JP5751104B2 - Method for producing trans isomer of cyclohexanetricarboxylic acid anhydride - Google Patents

Description

  The present invention relates to a process for producing a trans form of cyclohexanetricarboxylic acid anhydride.

  Cyclohexanetricarboxylic acid anhydride is a color that constitutes paints, adhesives, molded products, resins for optical semiconductor encapsulants, or liquid crystal display devices (LCD), solid-state imaging devices (CCD), electroluminescence (EL) devices, etc. Thermosetting resin composition curing agent, polyimide resin, polyamideimide resin, polyamide resin, polyester resin, alkyd resin and other raw materials, modifiers, plasticizers, etc. It is useful as a lubricating oil raw material, medical and agrochemical intermediates, paint resin raw materials, toner resins and the like.

As a method for producing cyclohexanetricarboxylic acid anhydride, cis, cis-1,2,4-cyclohexanetricarboxylic acid obtained by hydrogenation of trimellitic acid and then recrystallization using tetrahydrofuran and / or acetonitrile as a solvent is anhydrous. A method of dehydration using a dehydrating reagent such as acetic acid (Patent Document 1), obtained by heating a trimellitic acid alkyl ester in the presence of a noble metal-based hydrogenation catalyst and an aliphatic alcohol to perform nuclear hydrogenation 1, 2, A method of dehydrating and ring-closing 1,2,4-cyclohexanetricarboxylic acid obtained by hydrolyzing 4-cyclohexanetricarboxylic acid alkyl ester in a sulfolane and / or dimethyl sulfoxide solvent, or 1,2,4- A method of dehydrating and cyclizing cyclohexanetricarboxylic acid by heating and melting (Patent Document 3) It is shown.

However, cis, cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride is obtained from (Patent Document 1) (Patent Document 2), and (Patent Document 3) is obtained from a mixture of cis, cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, still trans, trans An industrial production method of only -1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride is not known.

US Pat. No. 5,412,108 JP-A-8-325196 International Publication No. 2005/049597

An object of the present invention is to provide an industrial production method of trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride which has not yet been industrially obtained as a single component.

  As a result of extensive studies, the present inventor is an isomer of cyclohexanetricarboxylic acid that is a raw material for cyclohexanetricarboxylic anhydride (cis, cis-1,2,4-cyclohexanetricarboxylic acid and trans, trans-1, It was found that the solubility of 2,4-cyclohexanetricarboxylic acid) in water was significantly different, and that trans, trans-1,2,4-cyclohexanetricarboxylic acid had a lower solubility. Furthermore, it is possible to isolate trans, trans-1,2,4-cyclohexanetricarboxylic acid from these mixtures by crystallization using the characteristics, and further, this trans, trans-1,2,4-cyclohexanetricarboxylic acid It has been found that trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride can be produced industrially by dehydration, leading to the present invention.

That is, the present invention provides trans, trans-1,2,4-cyclohexanetricarboxylic acid from a mixture of cis, cis-1,2,4-cyclohexanetricarboxylic acid and trans, trans-1,2,4-cyclohexanetricarboxylic acid. A process for producing trans, trans-1,2,4-cyclohexanetricarboxylic acid, characterized in that the mixture comprises cis, cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride Of trans, trans-1,2,4-cyclohexanetricarboxylic acid, which is obtained by hydrolysis of a mixture of the product, trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride. It relates to a manufacturing method .
The present invention also includes trans, trans-1,2,4-cyclohexanetricarboxylic acid-1, characterized by dehydrating trans, trans-1,2,4-cyclohexanetricarboxylic acid obtained by the production method. It relates to a method for producing 2-anhydrides.

According to the present invention, a single component of trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride can be produced industrially. This allows the use of trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride alone or the cis, cis-1,2,4-cyclohexanetricarboxylic acid obtained by known production methods. Mixing with -1,2-anhydride is useful in that isomers can be mixed in an arbitrary ratio, and physical properties can be controlled.

[1. Production of cyclohexanetricarboxylic acid isomer mixture used for purification]
Although the manufacturing method of the cyclohexanetricarboxylic acid isomer mixture used as the raw material of the present invention is not particularly limited, it is necessary to contain trans, trans-1,2,4-cyclohexanetricarboxylic acid represented by the following formula (4). Become.
The cis, cis-1,2,4-cyclohexanetricarboxylic acid represented by the following formula (3) undergoes isomerization by heating. When cis, cis-1,2,4-cyclohexanetricarboxylic acid is heated and melted at 150 ° C. to 250 ° C., trans, trans-1,2,4-cyclohexanetricarboxylic acid is produced at a certain ratio. At this time, dehydration condensation also proceeds to produce cyclohexanetricarboxylic acid anhydride. For example, by using the method described in (Patent Document 3), trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride represented by the following formula (1) and the following formula (2) A mixture of cis, cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride as shown in FIG. Hydrolysis progresses by adding 0.5 to 5 times by weight, preferably 1 to 3 times by weight of water to this anhydride isomer mixture and heating, and isomer mixture of cyclohexanetricarboxylic acid as a purification raw material Can be obtained. In this case, the heating temperature is preferably 60 to 100 ° C, more preferably 75 to 85 ° C.

