JPH0425996B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a highly basic alkaline earth metal salicylate type detergent, which is useful primarily as a detergent for lubricating oils or fuel oils or as an alkaline detergent. The purpose is to obtain mineral oil additives industrially advantageously.

Generally, basic salicylates and basic phenates are used as additives in lubricating oils for internal combustion engines to neutralize acids such as oxyacids and sulfuric acids, disperse sludge, lacquer, carbon, etc., and prevent corrosive wear, ring group blockage, and piston rings. It is highly effective in preventing stalemate. Basic salicylates have particularly excellent thermal stability and retain their activity as detergents over long periods of time.

Here, basic salicylates and basic phenates can be roughly divided into the following two types from the viewpoint of their acid neutralizing function as detergents.
That is, one of them is called a normal salt that contains a stoichiometric amount of metal per carboxylic acid group of salicylic acids or per hydroxyl group of phenols.
The other types are called basic salicylates and basic phenates, or overbased salicylates and overbased phenates, which contain more than a stoichiometric amount of metal. It is conventionally believed that the normal salt of salicylic acids is produced by the reaction of 1 mole of salicylic acids and 1/2 gram of alkaline earth metal reagent, and 1 mole of salicylic acids is equivalent to 1 gram. Similarly, 1 mole of monovalent phenols is 1 gram equivalent.

Conventional methods for producing basic alkaline earth metal salicylates include a method of reacting an alkaline earth metal reagent with an alkyl salicylic acid or a metal salt thereof as a starting material in the presence of a suitable reaction promoter and solvent, and the product thereof. A generally known method is to further blow carbon dioxide into the water.

The technology related to these manufacturing methods is as follows:
For example, in Special Publication No. 62-4112, alkyl salicylic acid,
A method for producing a basic alkyl salicylate by heating and stirring a xylene solution, methanol and calcium hydroxide mixture and then blowing carbon dioxide into the mixture is disclosed, and also published in
No. 46-37581 includes alkyl salicylic acids or salts thereof;
After heating and reacting sulfur, an alkaline earth metal reagent, a carboxylic acid or its salt, and an alkylene glycol alkyl ether in the presence of a solvent such as methanol, xylene or mineral oil, a basic alkaline earth sulfide is prepared by blowing carbon dioxide into the reaction mixture. A method of making metalloid salicylates is presented.

However, since all of these methods use expensive alkylsalicylic acids or their salts as starting materials, a process for producing alkylsalicylic acids or their salts is required, which complicates the process, and the production cost is higher than that for phenates and sulfonates. You can't avoid what will happen.

Regarding conventional methods for producing basic phenates, for example, there is U.S. Pat. A method is described in which a basic sulfurized alkaline earth metal phenate is produced by simultaneously performing a sulfurization reaction and a metal addition reaction, and then reacting the reactant with carbon dioxide. However, basic phenates have disadvantages in that they have poorer thermal stability than basic salicylates when added to lubricating oils and fuel oils, and have inferior efficacy and service life as additives.

Therefore, the present inventors took the above-mentioned problems into account, aimed at establishing a new manufacturing method for basic salicylate type detergents, and as a result of intensive research, surprisingly, they found that expensive alkyl salicylic acid or The production process is completely different from the method using salts, which is extremely simple, in that alkylphenols are used as raw materials, direct metal addition is performed with an alkaline earth metal reagent, and the resulting product is further treated with carbon dioxide gas. The present invention was completed by discovering that a basic salicylate or a mixture of the salicylate and phenate can be obtained through a simple process. A feature of the present invention is that it does not use so-called crosslinking or sulfiding agents such as sulfur, sulfur compounds and other compounds commonly used in the production of phenate type detergents, and that it By keeping the amount of dihydric alcohol present in the product below a certain limit, it has become possible to significantly increase the salicylate content in the product.

