JPH07268374A - Petroleum additive and production of alkaline earth metallic salt of aromatic hydroxycarboxylic acid - Google Patents

Abstract

PURPOSE:To provide a method for economically producing an alkaline earth metallic salt of an aromatic hydroxycarboxylic acid having a high base number by which problems of decarboxylation due to the distillation at high temperatures can be avoided and obtain a petroleum additive comprising the alkaline earth metallic salt of the aromatic hydroxycarboxylic acid of a specific composition prepared by the method. CONSTITUTION:This petroleum additive is obtained by reacting an alkaline earth metallic salt of phenols with carbon dioxide, then react the free phenols contained in the system with an alkaline earth metallic reagent in an amount of 2.0-15.0mol based on 1mol alkaline earth metallic reagent in the case of adding no water and 1.5-10.0mol dihydric alcohols and 0.01-10.0mol water in the case of adding the water and further react the resultant reactional product with the carbon dioxide. The resultant petroleum additive comprises the alkaline earth metallic salt of the aromatic hydroxycarboxylic acid at (0.4-1)/1 ratio of the salicylic acid skeleton to the whole benzene nuclei in the product substantially without containing an alkali metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a petroleum additive consisting of an alkaline earth metal salt of an aromatic hydroxycarboxylic acid having a specific composition having a high base number and a method for producing the same, which is mainly a lubricating oil. It is intended to industrially obtain an additive for petroleum oil, a petroleum additive which is particularly useful as a detergent.

[0002]

2. Description of the Related Art Generally, an alkaline earth metal salt of an aromatic hydroxycarboxylic acid is also called an alkaline earth metal salicylate, which is used as a petroleum additive for internal combustion engine lubricating oils and fuel oils. Neutralization, sludge,
It is extremely effective in the dispersion of lacquer, carbon, etc., and the prevention of corrosive wear, ring groove clogging, and piston ring sticking. Aromatic hydroxycarboxylic acid alkaline earth metal salts are particularly excellent in thermal stability and retain their activity as detergents for a long period of time.

Conventionally, in order to produce an alkaline earth metal salt of an aromatic hydroxycarboxylic acid, first, an alkali metal salt of an alkylphenol is formed, and this is carboxylated by a Kolbe-Schmidt reaction to obtain an alkali aromatic hydroxycarboxylic acid obtained. A method of making an alkaline earth metal salt by a complicated method such as a method of neutralizing a metal salt with an inorganic acid and then reacting it with an alkaline earth metal reagent or a method of metathesis using calcium chloride etc. has been adopted. It was Moreover, this method is a complicated and multi-step process in which a further water washing step is indispensable in order to completely remove strong acids, strong alkalis and strong electrolytes such as chlorides that promote corrosion of metal parts such as engines. There is.

Contrary to conventional wisdom, however, the present inventors have discovered that the reaction of an alkaline earth metal salt of a phenol with carbon dioxide produces an aromatic hydroxycarboxylic acid alkaline earth metal salt, The method is disclosed (Japanese Patent Publication No. 6-717, Japanese Patent Publication No. 4-25996). That is, an aromatic hydroxycarboxylic acid alkaline earth metal of an extremely simple process in which an alkylphenol is reacted as a raw material with an alkaline earth metal reagent to directly add a metal, and the resulting product is treated with carbon dioxide gas. It is a method of producing salt.

This method produces an alkali metal salt on the way.
Since there is no need to decompose and there is no need to wash the strong electrolyte with water, it is possible to obtain an aromatic hydroxycarboxylic acid alkaline earth metal salt by a much simpler process than the conventional method. Industrially advantageous production. Is the law.

[0006]

However, this method is
Since the reaction between an alkaline earth metal salt of a phenol and carbon dioxide is used, as shown in the following general formula (I), an equivalent amount of the aromatic hydroxycarboxylic acid alkaline earth metal salt is contained in the reaction product. Free alkylphenols remain.

[0007]

[Chemical 1] (Here, M represents an alkaline earth metal, and R represents hydrogen, a hydrocarbon group, or halogen.)

