JPS6277350A - Production of dialkali metallic salt of naphthalene-2,6-dicarboxylic acid - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an acid part for a heat- resistant polyester raw material in high reaction reproducibility and in high yield, by heating an alkali metallic salt of naphthoic acid as a raw material in the presence of a catalyst under pressure of a carbonic acid gas by the use of a specific compound as a dispersion medium or a solvent. CONSTITUTION:An alkali metallic salt of naphthoic acid and/or a dialkali metallic salt of naphthalenedicarboxylic acid is reacted in the presence of a catalyst (preferably zinc compound) under pressure of a carbonic acid gas (preferably 10-70kg/cm<2> G) at 350-500 deg.C, preferably 380-470 deg.C by the use of an aprotic polycyclic aromatic compound having 2-3 rings as a dispersion medium or a solvent to give the aimed compound. Naphthalene, lower alkylnaphthalene, diphenyl, diaryl ether, etc., are used as the aprotic polycyclic aromatic compound having 2-3 rings and the amount of it used is 0.5-10, usually 1-5 times as much as the raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing a dialkali metal salt of naphthalene-2,6-dicarboxylic acid.

naphthalene-2,6-dicarboxylic acid dialkali metal jl
can be easily converted into the corresponding carbonic acid, that is, naphthalene-2,6-dicarboxylic acid, by acid precipitation, but this naphthalene-2,6-dicarboxylic acid has been attracting attention in recent years as an acid moiety in heat-resistant polyester raw materials. , is a compound with an industrially high value (see #if Publication No. 54-945).

BACKGROUND OF THE INVENTION Conventionally, the so-called Henkel process has been proposed as one of the methods for producing naphthalene-2,6-dicalphone/alkali metal. This method uses naphthalene monocalphone M (
Alkali metals of naphthoic acid) or dialkali metals of naphthalene dicarboxylic acid, or mixtures thereof, are used as catalysts such as cadmium, zinc, mercury liquefaction, or/\rokenide, sulfate, carbonate. m, with Calhon resistant ■ red T9,) under pressure of father's sake, 350
It is better to heat it to a temperature higher than °C. From naphthoic acid alkali metal salt, naphthalene-2,6-carphone dialkali metal salt and naphthalene are produced by a disproportionation reaction, and naphthalene dicarboxylic acid dialkali metal j3! (a) B, Rae
cke.

Angew, CheIm, 70. l (195
8); b) B. Raecke et al., Org, Sy.
n, Co11. Vol 5.813 (1973)
; c) Yamashita et al., compounding, 20.501 (In2)
;d) E, McNelis.

J, Org, Chem,, 3a, 1208 (+9
65); e) U.S. Pat. No. 2,823,231: f) 4ν
See Publication No. 51-10224].

Most of the naphthoic acid alkali metal salts or decaphthalene dicarboxylic acid dialkali metal salts, which are the raw materials of the Henkel process, and the product naphthalene-2,6-dicarboxylic acid dialkali metal salts all have a melting point of 400°C. These are the above compounds. These alkali metal salts are soluble in protic solvents such as water and alcohol, but at temperatures above 350°C, which is the reaction temperature of the Henkel method, protic solvents react with the alkali metal salts and dissolve them. Because it decomposes, it cannot be used as a reaction solvent.For this reason, conventionally, naphthalene-2,6-dicarboxylic acid and an alkali metal salt were used by Henkel! When manufacturing A, a method has been proposed in which a combined powder of raw materials and a catalyst (B) is heated and reacted under pressure with carbonic acid sludge without a solvent to produce a solid product.

However, in this method, since the raw material *18 and the product are solid, there is a disadvantage that the operations for charging them into the reactor and taking them out from the reactor are more complicated than in the case of liquids.

In addition, because the present invention is a conventional method or a solvent-free reaction, problems arise in that the +IT compatibility of the reaction is poor and the yield and selectivity of the target product are low. It revealed that.

That is, the reaction is usually carried out by heating the reactor, or
Because the raw materials and products are high melting point solids and the absence of solvent, heat transfer between the reaction mixtures is slow and non-uniform. For this reason, some parts of the reaction mixture are overheated and a large amount of carbides are produced, and some parts of the reaction mixture have insufficient reaction heat and the reaction is incomplete, resulting in the remaining raw materials and the target naphthalene-2,6-dicarboxylic resistance. By-products of isomers other than dialkali metal salts become visible. As a result, both the yield and selectivity of the dialkali metal salt of naphthalene-2,6-dicarboxylic acid, which is [1], were low, and the reproducibility of the reaction was also poor.

Problems to be Solved by the Invention The title of the present invention was created by intensive study to solve the problems of the conventional method.
The present invention has been completed by discovering a method that improves the yield and selectivity of dialkali metal dicarboxylic acid salts and improves the reproducibility of the reaction.