[2. Purification of trans, trans-1,2,4-cyclohexanetricarboxylic acid]
The purification of cyclohexanetricarboxylic acid in the present invention is carried out by adding 1 to 5 times by weight, preferably 2 to 3 times by weight of water to the isomer mixture of cyclohexanetricarboxylic acid, and heating (preferably 20 to 100 ° C.). Cis, cis-1,2,4-cyclohexanetricarboxylic acid having higher solubility in water is preferentially dissolved by transcrystallization, trans-1, trans-1,2, 4-cyclohexanetricarboxylic acid can be obtained.

[3. Dehydration condensation]
Trans, trans-1,2,4-cyclohexanetricarboxylic acid is dehydrated (dehydration condensation), preferably in glacial acetic acid solvent (2-5 times by weight, preferably 2.5-3.5 times by weight), anhydrous Trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride is obtained by dehydration (dehydration condensation) using acetic acid (1.0 equivalent to 2.0 equivalent, preferably 1.1 to 1.3 equivalent). Can do.

The method of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the following examples, analysis was performed by gas chromatography and NMR.

<Example 1>
Liquid cyclohexanetricarboxylic acid anhydride (trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride 58% by mass obtained in the same manner as in Example 1 in a 300 mL eggplant type flask (Patent Document 3) , Cis, cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride 4% by mass) and 150 g of water were added and stirred at 80 ° C. for 1 hour. Thereafter, the reaction system was cooled to room temperature (25 ° C.) to precipitate crystals. The crystals were subjected to suction filtration using a Buchner funnel and then vacuum dried to obtain trans, trans-1,2,4-cyclohexanetricarboxylic acid with a yield of 80% and a purity of 97%.
Next, 30 g of the obtained trans, trans-1,2,4-cyclohexanetricarboxylic acid was charged into a 300 mL eggplant type flask using 105 g of glacial acetic acid as a solvent, and 15 g of acetic anhydride was added thereto. After raising the temperature of the reaction system to 100 ° C., the reaction was completed in 2 hours, and the solvent was removed using an evaporator to precipitate crystals. The obtained crystals were suction filtered using a Buchner funnel, and rinsed with 2 g of toluene twice. By vacuum drying, trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride was obtained with a yield of 95% and a purity of 99%.

According to the present invention, a single component of trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride can be produced industrially. This allows the use of trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride alone or the cis, cis-1,2,4-cyclohexanetricarboxylic acid obtained by known production methods. Mixing with -1,2-anhydride is useful in that isomers can be mixed in an arbitrary ratio, and physical properties can be controlled.
As a result, cyclohexanetricarboxylic acid anhydride can be used for paints, adhesives, molded products, optical semiconductor encapsulant resins, liquid crystal display devices (LCD), solid-state imaging devices (CCD), and electroluminescence (EL) devices. Thermosetting resin composition curing agent, polyimide resin, polyamideimide resin, polyamide resin, polyester resin, alkyd resin, etc. that can be suitably used for coating solution for protective film of color filter that constitutes etc. It has the potential to give further properties to plasticizers, plasticizers and lubricant oil raw materials, medical and agrochemical intermediates, paint resin raw materials, toner resins, and the like, and has great industrial significance.

Claims (2)

By crystallization using water, trans, trans-1,2,4-cyclohexane was obtained from a mixture of cis, cis-1,2,4-cyclohexanetricarboxylic acid and trans, trans-1,2,4-cyclohexanetricarboxylic acid. A process for producing trans, trans-1,2,4-cyclohexanetricarboxylic acid characterized by separating tricarboxylic acid , wherein the mixture is cis, cis-1,2,4-cyclohexanetricarboxylic acid-1, Trans, trans-1,2,4-cyclohexane obtained by hydrolysis of a mixture of 2-anhydride and trans, trans-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride A method for producing tricarboxylic acid . Trans, trans-1,2,4-cyclohexanetricarboxylic acid-1, 2 characterized by dehydrating trans, trans-1,2,4-cyclohexanetricarboxylic acid obtained by the method according to claim 1 -Method for producing anhydride.