Reaction products containing an alkaline earth metal salt of an aromatic hydroxycarboxylic acid and an equivalent amount of free alkylphenols have a low base number. Moreover, since alkylphenol is the most expensive material used,
Although it is recovered by distillation, the alkaline earth metal salt of aromatic hydroxycarboxylic acid is partially decarboxylated because it is exposed to a high temperature of 200 ° C. or higher.

Further, since the alkaline earth metal salt of aromatic hydroxycarboxylic acid has a difficulty in solubility in oil, it is desirable that the starting alkylphenol has a C ₉ or more alkyl group, preferably a C ₁₂ or more alkyl group. . However, these long-chain alkylphenols have high boiling points and are difficult to recover by distillation. Further, even if it can be recovered by distillation, it not only increases the utility to be spent, but also exposes it to a higher temperature than when recovering short-chain alkylphenols.
Decarboxylation is promoted.

The object of the present invention is to provide a process which makes it possible to avoid the problem of decarboxylation by distillation at high temperature and yet to produce an alkaline earth metal salt of aromatic hydroxycarboxylic acid of high base number economically. The present invention also provides a petroleum additive comprising the novel aromatic hydroxycarboxylic acid alkaline earth metal salt obtained by this method.

[0011]

Accordingly, as a result of repeated studies to solve these problems, the present inventors have found that free alkylphenols produced in the process of producing an alkaline earth metal salt of aromatic hydroxycarboxylic acid. In addition, by further reacting with an alkaline earth metal reagent and repeating the step of treating with carbon dioxide gas, it is possible to increase the base number of the product and to reduce the amount of free alkylphenols. The inventors have found that a petroleum additive composed of an alkaline earth metal salt of an aromatic hydroxycarboxylic acid does not substantially contain an alkali metal and has a novel specific composition, and completed the present invention.

That is, the gist of the present invention is that an aromatic hydroxycarboxylic acid is characterized in that the ratio of the salicylic acid skeleton in the product to the total benzene nuclei is substantially free of alkali metal and is 0.4 to 1/1. A petroleum additive consisting of an acid alkaline earth metal salt; and, after reacting an alkaline earth metal salt of a phenol with carbon dioxide, the free phenol contained in the system is mixed with an oxide of an alkaline earth metal or An alkaline earth metal reagent consisting of hydroxide or a mixture thereof is added in an amount of 2.0 to 1 dihydric alcohol in the case where water is not added to 1 mol of the alkaline earth metal reagent.
Use 5.0 moles, and if water is added 0.01 to 10.0 moles of water, dihydric alcohols 1.5 to
A method for producing an alkaline earth metal salt of an aromatic hydroxycarboxylic acid is characterized by reacting with 10.0 mol and then again reacting with carbon dioxide.

The present invention will be described in detail below. The main production steps and operating conditions of the aromatic hydroxycarboxylic acid alkaline earth metal salt of the method of the present invention are as follows.

(A) First Carboxylation Step This step is a step of carboxylating an alkaline earth metal salt of phenols as a starting material to obtain a hydroxycarboxylic acid component. That is, an alkaline earth metal salt of a phenol is used at a reaction temperature of about 150 to 240 ° C., preferably about 160 to 230 ° C., a reaction pressure of about 5 to 10,000 KPa,
It is preferably reacted with carbon dioxide under reduced pressure, normal pressure or increased pressure of about 10 to 5,000 KPa. This reaction is usually completed within about 1 to 10 hours.

When reacting the alkaline earth metal salt of phenols with carbon dioxide, if a large amount of water and alcohols are present in the system, the carboxylation rate will decrease,
When water and alcohols are present in the reaction system, it is preferable to remove most of the water and alcohols, and then to react with carbon dioxide, preferably after the total amount is removed, because the amount of hydroxycarboxylic acid produced is reduced.

(B) Metal Addition Step The reaction product after the first carboxylation step, that is, the carboxylation reaction product containing free phenols, is added to the below-mentioned dihydric alcohols, alkaline earth metal reagents and, if necessary, A predetermined amount of water was added, and the mixture was allowed to react at a reaction temperature of 6
The reaction is carried out in the range of 0 to 200 ° C, preferably about 90 to 190 ° C. At that time, the reaction is carried out under reduced pressure, normal pressure or increased pressure of about 1 to 1,000 KPa. Before the next carboxylation step, the water produced in the metal addition reaction step and the added water are about 90% or more, preferably about 99.9% or more of the total amount, more preferably the total amount, and the dihydric alcohols are in the system. It is distilled off so that the amount remaining in is usually about 0.4 mol or less, preferably about 0.3 mol or less, more preferably about 0.2 mol or less, per mol of the metal of the free phenol salt. If a large amount of water and dihydric alcohols remain in the system, the carboxylation rate will decrease in the subsequent second carboxylation step, and the amount of alkaline earth metal hydroxycarboxylic acid salt produced will decrease. This reaction is usually completed within about 1 to 9 hours.

