JP6699940B2 - Method for producing tetracarboxylic dianhydride having ester group - Google Patents

Description

  The present invention relates to a method for producing a tetracarboxylic dianhydride having an ester group, which is useful as a resin raw material such as polyimide and polyester, a curing agent for epoxy resins and polyurethane resins, and an additive.

  Among tetracarboxylic dianhydrides having an ester group, the following general formula (2)

（式中、Ａは芳香族炭化水素基又は環状炭化水素基を表し、Ｒ_１及びＲ_２は同一又は異なって炭素数１〜１２のアルキル基、ハロゲン原子、炭素数４〜１２のシクロアルキル基、又は炭素数６〜１２の芳香族炭化水素基を表し、ｍ及びｎは０または１〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていても良い。）
で表される、主骨格（上記一般式（２）におけるＡに相当する部分）が芳香族炭化水素基又は環状炭化水素基に代表される環状骨格であって、該主骨格に直接アリール基が付加したテトラカルボン酸二無水物は、高ガラス転移温度(高耐熱性)、高透明性、低吸水率、低誘電性、高有機溶媒溶解性および高エッチング特性を有することから、各種電気デバイスにおける電気絶縁膜およびフレキシブルプリント配電板、電子ペーパー用基板、液晶ディスプレー用基板、有機ＥＬディスプレー用基板、太陽電池用基板、感光材等として有益であり、活発な開発検討がされている（例えば特許文献１）。

(In the formula, A represents an aromatic hydrocarbon group or a cyclic hydrocarbon group, and R ₁ and R ₂ are the same or different and are an alkyl group having 1 to 12 carbon atoms, a halogen atom, a cycloalkyl group having 4 to 12 carbon atoms. Or an aromatic hydrocarbon group having 6 to 12 carbon atoms, m and n each represent 0 or an integer of 1 to 4. When R ₁ and/or R ₂ are present in plurality, each is the same or different. It may be.)
The main skeleton (portion corresponding to A in the general formula (2)) represented by is a cyclic skeleton represented by an aromatic hydrocarbon group or a cyclic hydrocarbon group, and an aryl group is directly attached to the main skeleton. The added tetracarboxylic acid dianhydride has a high glass transition temperature (high heat resistance), high transparency, low water absorption, low dielectric properties, high organic solvent solubility and high etching characteristics, and therefore, in various electric devices. It is useful as an electric insulating film and a flexible printed power distribution board, a substrate for electronic paper, a substrate for liquid crystal display, a substrate for organic EL display, a substrate for solar cells, a photosensitive material, etc. 1).

  On the other hand, although various known methods for producing a tetracarboxylic dianhydride having an ester group, among them, since the halides of trimellitic anhydride as a raw material are easily available, bisphenols and anhydrous Various methods of reacting with trimellitic acid halide have been studied (for example, Patent Documents 2 and 3). However, in these known production methods, the reaction between bisphenols in which two aryl groups are connected by an alkyl group and trimellitic acid chloride is almost the same as in the reaction between bisphenol A and trimellitic acid halide. The reaction of bisphenols in which the aryl group is directly connected to the cyclic skeleton and trimellitic acid halide is hardly known, and the known method is insufficient in terms of yield and purity. However, it is difficult to say that this method is industrially feasible because it becomes difficult to stir.

JP, 2007-91701, A JP-A-63-303976 Japanese Patent Laid-Open No. 08-53436

  An object of the present invention is to provide a tetracarboxylic acid dianhydride having a cyclic skeleton represented by an aromatic hydrocarbon group or a cyclic hydrocarbon group as a main skeleton, and an aryl group directly added to the main skeleton with high purity and high purity. An object of the present invention is to provide a method for producing the compound with high yield and industrial advantage.

  The present inventors have found that the above problems can be solved by reacting trimellitic anhydride halide with bisphenol in the presence of nitriles and aromatic hydrocarbons. Specifically, the following inventions are included.