Means for Solving the Problems The present invention provides an aprotic polycyclic product having 2 to 3 rings, in which a naphthalene dicarboxylic acid alkali metal salt and/or a dialkali metal naphthalene dicarboxylic acid is reacted with a catalyst under pressure of carbon dioxide gas. This is a process V for producing a dialkali gold salt in naphthalene-2,6-dicarboxylic solution, which is characterized by using an aromatic compound as a dispersion medium or solvent and heating in the dispersion medium or solvent.

The raw material for the method of the present invention is 1 liter of alkali gold naphthoate.
or a dialkali metal salt in naphthalene dicarbonate, or a mixture thereof. As the alkali metal naphthoic acid salt, the 1- or 2-isomer or a mixture thereof can be used. In addition, as dialkali gold naphthalene dicarboxylic acid Jrs tp, 1.2-11.3-1l, 4
-11.5-, l, 6-11.7-1l, 8-12,3
The -12,6-72.7-isomer or a mixture thereof can be used. However, among the above isomers, naphthalene-
The 2,6-dicarbonate dialkali-resistant metal salt is the object compound of the present invention, but it can be used as a raw material when it itself is contained in a small amount or when a crude mixture is used. As for the alkali metal salt, similar results are obtained for potassium as in the usual Henkel method.

As the catalyst, any catalyst used in the disproportionation reaction or rearrangement reaction in IIQ's Henkel process can be used. Representative examples include cadmium, zinc, and mercury compounds. However, cadmium and mercury compounds have +1 toxicity and are expensive.
From an industrial point of view, the use of zinc compounds or IIT is preferable.

Examples of the zinc compound include zinc halides such as zinc chloride, zinc bromide, and zinc iodide, calphonic zinc such as naphthalene zinc and naphthalene dicarboxylic zinc, zinc oxide, and zinc carbonate. It is also possible to add a small amount of alkali halides such as potassium chloride, potassium bromide, potassium iodide, sodium bromide, and sodium iodide as a supporting catalyst.The use of the catalyst is as follows:
Usually, it is 1 to lomo% based on the raw material.

It is preferable that the raw material and the catalyst are combined by more than 17 times. For this purpose, the catalyst is added to an aqueous solution of the raw material and mixed well, and then the water is heated and distilled off. There is a method of grinding the raw material and the catalyst, and a method of stirring and mixing them in a dispersion medium or solvent of a polycyclic aromatic compound, which will be described later. There is no problem with the present invention.

For unreleased Ql, the original '1 and the catalyst are mixed in a dispersion medium or solvent with the addition of carbonic acid residue 1! , heat the reaction under the following conditions. The dispersion medium or solvent used here should be stable under the reaction conditions.
It is a substance that becomes a static body under reaction conditions 11.

Such substances may be either intermediate or intermediate compounds. , 4-: The disproportionation reaction and/or rearrangement reaction Iε in the invention substantially proceeds at 350 to 500'C. Therefore, if the substance has a melting point of 50 (1°C or less, critical temperature 350°C or more), any anti-f
It becomes liquid under 5 conditions and can be used as a dispersion medium or solvent. As a result of searching for a substance that has such a melting point and critical temperature, is stable under reaction conditions F, and improves the reaction yield, the wood seller and others found that it satisfies these requirements. We have discovered an aprotic polycyclic aromatic compound having 2 to 3 rings.

Specific examples of aprotic polycyclic aromatic compounds include naphthalene, lower alkylnaphthalenes such as methylnaphthalene and dimethylnaphthalene, lower alkyl di-containers such as diphenyl, methyldiphenyl and dimethyldiphenyl, diaryl ethers such as diphenyl ether, and terphenates. Examples include chlorine, anthracene, phenanthrene, and mixtures thereof. The amount used is usually 1 to 5 times the amount of the original.

The solubility of the raw material and catalyst of the present invention in the polycyclic aromatic compound is extremely low. Therefore, the raw materials and catalyst are usually in the form of a slurry dispersed in the polycyclic aromatic compound! C. It will be subjected to reaction.

At this time, in order to improve the dispersion of the original material and the catalyst, it is desirable that the raw materials and the catalyst, or a mixture thereof, be pulverized in advance.

The presence of cold water severely inhibits the reaction of the present invention. Therefore, in carrying out the reaction of the present invention, good reaction results can be obtained by dehydrating and drying the raw materials, the catalyst, and the polycyclic aromatic compound in advance. As for the dehydration and drying method, any commonly used method can be used, such as heating ventilation drying or heating vacuum drying for raw materials and catalysts, distillation purification for the polycyclic aromatic compounds, etc. I can do it. Furthermore, the method shown below can be added as one of them.

