JPH1121578A - Overbased sulfided alkaline earth metal phenate concentrate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an overbased sulfided alkaline earth metal phenate concentrate having a high base value, a viscosity (at 100 deg.C) of 1,000 cSt or above and excellent hydrolysis stability and oil solubility and a process for producing an overbased sulfided alkaline earth metal phenate concentrate having a base value and excellent hydrolysis stability and oil solubility. SOLUTION: An alkaline earth metal reagent (e.g. an alkaline earth metal oxide, an alkaline earth metal hydroxide or a mixture thereof), 1-100 equivalents, per mol of the reagent, of a phenol and sulfur or these and water are fed into a reactor, and a dihydric alcohol is added to the charge while the pressure inside the reactor is in the range of 10-250 kPa.g and reacted. Next, excess dihydric alcohol and at least excess water are separated by distillation, and the obtained distillation bottom is treated with carbon dioxide in the presence of 0.3-0.8 mol, per mol of the reagent, of water, and 0.001-0.3 mol, per mol of the reagent, of a fatty acid is added to the system at the latest before the treatment with carbon dioxide, and excess phenol is separated by distillation from the product of treatment with carbon dioxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a novel overbased alkaline earth metal phenate concentrate and a novel overbased alkaline sulfide useful as a detergent or dispersant for lubricating oil or fuel oil or as an alkaline detergent. The present invention relates to a method for producing a metal-like phenate concentrate.

[0002]

2. Description of the Related Art Alkaline earth metal phenates are main additives used in addition to lubricating oils for internal combustion engines, and mainly neutralize acidic substances generated by the combustion of fuel in internal combustion engines to neutralize metal. It is used for the purpose of suppressing corrosion and deterioration of lubricating oil, and at the same time, promoting the dispersal of sludge and its precursors in oil to suppress sticking and wear of engine parts. For this purpose, heat resistance and oil solubility are important, and sulfurization of alkylphenol is a known technique to improve the heat resistance and oil solubility. The base number is an index of the acid neutralizing ability, and the larger the value, the higher the acid neutralizing ability of the additive. Are referred to as "overbased" alkaline earth metal phenates. Improvement of the base number is an important research and development issue from the viewpoint of improving the economics of additives, and many attempts have been reported so far. For example, Tables 1 to 501399, Tables 1 to 5
In No. 01400, 2 to 40% by mass of carboxylic acids based on the total mass is contained in the phenate, and the metal addition reaction is performed in 1%.
Base number 300 mg KO
It has succeeded in obtaining a product exceeding H / g and having a viscosity of 1000 cSt or less at 100 ° C. However, in these methods, it was necessary to repeat the metal addition reaction two or more times in order to obtain a product satisfying the two favorable characteristics of high base number and low viscosity at the same time. Also, Japanese Patent Application Nos. 4-75252 (Japanese Patent Application Laid-Open No. 5-238976), Japanese Patent Application No. 4-238988 (Japanese Patent Application Laid-Open No. 6-65192), and Japanese Patent Application No.
According to the method of JP-A-355682 (JP-A-6-184581), it is possible to improve the base number of an overbased sulfurized alkaline earth metal phenate, but it has disadvantages such as a dark hue and poor oil solubility. I was In addition, Tokio Table 1
Pp. 501399 and pp. 501501400 suggest that the addition of a fatty acid improves the base number. However, since the metal addition reaction needs to be carried out a plurality of times, the number of steps increases and the production cost increases. Had.

The inventors of the present invention have proposed a method for producing an overbased sulfurized alkaline earth metal phenate using an excess amount of alkylphenol relative to an alkaline earth metal reagent. Water that should be removed to the outside of the system before carbon dioxide treatment as a factor that reduces the stability of carbon dioxide is specified after distilling excess dihydric alcohol and water of reaction from the intermediate product after completion of the metal sulfide addition reaction. And a method of adding a specific amount of a fatty acid before the carbon dioxide treatment. A single metal addition reaction is performed, and a base number of 250 to 400 mg KOH / g and 100 ° C. Viscosity 1
We have succeeded in obtaining products of 000 cSt or less. However, it was still difficult to obtain a product having a base number greater than 400 mg KOH / g and a viscosity at 100 ° C. of 1000 cSt or less.