(C) Second Carboxylation Step This step may be performed in the same manner as the first carboxylation step. That is, the product obtained in the above metal addition step is reacted at a reaction temperature of about 150 to 240 ° C., preferably about 160.
The reaction is carried out with carbon dioxide under reduced pressure, normal pressure or increased pressure of about 230 ° C and a reaction pressure of about 5 to 10,000 KPa, preferably about 10 to 5,000 KPa. This reaction is usually about 1
It is almost finished within 10 hours.

The above-mentioned metal addition step and carboxylation step may be repeated. In that case, the conditions defined in (b) and (c) above may be repeated.

Unreacted phenols in the reaction product after the second carboxylation reaction are recovered by distillation or the like if necessary, but normally, as described above, when the distillation and recovery are attempted, the product is decarboxylated. Is not generated and the yield of the product is lowered, so that the product is not recovered. A small amount of insoluble substances remaining in the reaction product can be removed by an operation such as filtration or centrifugation.

The alkaline earth metal salt of the phenol, which is the starting material, may be produced by any means. For example, phenols are replaced with monohydric alcohols having 1 to 9 carbon atoms such as methanol, ethanol, propanol, butanol, or ethylene glycol,
Reaction with an alkaline earth metal alcoholate of a dihydric alcohol having 2 to 6 carbon atoms such as propylene glycol, or an oxide of an alkaline earth metal in the presence or absence of a phenol or a monohydric or dihydric alcohol. It can be prepared by reacting with a hydroxide or a simple metal.

The preferred phenols of the alkaline earth metal salt raw material for phenols of the present invention have 4 to 36 carbon atoms.
Examples thereof include mono- or di-substituted phenols having a hydrocarbon side chain having a number of carbon atoms, preferably 8 to 32 carbon atoms, such as an alkyl group, an alkenyl group and an aralkyl group.
Specifically derived from hydrocarbon groups such as butyl, amyl, octyl, nonyl, dodecyl, cetyl, octadecyl, ethylhexyl and triacontyl, or petroleum hydrocarbons such as liquid paraffin, wax and olefin polymers (polyethylene, polypropylene, polybutene, etc.). The phenols having the groups described above are used alone or in a mixture thereof. Usually about 130 ° C, preferably about 120 ° C
It is desirable that it can become liquid. Specific examples of these phenols include butylphenol, octylphenol, nonylphenol, dodecylphenol, cetylphenol, octadecylphenol, alkylphenol alkylated with polybutene, dinonylphenol and didodecylphenol.

Preferred alkaline earth metal salt raw materials for phenols of the present invention are the above-mentioned calcium, barium, strontium and magnesium salts of phenols, with calcium and barium salts being preferred,
A calcium salt is particularly preferable.

In carrying out the first carboxylation step of the step (a) of the present invention, a solventless method which has been conventionally adopted in many salicylic acid industries is also possible. However, depending on the type of phenol, the use of the product and the production equipment, it may be possible or desirable to use the solvent at the appropriate stage. Almost all of the solvents that have been conventionally used in the Kolbe-Schmidt method can be used as the solvent. For example, light aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, diphenyl, diphenylmethane, and naphthalene, pentane,
Octane, decane, kerosene, light oil, cyclohexane,
Light aliphatic hydrocarbons such as methylcyclohexane, ketones such as methylethylketone, diethylketone, diisopropylketone and acetophenone, ethers such as diphenylether, diisobutylether, dioxane and anisole, amines such as n-heptylamine and triethylamine, dimethylformamide Amides and the like can be used. In addition, the raw materials phenols used for the production of alkaline earth metal salts of phenols themselves, as well as petroleum-based medium to heavy oils such as lubricating oil base materials can be used. For example, when an aromatic hydroxycarboxylic acid alkaline earth metal salt is produced for the purpose of producing a lubricating oil detergent, a lubricating oil base usually used as a diluent, for example, a viscosity of about 0.5 to 35 cSt (100 The lubricating oil (° C.) Can also be used as a solvent for the reaction system.

