 to 4. If a low viscosity boron-containing substituted hydroxyaromatic carboxylic acid ester derivative is desired, it is desirable that R ^{2 be} a linear hydrocarbon group.

In the method of the present invention, first, at least one substituted hydroxyaromatic carboxylic acid represented by the general formula (I) is reacted with at least one hydroxy compound to form an ester derivative. In this reaction, the molar ratio of the substituted hydroxyaromatic carboxylic acid to the hydroxy compound is 1: 0.01-
The range of 1: 3, preferably 1: 0.2 to 1: 1.5 is desirable, and the reaction temperature is usually selected in the range of 100 to 300 ° C, preferably 150 to 250 ° C. This reaction may be carried out without a catalyst or may be carried out in the presence of an acid or alkali catalyst. When carrying out this reaction, a solvent,
For example, hydrocarbon oil or the like can be used. The substituted hydroxyaromatic carboxylic acid can be produced, for example, by hydrolyzing a product obtained by a known Kolbe-Schmidt reaction from an alkali metal salt of phenols and carbon dioxide.

Next, by reacting and / or mixing at least one kind of the ester derivative thus obtained and at least one kind of the boron-containing compound, the boron-containing substituted hydroxyaromatic carboxylic acid ester derivative of the present invention. To manufacture. Examples of the boron-containing compound used in this case include boric acid such as orthoboric acid, metaboric acid, and tetraboric acid, diboron trioxide, halogenated boric acid, boric acid amide, and boric acid esters. These boron-containing compounds may be used alone or in combination of two or more. The molar ratio of the ester derivative to the boron-containing compound is 1: 0.05 to 1: 2, preferably
The range of 1: 0.1 to 1: 1 is desirable. Further, when the reaction is carried out, the reaction temperature is usually selected in the range of 80 to 250 ° C, preferably 100 to 200 ° C. In carrying out this reaction, a solvent such as a hydrocarbon oil can be used. The boron-containing substituted hydroxyaromatic carboxylic acid ester derivative of the present invention, after the ester derivative is obtained from the substituted hydroxyaromatic carboxylic acid represented by the general formula (I) and the hydroxy compound as in the above method, In addition to the method of adding a boron-containing compound,
For example, it can also be produced by a method of reacting and / or mixing a substituted hydroxyaromatic carboxylic acid represented by the general formula (I), a hydroxy compound and a boron-containing compound at the same time in the absence of a catalyst or in the presence of a catalyst. . At this time, the kind and mixing ratio of each component, the reaction conditions and the like may be selected according to the method described above.

Next, the additive composition for lubricants of the present invention is
A composition comprising (a) a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative obtained as described above, and (b) an ashless type dispersant, which has high temperature stability (high temperature detergency). It is used as an ashless detergent dispersant that is excellent and has the effect of dispersing fine particles. The ashless dispersant of the component (b) is not particularly limited, and conventionally known ones, for example, carboxylic acid imide type, carboxylic acid ester type, hydroxybenzylamine type, etc. may be used alone or in combination. it can. The preferred acid site of the carboxylic acid imide type and the carboxylic acid ester type is succinic acid, and a carboxylic acid having a hydrocarbon group having a molecular weight of 200 or more in the molecular structure is suitable. The hydrocarbon group is an alkyl group or an alkenyl group, and may have a non-hydrocarbon substituent and a hetero atom in the chain or ring. The above-mentioned carboxylic acid imide system and carboxylic acid ester system are reaction products of a carboxylic acid derivative and (1) an organic nitrogen compound having at least one —NH— group, for example, amine, urea, hydrazine,
(2) Reaction products with hydroxy compounds such as phenols and alcohols. In addition, the reaction product of the carboxylic acid derivative and the reactive metal or the reactive metal compound may be contained in the range not affecting. In addition, these post-treatment products are also useful. Examples of post-treatment agents include:
Sulfur and sulfur compounds, urea, thiourea, guanidine, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds, etc. (these carboxylic acid imides and carboxylic acids For details of ester type, see Japanese Patent Publication No. 3-60876.
No. publication).