Further, in carrying out the present invention, it is preferable that the reaction rate of the alkaline earth metal reagent is significantly increased by blending the alkaline earth metal reagent in a smaller amount than the theoretical amount with respect to the gram equivalent of the phenol. Thus, basic alkaline earth metal salicylate having a high degree of basicity can be produced more effectively. On the other hand, when using an alkaline earth metal reagent in an amount larger than the theoretical amount, in order to increase the reaction rate of the alkaline earth metal reagent and produce a basic alkaline earth metal salicylate with good performance, for example, It is necessary to use a suitable solvent such as an expensive higher alcohol.

The first object of the present invention is to produce a basic salicylate type detergent with high acid neutralizing ability by discovering a new production method not found in conventional methods.

A second object of the present invention is to provide a method for producing a basic salicylate type detergent that uses inexpensive raw materials, reduces the amount of raw materials used, and saves as much labor as possible in the manufacturing process.

That is, the gist of the present invention is to react a reaction raw material mixture consisting of a phenol, a dihydric alcohol, and an alkaline earth metal reagent consisting of an alkaline earth metal oxide and/or hydroxide in the absence of a sulfurizing agent to produce phenols. A basic alkaline earth metal is added to the alkaline earth metal reagent, and the resulting product is treated with carbon dioxide after reducing the residual amount of dihydric alcohol in the reaction system to 0.55 mol or less per gram of alkaline earth metal reagent. The invention consists in a method for producing a similar metal salicylate type detergent.

The phenols used in the present invention have 4 to 4 carbon atoms.
Mention may be made of phenols having a hydrocarbon side chain having 36 carbon atoms, preferably 8 to 32 carbon atoms, such as an alkyl group, an alkenyl group, an aralkyl group, and the like. Specifically, hydrocarbon groups such as butyl, amyl, octyl, nonyl, dodecyl, cetyl, ethylhexyl, triacontyl, etc., or petroleum hydrocarbons such as liquid paraffin, wax, and olefin polymers (polyethylene, polypropylene, polybutene, etc.) The phenols having groups can be used alone or as a mixture thereof.
It is desirable that it can exist in a liquid state usually at about 130°C, preferably at about 120°C. Para hydrocarbon substituted phenols are particularly preferred since the use of phenols having a hydrocarbon side chain in the para position increases the formation of salicylate.

As the alkaline earth metal reagent, oxides or hydroxides of these can be used, and examples thereof include oxides or hydroxides of calcium, barium, strontium, magnesium, and the like. The alkaline earth metal reagent is used in a gram equivalent ratio of about 20 to 0.01 per hydroxyl group of the phenol used, but it is particularly preferably used in a gram equivalent ratio of about 0.99 to 0.01. A basic salicylate with a high reagent reaction rate is obtained. Gram equivalent ratio approximately 0.01
When used in the following, it is disadvantageous from an economic point of view, not only in terms of product performance and yield, but also in the cost of recovering unreacted phenols. The industrially preferred blending ratio of the alkaline earth metal reagent to the phenols is about 0.30 to 0.80, and the most preferred blending ratio is about 0.50 to 0.67 gram equivalent/gram equivalent. When the reaction is carried out using 0.99 gram equivalent or less of alkaline earth metal reagent per gram equivalent of the hydroxyl group of the phenol, the reaction proceeds smoothly and basic salicylate and basic phenate can be obtained in good yield.

Next, as the dihydric alcohol, one that has a relatively low boiling point, low viscosity, and high reactivity is used. Particularly preferred are ethylene glycol and propylene glycol. The amount of this dihydric alcohol used is approximately 0.80 to 1 gram equivalent of alkaline earth metal reagent.
3.5 mol is preferred, especially about 1.0 to 2.5 mol. Dihydric alcohols help convert phenols into oil-soluble substances through the reaction with alkaline earth metal reagents, stabilize them, and some of them are incorporated into salicylates and phenate products to produce multi-equivalent salicylates and multi-equivalent phenates. If the amount of dihydric alcohol used is too small, the product conversion rate of the reaction raw material, especially the alkaline earth metal reagent, will decrease. If the amount of dihydric alcohol used is too large, the metal addition reaction to phenols will proceed smoothly, but the time and utility for distilling off the excess dihydric alcohol from the reaction product will become excessively long.

