JP2013028578A - Method of producing amide group-containing tetracarboxylic dianhydride - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of easily producing highly pure amide group-containing tetracarboxylic dianhydride.SOLUTION: In the method of producing amide group-containing tetracarboxylic dianhydride by reacting dicarboxylic anhydride-containing acid chloride with diamine in a solution, the reaction solution of the amide group-containing tetracarboxylic dianhydride forms an oversaturated state according to the progress of the reaction, and then, the amide group-containing tetracarboxylic dianhydride is precipitated.

Description

  The present invention relates to a method for producing an amide group-containing tetracarboxylic dianhydride with high purity.

  In recent years, the importance of polyimide as a heat-resistant insulating material in electronic devices has been increasing. Polyimide has not only excellent heat resistance, but also chemical resistance, radiation resistance, electrical insulation reliability, excellent mechanical properties, etc., so flexible printed wiring substrates, tape automation bonding circuit substrates, Currently, it is widely used in various applications such as chip-on-film circuit substrates, optical waveguide materials, protective films for semiconductor elements, and interlayer insulating films in multilayer circuits. Polyimide is advantageous in that it is easy to improve the physical properties by changing the monomer, and it is easy to meet the increasingly demanded characteristics in recent years.

  In recent years, with the progress of multilayer wiring, low linear thermal expansion characteristics are becoming important as required characteristics of interlayer insulating films. When the polyimide precursor film formed on the wiring layer is imidized, the thermal stress generated in the process of cooling from the imidization temperature to room temperature is caused by partial peeling of the metal wiring layer and the film, cracking, degradation of CMP resistance, etc. It is necessary to reduce the thermal stress as much as possible because it may cause a serious problem in electrical reliability.

  From the viewpoint of suppressing ion migration, it is preferable to use a polyimide varnish to coat and dry it to form an interlayer insulating film. In order to obtain a polyimide varnish that is stable at room temperature, polyimide is a general-purpose material. It is necessary to have a high solubility at room temperature in a volatile organic solvent.

  A polyamideimide having a specific amide group-containing tetracarboxylic dianhydride and a diamine is disclosed as a polyimide for solving these problems (Patent Document 1).

JP 2010-106225 A

  According to the study by the present inventors, it has been clarified that the solubility in CTE or organic solvent changes when the molecular weight of polyimide changes. It was also found that the molecular weight of polyamic acid, which is a polyimide precursor obtained by polymerization, is greatly influenced by the chemical purity of diamine and acid dianhydride. In particular, low-purity acid dianhydrides contain impurities and cause variations in the polymerization. Therefore, in order to stably obtain a good quality polymer, acid dianhydrides with high chemical purity are used for the polymerization. There is a need.

  Therefore, an object of the present invention is to provide a method for easily producing a specific monomer with high purity.

  In a method for producing an amide group-containing tetracarboxylic dianhydride by reacting a dicarboxylic acid anhydride-containing acid chloride and a diamine in a solution, the reaction solution of the amide group-containing tetracarboxylic dianhydride is supersaturated as the reaction proceeds. Provided is a method for producing an amide group-containing tetracarboxylic dianhydride that forms a state and then precipitates an amide group-containing tetracarboxylic dianhydride. According to this, since the system is already supersaturated at the end of the reaction, impurities at the time of precipitation can be easily reduced, and thus a high-purity monomer can be produced.

  In addition, the present invention provides a method for producing the amide group-containing tetracarboxylic dianhydride, wherein the amidation reaction is performed at −50 ° C. or higher and 40 ° C. or lower.

  In addition, the present invention provides a method for producing the amide group-containing tetracarboxylic dianhydride, characterized in that the solvent constituting the reaction solution contains ethyl acetate, and further ethyl acetate.

  Moreover, the manufacturing method of the said amide group containing tetracarboxylic dianhydride characterized by the said dicarboxylic anhydride containing acid chloride having an aromatic ring was provided.

  Further, the present invention provides a method for producing the amide group-containing tetracarboxylic dianhydride, wherein the dicarboxylic anhydride-containing acid chloride is trimellitic anhydride chloride.

  In addition, the present invention provides a method for producing the amide group-containing tetracarboxylic dianhydride, wherein the diamine is an aromatic diamine or an aliphatic diamine.

  Further, the present invention provides a method for producing the amide group-containing tetracarboxylic dianhydride, characterized in that the diamine is 2,2'-bis (trifluoromethyl) benzidine (hereinafter referred to as TFMB).

  Further, the present invention provides a method for producing the amide group-containing tetracarboxylic dianhydride, characterized in that a solvent having a lower solubility of the amide group-containing tetracarboxylic dianhydride than the reaction solvent is added after the amidation reaction.

  Further, the amide group-containing tetracarboxylic dianhydride obtained by adding the amide group-containing tetracarboxylic dianhydride obtained after the precipitation operation to a solvent having a lower solubility than the reaction solvent and heating and then separating the amide group-containing tetracarboxylic dianhydride. A manufacturing method was provided.

  The amide group-containing tetracarboxylic dianhydride has a concentration of 0.15 mmol / ml or more when a supersaturated state is formed in the amidation reaction. A manufacturing method was provided.