On the other hand, the hydroxybenzylamine system includes hydrocarbon-substituted phenols such as sulfur-bridged phenol and methylene-bridged phenol, formaldehyde,
Nitrogen compounds having at least two -NH- groups, such as reaction products with polyamines. In the additive composition for lubricants of the present invention, the additive for lubricants comprising the boron-containing substituted hydroxyaromatic carboxylic acid ester derivative as the component (a) and the ashless dispersant as the component (b) are used. The blending ratio with is 10:90 to 99: 1 by weight,
It is preferably in the range of 15:85 to 75:25.

In the lubricating oil composition of the present invention, (a) the above-mentioned boron-containing substituted hydroxyaromatic carboxylic acid ester derivative, and (b) the above ashless dispersant are added to a lubricating base oil. It is a thing. The component (a) and (b)
The components are preferably blended in a proportion of 1 to 30% by weight, preferably 2 to 20% by weight, based on the total amount of the lubricating oil composition, with respect to the base oil. As the base oil, mineral oil or synthetic oil is used. The mineral oil may be any of the fractions such as paraffinic mineral oil, naphthenic mineral oil and aromatic mineral oil, and may be used after undergoing any refining method such as solvent refining, hydrorefining or hydrocracking. As the synthetic oil, polyphenyl ether, alkylbenzene, alkylnaphthalene, ester-based, glycol-based, or polyolefin-based synthetic oil can be used. As a lubricating oil fraction, the kinematic viscosity (100 ° C) is usually 1 to 50c.
St, preferably in the range of 3 to 10 cSt.

As the ester synthetic oil, an ester of a monobasic acid or a dibasic acid and an alcohol, for example, a dibasic acid having 6 to 16 carbon atoms and a linear or branched alcohol having 5 to 20 carbon atoms is reacted. It is possible to use a synthetic oil composed of the thus obtained ester. Particularly preferred are adipic acid ester, sebacic acid ester, azelaic acid ester, trimethylolpropane ester, trimethylolethane ester, pentaerythritol ester, neopentyl glycol ester and the like. As the polyolefin-based synthetic oil, liquid refined products obtained by low polymerization or copolymerization of lower olefins such as ethylene, propylene, butylene, octene, decene and dodecene, mixtures thereof and hydrogenated refined products thereof are suitable. Further, a complex ester composed of a dibasic acid, glycol, a monobasic acid or the like, or an α-olefin / dibasic acid copolymer ester can also be used.

In the lubricating oil composition of the present invention, as the base oil, one kind of the above-mentioned mineral oil may be used, two or more kinds thereof may be used in combination, and one kind of the synthetic oil may be used, You may use it in combination of 2 or more type. Further, one or more of the mineral oil and one or more of the synthetic oil may be used in combination. In the lubricating oil composition of the present invention, in addition to the above-mentioned additive composition for lubricants, various additive components conventionally used in conventional lubricating oil compositions as desired, within a range not impairing the object of the present invention, For example, an antioxidant, a rust preventive, an antifoaming agent, a viscosity index improver, a pour point depressant, an antiwear agent, an antiemulsifier, a metallic detergent and the like can be added in an appropriate amount. The lubricating oil composition of the present invention can be used, for example, as a lubricating oil for internal combustion engines, gear oils, bearing oils, transmission fluids, shock absorber oils, industrial lubricating oils, etc., but especially for internal combustion engines (for diesel engines and methanol engines). Useful as a lubricating oil composition.

[0027]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Reference Example 1 In a 2 liter autoclave, polybutene (Mw: 9
87) 1100 g, cetyl bromide 6.4 g (0.021 mol)
And 115 g (1.2 mol) of maleic anhydride were added, the atmosphere was replaced with nitrogen, and the mixture was reacted at 240 ° C. for 5 hours. The temperature was lowered to 215 ° C, unreacted maleic anhydride and cetyl bromide were distilled off under reduced pressure, the temperature was lowered to 140 ° C, and the mixture was filtered. The yield of the obtained polybutenyl succinic anhydride was 1099 g. In a 2 liter separable flask, 500 g of the obtained polybutenyl succinic anhydride and tetraethylene pentamine (TEP
A: manufactured by Tosoh Corporation) 64 g (0.34 mol) and mineral oil 3
00 g was added, and the mixture was reacted at 150 ° C. for 2 hours under a nitrogen stream. The temperature was raised to 200 ° C., unreacted TEPA and generated water were distilled off under reduced pressure, the temperature was lowered to 140 ° C., and filtration was performed. The yield of the obtained polybutenyl succinimide was 784 g.