[1]
In the presence of nitriles and aromatic hydrocarbons, trimellitic anhydride halide and the following general formula (1)

（式中、Ａは芳香族炭化水素基又は環状炭化水素基を表し、Ｒ_１及びＲ_２は同一又は異なって炭素数１〜１２のアルキル基、ハロゲン原子、炭素数４〜１２のシクロアルキル基、又は炭素数６〜１２の芳香族炭化水素基を表し、ｍ及びｎは０または１〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていても良い。）
で表されるビスフェノール類とを反応させる、以下一般式（２）

(In the formula, A represents an aromatic hydrocarbon group or a cyclic hydrocarbon group, and R ₁ and R ₂ are the same or different and are an alkyl group having 1 to 12 carbon atoms, a halogen atom, a cycloalkyl group having 4 to 12 carbon atoms. Or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and m and n each represent 0 or an integer of 1 to 4. When R ₁ and/or R ₂ are present in plurality, each is the same or different. It may be.)
The following general formula (2) is used to react with a bisphenol represented by

（式中、Ａ、Ｒ_１、Ｒ_２、ｍ及びｎの意味は上述の通りである。）
で表されるテトラカルボン酸二無水物の製造方法。

(In the formula, the meanings of A, R ₁ , R ₂ , m and n are as described above.)
The manufacturing method of the tetracarboxylic dianhydride represented by.

[2]
The bisphenols represented by the above general formula (1) are represented by the following general formula (3)

（式中、Ｒ_１、Ｒ_２、ｍ及びｎの意味は上述の通りである。）
又は以下一般式（４）

(In the formula, the meanings of R ₁ , R ₂ , m and n are as described above.)
Or the following general formula (4)

（式中、Ｒ_１、Ｒ_２、ｍ及びｎの意味は上述の通りであり、ｘは１〜１２の整数を表す。）で表わさせる請求項１記載のテトラカルボン酸二無水物の製造方法。

(Wherein R ₁ , R ₂ , m and n have the same meanings as described above, and x represents an integer of 1 to 12), and the production of the tetracarboxylic dianhydride according to claim 1. Method.

[3]
The method for producing a tetracarboxylic dianhydride according to claim 1 or 2, further comprising reacting in the presence of an acid scavenger.

[4]
The method for producing a tetracarboxylic dianhydride according to claim 3, wherein the acid scavenger is pyridine.

[5]
Furthermore, the process of precipitating the crystal|crystallization of the tetracarboxylic dianhydride represented by said General formula (2) from the solution containing nitriles and aromatic hydrocarbons, filtering, and collecting is included. A method for producing the tetracarboxylic dianhydride described.

  According to the present invention, a tetracarboxylic dianhydride represented by the general formula (2), which has an aromatic hydrocarbon group or a cyclic hydrocarbon group as a main skeleton, and an aryl group is directly added to the main skeleton. Can be produced in a short period of time with a high purity and a high yield, and without obstacles in industrial practice such as difficulty in stirring during the reaction.

  Furthermore, after completion of the reaction, the above-mentioned general formula (2) precipitated from the reaction solution containing nitriles and aromatic hydrocarbons without separately performing a step of removing by-products such as inorganic salts by-produced in the reaction A highly pure tetracarboxylic acid dianhydride can be obtained only by filtering and recovering crystals of the tetracarboxylic acid dianhydride represented by.