The amount of free phenols in the reaction product obtained from the first carboxylation step of step (a) is
Although it varies depending on the carboxylation rate of the alkaline earth metal salt of phenols, an equivalent amount to the alkaline earth metal salt of phenols as a starting material is a guideline (in the reaction of the present invention, the above-mentioned general formula (I 1 mol of the alkaline earth metal salt of phenol, which is the raw material on the left side of (), is calculated as 1 equivalent). Therefore, the amount of free phenol in the product obtained in the first carboxylation step is the same as the above-mentioned amount if free phenols were present in the alkaline earth metal salt of the starting phenols from the beginning. It is the sum of the free phenol produced by carboxylation. Based on this, metal addition in the step (b) described below is performed.

As the alkaline earth metal reagent used in the metal addition step of the step (b) of the present invention, alkaline earth metals, alkaline earth metal alcoholates and alkaline earth metal alkyls can be used. In the present invention, an alkaline earth metal oxide or hydroxide or a mixture thereof is used from the economical aspect. For example, oxides or hydroxides of calcium, barium, strontium, magnesium and the like, or mixtures thereof are used. In the above step (a), that is, in the product of the first carboxylation step, the phenols (the free phenols generated in the reaction step of reacting the above-mentioned alkaline earth metal salt with carbon dioxide and the alkaline earth of the starting alkylphenol) The amount of the alkaline earth metal reagent to be added to the total amount of free phenol contained in the metal salt from the beginning) is 0.99 equivalent or less per 1 equivalent of the phenol,
It is preferably 0.3 to 0.95 equivalent.

If the amount of the alkaline earth metal reagent with respect to the phenols is too large, the intermediate will gel and the reaction will not proceed any further, and the desired good product cannot be obtained.
Further, if the amount is too small, the yield of the product relative to the raw material decreases,
It is economically disadvantageous.

As the dihydric alcohol used in this step (b), those having a relatively low boiling point, a low viscosity and a high reactivity are used. The dihydric alcohols preferably have 2 to 6 carbon atoms, and ethylene glycol and propylene glycol are particularly preferable. The dihydric alcohols assist the conversion into an oil-soluble substance by the reaction of the phenols and the alkaline earth metal reagent and stabilize the same, and a part thereof is incorporated into the product salicylate to form a multi-equivalent salicylate. In the present invention, the metal addition reaction may be carried out with or without the addition of water having a reaction promoting effect.

When water is added, the amount of the dihydric alcohol used is about 1.5 to 10.0 mol, preferably about 1.5 to 8.0 mol, per 1 mol of the alkaline earth metal reagent added.
Molar is suitable. When water is not added, the amount of the dihydric alcohol used is about 2.0 to 15.0 mol, especially about 2. 1 mol, per 1 mol of the alkaline earth metal reagent to be added.
0 to 10.0 mol is preferable.

If the amount of the dihydric alcohols used is too small, the product conversion rate of the reaction raw materials, particularly the alkaline earth metal reagent added, is lowered. On the other hand, if the amount is too large, the metal addition reaction to the free phenol will proceed smoothly, but the time and utility for distilling off the excess dihydric alcohol from the reaction product will be too long.

When water is added to the reaction system in order to accelerate the reaction in the metal addition reaction step of the free phenols and the alkaline earth metal reagent to be added, not only distilled water but also can water, industrial water, metal addition Water produced by the reaction can be used, and the quality thereof is not particularly limited, and water in any state such as cold water, hot water, steam, etc. can be used. The water used to accelerate the metal addition reaction may be added to water alone, or part or all of it may be added as a mixture with other raw materials such as dihydric alcohols and higher alcohols described below. Good. The timing of adding water to the reactor is not particularly limited and may be before or after all the reaction raw materials other than water are mixed, but it is preferable to add water within about 1 hour after mixing all the reaction raw materials. The amount of water used for accelerating the metal addition reaction into the reaction system is about 0.01-10.0 mol, preferably 0.05-3.mol, per 1 mol of the alkaline earth metal reagent added.
It is 0 mol. When water is added to the reaction system from the outside to carry out the metal addition reaction, the reaction proceeds smoothly compared to the case where the reaction is performed under the same conditions except that water is not added, and the reaction raw material, especially the alkaline earth to be added. Product conversion rate of metal reagents is high. Therefore, if the amount of water added to the reaction system is too small, the product conversion rate of the alkaline earth metal reagent added will decrease. On the contrary, if the amount is too large, the advantage that the distillation step after the reaction is simplified is lost.