Reference Example 2 Reference Example 1 was placed in a 500 ml separable flask.
240 g of the polybutenyl succinimide obtained in the above and 28 g of boric acid were added, and the mixture was reacted at 150 ° C. for 4 hours under a nitrogen stream. The produced water was distilled off under reduced pressure at 150 ° C, the temperature was lowered to 140 ° C, and the mixture was filtered. The yield of the obtained borated polybutenyl succinimide was 231 g.

Reference Example 3 Hexadecylphenol 319 was placed in a 1 liter flask.
g (1 mol) and xylene 200 g were added and stirred to be uniform. The mixture was heated to 70 ° C., 80 g of 48 wt% NaOH aqueous solution was added, and xylene was refluxed for 2 hours under a nitrogen stream to distill off water. The reaction solution was transferred to a 1 liter autoclave and pressurized with carbon dioxide to 10 kg / cm ² G to obtain 1
The reaction was carried out at 55 ° C for 1 hour. The temperature was lowered to 80 ° C., the mixture was transferred to a 2 liter flask, 120 g of xylene was added, and the mixture was stirred so as to be uniform. Further, 250 g of 20 wt% sulfuric acid was added over 30 minutes and the reaction was carried out for 1 hour. The reaction solution was washed with water, phase-separated, and then filtered to remove xylene. The yield of the obtained reaction product was 312 g.

Reference Example 4 The procedure of Reference Example 3 was repeated except that 262 g (1 mol) of dodecylphenol was used instead of hexadecylphenol. The yield of the obtained reaction product was 260 g. Reference Example 5 Reference Example 3 was carried out in the same manner as Reference Example 3 except that 262 g of a mixed alkylphenol having 11 to 15 carbon atoms was used instead of hexadecylphenol. The yield of the obtained reaction product was 257 g.

Example 1 300 g of the reaction product obtained in Reference Example 3 and 100 g of hexadecylphenol were placed in a 500 ml flask.
, And react under nitrogen stream at 250 ° C for 5 hours,
The produced water and hexadecylphenol were distilled off under reduced pressure at ℃.
The yield of the obtained reaction product was 195 g. This product is a mixture of compounds represented by the following formulas (III) and (IV) according to the results of electrolytic desorption / ionization mass spectrometry, proton nuclear magnetic resonance spectroscopy, and carbon-13 nuclear magnetic resonance spectroscopy. Was confirmed. From the result of liquid chromatographic analysis (detector: differential refractometer), the ratio of the compounds represented by the formulas (III) and (IV) was 78% for the compound of the formula (III).
The area% and the compound of formula (IV) were confirmed to be 22 area%. Formula (II) collected by liquid chromatography
Electrolytic deionization of the compound [(hexadecylsalicylic acid) hexadecylphenyl ester] represented by I) and the compound [(hexadecylhydroxybenzenecarboxylic acid) bis (hexadecylphenyl) ester] represented by the formula (IV) The results of mass spectrometry, proton nuclear magnetic resonance spectroscopy and carbon-13 nuclear magnetic resonance spectroscopy are shown in FIGS. 1, 2 and 3 and FIGS. 4, 5 and 6, respectively.

[0032]

[Chemical 7]

Next, in a 300 ml flask,
166 g (0.25 mol) of the above reaction product and 7.7 g of boric acid
(0.125 mol) was added, and the mixture was reacted under a nitrogen stream at 150 ° C. for 4 hours, then the produced water was distilled off under reduced pressure, and pressure filtration was performed.
The yield of the obtained boron-containing reaction product was 128 g, and the boron content was 0.75% by weight. The result of infrared spectroscopy of this boron-containing reaction product is shown in FIG.

Example 2 In the same manner as in Example 1 except that 69 g of nonylphenol was used instead of hexadecylphenol, the compound of formula (V) was used.

[0035]

Embedded image

After obtaining a reaction product containing a compound represented by the formula (where x is a real number of 1 to 2), 110 g of a boron-containing reaction product was obtained. The boron content of this product is 0.8
It was 8% by weight.