  In the bisphenols represented by the above general formula (1) used in the present invention, A representing the skeleton of the bisphenols represents an aromatic hydrocarbon group or a cyclic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, and an indenyl group.Examples of the cyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, and a cyclo group. Dodecyl group and alkyl (eg, alkyl having 1 to 4 carbons) substituted cyclopentyl group, alkyl (eg, alkyl having 1 to 4 carbons) substituted cyclohexyl group, etc., having 4 to 16 carbon atoms (preferably 5 to 12 carbon atoms) The cycloalkyl group or the alkyl-substituted cycloalkyl group of is exemplified. Among these aromatic hydrocarbon groups or cyclic hydrocarbon groups, the availability of the bisphenols represented by the general formula (1) and the obtained tetracarboxylic dianhydride represented by the general formula (2) are obtained. From the viewpoint of usefulness, a fluorenyl group or a cycloalkyl group having 5 to 16 carbon atoms is preferable, and a fluorenyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group are particularly preferable.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ₁ and R ₂ in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and s- Examples thereof include linear or branched alkyl groups such as a butyl group, a t-butyl group, a pentyl group, and a hexyl group. From the viewpoint of availability of the bisphenols represented by the above general formula (1), these carbon atoms have 1 carbon atoms. Among the alkyl groups having 1 to 12, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and a linear chain having 1 to 3 carbon atoms. A branched or branched alkyl group is particularly preferred. Examples of the cycloalkyl group having 4 to 16 carbon atoms include a cyclopentyl group, a cyclohexyl group, an alkyl (for example, alkyl having 1 to 4 carbon) substituted cyclopentyl group, an alkyl (for example, alkyl having 1 to 4 carbon) substituted cyclohexyl group, and the like. And a cycloalkyl group having 4 to 16 carbon atoms (preferably 5 to 8 carbon atoms) or an alkyl-substituted cycloalkyl group are exemplified. Among these cycloalkyl groups, bisphenols represented by the above general formula (1) are available. A cyclopentyl group or a cyclohexyl group is preferable from the viewpoint of properties. Examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, an alkyl (for example, alkyl having 1 to 4 carbon atoms) substituted phenyl group, and a naphthyl group. Among these aromatic groups, the above general formula (1) is used. From the viewpoint of availability of the bisphenols represented, a phenyl group or an alkyl-substituted phenyl group (eg, methylphenyl group, dimethylphenyl group, ethylphenyl group, etc.) is preferable, and a phenyl group is particularly preferable. Examples of the halogen atom include fluorine, chlorine, bromine and the like. From the viewpoint of availability of the bisphenol represented by the general formula (1), chlorine or bromine is preferable.

The number of the substituents R ₁ and R ₂ represented by m and n is 0 or an integer of 1 to 4, and preferably 0 or 1 from the viewpoint of availability of the bisphenol represented by the general formula (1). Or 2. m and n may be the same or different, but are usually the same.

Among these substituents (R ₁ and R ₂ ), the number of substituents is 1 (m=n=1) from the viewpoint of availability of the bisphenol represented by the general formula (1). The substituent is a methyl group, an ethyl group, a phenyl group, the number of substituents is 2 (m=n=2), and the substituents are all methyl groups or phenyl groups. , Or those having no substituent, that is, m=n=0 is preferable, and particularly, those having one substituent and being a methyl group or having no substituent are preferable.

  Specific examples of the bisphenols represented by the general formula (1) detailed above include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl). ) Fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl) Cyclopentane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclopentane, 1,1-bis(4-hydroxy) -3-Phenylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy- 3-Methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane,1,1-bis(4 -Hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3) ,5-Dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy) -3-Phenylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane, 1, Examples of 1-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane and 1,1-bis(4-hydroxy-3-phenylphenyl)cyclododecane are represented by the above general formula (1). Among the bisphenols, from the viewpoint of availability of the bisphenols represented by the general formula (1) and usefulness of the obtained tetracarboxylic dianhydride represented by the general formula (2), 9,9- Bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9- Bis(4-hydroxy-3-phenylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclopentane, 1,1-bis (4-Hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1- Bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)-3,3,5-trimethylcyclohexane, 1,1- Bis(4-hydroxyphenyl)cyclododecane and 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane are preferable, and particularly 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis( 4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 1,1 -Bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecane and 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane are preferred.