[0004] On the other hand, such products are often used as lubricating oil additives for marine engines, and therefore, are required to have stability against moisture and water vapor. Generally, a commercially available alkaline earth metal phenate type additive is used as an additive having high hydrolysis stability, but is diluted to a state of use as a lubricating oil (base number: 30 mg KOH / g) and subjected to ASTM D26.
When the test was carried out without using a copper catalyst in the hydrolysis stability test method specified in 19-88, the base number retention after 24 hours was about 30%. As described above, conventional alkaline earth metal phenates having a high base value and excellent hydrolysis stability have not been known.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to concentrate an overbased sulfurized alkaline earth metal phenate having a high base number, a viscosity of not more than 1000 cSt at 100 ° C., and having excellent hydrolysis stability and oil solubility. And a method for producing an overbased sulfurized alkaline earth metal phenate concentrate having a high base value and excellent hydrolysis stability and oil solubility.

[0006]

The present inventors have made various studies to solve these problems, and as a result, surprisingly, the amounts of the reaction raw materials and the reactants are set within a specific range. It was found that the order of addition of the dihydric alcohol to the reactor and the reaction pressure in the step of adding the dihydric alcohol to the reactor greatly affected the base number and the hydrolysis stability of the product. Was completed.

That is, the present invention relates to an alkaline earth metal oxide, an alkaline earth metal hydroxide or a mixture thereof (hereinafter referred to as an alkaline earth metal reagent), in an amount of 1 to 100 equivalents per mole of the alkaline earth metal reagent. Phenols and sulfur, or these and water, are charged into a reactor, and a dihydric alcohol is added to the charged mixture at a pressure in the reactor of 10 to 10.
The reaction mixture was added at 250 kPa-G and allowed to react, and the bottom of the distillation column obtained by distilling off the excess amount of dihydric alcohol and at least the excess amount of water was added in an amount of 0.3 to 0 per mole of the alkaline earth metal reagent. Treated with carbon dioxide in the presence of 0.8 moles of water and 0.001 mole per mole of alkaline earth metal reagent.
Concentrating an overbased sulfurized alkaline earth metal phenate, characterized in that 1 to 0.3 mol of fatty acids is present at the latest before carbon dioxide treatment, and further, excess phenols in the carbon dioxide treated material are distilled off. It is intended to provide a method of manufacturing a product.

In the present invention, the base number is from 350 to 500.
mgKOH / g and a viscosity at 100 ° C. of 100
0 cSt or less, and the fatty acids are 1 to 20% by mass of the total amount.
And a base number of 30 m with a lubricating base oil of SAE No. 40
gKOH / g, ASTM without addition of copper catalyst
Hydrolysis is performed in the same manner as the hydrolysis stability test method of D2619-88, and the base number retention of the supernatant oil obtained by centrifuging the sample after 24 hours is 70% or more. An overbased sulfurized alkaline earth metal phenate concentrate is provided.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The phenols used in the present invention are, for example, those having 4 to 36 carbon atoms, preferably 8 carbon atoms.
Phenols having up to 32 hydrocarbon side chains, for example, alkyl groups, alkenyl groups, aralkyl groups and the like can be mentioned. Specific examples of these phenols include:
Butyl, amyl, octyl, nonyl, dodecyl, cetyl, ethylhexyl, hydrocarbon groups such as triacontyl,
Alternatively, phenols having a group derived from petroleum hydrocarbon such as liquid paraffin, wax, and olefin polymer (polyethylene, polypropylene, polybutene, etc.) may be mentioned. The phenols are used alone or in a mixture of two or more. Phenols are usually about 130
Desirable are those which can become liquid below ℃, preferably below about 120 ℃.

As the alkaline earth metal reagent, an oxide or hydroxide of an alkaline earth metal or a mixture thereof is usually used. For example, calcium, barium,
An oxide or hydroxide such as strontium and magnesium is used. The amount of the phenol used is 1 to 100 equivalents, preferably 1.6 to 10 equivalents, per 1 mol of the alkaline earth metal reagent. If the amount of the phenol relative to the alkaline earth metal reagent is too small, the intermediate will gel and the reaction will not proceed further, and the desired good product cannot be obtained. On the other hand, if the amount of the phenol relative to the alkaline earth metal reagent is too large, not only the yield of the product relative to the raw material decreases, but also the utility and time spent for recovering the phenol increase, which is economically disadvantageous.

