JPS61282336A - Production of metal salt of aromatic hydroxycarboxylic acid - Google Patents

Abstract

PURPOSE:To obtain the titled compound readily in one stage, by reacting an alkaline earth metal salt of a phenol with CO2 as raw materials while heating. CONSTITUTION:An alkaline earth metal salt of a phenol expressed by the formula I (M is alkaline earth metal; R is H, 1-40C hydrocarbon group or halogen), preferably in an anhydrous state, e.g. calcium phenolate, is reacted with CO2 in a solvent, preferably at 140-270 deg.C for 0.1-50hr under preferably 2-50kg/cm<2> CO2 pressure to afford the aimed compound expressed by formula II, which is deposited with an acid, e.g. hydrochloric acid, etc., to give readily a free aromatic hydroxycarboxylic acid. Be, Mg, Ca, Sr, Ba, etc., may be cited as the alkaline earth metal in the alkaline earth metal salt of the phenol. EFFECT:The free aromatic hydroxycarboxylic acid can be obtained simultaneously by deposition with the acid, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a new method for producing alkaline earth metal salts of aromatic hydroxycarboxylic acids, and specifically relates to a method for producing alkaline earth metal salts of aromatic hydroxycarboxylic acids. The present invention relates to a method for producing alkaline earth metal salts of aromatic hydroxycarboxylic acids, which is characterized by carrying out a reaction with carbon dioxide.

(Prior Art) Aromatic hydroxycarboxylic acids, which are important in practice, have conventionally been produced using the so-called Kolbe-Schmidt method, which is based on the reaction between an alkali metal salt of phenol and carbon dioxide.
Schmitt t') reaction. Until now, various improved methods have been developed, but all have a common feature in that they use a group IA alkali metal compound (a) Kirk-Oth
mer.

Encyclopedia of Chemica
l Technology 3rd ed, Vol.
20. P, 506 (1982); b) A, S.
Lindsey and H., Jeskey, C.
hem.

Rev. Mutual 7, 583 (1957)). For example, the final alkaline earth metal Bw of aromatic hydroxycarboxylic acid
Even when manufacturing M, it was customary to use an alkali metal salt in the carboxylation step (c) B
, P, 729.376 (1955); d) B, P.
738, 928 (1955)).

(Problem to be solved) In other words, in the conventional method, even if the target product is an alkaline earth metal salt of an aromatic hydroxycarboxylic acid, an alkali metal salt of phenols is used as a raw material, and the aromatic hydroxycarboxylic acid is first An alkali metal salt is prepared, and then the alkali metal is exchanged with an alkaline earth metal, or once the acid is made into a free acid, it is converted into an alkaline earth metal salt again.
A roundabout method called f-ro has been adopted.

The present invention provides a method for directly producing the target product, an alkaline earth metal salt of an aromatic hydroxycarboxylic acid, in place of such a roundabout method.

(Means for Solving the Problems) Surprisingly, contrary to conventional wisdom, the present inventors have discovered that alkaline earth metal salts of aromatic hydroxycarboxylic acids can also be used in the reaction of alkaline earth metal salts of phenols with carbon dioxide. The present invention was completed based on the discovery that t is generated.

That is, the gist of the present invention resides in a method for producing an alkaline earth metal salt of an aromatic hydroxycarboxylic acid, which comprises reacting an alkaline earth metal salt of a phenol with carbon dioxide.

In the present invention, an alkaline earth metal salt of an aromatic hydroxycarboxylic acid is produced by heating and reacting an alkaline earth metal salt of a phenol with carbon dioxide. This reaction is presumed to proceed according to the general formula of Honjiji C.

Here, M is an alkaline earth metal, and R is a H1 hydrocarbon group or a halogen.

Examples of phenols used in the present invention include phenol,
and phenols having a hydrocarbon chain having 1 to 40 carbon atoms, such as an alkyl group, an alkenyl group, an aralkyl group, etc. or a nuclear substituent such as a halogen such as chlorine, AX, fluorine, iodine, etc., or a mixture thereof. hydrocarbon chain R
Specific examples of groups include methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, nonyl, dotesyl,
These include hydrocarbon groups such as cetyl, ethylhexyl, and doriacontyl, or groups derived from petroleum hydrocarbons such as olefin polymers (polyethylene, polypropylene, polybutene, etc.), liquid paraffin, and wax.