In the present invention, a diluent or solvent (hereinafter referred to as diluent) having an appropriate viscosity can be added to facilitate handling of reactants, reaction intermediates, products, etc. For example, when recovering excess unreacted phenols from the reaction product after carbon dioxide treatment by distillation, it is necessary to collect the excess unreacted phenols by distillation. By carrying out the reaction in the presence of a diluent, the bottom of the reaction column can be obtained in the desired liquid state. Note that, along with the distillation of unreacted phenols, a portion of the diluent is also usually distilled out. Therefore, when the recovered phenols are used in repeated reactions, it is preferable to use a diluent that does not directly affect the reaction. The reaction may be carried out in the presence of a diluent. Examples of preferred diluents include petroleum fractions or petroleum lubricating oil fractions of suitable viscosity, such as paraffinic, naphthenic, aromatic, or mixed base oils. Other organic solvents can also be used as diluents if they exhibit hydrophobicity and hydrophilicity and are harmless in terms of reaction and product usage. The main manufacturing process and operating conditions of the basic salicylate type detergent in the present invention are as follows.

(a) Metal addition step Preferably about 0.99 to 1 gram equivalent of phenols, dihydric alcohols, and the phenols
0.01 gram equivalent of alkaline earth metal reagent is reacted at a reaction temperature in the range of about 60-200°C, preferably about 90-190°C. The order of charging into the reaction vessel is to first charge the phenols, then the alkaline earth metal reagent, and then the alkaline earth metal reagent.
Most preferably, the dihydric alcohol is charged last. This reaction is usually almost completed within a range of about 1 to 9 hours. About 30% or more of the water produced in the above metal addition reaction step, especially most of the produced water, preferably substantially all, is distilled off and the amount of free dihydric alcohol component remaining in the reaction system is reduced. It is necessary to distill off the dihydric alcohol prior to the carbon dioxide treatment step described below, preferably to less than about 0.55 moles per gram formula weight of alkaline earth metal reagent. After the metal addition reaction step, the smaller the remaining amount of dihydric alcohol in the intermediate product obtained by distilling off the water and excess dihydric alcohol in the system, the easier it will be for nuclear carbonation (salicylic acid skeleton formation) in the next carbonation step. It has been found that the reaction rate tends to increase.

Furthermore, if the proportion of the dihydric alcohol component in the product becomes too large, there is a tendency for the product's performance as an alkaline detergent to decrease somewhat. Also, if a large amount of water remains, the stability of the product will deteriorate.
May result in gelation or solid formation.

(b) Carbon dioxide treatment process In order to further increase the stability and oil solubility of the product, the liquid distillation residue that has undergone the above metal addition reaction process is then placed in an autoclave and the reaction temperature is approximately 100~100℃.
A reaction temperature of 300°C, preferably about 130 to 200°C, and a reaction temperature of 1 Kg/cm ² ·G or more, preferably 2 to 30 Kg/cm ² ·
React with carbon dioxide under the reaction pressure conditions of G (carbon dioxide absorption step). If necessary, this product is further heated under an atmosphere of carbon dioxide, preferably under pressure (more than 1 kg/cm ² ·G, particularly preferably 2 to 30 kg/cm ² ·G), preferably at about 100 to 300°C, Especially about 130~
Hold at 230°C for several minutes to more than ten hours (stabilization step). The stabilization step is generally carried out at a higher temperature than the carbon dioxide absorption step, but as is clear from the temperature and pressure ranges of each step above, when the conditions of both steps match. In this case, the carbon dioxide absorption step and the stabilization step cannot be distinguished. In the carbon dioxide absorption step, carbon dioxide is reacted and introduced into the side chains of phenols and the phenolic aromatic nucleus. Carbon dioxide treatment further improves the performance of the product as a lubricating oil additive and fuel oil additive (in particular, the cleanliness and stability of engine oil when added to engine oil). If necessary, add an alkaline earth metal reagent and a dihydric alcohol to the reaction product after carbon dioxide treatment, perform the metal addition reaction as described above again, and then repeat the carbon dioxide treatment operation one or more times. It is also possible to carry out further metal additions. For economic reasons, unreacted phenols in the reaction product after carbon dioxide treatment are
It is preferable to recover some or most of these phenols, and the recovered phenols can also be used as raw materials. Further, it is preferable that the surplus dihydric alcohol in the metal addition step be recovered after the carbon dioxide treatment if necessary. If the unreacted phenols are distilled in the presence of a common diluent such as high-boiling mineral oil, the distillation residue can be obtained in a preferred liquid state. A small amount of remaining insoluble substances can be removed by an operation such as filtration or centrifugation before or after recovery of the phenols.