Next, a dihydric alcohol having a relatively low boiling point, a low viscosity and a high reactivity is used. The dihydric alcohol preferably has 2 to 6 carbon atoms,
Particularly, ethylene glycol and propylene glycol are preferred. Dihydric alcohols help the conversion of phenols to oil-soluble substances by reaction with alkaline earth metal reagents,
It is stabilized and partly incorporated into the product phenate to form multi-equivalent phenate. In the method of the present invention, the metal addition reaction may be carried out with or without the addition of water having a reaction promoting effect. About 0.15 to 3.0 moles, especially about 0.3 moles per mole of metal reagent
~ 1.5 mol is preferred. When the reaction is carried out without adding water, the amount of the dihydric alcohol used is the alkaline earth metal reagent 1
About 1.0 to 3.0 moles, particularly about 1.2 to 3.0 moles per mole
2.0 moles is preferred. If the amount of the dihydric alcohol used is too small, the conversion of the reaction raw materials, particularly the product of the alkaline earth metal reagent, decreases.If the amount is too large, the metal addition reaction to the phenols proceeds smoothly, but the excess The time and utility for distilling off the dihydric alcohol is excessive.

[0012] The amount of sulfur used is
0.001 to 3.0 mol per mol, preferably 0.0
1 to 0.5 mol, more preferably 0.05 to 0.4 mol is used. As the amount of sulfur used decreases, the viscosity of the product decreases, but if it is too large, not only does it make it difficult to obtain a product with a high base number because the overbasing of the product decreases, but also the viscosity of the product becomes extremely high As a result, it is impossible to obtain the desired product having a low viscosity and a high base number.

When water is added to the reaction system in the metal addition reaction step of the alkaline earth metal reagent to the phenol in order to accelerate the reaction, not only distilled water but also canned water, industrial water, or metal addition reaction is used. The quality of the water is not particularly limited, and water in any state such as cold water, hot water, and steam can be used. The water used for promoting the metal addition reaction may be added to the reactor alone with water, or part or all of the water may be added as a mixture with other raw materials such as phenols and dihydric alcohols. The timing of adding water to the reactor is not particularly limited, and may be before or after all of the reaction materials other than water are mixed, but it is preferable to add the water within about one hour after mixing all of the reaction materials.

The amount of water used to promote the metal addition reaction into the reaction system is about 0.01 to 10 mol, preferably 0.1 to 10 mol, per mol of the alkaline earth metal reagent used.
2.0 moles. When the metal addition reaction is carried out by adding water from the outside to the reaction system, the reaction proceeds smoothly compared with the case where the reaction is carried out under the same conditions except that water is not added, and the reaction raw material, particularly the alkaline earth metal reagent Product conversion rate increases.
Therefore, if the amount of water added to the reaction system is too small, the product conversion of the alkaline earth metal reagent will decrease. Conversely, if the amount is too large, the advantage that the distillation step after the reaction is simplified is lost.

The addition of water co-existing during the carbon dioxide treatment involves reacting a raw material mixture comprising phenols, dihydric alcohols, alkaline earth metal reagents and sulfur, or water to this. After completion of the metal sulfide addition reaction, distillation is generally carried out after distilling off water and excess dihydric alcohol. There is no limitation on the quality and state of the water coexisting during the carbon dioxide treatment, similarly to the water used for promoting the metal addition. The amount of water in the reaction system is from 0.3 to 0.8 mol, preferably from 0.3 to 0.8 mol per mol of the alkaline earth metal reagent.
Adjust to 0.6 mole. If there is an excess of dihydric alcohol in the system, any water in the system such as water added at the time of distillation and water generated by the reaction is distilled off as a forerunner. After distilling off the excess, it is necessary to add a predetermined amount of water. On the other hand, if there is no excess dihydric alcohol in the system,
After the completion of the reaction, only the excess amount may be distilled off, leaving only a predetermined amount of water from the water present in the system, such as water added for promoting the reaction before the metal sulfide addition reaction or water generated during the reaction. However, when the remaining amount is unclear, it is preferable to add a predetermined amount of water after once distilling off the entire amount of water. The amount of water coexisting during carbon dioxide treatment increases the base number of the product as it increases, but if the amount is too large, the product is too hydrolyzed, causing a decrease in the base number and oil solubility, and if the amount is too small, The effect of improving the base number of the product cannot be sufficiently obtained.