Example 3 In Example 1, 250 g of the reaction product obtained in Reference Example 4 was used in place of the reaction product obtained in Reference Example 3, and dodecylphenol 82 was used in place of hexadecylphenol.
In the same manner as in Example 1 except that g was used, the formula (VI)

[0038]

[Chemical 9]

After obtaining a reaction product containing a compound represented by the formula (where x is the same as above), 107 g of a boron-containing reaction product was obtained. The boron content of this product is 0.89
% By weight.

Example 4 In Example 1, 250 g of the reaction product obtained in Reference Example 5 was mixed in place of the reaction product obtained in Reference Example 3 with 11 to 15 carbon atoms in place of hexadecylphenol. In the same manner as in Example 1 except that 82 g of alkylphenol was used, the compound of formula (VII)

[0041]

[Chemical 10]

[Wherein R is the number of carbons 11, 12, 13, 1]
4,15 alkyl groups are shown, and x is the same as above. ] After obtaining a reaction product containing a compound represented by
109 g of a boron-containing reaction product was obtained. The boron content of this product was 0.91% by weight.

Example 5 A 500 ml flask was charged with 306 g of the reaction product obtained in Reference Example 4 and 61 g of ethylene glycol,
The reaction was carried out at 220 ° C for 5 hours under a nitrogen stream, and the produced water and ethylene glycol were distilled off under reduced pressure at 220 ° C. The yield of the obtained reaction product was 168 g. Also, this is an expression
(VIII)

[0044]

[Chemical 11]

It was a mixture containing the compound represented by Next, in a 300 ml flask, 160 g (0.25 mol) of the above reaction product and 11.6 g (0.2
(188 mol) was added, and the mixture was reacted at 150 ° C. for 4 hours under a nitrogen stream, then, the produced water was distilled off under reduced pressure, and pressure filtration was performed. The yield of the obtained boron-containing reaction product was 102 g, and the boron content was 1.15% by weight.

Example 6 In Example 1, 153 g of the reaction product obtained in Reference Example 4 was used in place of the reaction product obtained in Reference Example 3, and tridecyl alcohol 1 was used in place of hexadecylphenol.
Example 1 was repeated except that 50 g was used.
(IX)

[0047]

[Chemical 12]

After obtaining a reaction product containing a compound represented by the formula (where x is the same as above), 110 g of a boron-containing reaction product was obtained. The boron content of this product is 0.86
% By weight.

Examples 7 to 12 Preparation of additive composition for lubricant (ashless type detergent dispersant) 75% by weight of ashless type dispersant (polybutenyl succinimide) obtained in Reference Example 1 was used. 25% by weight of the boron-containing reaction product obtained in Examples 1 to 6 was blended to prepare a lubricant additive composition.

Examples 13 and 14 Preparation of additive composition for lubricant (ashless detergent dispersant) 75% by weight of ashless dispersant (borated polybutenyl succinimide) obtained in Reference Example 2 And 25% by weight of the boron-containing reaction product obtained in Examples 1 and 2 were blended to prepare an additive composition for a lubricant.

Examples 15-22 Preparation of Lubricating Oil Compositions 10% by weight of the additive composition for lubricants of Examples 7-14 (boron-containing reaction) was added to mineral oil of 500 neutral fraction, based on the total amount of the lubricating oil composition. Product 2.5% by weight, ashless dispersant 7.
5% by weight) to prepare a lubricating oil composition. The performance of this lubricating oil composition was evaluated by the following hot tube test. The results are shown in Table 1.

<Hot tube test conditions> In a glass tube having an inner diameter of 2 mm, the test oil was 0.3 ml / hr and air was 10
The flow of milliliter / min was continued for 16 hours while maintaining the temperature of the glass tube at 310 ° C. The lacquer attached to the glass tube and the color sample were compared, and a rating of 10 points for transparent and a score of 0 for black were given, and the weight of the lacquer attached to the glass tube was measured. The higher the score,
In addition, the smaller the lacquer weight, the higher the performance.