Although the details of the exact structure of the reaction product of the method of the present invention are unknown, the oil layer obtained by hydrolyzing the reaction product and extracting the hydrolysis with a solvent such as hexane contains both salicylic acids and phenols. Since this was detected, it is thought that some of the raw material phenols were converted to salicylate by reaction with carbon dioxide. In addition, since the reaction product contains more than the theoretical amount of alkaline earth metal element per total gram equivalent of phenols and salicylic acids, the product is a skeleton of basic alkaline earth metal salicylate and basic alkaline earth metal phenate. It is thought that it contains. On the other hand, is the reaction product a mixture of molecules consisting only of salicylate bone cores and molecules consisting only of phenate bone cores, or is it a compound that has both a salicylate skeleton and a phenate skeleton in one molecule, or is it a compound that has both a salicylate skeleton and a phenate skeleton? The details of the bonding mode between the skeleton, the alkaline earth metal element, and the reacted dihydric alcohol are unknown, and furthermore, the bonding mode in the product of carbon dioxide other than that used for conversion to salicylate among the reacted carbon dioxide is unknown. The manner is unclear, and the reaction product of the present invention may also be referred to as a complex of basic alkaline earth metal salicylate and basic alkaline earth metal phenate. As mentioned above, although the detailed structure of the reaction product of the present invention is unknown, it contains a relatively large amount of basic alkaline earth metal salicylate skeleton. Described as a salicylate type detergent. However, as mentioned above, this name does not describe the exact name of the chemical product, and the present invention is not bound by the above assumptions or theories; the above name is used merely for convenience of understanding. . The reaction product of the present invention is a lubricating oil detergent,
It is effective as a mineral oil additive such as a detergent for fuel oil, and the content ratio of salicylate core to phenate core is relatively high (e.g., the ratio of salicylate core to the total amount of salicylate core and phenate core is (approximately 40 to 95 mol%), therefore, when added to mineral oil, the thermal stability of the mineral oil composition is good and the action of the detergent lasts for a long time.

As described above, according to the present invention, although relatively inexpensive phenols are used as starting materials, it is possible to produce a substantially expensive basic salicylate type detergent that contains some basic phenate. Despite employing a relatively simple process and a small number of raw materials, it is possible to produce a basic salicylate-type detergent with a large amount of alkaline earth metal added per salicylic acid in good yield with respect to the metals used. Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Nonylphenol (p-nonylphenol purity 87.6%) was placed in a 4-neck flask equipped with a stirrer, cooling tube, nitrogen gas introduction tube, and thermometer.
Charge 881.2 g (4.0 moles) and 57.1 g (1.00 gram formula weight) of 98.3% pure calcium oxide and stir. Add ethylene glycol to the resulting suspension.
83.8 g (1.35 mol) was added at 132°C under normal pressure in a nitrogen stream, and after stirring at 135°C for about 5 hours, the pressure in the reaction system was gradually reduced to remove the produced water and most of the unreacted ethylene glycol. 49.7g (0.80mol)
When a small amount of nonylphenol was distilled off, 950.0 g of a dark yellow-green liquid distillation residue was obtained. The final distillate temperature at this time was 87℃ (6mmHg)
It was hot. Next, 940.0 g of the distillation residue was sealed in an autoclave, and under pressure (first pressurized with carbon dioxide to 10 kg/cm ² G, the autoclave was closed,
Carbon dioxide is absorbed, and when the pressure drops due to absorption (in this example, 5 kg/cm ² ·G), carbon dioxide is added again to repressurize to 10 kg/cm ² ·G, and this operation is repeated as necessary. Hereinafter, this operation will be referred to as "Kg/cm ² ·G or less". ), at a heating temperature of 150 to 155°C, to absorb carbon dioxide. After that, under pressure (initial pressure 5
Kg/cm ² ·G) When kept at 180° C. for 2 hours, 975.2 g of a dark yellow-green reaction product solution was obtained.