That is, it is a method in which a slurry consisting of a mixture of raw materials, catalyst, and the polycyclic aromatic compound is heated and a part of the slurry is distilled off, and if water is contained, this is used as the first distillation fraction. It can be easily removed from the mixture by distillation. In this method, the polycyclic aromatic compound has a boiling point of 20% at normal pressure.
It is a compound with a crystalline boiling point of 0''C or higher, and is based on the fact that it has a large boiling point Xi- with water.

The raw wood, the catalyst, and the polycyclic aromatic compound may be introduced into the Sannagi reactor either singly or as a mixture. When a mixture of three groups is introduced, a method of heating the mixture above the melting point of the polycyclic aromatic compound to form a slurry and introducing the slurry into a reactor is also a preferable method that takes advantage of the features of the present invention. Implementation 7'H5's -.

The raw materials, catalyst, and polycyclic aromatic compound introduced into the reactor in this manner are heated under pressure to cause a reaction. At this time, it is preferable to stir the contents of the reactor in order to ensure uniform dispersion of the original material 4 and the catalyst and uniform heat transfer. There is no problem in terms of the quality of the wood, regardless of whether the type of pottery is a batch type or a continuous type.

The pressure of 33M waste is 5 to η when converted to the pressure at 100°C.
100Kg/CQ1211 G, preferably 10-7
It is in the range of 0Kg/cm'・G. The reaction temperature is basically the same as the previously known reaction temperature of Henckelnian. That is, the temperature is usually in the range of 350 to 500 °C, although it varies depending on the type of material and catalyst, and from the viewpoint of causing the reaction to occur quickly and suppressing side reactions such as carbide formation, the temperature is 380 to 470 °C. The preferred range is 0.000 m. The time varies depending on the reaction temperature, but is usually in the range of 5 minutes to 3 hours.

After the reaction is completed, the reaction mixture is taken out from the reactor and separated for 1 minute.
Perform purification operation. When taking out the reaction mixture, a method of keeping the reaction mixture at a temperature higher than the melting point of the polycyclic aromatic compound and taking it out in the form of a slurry is specially mentioned as a simple method that takes advantage of the features of the present invention.

Add toluene or xylene to the reaction mixture taken out.
! When a solvent and water are added, the polycyclic aromatic compound has 4
On the other hand, the product naphthalene-2
, 6-dicarbonate dialkali metal +14 is soluble in water. Further, the catalyst and by-product carbide become insoluble in both. These are separated by hs or minute M'J operation, and an aqueous solution of naphthalene-2,6-dicarboxylic alkali Jinku Jia is prepared.

From this aqueous solution, t! A naphthalene-2,6-dicarboxylic solution can be obtained by acid precipitating in two atmospheres.

The present invention will be explained in more detail in Examples and Comparative Examples below.
S1.

Examples 1 to 12 For naphthalene-1,8-dicarboxylic dipotassium, that is, to 1,8-naphthalic dipotassium qjlo, Og, zinc chloride and potassium iodide were added to the dicarboxylic t-salt at amo% each or 1 mol each. % and powder it in a whole mill? After adjusting the conditions, the mixture was charged into a reactor equipped with a stirrer.

Add a polycyclic aromatic compound of a predetermined M to this and heat to 100°C.
After replacing the inside of the reactor with carbonic acid scum, carbonic acid scum was introduced to a predetermined pressure (initial pressure in Table 1). Next, the mixture in the reactor was heated to a predetermined reaction temperature at a rate of 4°C/win while stirring, and further stirred at the same temperature for 1 hour to complete the reaction.

After the reaction is complete, add 200 g of toluene and 2 g of water to the reaction mixture.
ooJ was added and stirred well. After removing solids that were insoluble in both the aqueous layer and the toluene layer, the aqueous layer was separated. A portion of this aqueous layer was collected, and using high performance liquid chromatography, the amount of naphthalene 2.6 dicarboxylic potassium contained therein was quantified using an internal standard method, and the yield was calculated.

As polycyclic aromatic compounds, naphthalene, methylnaphthalene, diphenyl, 44 compounds of diphenyl ether and diphenyl (mixing ratio 7:3), and phenanthrene were used, respectively. The results are shown in Table 1.

Comparative Example 1 'Jk The same operation as in Example 1 was performed except that naphthalene as the polycyclic aromatic compound was not added. The results are shown in Table 1.

(Left below) Examples 13 to 21 Zinc iodide was used instead of the combination of zinc chloride and potassium iodide as a catalyst in Example 3.

combination of zinc zinc oxide and potassium bromide,
730g of naphthalate coexisted using zinc 1,8-naphthalate, a combination of zinc 1,8-naphthalate and potassium iodide, zinc oxide, a combination of zinc oxide and potassium iodide, cadmium iodide, and cadmium chloride. A similar reaction was performed below. The amount of catalyst is 5oofL% based on the 1.8-naphthalate dipotassium resistance of the raw material. The results are shown in Table 2.