  Examples of the trimellitic anhydride halide used in the present invention include trimellitic anhydride chloride, trimellitic anhydride bromide, trimellitic anhydride iodide, trimellitic anhydride fluoride, and among these trimellitic anhydride halides, inexpensive And trimellitic anhydride chloride is preferably used because of its good availability. The amount of trimellitic anhydride halide used is usually 2 to 3 mol, and preferably 2.1 to 2.5 mol, based on 1 mol of the bisphenol represented by the general formula (1). By setting the amount of trimellitic anhydride halide used to be 2 mol or more, the reaction is allowed to proceed sufficiently and the reaction intermediate monoester (reaction product of trimellitic anhydride halide 1 mol and bisphenol 1 mol) remains. By reducing the rate, it becomes possible to further improve the target production rate of the tetracarboxylic dianhydride represented by the general formula (2). When the amount used is 3 mol or less, the trimellitic anhydride halide and its decomposition products are less likely to remain as impurities. Therefore, the obtained tetracarboxylic acid dianhydride represented by the general formula (2) is obtained. It is possible to further improve the purity of the product.

  The nitriles used in the present invention may be either aliphatic nitriles or aromatic nitriles, and specifically, for example, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, benzonitrile, 4-cyano. Toluene and phenylacetonitrile are exemplified, and acetonitrile and benzonitrile are preferable because they are inexpensively available. These nitriles may be used alone or in combination of two or more.

  The aromatic hydrocarbons used in the present invention may have a halogen atom, and specific examples thereof include benzene, toluene, ethylbenzene, xylene, mesitylene, monochlorobenzene and dichlorobenzene, which are inexpensive and available. Therefore, toluene, xylene, monochlorobenzene and dichlorobenzene are preferable. These aromatic hydrocarbons may be used alone or in combination of two or more.

  The use ratio of the nitriles and the aromatic hydrocarbons is usually nitriles/aromatic hydrocarbons=90/10 to 10/90, preferably 85/15 to 15/85 by weight. By controlling the use ratio of the nitriles to 90% by weight or less, it is possible to suppress the increase in the viscosity of the reaction solution during the reaction and perform sufficient stirring, and the use ratio of the nitriles is 10% by weight ratio. With the above, the reaction rate can be further improved. The total amount of nitriles and aromatic hydrocarbons used is usually 1 to 30 times by weight, preferably 2 to 8 times by weight, based on 1 time by weight of the bisphenol represented by the general formula (1).

  In addition to the above-mentioned nitriles and aromatic hydrocarbons, bisphenols represented by the general formula (1), trimellitic anhydride halide and tetracarboxylic dianhydride represented by the general formula (2) are produced. It is also possible to appropriately use other inert organic solvent in combination, but it is preferable not to use other organic solvent in combination, because the effect of the present invention is exhibited more.

  When carrying out the present invention, it is preferable to carry out the reaction in the presence of an acid scavenger, because the reaction rate can be further improved. The acid scavenger in the present invention refers to a compound that traps hydrogen halide, which is a byproduct when the bisphenol represented by the general formula (1) is reacted with a trimellitic anhydride halide. Specific examples include organic tertiary amines such as pyridine, triethylamine and N,N-dimethylaniline, epoxies such as propylene oxide and allyl glycidyl ether, and inorganic bases such as potassium carbonate and sodium hydroxide. Of these, pyridine is preferable because it is easily removed after the reaction. When the acid scavenger is used, for example, it is used in an amount of usually 2 to 3 mol, preferably 2.1 to 2.5 mol, based on 1 mol of the bisphenol represented by the general formula (1). When the amount of the acid scavenger used is 2 mol or more, the reaction rate is improved, and when it is 3 mol or less, it is possible to suppress the generation of impurities.