The fatty acids to be present before the carbon dioxide treatment include, for example, those having 10 to 30 carbon atoms, preferably 16 carbon atoms.
To 24 fatty acids or salts thereof, and in the case of a salt, an alkaline earth metal salt is preferable. Examples of the alkaline earth metal include calcium, barium, magnesium, strontium and the like. Further, it is more preferable that the alkyl group has a straight chain. Specific examples of the fatty acids include, for example, decanoic acid, capric acid, lauric acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid, melicic acid and the like. is there. The fatty acids may be a mixture having a molecular weight distribution, and commercially available stearic acid having a stearic acid purity of about 60 to 70% can be used. The amount of the fatty acids is 0.001 to 0.3 mol, preferably 0.01 to 1 mol per mol of the alkaline earth metal reagent.
０．３0.3 mol, more preferably 0.05-0.3 mol, and most preferably 0.05-0.2 mol. If the amount of the fatty acid to be added is small, the base number of the phenate is not further improved, and the hue and the oil solubility are reduced. If it is too large, the base number will decrease.

In the present invention, a diluent or a solvent (hereinafter, referred to as a diluent) having an appropriate viscosity can be added to facilitate the handling of a reaction product, a reaction intermediate, or a product. For example, when recovering excess unreacted phenols from the reaction product after completion of the metal addition reaction step or carbon dioxide treatment by distillation, the reaction should be performed at a high boiling point and in the presence of a diluent having an appropriate viscosity. As a result, the bottom of the reaction column can be obtained in a desired liquid state. Note that, usually, a part of the diluent is also distilled off as the unreacted phenols are distilled off. Therefore, when repeatedly using the recovered phenols for the reaction, a diluent that does not directly affect the reaction is desirable. The reaction may be performed in the presence of a diluent. Examples of preferred diluents include petroleum fractions of appropriate viscosity, such as paraffinic, naphthenic, aromatic, or mixed base oils, for example, having a boiling point of about 220-550 ° C and a viscosity of about 2 at 100 ° C. 40cS
and a lubricating oil fraction of t. Other organic solvents also exhibit hydrophobicity and lipophilicity, and can be used as a diluent if they are harmless at the time of reaction or in the application of the product. For example, higher alcohols having 8 to 24 carbon atoms can be used.

In the method for producing an overbased alkaline earth metal phenate concentrate of the present invention, first, an alkaline earth metal reagent, phenols and sulfur, or water and these are charged into a reactor to form a charged mixture. I do. Also,
These may be charged with fatty acids together. The order of charging these reactants and reactants is not particularly limited and may be appropriately selected.

A dihydric alcohol can be added to the above mixture at a reactor pressure of 0 to 250 kPa-G. In order to obtain an overbased alkaline earth metal phenate concentrate having sufficient properties as referred to in the present invention, the concentration is preferably 10 to 250 kPa-G, particularly 20 to 23 kPa-G.
It is preferable to add the dihydric alcohol in a state of 0 kPa-G. By adding the dihydric alcohol to the above mixture in this pressure range, an overbased sulfurized alkaline earth metal phenate concentrate having a high base value and excellent hydrolysis stability can be produced. The addition of the dihydric alcohol is performed within the above-mentioned range of the pressure in the reactor, and it is preferable that at least 60% by mass or more, preferably 80% by mass or more of the total amount of the dihydric alcohol be performed within the above-mentioned range.

The temperature of the charged mixture when adding the dihydric alcohol is preferably 60 ° C. or higher, particularly preferably 120 ° C. or higher. The upper limit temperature of the charged mixture at the time of adding the dihydric alcohol is usually not higher than the boiling point of the charged mixture, but is preferably not higher than 200 ° C. It is preferable that the dihydric alcohol to be added is also heated to this temperature range in advance. The addition time of the dihydric alcohol is usually 20 to
90 minutes, preferably 30 to 60 minutes. After completion of the addition of the dihydric alcohol, the reaction is carried out at a temperature of about 60 to 200 ° C, preferably about 90 to 190 ° C. The pressure is not particularly limited, and is selected in the range of 0.01 to 21 atm · A, preferably 0.1 to 11 atm · A. This reaction is almost completed within a period of usually 1 to 9 hours.