A two-necked pear-shaped flask for No. 2 was filled with 950.0 g of the reaction product solution after the carbon dioxide treatment and 233.6 g of 150 neutral oil (paraffinic lubricating oil with a viscosity of 5.386CS at 99°C (210〓)), From this, a small amount of ethylene glycol, most of unreacted nonylphenol, and a small amount of lubricating oil fraction were distilled off under reduced pressure to obtain 452.0 g of distillation residue. The final distillate temperature at that time was 167°C (3 mmHg).

When the extremely small amount of undissolved matter contained in the above-mentioned distillation residue is removed by centrifugation, a basic calcium salicylate type product is obtained, which is a very dark yellow transparent viscous liquid final product as shown below. cleaning agent
449.7g was obtained. As a result of analysis, this final product contained 0.8 wt% of unreacted nonylphenol, 47.1 wt% of 150 neutral oil, and 52.1 wt% of active ingredients.

According to mass balance calculations, the active ingredient in the product contains 302% of the theoretical amount of calcium per reacted nonylphenol.

The analysis results of the final product are as follows.

Viscosity 100℃ (CS) 104.3 Base number (JISK 2500) (KOHmg/g) 234 Calcium (wt%) 8.37 Some of the final products with these properties are made using silica gel as an adsorbent and n-hexane as a displacing agent. The active ingredient was isolated by column chromatography.

The isolated pale yellow powder active ingredient was hydrolyzed using an excess IN sulfuric acid aqueous solution, and the resulting oil layer was analyzed by liquid chromatography, and nonylsalicylic acid was detected. As a result, it was found that 61.3% of the nonylphenol incorporated into the product was converted to nonyl salicylate.

Example 2 Nonylphenol (p
771.1g (3.5 mol)
Then, 57.1 g (1.0 gram formula weight) of calcium oxide with a purity of 98.3% was charged and stirred. To the resulting suspension, 105.6 g (1.7 mol) of ethylene glycol was added at 130°C under normal pressure in a nitrogen stream, and after stirring at 130°C for about 5 hours, the pressure inside the reaction system was gradually reduced to produce water, When 1.15 mol of most unreacted ethylene glycol and a small amount of nonylphenol were distilled off, 840.4 g of a distillation residue was obtained. The final distillate temperature at this time was 91°C (8 mmHg). next,
The distillation residue is sealed in an autoclave, and carbon dioxide is absorbed under pressure (below 1 kg/cm ² ·G) at a heating temperature of 120°C. After that, under pressure (initial pressure 1Kg/
cm ² ·G) and held at 175°C for 2 hours.

850.0 g of the reaction product solution after the carbon dioxide treatment described above and 235.5 g of 150 neutral oil (paraffinic lubricating oil with a viscosity of 5.386CS at 99°C (210〓)) were sealed in a two-necked pear-shaped flask for No. 2. A small amount of ethylene glycol, most of unreacted nonylphenol, and a small amount of lubricating oil fraction were distilled off under reduced pressure to obtain 475.1 g of distillation residue. The final distillate temperature at that time was 158°C (1 mmHg).

When a very small amount of undissolved matter contained in the distillation residue was removed by centrifugation, 472.9 g of a final product having the following properties was obtained. As a result of analysis, unreacted nonylphenol was found in this final product.
It contained 1.0 wt%, 150 neutral oil 48.1 wt% and 50.9 wt% active ingredients.

According to mass balance calculations, the active ingredient in the product contains 295% of the theoretical amount of calcium per reacted nonylphenol.

The analysis results of the final product are as follows.