Comparative Examples 2 to 10'J? In Examples 13-21, similar reactions were carried out without the addition of naphthalene. The results are shown in Table 2 for Example 13~
It is also listed together with the results of 21.

(Hereinafter F margin) Examples 22 to 26 Instead of the 1,8-naphthoic acid potassium salt as the raw material in Example 3, naphthalene-2,3-dipotassium dicarphonate Flj, 2-potassium naphthoate 1j4.1.8- Mixture of naphthoic acid potassium salt and 2-naphthoic acid potassium salt (heavy iJ-ratio l, 1), isomer mixture of naphthalenedicarbone dipotassium salt, i.e. 2.6-12.7-
A similar reaction was carried out in the presence of 30 g of naphthalene using a mixture of 21,6-11.7-11,3-isomers in Gensai 1 and using a combination of zinc chloride and potassium iodide or cadmium iodide as a catalyst. I did it.

The results are shown in Table 3. In addition, the catalyst is early. Both are 8mo% relative to original #I.

Comparative Examples 11-15 In Examples 22-26, the same reactions were carried out without adding naphthalene. The results are shown in Table 31, Example 22~
It is also listed together with the results of 26.

Effects of the Invention In the present invention, by using a polycyclic aromatic compound as a reaction dispersion medium or solvent, the reproducibility of the reaction is improved by +1.
Furthermore, the yield and selectivity of the target dialkali metal salt of naphthalene-2,6-dicarboxylic acid were improved.

The present invention has made it possible to produce naphthalene-2,6-dicarboxylic acid cheaply and easily, paving the way for commercial production.

Agent Patent Attorney Masaru Inoue'r Itozogoneyama Niray 13 See-ri November 8, 1985[] Director General of the Special Correction Agency Tono 1 ・l'Gji1 Indication 1985 Special Edition fI No. 215179 No. 2, Benefits of the invention - Method for manufacturing dialkali metal salt of naphthalene-2,6-dicarphonic acid 3, Supplement 1 ■ Relationship with outside of the vehicle of the person performing the 2 Patent applicant address: 2-6 Otemachi, Chiyoda-ku, Tokyo Number 3 name (6
65) Nippon Steel Corporation Representative Takeshi 1) Yutaka (and 1 other person) 4. Agent 101 Address 2-19-45 Kanda Tsukasa-cho, Chiyoda-ku, Tokyo Detailed explanation of the invention in the specification subject to amendment Fence 6, Contents of amendment (1) Page 7, line 11 of the specification "...1~IOmo Q
%. Add the following communication after j.

"Also, the use of OM as a catalyst is usually 1 to 1
Omo1%. In the following sentence Q, catalysts and co-catalysts are collectively referred to as catalysts without any particular distinction. (2) Yu] In the 6th line of page 12 of the specification, ``mata catalyst'' is corrected to ``also catalytic zinc compounds or cadmium compounds.''

(3) Amend Table 1 on page 15 of the J Deposit as shown in the attached sheet.

(4) On page 16, line 11 of the specification, "B11Io is a percentage of B11Io." is corrected to the following sentence.

If the catalyst is a single compound, it is 8 mo1%, and in the case of a combination, it is 8111 osL for each compound.
%. (4) Tables 2 and 3 on page 17 of the specification are corrected as shown in the attached sheet.

(5) On page 18, line 6 of the specification, [Mixture J with toe acid dipotassium salt] is corrected to "mixture with toe acid resistant potassium salt."

(6) Akira 1ffit 18th page 13th line c+ “” 14
The deviation of row ['l)r catalyst jJ-c't' is also 8mof1% with respect to the original ['. ” is revised to the following sentence J7.

“In the case of cadmium iodide, it is 8 m
o1%, and in the case of a combination of nΔzinc and potassium iodide, it is 8 mou% for each. ”

Claims (2)

[Claims] (1) Naphthoic acid alkali metal salt and/or naphthalene dicarboxylic acid dialkali metal salt are mixed together with a catalyst under carbon dioxide gas pressure, using an aprotic polycyclic aromatic compound having 2 to 3 rings as a dispersion medium or solvent; 1. A method for producing a dialkali metal salt of naphthalene-2,6-dicarboxylic acid, the method comprising heating at . (2) An aprotic polycyclic aromatic compound having 2 to 3 rings,
The method according to claim (1), which is naphthalene, lower alkylnaphthalene, diphenyl, lower alkyl diphenyl, diaryl ether, terphenyl, anthracene, phenanthrene, or a mixture thereof.