In the carbon dioxide treatment step, after completion of the metal addition reaction, excess dihydric alcohols and at least excess water in the system are distilled off, and if fatty acids are not added first or fatty acids added first If the amount is small,
After adding fatty acids to a predetermined amount and allowing a predetermined amount of water to exist in the system, the reaction temperature is about 50 to 230 ° C.
Preferably, it is reacted with carbon dioxide under a temperature condition of 80 to 200 ° C. This reaction may be performed under reduced pressure, normal pressure, or increased pressure. Usually, a range of 0.01 to 51 atm.A, preferably 0.1 to 31 atm.A is employed. The reaction is generally carried out until the absorption of carbon dioxide is substantially stopped, and is for 20 minutes to 10 hours, usually 20 minutes to 3 hours.
The product obtained here may be further subjected to 0 to 20 atm. G, preferably 0 to 10 atm.
It is maintained at a pressure of G at about 100 to 230 ° C. for several minutes to several tens of hours. The carbon dioxide treatment further improves the performance of the product as a lubricating oil additive and a fuel oil additive, in particular, oil solubility and stability in engine oil when added to engine oil.

The timing of adding the fatty acids may be any time from the time when the raw materials are added to the reactor to before the carbon dioxide treatment step, but is preferably before the water added during the carbon dioxide treatment. An alkaline earth metal reagent and a dihydric alcohol or, if necessary, a fatty acid are added to the reaction product after the carbon dioxide treatment, and a metal addition reaction as described above is performed again. By repeating the above, further metal addition can be performed. It is preferable to recover some or most of the unreacted phenols in the reaction product after the carbon dioxide treatment from the viewpoint of economy and the like, and it is also possible to reuse the recovered phenols as a raw material. it can. If the unreacted phenols are distilled in the presence of a normal diluent such as a high-boiling mineral oil, the distillation residue can be obtained in a preferable liquid form. Insoluble substances in the distillation residue can be removed by an operation such as filtration or centrifugation before or after the recovery of phenols.

The overbased sulfurized alkaline earth metal phenate concentrate of the present invention has a base number of 350 to 500 mg KOH.
/ G, preferably 400 to 500 mg KOH / g, and the viscosity at 100 ° C. is 1000 cSt or less, preferably 100 to 1000 cSt, and the fatty acids are 1 to 20% by mass, preferably 5 to 15% by mass of the total amount.
It is. Here, the viscosity is a value measured by a Zeithooks cross-arm viscometer according to the test method of JIS K-2283. The overbased sulfurized alkaline earth metal phenate concentrate of the present invention is diluted to a base number of 30 mgKOH / g with a lubricating base oil of SAE viscosity standard No. 40, and 5% by mass of water and 93 ° C, 24% The base number retention after contacting for a time is 70% or more, preferably 80% or more, particularly preferably 90% or more. The overbased sulfurized alkaline earth metal phenate concentrate of the present invention has the above properties, and because of these properties, has a high base number and is excellent in hydrolytic stability and oil solubility.

The overbased sulfurized alkaline earth metal phenate concentrate of the present invention comprises a phenol, a dihydric alcohol, an alkaline earth metal oxide, an alkali metal hydroxide or a mixture thereof (hereinafter referred to as an alkaline earth metal reagent). That)
And sulfur, and particularly preferably obtained by the method for producing the overbased sulfurized alkaline earth metal phenate concentrate of the present invention. The overbased sulfurized alkaline earth metal phenate concentrate of the present invention can be used as a detergent or dispersant for lubricating or fuel oils or as an alkaline detergent. The applicable lubricating oil is not particularly limited,
For example, marine engine oil, power generation engine oil, hydraulic oil and the like can be mentioned. The applicable fuel oil is not particularly limited, and includes, for example, heavy oil for boilers. The amount of the overbased sulfurized alkaline earth metal phenate concentrate added to the lubricating oil or fuel oil is optional,
In a marine engine oil having a base number of about 30 mgKOH / g, it is usually 1 to 10% by mass, preferably 3 to 10% by mass.

[0025]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but these are merely examples and do not limit the present invention.