Specific examples of these phenols include phenol, cresol, ethylphenol, flobylphenol, octylphenol, nonylphenol, dodecylphenol, cetylphenol, alkylphenol alkylated with polybutene, chlorophenol, and flomophenol. The substituent R may be in any of the ortho, meta, and para positions relative to the phenolic hydroxyl group. It is easy to obtain para-form ones.

The metals used in the metal salts of phenols are alkaline earth metals, which are synonymous with the metals of group A of the periodic table, and include beryllium, manesium, calcium, strontium, barium, and radium.

The alkaline earth metal salts of phenols, which are the raw materials of the present invention, may be prepared by any manufacturing method, and if the phenols are mixed with monohydric alcohols such as methanol, ethanol, gropanol, butanol, etc. having 1 to 1 carbon atoms, 9 monohydric or dihydric alcohols, e.g. dihydric alcohols having 2 to 6 carbon atoms such as evapoethylene glycol and globylene glycol, or reacting phenols with monohydric or dihydric alcohols. It can be reacted with alkaline earth metal oxides, hydroxides, or elemental metals in the presence or absence;gg. Preferred phenolic alkaline earth metal salt raw materials of the present invention include the above-mentioned calcium salts of phenols,
Barium salt 1, strontium.

In carrying out this reaction, a solvent-free method, which has been conventionally employed in many salicylic acid industries, is also possible. However, depending on the phenol at, the use of the product, and the production equipment, it may be acceptable or even desirable to use a solvent at an appropriate stage. As the solvent, almost all those conventionally used in the Kolbe-Schmidt method can be used. For example, toluene, xylene,
Light aromatic hydrocarbons such as ethylbenzene, cumene, diphenyl, diphenylmethane, naphthalene, light aliphatic hydrocarbons such as pentane, octane, decane, kerosene, light oil, cyclohexane, methylcyclohexane, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, etc. Ketones, ethers such as diphenyl ether, diisobutyl ether, dioxane, and anisole, amines such as n-hebutylamine and triethylamine, and amides such as dimethylformamide can be used. In addition, phenols themselves, which are raw materials used in the production of phenols and alkaline earth metals, and petroleum-based medium to heavy oils such as lubricating oil base materials can also be used. For example, when producing an alkaline earth metal salt of an aromatic hydroxycarboxylic acid for the purpose of producing a lubricating oil detergent, a lubricating oil base material commonly used as a diluent, e.g. cst (10
The lubricating oil at 0° C.) can also be used as a graystone solvent.

The alkaline earth metal salt of phenol used in the present invention is preferably in an anhydrous state.

The presence of water reduces the yield of the target product. Furthermore, in the preparation of the metal salts, the use of gold or alcoholates of monohydric or dihydric alcohols often causes undesirable results such as a decrease in the carboxylation rate, so the use of phenol before starting the reaction with carbon dioxide is necessary. It is desirable to remove and recover preferably 0.2 mole or less, more preferably substantially all of the metal, per mole of metal.

The carbon dioxide used does not necessarily have to be pure (for example, it may contain nitrogen, hydrogen, methane, carbon oxide or inert gases such as argon). It is also observed that absorption of carbon dioxide is observed even when carbon dioxide is blown into the system under reduced pressure following the vacuum distillation process, and cases are often observed where the absorption rate of carbon dioxide exceeds the supply rate and the system becomes depressurized. 0.001
Although it is used in a wide range from 100 Kg/cti to 100 Kg/cti, it is preferable that the final value is 2 to 5 Kp/cti. Further, the temperature at which the alkaline earth metal salt of phenol and carbon dioxide is reacted is 100°C to 320°C, preferably 140°C to 270°C. The reaction time is usually preferably about 0.1 to 50 hours.

In this way, alkaline earth metal salts of aromatic hydroxycarboxylic acids are obtained. When a solvent is used in the reaction or subsequent treatment, the aromatic hydroxycarboxylic acid alkaline earth metal salt is obtained in a form dissolved or dispersed in the solvent.