Comparative Example 1 Dodecyl salicylic acid 2 obtained by further purifying the reaction product obtained in Reference Example 4 in a 500 ml flask.
Add 53g and 34g cresol, 250 ℃ under nitrogen stream
The resulting water and cresol were distilled off under reduced pressure at 250 ° C. to give a compound of formula (X)

[0054]

[Chemical 13]

Reaction product 151 containing compound represented by
g was obtained. Next, mineral oil of 500 neutral fraction was blended with 2.5% by weight of the above reaction product and 7.5% by weight of the ashless dispersant of Reference Example 2 based on the total amount of the lubricating oil composition. The product was prepared and its performance was evaluated by a hot tube test. The results are shown in Table 1.

Comparative Example 2 In the same manner as in Comparative Example 1, except that 114 g of salicylic acid was used instead of dodecylsalicylic acid and 115 g of hexadecylphenol was used instead of cresol in Comparative Example 1, the compound of formula (XI) was used.

[0057]

Embedded image

Reaction product 121 containing a compound represented by:
g was obtained. Next, using this reaction product, a lubricating oil composition was prepared in the same manner as in Comparative Example 1, and its performance was evaluated by a hot tube test. The results are shown in Table 1.

Comparative Example 3 A lubricating oil composition was prepared in the same manner as in Comparative Example 1 using a substituted hydroxyaromatic carboxylic acid ester derivative represented by the following formula (XII), and its performance was evaluated by a hot tube test. evaluated. The results are shown in Table 1.

[0060]

[Chemical 15]

Comparative Example 4 A lubricating oil composition was prepared in the same manner as in Comparative Example 1 using a substituted hydroxyaromatic carboxylic acid ester derivative represented by the following formula (XIII), and its performance was evaluated by a hot tube test. evaluated. The results are shown in Table 1.

[0062]

Embedded image

Comparative Example 5 In mineral oil of 500 neutral fraction, 2.5% by weight of overbased calcium phenate, which is a metal type detergent, and ashless type dispersant 7 of Reference Example 7, based on the total amount of the lubricating oil composition. A lubricating oil composition was prepared by blending 0.5% by weight, and its performance was evaluated by a hot tube test. The results are shown in Table 1.

Comparative Example 6 In a mineral oil of 500 neutral fraction, 2.5% by weight of overbased calcium salicylate which is a metal type detergent and 7.5% of an ashless type dispersant of Reference Example 2 based on the total amount of the lubricating oil composition. A lubricating oil composition was prepared by blending the composition in a weight percentage, and its performance was evaluated by a hot tube test. The results are shown in Table 1.

[0065]

[Table 1]

[0066]

[Table 2]

As can be seen from Table 1, Examples 15 to 15 using the lubricant additive composition comprising the boron-containing reaction product lubricant additive of the present invention and the ashless dispersant were used.
The lubricating oil composition of No. 22 is superior in the hot tube test to the lubricating oil compositions using the substituted hydroxyaromatic carboxylic acid ester derivatives of Comparative Examples 1 to 4 and the metal type detergents of Comparative Examples 5 and 6. The results were shown and excellent high temperature stability (high temperature detergency) was shown.

[0068]

INDUSTRIAL APPLICABILITY The boron-containing substituted hydroxyaromatic carboxylic acid ester derivative of the present invention is useful as an ashless-type detergent excellent in high-temperature stability (high-temperature detergency) in place of conventional metal-type detergents. A lubricant additive composition containing a lubricant additive comprising the ester derivative and an ashless dispersant has excellent high temperature stability (high temperature detergency) and has fine particle dispersibility. It is useful as an excellent ashless detergent dispersant for lubricating oils. Therefore, the lubricating oil composition of the present invention can be made ashless, and is particularly useful as a diesel engine oil and a methanol engine oil that comply with future emission regulations.

[Brief description of drawings]

FIG. 1 is a chart showing the results of electrolytic desorption / ionization mass spectrometry of (hexadecylsalicylic acid) hexadecylphenyl ester represented by the general formula (III) obtained in Example 1.

FIG. 2 is a chart showing the results of proton nuclear magnetic resonance spectroscopy of (hexadecylsalicylic acid) hexadecylphenyl ester represented by the general formula (III) obtained in Example 1.