Next, step (c), that is, the second carboxylation step is carried out. This step is substantially the same operation as the first carboxylation step of the above-mentioned step (a), and will be particularly described here. Needless to say.

In the present invention, a diluent or solvent having an appropriate viscosity (hereinafter referred to as "diluent") can be added to facilitate the handling of the reaction product, reaction intermediate, product or the like. Further, the reaction may be carried out in the presence of a diluent. For the purpose of producing a petroleum additive, examples of preferable diluents include petroleum fractions having a suitable viscosity, such as paraffinic, naphthenic, aromatic, or mixed base oils, for example, a boiling point of about 220. Mention may be made of lubricating oil distillates having a viscosity at 100 DEG C. to 550 DEG C. of about 0.5 to 40 cSt. It can be used as a diluent as long as it shows hydrophobicity and lipophilicity even in other organic solvents and is harmless during the reaction and in the use of the product. For example, carbon number 8
Up to 24 higher alcohols can also be used.

Both the phenols and a large amount of salicylic acids are detected in the oil layer obtained by hydrolyzing the reaction product thus obtained and extracting the hydrolyzate with a solvent such as hexane. It is presumed that the alkaline earth metal salt of aromatic hydroxycarboxylic acid of the present invention is a mixture containing a metal salt of salicylic acid as a main component and additionally containing a metal salt of phenols and free phenols. Further, in the present invention, as described above, the carboxylation reaction produces free phenols in an equimolar amount with the aromatic hydroxycarboxylic acid metal salt, and therefore, the chelate compound is represented by the general formula (I). Is inferred.

The petroleum additive consisting of the alkaline earth metal salt of aromatic hydroxycarboxylic acid of the present invention is produced by the above-mentioned production method and contains substantially no alkali metal (5 ppm or less), and the salicylic acid skeleton in the product is entirely contained. The ratio to the benzene nucleus, that is, metal-added phenols and salicylic acids and free (unreacted) phenols and salicylic acids is 0.4 to 1/1, preferably 0.4.
It is 5 to 0.99 / 1. The ratio of the salicylic acid skeleton to the metal-added benzene nucleus, that is, the metal-added phenols and salicylic acids, in the product is 0.55 to 1/1, preferably 0.6 to 0.99 / 1.
Is.

[0035]

EXAMPLES The present invention will now be described in more detail with reference to examples, but these are merely examples and do not limit the present invention.

Example 1 Octadecylphenol (p- was added to a 1-liter autoclave equipped with a stirrer, a cooling pipe, a nitrogen gas introducing pipe and a thermometer.
Octadecylphenol content 90.00%, o-octadecylphenol content 9.71%) 484.4 g
(1.4 mol), purity 94.9% calcium oxide 3
5.47 g (0.6 mol), 150 neutral oil (1
Paraffin-based lubricating oil with a viscosity of 5.27 cSt at 00 ° C) 1
68.3g was charged and stirred. 50.30 g (0.81 mol) of ethylene glycol and 1.08 water in this suspension
g (0.06 mol) of a mixed solution was added at 130 ° C. under a pressure of 200 KPa in a nitrogen stream, and this was added to 300 KPa, 130
The reaction was carried out at 0 ° C for 3 hours. Then, while gradually reducing the pressure of the reaction system, 11.88 g of generated water and added water, 53.83 g of a mixture of most of the added ethylene glycol and a small amount of octadecylphenol were distilled off, and a mustard-colored liquid was distilled. 673.8 g of residue was obtained. At that time, the temperature of the bottom product was 184 ° C, and the distillate temperature was 159 ° C (0.
It was 3 KPa).