If the aromatic hydroxycarboxylic acid alkaline earth metal salt can be used dissolved or dispersed in a solvent, or as a mixture with unreacted raw materials such as phenols and alkaline earth metals, it can be separated from the solvent and raw materials. do not have to. When it is desired to separate an aromatic hydroxycarboxylic acid alkaline earth metal salt from a solvent or an unreacted raw material, a conventional method can be used, such as a separation method using a membrane, a fractional precipitation method in which a solvent in which the target product is dissolved in lI is added, or a solvent. The target aromatic hydroxycarboxylic acid alkaline earth metal salt may be isolated by any suitable method, such as an extraction method using a solvent or a method in which the solvent is removed by evaporation or distillation.

Incidentally, if necessary, it is also easy to obtain the corresponding aromatic hydroxycarboxylic acid in the free acid form by a conventional method from the alkaline earth metal salt of the aromatic hydroxycarboxylic acid produced, and this is also within the scope of the present invention. be. For example, the produced aromatic hydroxycarboxylic acid alkaline earth metal salt or a mixture of this metal salt and a solvent or unreacted raw material may be mixed with an acid, such as hydrochloric acid or sulfuric acid. Aromatic hydroxycarboxylic acid in the form of a free acid can be easily obtained by acid precipitation by adding R1 nitric acid aqueous solution or the like.

(Effect of the invention) The method of the present invention requires relatively shorter steps than conventional methods.

Practically important alkaline earth metal salts of aromatic hydroxycarboxylic acids can be obtained relatively easily. At the same time, free aromatic hydroxycarboxylic acid can also be obtained by acid precipitation or the like.

(Example) The present invention will be specifically explained below with reference to Examples.

Example 1 Nonylphenol (a mixture of ortho and para isomers enriched in para isomers) 390.2Ii was placed in a stainless steel reaction vessel equipped with a stirrer, a gas inlet tube, a thermometer, a pressure gauge, and a distillation tube with ball pulp. (1.77 mol), calcium oxide powder with a purity of 98°4 wt% 39.9. f(0
, 70 mol), heated and stirred under a pressure of 6 to 1 A in a nitrogen stream, and when the temperature reached 160°C, aqueous ethylene glycol (containing 75 wt% ethylene glycol)
．． 8. After adding P (1,09 mol) ft and stirring under the same conditions for 3 hours, the pressure of the system was gradually lowered and the water-based fraction 35. The fraction 87.5I, which mainly consists of ethylene glycol and contains a small amount of nonylphenol, was distilled off at a temperature of 150° C. and 10 mHy to prepare a calcium nonyl felt solution.

The reaction vessel was sealed under reduced pressure, and 31
Carbon dioxide was injected at a flow rate of 5 Nmj/min. 3
After 0 minutes, the temperature was raised to 178°C, the volume was adjusted to 6 kg/1 dl, and the mixture was stirred for 2 hours under the same conditions, resulting in a reaction product solution of 421. Obtained OI.

After mixing 150 neutral oil (paraffinic lubricating oil with a viscosity of 5.38 cSt at 99°C) 192.4.1 to this reaction product solution 294.7II, vacuum distillation was carried out,
A distillation residue of 312.1y was obtained by removing a fraction consisting mainly of nonylphenol and containing a small amount of oil and the like with a column top temperature of up to 191°C at 1.5 mHl. Removal of a small amount of impurities gave a very dark yellow-red, transparent and viscous oil solution of the reaction product 308.211 with the following properties:

Calcium (wt%) 6.11 Acid value after acid neutralization (dKOH/#) 50.6 Also, the above final product was diluted with hexane, neutralized with 1N sulfuric acid aqueous solution, and the hexane layer was thoroughly washed with water. Thereafter, hexane was distilled off using an evaporator, and the resulting sample was separated by liquid chromatography.It was confirmed by C-NMH measurement that the nonylphenol carboxylated product was essentially nonylsalicylic acid.

Example 2 A long chain alkylphenol with an average molecular weight of 585 (hydroxyl value 96 trdiKOH/I) of 192.2. ? , 98.4% pure calcium oxide 8.2. ! Prepare i+, add p to 2 in nitrogen stream,
The mixture was heated and stirred under a pressure of /ci/L, and when the temperature reached 160°C, ethylene glycol 17.8.9 was added. After stirring under the same conditions for 3 hours, the system pressure was gradually lowered to 24 xx
3. Water-based distillate with HJ top temperature up to 30°C.
II, 21.7 J of a fraction mainly composed of ethylene glycol was distilled off at a further 5 mHy to a tower top temperature of 145°C.