Viscosity 100°C (CS) 108.7 Base number (KOHmg/g) 226 Calcium (wt%) 8.07 Nonyl salicylate skeleton (mol%) 38.4 (ratio of nonylphenol to reaction) Comparative example 1 Nonylphenol in the same container as Example 1 (p-
881.2 g (4.0 mol) of calcium oxide (87.6% O-isomer, 12.4% o-isomer) and 57.1 g (1.0 gram formula weight) of 98.3% pure calcium oxide are charged and stirred. To the resulting suspension, 105.6 g (1.7 mol) of ethylene glycol was added at 135°C under normal pressure in a nitrogen stream, and after stirring at 135°C for about 4.5 hours, the pressure inside the reaction system was gradually reduced to produce water, When 0.90 mol of most unreacted ethylene glycol and a small amount of nonylphenol were distilled off, 965.8 g of a distillation residue was obtained. The final distillate temperature at this time was 87°C (7 mmHg). next,
The distillation residue is sealed in an autoclave, and carbon dioxide is absorbed under pressure (5 kg/cm ² ·G or less) at a heating temperature of 120°C. After that, under pressure (initial pressure 5Kg/
cm ² ·G) was maintained at 180°C for 2 hours.

A two-neck pear-shaped flask for No. 2 was filled with 950 g of the reaction product solution after the carbon dioxide treatment and 228.9 g of 150 neutral oil (paraffinic lubricating oil with a viscosity of 5.386CS at 99°C (210〓)). A small amount of ethylene glycol, most of unreacted nonylphenol, and a small amount of lubricating oil fraction were distilled off under reduced pressure to obtain 446.2 g of distillation residue. The final distillate temperature at that time was 157°C (1 mmHg).

When a very small amount of undissolved matter contained in the distillation residue was removed by centrifugation, 444.7 g of a final product having the following properties was obtained.

According to mass balance calculations, the active ingredient in the product contains 310% of the theoretical amount of calcium per reacted nonylphenol.

The analysis results of the final product are as follows.

Viscosity 100℃ (CS) 128.3 Base number (KOHmg/g) 233 Calcium (wt%) 8.32 Nonyl salicylate skeleton (mol%) 4.81 Example 3 Nonylphenol (p-form 87.6%) was placed in the same reaction vessel as Example 1. , o-form 12.4%) 815.1 g (3.7 mol) and 57.1 g of calcium oxide with a purity of 98.3%
(1.0 gram formula weight) and stir. 83.8 g (1.35 mol) of ethylene glycol was added to the resulting suspension at 130°C under normal pressure in a nitrogen stream, and after stirring at 130°C for about 5 hours, the pressure inside the reaction system was gradually reduced to produce water, Most unreacted ethylene glycol
When 1.10 mol and a small amount of nonylphenol were distilled off, 860.7 g of distillation residue was obtained. The final distillate temperature at this time was 99°C (6 mmHg).
Next, the distillation residue is sealed in an autoclave,
Carbon dioxide is absorbed under pressure (5 kg/cm ² ·G or less) at a heating temperature of 150°C. Thereafter, the mixture was held at 185° C. for 4 hours under pressure (initial pressure 15 kg/cm ² ·G).

A two-necked pear-shaped flask for No. 2 was filled with 850 g of the reaction product solution after the carbon dioxide treatment and 230.6 g of 150 neutral oil (paraffinic lubricating oil with a viscosity of 5.386CS at 99°C (210〓)). A small amount of ethylene glycol, most of unreacted nonylphenol, and a small amount of lubricating oil fraction were distilled off under reduced pressure to obtain 463.2 g of distillation residue. The final distillate temperature at that time was 161°C (2 mmHg).

When a very small amount of undissolved matter contained in the distillation residue was removed by centrifugation, 460.9 g of a final product having the following properties was obtained.

According to mass balance calculations, the active ingredient in the product contains 295% of the theoretical amount of calcium per reacted nonylphenol.

The analysis results of the final product are as follows.

