JPH04279578A - 4,4',5,5'-binaphthyltetracarboxylic acid dianhydride and its production - Google Patents

Abstract

PURPOSE:To obtain high-purity 4,4',5,5'-binaphthyltetracarboxylic acid dianhydride useful as a raw material for polyimide resin. CONSTITUTION:A 4-halogenonaphthalic acid or an alkali metallic salt thereof is dehalogenated and dimerized in the presence of (1) a palladium catalyst, (2) water and (3) a polyhydric alcohol and/or a formaldehyde, then the dimerized product is precipitated with an acid and the prepared crystal is made anhydrous to give 4,4',5,5'-binaphthyltetracarboxylic acid dianhydride.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to 4,4',5,5'-binaphthyltetracarboxylic dianhydride and a method for producing the same. Specifically, the present invention relates to a novel 4,4',5,5'-binaphthyltetracarboxylic dianhydride that is valuable as a raw material for highly functional polyimide resins, and a method for producing the same.

0002

BACKGROUND OF THE INVENTION Biphenyl tetracarboxylic acids or their anhydrides have been known, but binaphthyltetracarboxylic dianhydride has not been known.

0003

SUMMARY OF THE INVENTION An object of the present invention is to provide a raw material suitable for producing a highly functional polyimide resin having excellent heat resistance and other physical properties.

0004

[Means for Solving the Problem] As a result of repeated studies to achieve the above object, the present inventors have developed a new substance, 4,4',5,5'-binaphthyl. The present invention was achieved by discovering that tetracarboxylic dianhydride is suitable as a raw material for polyimide resin, and by establishing an industrially advantageous method for producing this material. That is, the gist of the present invention is to provide 4,4',5,5'-binaphthyltetracarboxylic dianhydride, and to prepare 4-halogenonaphthalic acid or an alkali metal salt thereof using (1) a palladium catalyst, ( 2) dehalogenated dimerization in the presence of water and (3) polyhydric alcohol and/or formaldehyde, followed by acid precipitation of the dimerized product, and anhydrification of the obtained crystals to produce 4,4', An object of the present invention is to provide a method for producing 5,5'-binaphthyltetracarboxylic dianhydride.

[0005] The present invention will be explained in detail below. The 4,4',5,5'-binaphthyltetracarboxylic dianhydride of the present invention is a new substance that has not been described in any literature, and its structure was confirmed from the analysis results shown in Examples below. The compound of the present invention is
For example, as detailed below, 4-halogenonaphthalic acid or an alkali metal salt thereof and a palladium catalyst are combined in a mixture of water and a polyhydric alcohol, or water and formaldehyde, or water, a polyhydric alcohol, and formaldehyde. It can be industrially advantageously produced by dehalogenation dimerization in the presence of halogens.

[0006] Specific examples of 4-halogenonaphthalic acid used as a raw material include 4-chloronaphthalic acid, 4-bromonaphthalic acid, 4-iodonaphthalic acid, etc. Among them, 4-chloronaphthalic acid, 4- Bromonaphthalic acid is preferred, and it is particularly preferred to use 4-chloronaphthalic acid, which is inexpensive. Further, as the alkali metal salt, sodium salt, potassium salt, lithium salt, etc. are used. Note that 4-halogenonaphthalic acid can also be used in the form of anhydride.

Palladium catalysts used in the production of the substances of the present invention include palladium salts of inorganic acids such as palladium chloride and palladium nitrate; palladium salts of organic acids such as palladium acetate and palladium phthalate; -diketone-containing palladium chelate salts and metallic palladium. Among these, those in which metallic palladium is supported on a carrier such as activated carbon, silica, alumina, silica alumina, titanium oxide, magnesia, diatomaceous earth, graphite, barium carbonate, calcium carbonate, or zeolite are preferred, and palladium-activated carbon catalysts are particularly preferred. . The metal palladium supported on these palladium-carrier catalysts is preferably about 0.1 to 20% by weight, particularly about 0.5 to 10% by weight, based on the palladium-carrier. The amount of palladium catalyst used is 4-halogenonaphthalic acid 1
100 to 0.00 in terms of palladium atoms per mole
1 mg atom, preferably 30-0.1 mg atom.