Next, the system was sealed and heated to 172°C, and then heated to 292N
6.0 Kg/a by blowing into a calcium salt solution of long-chain alkylphenol in carbon dioxide at a flow rate of ml/min.
From the point at which the pressure reached
．． After stirring for 0 hours, a shrimp brown translucent viscous reaction product solution 19B, 9.9 was obtained. This reaction product solution 130
．． 0. After diluting P with 150 neutral oil 22.9.9, it was distilled under reduced pressure to 2.5 yamHg and the top temperature was 20.
Fraction 26.81-, which is mainly composed of alkylphenols and contains a small amount of oil, was distilled off to obtain a distillation residue of 123.6j'. After removing 0.3.9% of the undissolved content from the hexane diluted solution of this distillation residue by centrifugation, the supernatant was distilled off in hexane, and a very dark red transparent viscous carboxylated product and unrecovered alkylphenol were obtained. An oil solution was obtained. The calcium content of this oil solution is 2.7
1wt%, and the acid value after acid neutralization is 19.1myKOH/
, 9.

Example 3 Dodecylphenol 393 was added to the same reaction vessel as in Example 1.
．． 5j', 98.4% purity calcium oxide 34.2.
9', heated and stirred under a pressure of 6 to 100 ml in a nitrogen stream, and when the temperature reached 165°C, 74% of ethylene glycol was added.
After 3 hours of stirring under the same conditions, the system was brought to atmospheric pressure and 145.7N of 150 neutral oil was added.

Next, the pressure of the system is gradually lowered, and the fraction 12.6.9° is mainly water with a top temperature of 92°C at 28 mH7i. A fraction of 84.6 g was distilled off. Next, the system was sealed and the temperature was lowered to 120°C, and then the temperature was reduced to 292 Nmj/mi.
Carbon dioxide was injected into the calcium salt solution of dodecylphenol at a flow rate of n. After 30 minutes, the temperature was raised to 178°C, the pressure was adjusted to 6 Kg/ad, and the mixture was stirred for 2 hours under the same conditions to obtain a reaction product solution of 574.4 J'a. .9Y150 22-toral oil 37. After diluting with ON, 3 mHI under reduced pressure.
The fraction mainly composed of dodecylphenol with a top temperature of 195°C is 197.5. ! i' was distilled off to obtain a distillation residue of 278.0.9. After removing 1.21% of the undissolved content from the hexane diluted solution of this residue by centrifugation, the supernatant hexane was distilled off to obtain a very dark yellowish red transparent viscous oil solution of the reaction product.

The calcium content of this oil solution was 6.29 wt%, and the acid value after acid neutralization was 45.6 mg KOH/11.

Example 4 A reaction was carried out in the same manner as in Example 1 except that barium oxide was used instead of calcium oxide, and an aromatic hydroxycarboxylic acid barium salt (substantially nonylsalicylic acid barium salt) was obtained.

Example 5 282.3.9% phenol, 76.71% barium oxide and 153.3F water were mixed in a reaction vessel similar to Example 1.
Heat and stir at 160"C for 3 hours under a pressure of Kg/all,
Next, gradually lower the system pressure x o OmHy until the top temperature is 8
Fraction 200.8.9 containing water up to 7.5° C. and some phenol was distilled off.

Add phenol 28O to the obtained barium ferulate solution.
After adding N''k, reaction with carbon dioxide was carried out in the same manner as in Example 3 to obtain reaction product 610, OII.This reaction product (aromatic hydroxycarboxylic acid mainly composed of barium hydroxybenzoate) The acid value after acid neutralization of barium salt) was 61.0 town KOH#.

Example 6 A reaction was carried out in the same manner as in Example 1 except that Kp-chlorophenol was used instead of nonylphenol, and an aromatic hydroxycarboxylic acid calcium salt (mainly a chlorohydroxybenzoic acid calcium salt) was obtained.

Claims (1)

[Claims] A method for producing an alkaline earth metal salt of an aromatic hydroxycarboxylic acid, which comprises reacting an alkaline earth metal salt of a phenol with carbon dioxide.