Example 1 A 1-liter autoclave equipped with a stirrer, a gas inlet tube and a thermometer was charged with 97.9% pure dodecylphenol 5
31.2 g (1.9 mol), 40.91 g (0.7 mol) of calcium oxide having a purity of 96.0% and sulfur 3.37
g (0.105 mol) (0.15 mol per mol of calcium oxide), 25.2 g (0.091 mol) of stearic acid
Mol) (0.13 mol per mol of calcium oxide) and stirred. The obtained suspension was heated to 125 ° C., and 65.21 g (1.05 mol) of ethylene glycol having a purity of 94.5% was added to the suspension at 125 ° C. and 60 kP.
The mixture was added under a-G pressure for 30 minutes, and stirred at 130 ° C. under a pressure of about 500 kPa-G for about 3.0 hours in a sealed condition. The distilled water, a part of unreacted ethylene glycol and a small amount of dodecylphenol were distilled off to obtain 791.9 g of a liquid distillation residue. The final distillation temperature at this time is 1
The temperature was 41 ° C (5 mmHg). Next, the distillation residue 7
After adding 5.67 g (0.32 mol) of water (0.45 mol per mol of calcium oxide) to 91.9 g, carbon dioxide was absorbed at a temperature of 150 ° C. from a reduced pressure state for 30 minutes. At this time, the supply rate of carbon dioxide to the autoclave was 0.315 l / min. Then, the temperature was raised to 178 ° C., and the pressure was increased again with carbon dioxide until the gauge pressure reached 5.0 atm.
I got To the reaction product was added 58.92 g of 150 neutral oil as a diluent. The reaction product was transferred to a 1-liter three-necked pear-shaped flask at 820.78 g and distilled under reduced pressure to distill off a small amount of ethylene glycol and most of unreacted dodecylphenol.
I got The final distillation temperature at that time is 225 ° C. (3 mmH
g). Thereafter, the distillation residue was diluted with a large amount of hexane, and 2.15 g of insoluble matter was removed by centrifugation. Then, hexane added in a large amount was removed by distillation to obtain 167.09 g of a final product. Properties of final product and S
AE standard No. 40 lubricating base oil with a base number of 30 mg KOH /
g ASTM D2619 without addition of copper catalyst
93 ° C. in the same operation as the hydrolysis stability test method of -88.
For hydrolysis. As a result of measuring the base number of the supernatant oil obtained by centrifuging the sample after 24 hours, the base number retention after hydrolysis was 95%.

Example 2 Example 2 was repeated except that the amount of water was 0.5 mol per mol of calcium oxide. The yield of the final product was 164.39 g. Properties of final product and SAE
Diluted to a basicity of 30 mg KOH / g with standard No. 40 lubricating base oil and tested without using a copper catalyst in the hydrolysis stability test method of ASTM D2619-88.
Table 1 shows the retention of the base number after the lapse of time.

Example 3 The addition amount of dodecylphenol was 3.0 mol per 1 ml of calcium oxide, the addition amount of water was 0.4 mol per 1 mol of calcium oxide, and the addition amount of sulfur was 0.2 mol per 1 mol of calcium oxide. The procedure was the same as in Example 1, except that the amount of stearic acid added was 0.1 mol per mol of calcium oxide. The yield of the final product was 163.68 g. Finished product properties and diluted to 30mgKOH / g basified with SAE No. 40 lubricating base oil, ASTM D2
Table 1 shows the retention of base number 24 hours after the test was performed without using a copper catalyst in the hydrolysis stability test method of No. 619-88.

Example 4 Reactor pressure at the time of adding ethylene glycol was 200 kPa
The same operation as in Example 1 was performed except that -G was used. The yield of the final product was 167.71 g. The properties of the final product,
30mgKOH basified with SAE No.40 lubricating base oil
/ G, and tested in the hydrolysis stability test method of ASTM D2619-88 without using a copper catalyst. The base number retention after 24 hours is shown in Table 1.

Example 5 Reactor pressure at the time of adding ethylene glycol was 200 kPa
The same operation as in Example 2 was performed except that -G was used. The yield of the final product was 166.01 g. The properties of the final product,
30mgKOH basified with SAE No.40 lubricating base oil
/ G, and tested in the hydrolysis stability test method of ASTM D2619-88 without using a copper catalyst. The base number retention after 24 hours is shown in Table 1.

Example 6 Instead of 0.91 mol of stearic acid, 0.46 mol of calcium stearate was used, and the calcium oxide was 1.4 mol.
The procedure was performed in the same manner as in Example 1 except that the amount was changed to 4 mol. The yield of the final product was 165.91 g. Properties of the final product and 30mg basified with SAE No. 40 lubricating base oil
Table 1 shows the base number retention rate after 24 hours of diluting to KOH / g and performing the test without using a copper catalyst in the hydrolysis stability test method of ASTM D2619-88.