3 is a chart showing carbon-13 nuclear magnetic resonance spectroscopy results of (hexadecylsalicylic acid) hexadecylphenyl ester represented by the general formula (III) obtained in Example 1. FIG.

FIG. 4 is a chart showing the results of electrolytic desorption / ionization mass spectrometry of the (hexadecylhydroxybenzenecarboxylic acid) bis (hexadecylphenyl) ester represented by the general formula (IV) obtained in Example 1.

5 is a chart showing the results of proton nuclear magnetic resonance spectroscopy of the (hexadecylhydroxybenzenecarboxylic acid) bis (hexadecylphenyl) ester represented by the general formula (IV) obtained in Example 1. FIG.

FIG. 6 is a chart showing carbon-13 nuclear magnetic resonance spectroscopy results of (hexadecylhydroxybenzenecarboxylic acid) bis (hexadecylphenyl) ester represented by the general formula (IV) obtained in Example 1.

7 is a chart showing an infrared spectroscopic result of the boron-containing reaction product obtained in Example 1. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C10M 125: 26 139: 00) A C10N 10:06 30:04 30:06 40:25 60:14 (72) Inventor Minoue Fuyasu 1280 Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (10)

[Claims] 1. A compound of the general formula (I) [In the formula, Ar ¹ is a polyvalent aromatic nucleus, R ¹ is an organic group, and p is 1
To 3 integer, n represents an integer of 1 to 4, m is an integer of 1 to 3, when R ¹ is more than one, a plurality of R ¹ may be the same or different. ] A boron-containing substituted hydroxyaromatic carboxylic acid ester derivative comprising a reaction product and / or a mixture of an ester derivative obtained from a substituted hydroxyaromatic carboxylic acid and a hydroxy compound represented by 2. The boron-containing substituted hydroxyaromatic carboxylic acid ester derivative according to claim ¹ , wherein Ar ¹ is a benzene or naphthalene residue and R ¹ is a hydrocarbon group in the general formula (I). 3. The boron-containing substituted hydroxyaromatic carboxylic acid ester derivative according to claim 1, wherein the hydroxy compound is an aliphatic or aromatic monohydric or polyhydric alcohol or a mixture thereof. 4. The boron-containing substituted hydroxyaromatic carboxylic acid according to claim 1, wherein the boron-containing compound is at least one selected from boric acid, diboron trioxide, halogenated boric acid, boric acid amide and boric acid esters. Ester derivative. 5. A compound represented by the general formula (I): [Wherein Ar ¹ is a polyvalent aromatic nucleus, R ¹ is an organic group, and p is 1
To 3 integer, n represents an integer of 1 to 4, m is an integer of 1 to 3, when R ¹ is more than one, a plurality of R ¹ may be the same or different. ] At least one type of substituted hydroxyaromatic carboxylic acid represented by and at least one type of hydroxy compound are reacted in the absence of a catalyst or in the presence of a catalyst to obtain an ester derivative, which is then reacted with a boron-containing compound and / or Alternatively, the method for producing a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative according to any one of claims 1 to 4, characterized in that it is mixed. 6. A compound represented by the general formula (I): [Wherein Ar ¹ is a polyvalent aromatic nucleus, R ¹ is an organic group, and p is 1
To 3 integer, n represents an integer of 1 to 4, m is an integer of 1 to 3, when R ¹ is more than one, a plurality of R ¹ may be the same or different. ] At least one of the substituted hydroxyaromatic carboxylic acid represented by the above formula, at least one of the hydroxy compound and the boron-containing compound are reacted and / or mixed in the presence of no catalyst or a catalyst. 5. The method for producing a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative according to any one of 4 to 4. 7. A lubricant additive comprising the boron-containing substituted hydroxyaromatic carboxylic acid ester derivative according to any one of claims 1 to 4. 8. A lubricant additive composition comprising (a) a boron-containing substituted hydroxyaromatic carboxylic acid ester derivative according to any one of claims 1 to 4 and (b) an ashless dispersant. Stuff. 9. At least claim 1 for a lubricating base oil
A lubricating oil composition comprising the boron-containing substituted hydroxyaromatic carboxylic acid ester derivative according to any one of claims 1 to 4. 10. The lubricating oil composition according to claim 9, which is a lubricating oil composition for an internal combustion engine.