Then, 178 g was added to 671.1 g of the distillation residue.
500KPa by blowing carbon dioxide from 8 ℃
The pressure was increased to, and the state was maintained for 4 hours to obtain 697.5 g of a dark gray yellow red liquid reaction product. (Reaction product-A)

Next, the reaction system was cooled to 100 ° C. and depressurized to normal pressure, and 697.5 g of this carboxylation reaction product was added to calcium oxide 1 having a purity of 94.9%.
7.73 g (0.30 mol) was charged and stirred. To this suspension, 93.15 g (1.5 mol) of ethylene glycol was added at 130 ° C. under a pressure of 200 KPa in a nitrogen stream, and this was reacted at 300 KPa and 130 ° C. for 3 hours.
Then, while gradually reducing the pressure of the reaction system, 4.5
1 g, 95.82 g of a mixture of most of the added ethylene glycol and a small amount of octadecylphenol were distilled off to obtain 708.1 g of a dark gray-brown liquid distillation residue. At that time, the temperature of the bottom product was 185 ° C, and the distillate temperature was 158 ° C (0.3 KPa).

Next, 178 was added to 705.7 g of the distillation residue.
500KPa by blowing carbon dioxide from 8 ℃
The pressure was increased to, and the state was maintained for 4 hours to obtain 718.9 g of a dark grey-brown liquid reaction product. (Reaction product-B)

Next, 3.54 g of the insoluble matter contained in the reaction product was removed by filtration to obtain 713.6 g of a dark viscous, transparent, viscous liquid final product. General properties of this final product, and salicylate skeleton: phenol ratio (hydrolyzing a part of the product and extracting with hexane, the oil layer obtained was analyzed by liquid phase chromatography, and calculated from the obtained results; The same applies to the example of) in Table 1.

Comparative Example 1 In the same manner as in Example 1, the reaction product-A was treated with 696.9.
g, and the insoluble matter contained therein, 2.64 g, was removed by filtration, and a dark viscous, transparent viscous liquid final product 69 was obtained.
2.9 g was obtained. Table 1 shows the general properties of this final product and the salicylate skeleton: phenol ratio. Comparative Example 1
Indicates that the amount of released octadecylphenol was about 2.1 times that in Example 1.

Comparative Example 2 60.98 g of the final product obtained in Comparative Example 1 was transferred to a 1-liter three-neck pear-shaped flask, and vacuum distillation was carried out to recover the released octadecylphenol, and a mixture 73 of octadecylphenol and a lubricating oil fraction was added. 0.31 g was distilled off to obtain 528.67 g of a distillation residue.

At that time, the temperature of the bottom product was 230 ° C., and the distillate temperature was 217 ° C. (0.3 KPa). In order to prevent decarboxylation during vacuum distillation, the maximum temperature of the bottom product is 230
℃ was made. By the way, it took more than 4 hours to distill,
The time of exposure to high temperature of 200 ° C. or higher is about 3 hours.

As shown in Table 1, the final product obtained in Comparative Example 1 contained 34.% of released octadecylphenol.
Since it contained 15%, there should be 205.6 g of free octadecylphenol that can be recovered here, but as described above, only 73.31 g could be actually distilled off.

The properties of this distillation residue and the salicylate skeleton: phenol ratio are shown in Table 1. Comparative Example 2 is Example 1
The amount of carboxylic acid per mole of calcium (COO
H / Ca) is low, indicating that decarboxylation is occurring. Further, the amount of released octadecylphenol is larger than that in Example 1 because the distillation is not complete.

Example 2 Dodecylphenol (p-dodecylphenol content 93.42%, o in the same 1 liter autoclave as in Example 1)
-Dodecylphenol content 6.33%) 393 g
(1.49 mol), purity 94.9% calcium oxide 4
1.38 g (0.7 mol), 150 neutral oil (1
Paraffin-based lubricating oil with a viscosity of 5.27 cSt at 00 ° C) 1
96.4 g was charged and stirred. 58.68 g (0.95 mol) of ethylene glycol and 1.26 of water were added to this suspension.
g (0.07 mol) of the mixed solution was added at 130 ° C. under a pressure of 200 KPa in a nitrogen stream, and this was added to 300 KPa, 130 KPa.
The reaction was carried out at 0 ° C for 3 hours. Then, while gradually reducing the pressure of the reaction system, 10.96 g of produced water and added water, 59.83 g of a mixture of most of the added ethylene glycol and a small amount of dodecylphenol were distilled off, and a mustard-colored liquid was distilled. 619.9 g of residue was obtained. At that time, the temperature of the bottom product was 184 ° C, and the distillate temperature was 129 ° C (0.3 KP
It was a).