In the method of the present invention, water and a polyhydric alcohol, water and formaldehyde, or water and a polyhydric alcohol are added to a reaction system consisting of 4-halogenonaphthalic acid or an alkali metal salt thereof and a palladium catalyst. - The presence of alcohol and formaldehyde is an essential requirement. When an alkali metal salt of 4-halogenonaphthalic acid is used as a raw material, it is preferably used as an aqueous solution since it is water-soluble. On the other hand, when using 4-halogenonaphthalic acid or its anhydride as a raw material, it is difficult to dissolve in water, so it is best to add a base such as an alkali metal hydroxide to dissolve it in water to make an aqueous solution. desirable.

The amount of water is 0.1% (volume) or more, usually 1% or more, based on the total amount of the reaction medium containing the raw materials, palladium catalyst, polyhydric alcohol and/or formaldehyde, etc., supplied to the reaction. It is selected from a range of approximately 70% (capacity). Using an excessive amount of water will actually reduce the yield of the target product. Note that an inert organic solvent can be used in combination with water. Suitable organic solvents include, for example, ethers such as tetrahydrofuran and dioxane, ketones such as acetone, diethyl ketone and methyl ethyl ketone, and esters such as ethylene glycol diacetate, the amount of which varies depending on the solvent used. Although it varies, usually 0.01 to 1 part by weight of 4-halogenonaphthalic acid or its anhydride.
00 parts by weight.

The polyhydric alcohols used in the method of the present invention include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-propanediol, and 1,4-butanediol. Examples include divalent alcohols such as alcohol, trivalent alcohols such as glycerin, and tetravalent alcohols such as pentaerythritol. Among them, ethylene glycol, propylene glycol, , 2-butanediol, glycerin, and other divalent or trivalent alcohols are preferred. The amount of polyhydric alcohol to be used is usually 0.01 to 50 mol, preferably 0.1 to 10 mol, per 1 mol of 4-halogenonaphthalic acid. Outside this range, the yield of the target product will be low. descend. These polyhydric alcohols may be added in a predetermined amount at once, or may be supplied continuously or intermittently during the dehalogenation dimerization reaction.

On the other hand, as the formaldehyde, paraformaldehyde and commercially available 35% formalin solution are suitable. The amount of formaldehyde used is 4 on a monomer basis.
-Usually 0.01 to 50 per mole of halogenonaphthalic acid
mol, preferably 0.1 to 10 mol. In the method of the present invention, it is also preferable to use a halogen acceptor in combination to neutralize and remove halogen or hydrogen halide produced as a by-product in the dehalogen dimerization reaction. The halogen acceptor may be any substance that can accept halogen or hydrogen halide, and organic bases or inorganic bases are usually used.

Examples of organic bases include tertiary amines such as triethylamine, tributylamine and trioctylamine, and examples of inorganic bases include alkali metal compounds and alkaline earth metal compounds. Among these, alkali metal compounds are preferred, and specifically alkali metal inorganic acid salts such as carbonates, phosphates, and borates, organic acid salts such as acetates and phthalates, or hydroxides and alkoxides. etc. are used. Particularly preferred examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, potassium tert-butyrate, and the like. The amount of these halogen acceptors to be used is 0.01 to 100 mol, preferably 1 to 10 mol, per 1 mol of 4-halogenonaphthalic acid; outside this range, the yield of the target product decreases.

In the dehalogen dimerization reaction of the present invention, 4-halogenonaphthalic acid or an alkali metal salt thereof, a palladium catalyst, water, a polyhydric alcohol and/or formaldehyde are mixed, and if necessary, a halogen acceptor is added. and/or an organic solvent under a pressure of normal pressure to 200 kg/cm2, preferably normal pressure to 100 kg/cm2.
It is carried out by heating to a temperature of 250°C, preferably 50 to 200°C. The reaction is carried out in the presence of an inert gas such as nitrogen gas if necessary. The reaction time is appropriately selected depending on the type of raw materials, amount of catalyst, reaction temperature, pressure, etc., but is usually about 10 minutes to 24 hours. Further, the reaction can be carried out in any of a batch manner, a semi-batch manner, and a continuous manner.