  As a method for carrying out the present invention, for example, trimellitic anhydride halide and the bisphenol represented by the general formula (1) are added to a solution in which nitriles and aromatic hydrocarbons are mixed, and if necessary, acid trapping is performed. A method of intermittently or continuously adding the agent while maintaining it at 0°C to 30°C, and then at the same temperature or at 60°C to the reflux temperature of the solution, preferably at 70 to 90°C, and then continuing stirring, or anhydrous After adding the trimellitic acid halide and the bisphenol represented by the above general formula (1) to the nitriles and, if necessary, adding an acid scavenger intermittently or continuously while maintaining at 0°C to 30°C, A method in which aromatic hydrocarbons are further added, and then the temperature is kept at the same temperature or 60° C. to the reflux temperature of the solution, preferably 70 to 90° C., and then stirring is continued is exemplified. When an acid scavenger is added as needed, if the temperature of addition of the acid scavenger is lower than 0°C, the viscosity of the reaction mass may increase during the addition to make stirring difficult, and if higher than 30°C. In some cases, impurities are by-produced and the purity of the obtained tetracarboxylic acid dianhydride represented by the above formula (2) is lowered. After the addition of the acid scavenger is completed, the reaction rate can be improved by setting the reaction temperature to 60° C. or higher.

  After the above reaction, a post-treatment is carried out by a conventional method such as a step of removing an acid scavenger used as necessary and a by-produced inorganic salt (washing step etc.) and adsorption, and then the above-mentioned general formula (2 ) May be taken out, but crystals of the tetracarboxylic dianhydride represented by the above general formula (2) are precipitated from a solution containing nitriles and aromatic hydrocarbons. The tetracarboxylic acid represented by the above general formula (2), which is highly pure even without the above-mentioned post-treatment, is obtained by filtering, recovering and collecting (hereinafter, this step may be referred to as a crystallization step). It becomes possible to obtain the dianhydride. When the above reaction is carried out, some or all of the crystals of the tetracarboxylic dianhydride represented by the above general formula (2) may precipitate, but in the present invention, during the reaction. Even if crystals are precipitated in the above, the crystals are assumed to have been precipitated in the crystallization step.

  As the nitriles and aromatic hydrocarbons used in the crystallization step, the above-mentioned nitriles and aromatic hydrocarbons can be used. Further, the usage ratio and usage amount of the nitriles and aromatic hydrocarbons can be carried out within the same range as the above-mentioned ratio and usage amount. Further, for the nitriles and aromatic hydrocarbons used in the crystallization step, the nitriles and aromatic hydrocarbons used in the reaction may be directly used in the crystallization step, or if necessary, the reaction step may be carried out by concentration. The nitriles and aromatic hydrocarbons used in the crystallization step are removed by a method such as removing a part or all of the nitriles and aromatic hydrocarbons used in 1. and newly adding nitriles and aromatic hydrocarbons. You may adjust the kind of kind, the usage rate, and the usage amount suitably.

  As a method for carrying out the crystallization step, for example, after the above-mentioned reaction is completed, the reaction solution is cooled if necessary, the precipitated crystals are filtered off, and if necessary, the filtered crystals are washed with nitriles and dried. It is carried out by. When pyridine is used as the acid scavenger in the reaction, it is preferable that the crystals separated by filtration are further washed with acetonitrile so that the pyridine and the pyridine salt can be efficiently removed.

  Further, after the reaction is completed and before carrying out the above-mentioned crystallization step, a dehydrating agent such as acetic anhydride is added to the reaction solution and stirred at 50 to 100° C., preferably 65 to 85° C., to produce a by-product in the reaction. The ring-opened product (hydrolysis product of the tetracarboxylic acid dianhydride represented by the general formula (2)) can be converted into the tetracarboxylic acid dianhydride represented by the above formula (2), which is obtained. It is possible to improve the purity and yield of the tetracarboxylic acid dianhydride represented by the above formula (2). The amount of the dehydrating agent used is usually 0.1 to 0.5 mol, preferably 0.15 to 0.30 mol, based on 1 mol of the bisphenol represented by the above general formula (1) used in the reaction. .