Next, 612.9 g of the distillation residue was added with 178
500KPa by blowing carbon dioxide from 8 ℃
The pressure was increased to 4 hours, and the state was maintained for 4 hours to obtain 641.3 g of a dark gray yellow red liquid reaction product.

Next, the reaction system was cooled to 100 ° C. and depressurized to normal pressure, and 641.3 g of this carboxylation reaction product was added to calcium oxide 2 having a purity of 94.9%.
0.69 g (0.35 mol) was charged and stirred. 108.68 g (1.75 g of ethylene glycol was added to this suspension.
Mol) was added at 130 ° C. under a pressure of 200 KPa in a nitrogen stream, and this was reacted at 300 KPa and 130 ° C. for 3 hours. Thereafter, while gradually reducing the pressure of the reaction system, 4.11 g of produced water, 115.82 g of a mixture of most of the added ethylene glycol and a small amount of dodecylphenol were distilled off, and a dark grayish brown liquid distillation residue was obtained. 650.7 g
was gotten. At that time, the temperature of the bottom product was 180 ° C, and the distillate temperature was 128 ° C (0.3 KPa).

Next, 178 g of the distillation residue, 648.1 g, was added.
500KPa by blowing carbon dioxide from 8 ℃
The pressure was increased to, and the state was maintained for 4 hours to obtain 665.0 g of a dark grey-brown liquid reaction product.

Next, 3.04 g of the insoluble matter contained in the reaction product was removed by filtration to obtain 657.8 g of a dark fin-colored transparent viscous liquid final product. Table 1 shows the general properties of this final product and the salicylate skeleton: phenol ratio.

Comparative Example 3 A 500 l autoclave equipped with a stirrer, a cooling tube, a nitrogen gas introducing tube and a thermometer was placed in a dodecylphenol (p-
Dodecylphenol content 93.42%, o-dodecylphenol content 6.33%) 210.4 g (0.8 mol), purity 94.9% calcium oxide 23.65 g
(0.4 mol), 150 neutral oil (paraffinic lubricating oil with a viscosity of 5.27 cSt at 100 ° C) 112.21
g and charged. In this suspension, 34.08 g (0.56 mol) of ethylene glycol and 0.75 g (0.
04 mol) in a nitrogen stream under a pressure of 200 KPa,
It was added at 130 ° C., and this was reacted at 300 KPa and 130 ° C. for 3 hours. Thereafter, while gradually reducing the pressure of the reaction system, 8.91 g of produced water and added water, 36.36 g of a mixture of most of the added ethylene glycol and a small amount of dodecylphenol were distilled off, and a mustard colored liquid was distilled. 335.82 g of residue was obtained. At that time, the temperature of the bottom product was 193 ° C and the distillate temperature was 137 ° C (0.3 KPa).

Then, 178 g was added to 334.0 g of the distillation residue.
500KPa by blowing carbon dioxide from 8 ℃
The pressure was increased to, and the state was maintained for 4 hours to obtain 351.5 g of a dark gray yellow red liquid reaction product.

Next, the reaction system was cooled to 100 ° C., depressurized to normal pressure, and 351.5 g of this carboxylation reaction product was added to calcium oxide 1 having a purity of 94.9%.
Charge 6.77 g (0.3 mol) and stir. A mixed solution of 17.60 g (0.28 mol) of ethylene glycol and 0.39 g (0.02 mol) of water was added to this suspension at 130 ° C. under a pressure of 200 KPa in a nitrogen stream, and this was mixed with 3
The reaction was carried out at 00 KPa and 130 ° C. for 3 hours. Then, while gradually reducing the pressure of the reaction system, a mixture of most of the added ethylene glycol and a small amount of dodecylphenol 2
Evaporation of 8.66 g yielded 357.6 g of a dark gray-yellow red liquid distillation residue. Generation of produced water was not confirmed. At that time, the temperature of the bottom product was 173 ° C, and the distillate temperature was 152 ° C (0.3 KPa).