Comparative Example 1 The reactor pressure at the time of adding ethylene glycol was 300 kPa
The same operation as in Example 3 was performed except that -G was used. The yield of the final product was 165.61 g. The properties of the final product,
30mgKOH basified with SAE No.40 lubricating base oil
/ G, and tested in the hydrolysis stability test method of ASTM D2619-88 without using a copper catalyst. The base number retention after 24 hours is shown in Table 1.

COMPARATIVE EXAMPLE 2 Properties of a commercially available calcium phenate type additive product, and diluted to 30 mg KOH / g with a lubricating base oil of SAE standard No. 40, ASTM D2619-
Table 1 shows the retention of base number 24 hours after the test was carried out without using a copper catalyst in the hydrolysis stability test method of No. 88.

Comparative Example 3 Reactor pressure at the time of adding ethylene glycol was 0 kPa-G
The procedure was performed in the same manner as in Example 3 except that When adding ethylene glycol, 10ml to prevent air inflow
The nitrogen gas was allowed to flow at a flow rate of / min, and the generation of steam considered as reaction product water was confirmed in the exhaust gas. The yield of the final product was 163.32 g. The properties of the final product,
Base number 30mg KOH with SAE standard No. 40 lubricating oil
/ G, and tested in the hydrolysis stability test method of ASTM D2619-88 without using the same catalyst. The retention of base number after 24 hours is shown in Table 1.

[0035]

[Table 1]

APPLICATION EXAMPLES The overbased sulfurized alkaline earth metal phenate concentrate of the Example was basified with a lubricating base oil of SAE No. 40 by 30 mg.
After dilution to KOH / g and a cleanliness test, all the lubricating oils showed excellent cleanliness.

[0037]

According to the process for producing the overbased sulfurized alkaline earth metal phenate concentrate of the present invention, an overbased product having a high base number, good solubility in lubricating oil and excellent hydrolysis stability. A basic sulfurized alkaline earth metal phenate is obtained.
Further, the overbased sulfurized alkaline earth metal phenate concentrate of the present invention has a low viscosity, a high base number, good solubility in lubricating oil, and excellent hydrolysis stability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 135/20 C10M 135/20 // C10L 1/24 C10L 1/24 10/04 10/04 C10N 10:04 20:00 20 : 02 30:00 30:04 40:25 70:00 (72) Inventor Yukio Takagi 1134-2 Gongendo, Satte City, Saitama Prefecture Within the R & D Center of Kosmo Research Institute, Inc. (72) Inventor Jun Imai Saitama 1134-2 Gongendo, Satte City R & D Center, Kosmo Research Institute, Inc. (72) Inventor Haruhiko Takeya 1134-2, Gongendo, Satte City, Saitama Prefecture R & D Center, Kosmo Research Institute, Inc. (72) Inventor Koichi Tsumura 27-1 Shimotsu, Shimotsu-cho, Seagrass-gun, Wakayama Prefecture Inside the Cosmo Petrotech Shimotsu Plant (72) Inventor Makoto Nishishita 1-1-1 Shibaura, Minato-ku, Tokyo Cosmo Oil Co., Ltd.

Claims (2)

[Claims] 1. An alkaline earth metal oxide, an alkaline earth metal hydroxide or a mixture thereof (hereinafter referred to as an alkaline earth metal reagent), 1 to 100 equivalents of phenols per mole of an alkaline earth metal reagent, and Sulfur or these and water are charged into a reactor, and a dihydric alcohol is added to the charged mixture at a pressure in the reactor of 10 to 250 kPa-G and reacted, and then excess dihydric alcohol and at least excess The bottom of the distillation column obtained by distilling off water was added in an amount of 0.3 to 0.8 per mole of the alkaline earth metal reagent.
Treated with carbon dioxide in the presence of moles of water and 0.001 to 0.3 moles of fatty acids per mole of alkaline earth metal reagent are present at the latest by the carbon dioxide treatment. A process for producing an overbased alkaline earth metal phenate concentrate, comprising distilling off an amount of phenols. 2. A base oil having a base number of 350 to 500 mgKOH / g, a viscosity at 100 ° C. of 1,000 cSt or less, a fatty acid content of 1 to 20% by mass of the total amount, and a base oil of SAE No. 40 lubricating base oil. ASTM D2619-88 diluted without addition of copper catalyst.
Hydrolysis is carried out in the same manner as in the method for testing the hydrolysis stability of the above, and the base number retention of the supernatant oil obtained by centrifuging the sample after 24 hours is 70% or more, characterized by being overbased. Sulfated alkaline earth metal phenate concentrate.