  The tetracarboxylic acid dianhydride represented by the general formula (2) obtained by the above-mentioned method usually has a HPLC purity of 97% or more as measured by the method described below, so that the resin raw material such as polyimide or polyester can be used as it is. It can be used as a curing agent, an additive, etc. for epoxy resins and polyurethane resins, but if necessary, it can be subjected to adsorption treatment with various adsorbents and repetitive general purification such as recrystallization and distillation. The purity can be further increased.

  Examples of the present invention will be shown below, but the present invention is not limited thereto.

[1] HPLC measurement (residual rate, production rate and purity of each component)
The area percentage value when HPLC measurement was performed under the following measurement conditions was used as the residual rate of each component, the production rate, and the purity of the tetracarboxylic dianhydride represented by the general formula (2). However, the residual rate and production rate of each component are the corrected area percentage values obtained by cutting the peaks of trimellitic anhydride chloride, pyridine, and toluene.
Liquid chromatography measurement conditions:
Device: Hitachi L-2130
Column: ZORBAX CN (5 μL, 4.5φ×250 nm)
Mobile phase: hexane/THF, flow rate: 1.0 ml/min
Column temperature: 40°C, detection wavelength: UV254nm

[2] HPLC measurement (pyridine hydrochloride content)
HPLC measurement was carried out under the following measurement conditions to quantify pyridine hydrochloride contained in the tetracarboxylic dianhydride represented by the above formula (2).
Equipment: Shimadzu Corporation LC-2010AHT
Column: YMC-Pack ODS-AM (5 μL, 4.6φ×150 nm)
Mobile phase: ultrapure water/methanol/THF, flow rate: 1.0 ml/min
Column temperature: 40°C, detection wavelength: UV254nm

[3] Yellowness (yellowness index): YI
From the light transmittance of the N-methylpyrrolidone solution of tetracarboxylic dianhydride at a wavelength of 380 to 780 nm, using a spectrocolorimeter SE-6000 (manufactured by Nippon Denshoku Co., Ltd.), the yellowness (YI) was determined according to JIS K7373. Calculated.

<Example 1>
(Production example of tetracarboxylic dianhydride represented by the following formula (5) among the tetracarboxylic dianhydride represented by the above general formula (2))

130.20 g (344.0 mmol) of 9,9-bis(4-hydroxy-3-methylphenyl)fluorenone in a 1 L four-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a reflux condenser, trimellitic anhydride chloride. 166.60 g (791.2 mmol) (hereinafter sometimes referred to as TAC) and 260.28 g of acetonitrile were charged, and the mixture was stirred under a nitrogen atmosphere and cooled to 4°C. After cooling, 62.63 g (791.8 mmol) of pyridine was further added dropwise at 4°C to 10°C over 2 hours. After the completion of the dropping, 260.28 g of toluene was charged, and then the temperature was raised to reflux and the mixture was stirred under reflux (internal temperature 82 to 84° C.) for 3.5 hours.
After completion of stirring, the reaction solution was measured by HPLC. As a result, the residual rate of the raw material 9,9-bis(4-hydroxy-3-methylphenyl)fluorenone was 0.0%, and the monoester product (9,9-bis The production rate of (4-hydroxy-3-methylphenyl)fluorenone (1 mol) and anhydrous trimellitic chloride (1 mol) is 0.3%, and the tetracarboxylic acid represented by the above formula (5) is the target product. The yield of dianhydride was 97.8%.
After the reaction, the reaction solution was cooled to 26° C., and the precipitated crystals were filtered off at the same temperature. After separation by filtration, the crystals were further washed 4 times with 260.28 g of acetonitrile, and the obtained crystals were vacuum dried at 90° C. to give crystals of the tetracarboxylic dianhydride represented by the above formula (5) 240. 38 g (yield 96.2%) was obtained. The physical properties of the obtained tetracarboxylic dianhydride represented by the above formula (5) are as follows.
Purity: 98.6%
Pyridine hydrochloride content: 0.01% by weight
YI value: 2.1

<Example 2>
(Production example of tetracarboxylic dianhydride represented by the following formula (6) among the tetracarboxylic dianhydride represented by the above general formula (2))