Next, 178 was added to 352.6 g of the distillation residue.
500KPa by blowing carbon dioxide from 8 ℃
The pressure was increased to, and the state was maintained for 4 hours to obtain 354.6 g of a dark grayish brown liquid reaction product.

Next, the insoluble matter 1 contained in the reaction product
9.72 g was removed by filtration to obtain 329.4 g of a dark brown transparent viscous liquid final product. The general properties and salicylate skeleton: phenol ratio of this final product are shown in Table 1.

In Comparative Example 3, when the amount of the dihydric alcohol used was reduced during the metal addition of the free phenols,
It is shown that metal addition is not sufficiently carried out, the amount of insoluble matter produced is remarkably increased as compared with Example 2, and the carboxylation rate is also lowered.

[0057]

[Table 1]

As shown in the product property results of Table 1, the samples obtained in Examples 1 and 2 according to the present invention have a free phenol content higher than those of the samples obtained in Comparative Examples 1 and 2. Is low, and the conversion rate of the used phenol to the aromatic hydroxycarboxylic acid metal salt is high. Further, compared with Comparative Example 3, there is a feature that the amount of insoluble matter due to the unreacted substance of the alkaline earth metal reagent is small.

Reference Example 1 <Heat Resistance Test> A hot tube test (lacquer test) was performed according to the method of Komatsu Equipment Co., Ltd. Sample is 5
00 Neutral oil (viscosity at 100 ° C is 10.9
Paraffin type lubricating oil of 6 cSt) with a base number of 10 mgKOH /
It was diluted to g and used for measurement (test time 16
h, lacquer rating 1-10 points (the higher the score, the better the heat resistance).

Test results 310 ° C. 320 ° C. Example 1 7.5 7.0 Example 2 7.0 6.0 Commercial product 1 (manufactured by S company) 6.5 1.0 <alkali metal concentration> Na K (ppm ) Example 1 ND ^* ND Example 2 〃 〃 Commercial product 1 (manufactured by S company) 46 5 Commercial product 2 (manufactured by O company) 42 550 * ND: undetectable (1 ppm or less)

[0061]

According to the method of the present invention, after the carboxylation of the alkaline earth metal salt of phenols, the metal addition-carboxylation reaction is repeated to distill the free phenols that cause decarboxylation. It is possible to reduce the amount of free phenols and obtain a product with a high base number and a high acid number without performing recovery. In particular, this method is an economical method when a long-chain alkylphenol, which is difficult to recover by distillation, is used as a raw material. Also,
The product of the present invention is obtained by the above-mentioned production method and has a high base number, a high acid number and excellent heat resistance.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C10L 1/18 Z 6958-4H C10N 10:04 30:04 30:08 70:00 (72) Inventor Shinji Yamaoka 1134-2 Gongendo, Satte City, Saitama Cosmo Research Institute, Inc. R & D Center

Claims (3)

[Claims] 1. The ratio of the salicylic acid skeleton in the product to the total benzene nuclei is substantially 0.4 and is substantially free of alkali metal.
A petroleum additive consisting of an alkaline earth metal salt of an aromatic hydroxycarboxylic acid, characterized in that 2. After reacting an alkaline earth metal salt of a phenol with carbon dioxide, the free phenol contained in the system is converted from an alkaline earth metal oxide or hydroxide or a mixture thereof. Aromatic earth metal reagent is used to react with 1 mol of the alkaline earth metal reagent using 2.0 to 15.0 mol of dihydric alcohol, and is reacted with carbon dioxide again. Process for producing alkaline earth metal hydroxycarboxylic acid salt. 3. After reacting an alkaline earth metal salt of a phenol with carbon dioxide, the free phenol contained in the system is converted from an alkaline earth metal oxide or hydroxide or a mixture thereof. The alkaline earth metal reagent consisting of
A method for producing an alkaline earth metal salt of an aromatic hydroxycarboxylic acid, which comprises reacting 10.0 mol of dihydric alcohol with 1.5 to 10.0 mol and reacting again with carbon dioxide.