Viscosity 100°C (CS) 1158.1 Base number (KOHmg/g) 226 Calcium (wt%) 8.07 Nonyl salicylate skeleton (mol%) 80.6 Example 4 The same reaction vessel as Example 1 was used in the method of the present invention and recovered. Nonylphenol (p
-71.7%, o-form 28.3%) 965.2g (4.0 mol)
Then, 57.1 g (1.0 gram formula weight) of calcium oxide with a purity of 98.3% was charged and stirred. 83.8 g (1.35 mol) of ethylene glycol was added to the resulting suspension at 135°C under normal pressure in a nitrogen stream, and this
After stirring for a period of time, the pressure inside the reaction system was gradually reduced, resulting in water and most of the unreacted ethylene glycol.
When moles and a small amount of nonylphenol were distilled off, 1033.1 g of a distillation residue was obtained. The final distillate temperature at this time was 97°C (8 mmHg). next,
The distillation residue is sealed in an autoclave, and carbon dioxide is absorbed under pressure (3 kg/cm ² ·G or less) at a heating temperature of 150°C. After that, under pressure (initial pressure 5Kg/
cm ² ·G) was maintained at 180°C for 2 hours.

A two-necked pear-shaped flask for No. 2 was filled with 1000 g of the reaction product solution after the carbon dioxide treatment and 225.9 g of 150 neutral oil (paraffinic lubricating oil with a viscosity of 5.386CS at 99°C (210〓)). A small amount of ethylene glycol, most of unreacted nonylphenol, and a small amount of lubricating oil fraction were distilled off under reduced pressure to obtain 436.6 g of distillation residue. The final distillate temperature at that time was 167°C (3 mmHg).

When a very small amount of undissolved matter contained in the distillation residue was removed by centrifugation, 434.4 g of a final product having the following properties was obtained.

According to mass balance calculations, the active ingredient in the product contains 313% of the theoretical amount of calcium per reacted nonylphenol.

The analysis results of the final product are as follows.

Viscosity 100℃ (CS) 103.8 Base number (JIS K2500 (KOHmg/g) 235 Calcium (wt%) 8.39 Nonyl salicylate skeleton (mol%) 49.5 Example 1 is an example in which standard conditions were adopted, Example 2 Comparative Example 1 is an example in which a small amount of dihydric alcohol is distilled off in the distillation process after the metal addition reaction, and Example 3 is an example in which a large amount of dihydric alcohol is distilled off in the distillation process after the metal addition reaction. Example 4, which is an example in which alcohol was distilled off and treatment with carbon dioxide was performed under high temperature and high pressure, is an example in which a nonylphenol raw material with slightly lower para-isomer purity is used.

Reference example Thermal stability test The products of Examples 2 and 4 were each diluted with various base oils of the same series (paraffin type) but with different average molecular weights, and the base value was 77 mg/
Adjusted to KOH/g.

Determine the solidification point (time, evaporation loss) of this sample oil at 325°C, plot the solidification point in relation to evaporation loss with solidification time, and extrapolate the curve connecting each solidification point to 0 evaporation loss to determine thermal stability. (extrapolated solidification time). (Lubrication Eng., 33 No.2
('77), 83-90) As a result, 730 minutes in Example 2 and 730 minutes in Example 3.
It took 910 minutes.

The main measurement conditions are as follows.

Sample container 1.5ml aluminum open cup Sample amount 1000g±0.004g Base value 77mgKOH/g Temperature 325℃±3℃

Claims (1)

[Scope of Claims] 1. Phenol is produced by reacting a reaction raw material mixture consisting of a phenol, a dihydric alcohol, and an alkaline earth metal reagent consisting of an alkaline earth metal oxide and/or hydroxide in the absence of a sulfurizing agent. A basic alkali consisting of adding a metal to a compound, reducing the residual amount of dihydric alcohol in the reaction system to 0.55 mol or less per gram of alkaline earth metal reagent, and then treating the product with carbon dioxide. Method for producing earth metal salicylate type detergents. 2. The production method according to claim 1, in which the alkaline earth metal reagent is used in a ratio of 0.99 to 0.01 gram equivalent per gram equivalent of phenols in the raw materials.