In a 1 L four-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a reflux condenser, 109-66 g (288.2 mmol) of 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane and 139.56 g of TAC ( 663.1 mmol), 175.46 g of acetonitrile, and 43.86 g of toluene were charged, and the mixture was stirred under a nitrogen atmosphere and cooled to 5°C. After cooling, 52.63 g (665.4 mmol) of pyridine was further added dropwise at 5°C to 11°C over 1 hour. After the dropwise addition was completed, 43.86 g of acetonitrile and 175.46 g of toluene were charged, the temperature was raised to reflux, and the mixture was stirred under reflux (internal temperature 78 to 84° C.) for 4.5 hours.
After completion of stirring, the reaction solution was measured by HPLC. As a result, the residual rate of the raw material 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane was 0.0%, and the monoester body (1,1- Bis(4-hydroxy-3-methylphenyl)cyclododecane 1 mol and trimellitic anhydride chloride 1 mol reacted ester compound) production rate is 0.2%, tetracarboxylic acid represented by the above formula (6) The production rate of acid dianhydride was 96.9%.
After the reaction, the reaction mixture was cooled to 50° C., charged with 438.6 g of acetonitrile, 109.66 g of toluene and 7.18 g of acetic anhydride, heated to reflux, and stirred under reflux (internal temperature 79° C. to 82° C.) for 1 hour. After stirring, the mixture was cooled to 26° C., the precipitated crystals were filtered off at the same temperature, the filtered crystals were further washed 4 times with 202.94 g of acetonitrile, and the obtained crystals were vacuum dried at 120° C. to obtain the above formula ( 198.08 g (yield 94.3%) of crystals of tetracarboxylic dianhydride of 6) were obtained. The physical properties of the obtained tetracarboxylic dianhydride represented by the above formula (6) are as follows.
Purity: 99.0%
Pyridine hydrochloride content: 0.01% by weight
YI value: 2.9

<Example 3>
The reaction was carried out in the same manner as in Example 1 except that acetonitrile was changed to butyronitrile in Example 1, but 520.80 g of butyronitrile and 520.80 g of toluene were used, and after the reaction was completed, the reaction solution was measured by HPLC. did. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.0%
・Monoester: 0.3%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 97.5%

<Example 4>
The reaction was performed in the same manner as in Example 1 except that acetonitrile was changed to benzonitrile, 520.80 g of benzonitrile and 520.80 g of toluene were used, and after completion of the reaction, the reaction solution was measured by HPLC. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.0%
・Monoester: 0.6%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 97.2%

<Example 5>
Reaction was carried out in the same manner as in Example 1 except that dichlorobenzene was used instead of acetonitrile, and 260.40 g of dichlorobenzene and 260.40 g of acetonitrile were used, and after completion of the reaction, the reaction solution was measured by HPLC. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.0%
・Monoester: 0.03%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 98.5%

<Example 6>
The reaction was performed in the same manner as in Example 1 except that 520.80 g of acetonitrile and 130.20 g of toluene were used, and after the reaction was completed, the reaction solution was measured by HPLC. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.0%
・Monoester: 0.08%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 98.0%

<Example 7>
The reaction was performed in the same manner as in Example 1 except that 208.32 g of acetonitrile and 833.28 g of toluene were used, and after the reaction was completed, the reaction solution was measured by HPLC. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.0%
・Monoester: 0.05%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 98.3%

<Comparative Example 1>
When the reaction was carried out in the same manner as in Example 1 except that acetonitrile was changed to acetone, the viscosity of the reaction mass increased as the reaction proceeded, and stirring under reflux at 3.5 hours became difficult. The reaction liquid thus obtained was measured by HPLC. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.0%
・Monoester: 12.4%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 82.8%

<Comparative example 2>
When acetonitrile was changed to toluene in Example 1 and the reaction was carried out in the same manner with toluene alone, the viscosity of the reaction mass increased as the reaction proceeded, and stirring under reflux made it difficult for 3.5 hours. .. The reaction liquid thus obtained was measured by HPLC. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.7%
・Monoester: 11.6%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 84.8%

<Comparative example 3>
When toluene was changed to acetonitrile in Example 1 and the reaction was carried out by the same method using only acetonitrile, the viscosity of the reaction mass increased as the reaction proceeded, and the reaction mass solidified under reflux for 1 hour.