After the reaction is completed, the palladium catalyst used in the reaction is separated and recovered from the reaction solution by a conventional method, such as an extraction method, a crystallization method, or a reduction method. When a palladium-carried catalyst is used, the catalyst can be separated and recovered by filtration and used repeatedly in the dehalogenation dimerization reaction. The reaction product can be recovered by acid precipitation of the reaction solution from which the catalyst has been removed. As the acid used for acid precipitation, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid are generally used, and sulfuric acid is particularly preferred. The concentration of acid is 1-100
It is selected within the range of 5% to 40% by weight, preferably 5 to 40% by weight.
It is. The acid precipitation treatment is preferably carried out by dropping the reaction solution from which the catalyst has been removed into an acid, and the crystals precipitated by the acid precipitation are collected by filtration, dried, and then purified by a volatilization method.

[0015] Naphthalic acid, which is produced as a by-product during the dehalogenation dimerization reaction, is dehydrated and ring-closed when heated to 150 to 320°C under reduced pressure and volatilized as an anhydride, so that it can be easily separated from the target product. When the product after separation of naphthalic acid is further heated to a high temperature under reduced pressure, 4,4',5,5'-binaphthyltetracarboxylic dianhydride, which has been anhydrified by dehydration and ring closure, evaporates and is obtained as high-purity crystals. be able to.

[0016]

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Example 1 (1) Dimerization step: 503 ml of distilled water was placed in a stainless steel flask with a volume of 2000 ml, and 4-
Chloronaphthalic anhydride (50.87% water content) 328
．． 7 g and 169.8 g of potassium hydroxide,
Stir to dissolve. Then 5% by weight palladium carbon
Bonn catalyst (manufactured by NE Chemcat, water content 54.
64%) 33.7 g and 40% glycerin aqueous solution 16
5.5 g was added, heated to 102° C. under normal pressure, and reacted for 5 hours. After the reaction is complete, high performance liquid chromatography
As a result of analysis, the reaction solution contained dechlorinated potassium 1,8-naphthalic acid salt and
-Binaphthyltetracarboxylic acid tetrapotassium salt was produced. The conversion rate of 4-chloronaphthalic acid was 100%, and the yield of tetrapotassium 4,4',5,5'-binaphthyltetracarboxylic acid salt was 23%.

(2) Acid precipitation step: The reaction solution from the dimerization step was filtered to remove the palladium-carbon catalyst, and the filtrate was dropped into 1450 ml of a 15% sulfuric acid aqueous solution over 1 hour for acid precipitation. However, yellowish-white crystals precipitated out. Crystals were collected by filtration and dried under reduced pressure at 100° C. for 8 hours.

(3) Purification step: Crystal 1 obtained in the acid precipitation step
42.8 g was placed in a 500 ml flask and heated to 310°C under reduced pressure to remove the 1,8- produced by the dechlorination reaction.
Binaphthalic acid was separated and removed by volatilization as anhydride. The residue was subsequently heated to 350°C under reduced pressure to obtain 32.6 g of orange-white 4,4',5,5'-binaphthyltetracarboxylic dianhydride as a volatile substance. As a result of mass spectrum measurement of this substance, the molecular ion peak was m/e 3
The molecular weight was 94, which matched the molecular weight of the target product. Further, the decomposition pattern indicated that it was an anhydride, and this was also supported by the measurement results of Fourier transform infrared transmission spectrum (KBr method). From these results, this substance is 4,
It was confirmed that it was 4',5,5'-binaphthyltetracarboxylic dianhydride.

[0020]

According to the present invention, it is possible to industrially advantageously provide a novel 4,4',5,5'-binaphthyltetracarboxylic dianhydride that is valuable as a raw material for highly functional polyimide resins. can.

Claims (2)

[Claims] Claim 1: 4,4',5,5'-binaphthyltetracarboxylic dianhydride. Claim 2: 4-halogenonaphthalic acid or an alkali metal salt thereof is mixed with (1) a palladium catalyst, (2) water and (
3) Dehalogen dimerization in the presence of a polyhydric alcohol and/or formaldehyde, followed by acid precipitation of the dimerized product, and anhydrification of the obtained crystals 4,
A method for producing 4',5,5'-binaphthyltetracarboxylic dianhydride.