<Comparative example 4>
The reaction was carried out in the same manner as in Example 1 except that acetonitrile was changed to methyl ethyl ketone in Example 1, and 156.24 g of methyl ethyl ketone and 1848.84 g of toluene were used, and the mixture was stirred under reflux for 3.5 hours, and then the reaction liquid. Was measured by HPLC. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.0%
・Monoester: 3.0%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 87.6%

<Comparative example 5>
The reaction was carried out in the same manner as in Example 1 except that acetonitrile was changed to tetrahydrofuran in Example 1 and 169.26 g of tetrahydrofuran and 2304.54 g of toluene were used, and the mixture was stirred under reflux for 3.5 hours, and then the reaction liquid. Was measured by HPLC. The measurement results are shown below.
*9,9-bis(4-hydroxy-3-methylphenyl)fluorenone: 0.0%
・Monoester: 2.5%
-Tetracarboxylic acid dianhydride represented by the above formula (5): 85.2%

<Comparative example 6>
When a reaction was carried out in the same manner as in Example 2 except that acetonitrile was changed to acetone, the viscosity of the reaction mass increased as the reaction proceeded, and stirring under reflux at 3.5 hours became difficult. The reaction liquid thus obtained was measured by HPLC. The measurement results are shown below.
*1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane: 0.2%
・Monoester: 17.7%
-Tetracarboxylic dianhydride represented by the above formula (6): 77.6%

<Comparative Example 7>
When acetonitrile was changed to toluene in Example 2 and the reaction was carried out in the same manner with toluene alone, the viscosity of the reaction mass increased as the reaction proceeded, and stirring under reflux for 2.5 hours became difficult. .. The reaction liquid thus obtained was measured by HPLC. The measurement results are shown below.
・1,1-Bis(4-hydroxy-3-methylphenyl)cyclododecane: 1.0%
・Monoester: 18.5%
-Tetracarboxylic acid dianhydride represented by the above formula (6): 75.9%

Table 1 below shows a summary of the results of the above Examples and Comparative Examples.

Claims (4)

In the presence of at least one nitrile and aromatic hydrocarbon selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, benzonitrile, 4-cyanotoluene and phenylacetonitrile. , Trimellitic anhydride halide and the following general formula ( 3 )

(In the formula , R ₁ and R ₂ are the same or different and represent an alkyl group having 1 to 12 carbon atoms, a halogen atom, a cycloalkyl group having 4 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. , M and n represent 0 or an integer of 1 to 4. When there are a plurality of R ₁ and/or R ₂ , they may be the same or different.
Or the following general formula (4)

(In the formula, the meanings of R ₁ , R ₂ , m, and n are as described above, and x represents an integer of 1 to 12.)
The following general formula (2) is used to react with a bisphenol represented by

(In the formula, A is a fluorenyl group or a cycloalkyl group having 5 to 16 carbon atoms , and the meanings of R ₁ , R ₂ , m and n are as described above.)
The manufacturing method of the tetracarboxylic dianhydride represented by. Furthermore, the reaction in the presence of an acid scavenger, a manufacturing method of the tetracarboxylic acid dianhydride of claim 1 Symbol placement. The method for producing a tetracarboxylic dianhydride according to claim 2 , wherein the acid scavenger is pyridine. Furthermore, from a solution containing nitriles and aromatic hydrocarbons, to precipitate crystals of the tetracarboxylic dianhydride represented by the above general formula (2), according to claim 1 to 3 comprising a filtered recovered to step The method for producing a tetracarboxylic dianhydride according to any one of claims.