  According to the method for producing an amide group-containing tetracarboxylic dianhydride of the present invention, a highly pure amide group-containing tetracarboxylic dianhydride can be easily produced.

  In a method for producing an amide group-containing tetracarboxylic dianhydride by reacting a dicarboxylic acid anhydride-containing acid chloride and a diamine in a solution, the reaction solution of the amide group-containing tetracarboxylic dianhydride is supersaturated as the reaction proceeds. The present invention relates to a method for producing an amide group-containing tetracarboxylic dianhydride in which a state is formed and thereafter an amide group-containing tetracarboxylic dianhydride is precipitated. According to this, the product can be easily separated because the system is already supersaturated and uniform at the end of the reaction. Moreover, since it can be gently precipitated by passing through the supersaturated state, impurities are hardly taken into the crystal, and a highly pure amide group-containing tetracarboxylic dianhydride can be produced.

  Although it does not specifically limit as a dicarboxylic anhydride containing acid chloride used by this invention, For example, a trimellitic anhydride chloride can be used suitably.

  The diamine used in the present invention is not particularly limited, but p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2-methoxy-1,4. -Phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5 -Diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis (2-methylaniline), 4,4'-methylenebis (2-ethylaniline) ), 4,4′-methylenebis (2,6-dimethylaniline), 4,4′-methylenebis (2,6-die) Ruaniline), 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diamino Diphenylsulfone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzanilide, benzidine, 3,3′-dihydroxybenzidine, 3,3′-dimethoxybenzidine, 3,3 ′ -Dichlorobenzidine, o-tolidine, m-tolidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, octafluorobenzidine, 3,3 ', 5,5 '-Tetramethylbenzidine, 2,2', 5,5 ' Tetrachlorobenzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis ( 4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl ) Propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, p-terphenylenediamine, etc. It can be used suitably.

  Usually, in order to achieve a supersaturated state in the present invention, the amount of the solvent is controlled at the time of charging so that the concentration of the amide group-containing tetracarboxylic dianhydride at the end of the reaction exceeds the saturated concentration. However, it is desirable that the reactant is dissolved when both the dicarboxylic anhydride-containing acid chloride and the diamine are added.

  The amidation reaction will be described. The addition amount of the dicarboxylic acid anhydride-containing acid chloride with respect to the diamine may be any ratio, but is preferably twice or more in view of the chemical purity of the product. Furthermore, in order to prevent the by-product from being entrained and deposited, the ratio of the amount of the dicarboxylic anhydride-containing acid chloride to the diamine is preferably 2 to 2.5 times.

  As the reaction solvent used in the present invention, in the method for producing an amide group-containing tetracarboxylic dianhydride, various solvents can be used as long as the concentration of the amide group-containing tetracarboxylic dianhydride exceeds the saturation concentration at the end of the reaction. Solvents can be used. For example, ethyl acetate, tetrahydrofuran (THF), 1,4-dioxane, picoline, pyridine, acetone, chloroform, toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane, N-methyl-2-pyrrolidone, N, N- Dimethylacetamide (hereinafter referred to as DMAc), N, N-diethylacetamide, N, N-dimethylformamide (hereinafter referred to as DMF), hexamethylphosphoramide, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-2- Aprotic solvents such as imidazolidinone, 1,2-dimethoxyethane-bis (2-methoxyethyl) ether, n-heptane, hexane, pentane, and phenol, o-cresol, m-cresol, p-cresol, o -Chlorophenol, m- Examples include protic solvents such as chlorophenol and p-chlorophenol. These solvents may be used alone or in combination of two or more. Ethyl acetate is preferably used from the viewpoint of ease of treatment after the reaction and solubility of the raw materials.

  The concentration of the amide group-containing tetracarboxylic dianhydride during the formation of the supersaturated state is 0.15 mmol / ml or more in that the supersaturated state of the amide group-containing tetracarboxylic dianhydride in the reaction solution of the present invention is stably formed. It is preferable that In order to form a supersaturated state, a method of cooling after heating once, or a method of cooling by adding a poor solvent after heating may be used.

  In order for the amide group-containing tetracarboxylic dianhydride to stably form a supersaturated state after completion of the amidation reaction of the present invention, it is preferably carried out at −50 ° C. or higher, more preferably −30 ° C. or higher. Moreover, in order to avoid a side reaction, it is preferable to carry out at 40 degrees C or less and also 30 degrees C or less. Moreover, in the said range, the reaction at 20 degreeC is especially preferable at the point that the said reaction is completed quickly and operation becomes easy.

  In the present invention, it is preferable to use a deoxidizing agent because hydrochloric acid generated in the amidation reaction may cause a side reaction. In addition to propylene oxide, tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N, N-dimethylaniline, N, N-dimethylaminopyridine can be suitably used as the deoxidizer. Propylene oxide is particularly preferably used because of the suppression of side reactions and the ease of salt removal.

  After precipitation of the amide group-containing tetracarboxylic dianhydride, a solvent having low solubility of the amide group-containing tetracarboxylic dianhydride may be added to further improve the yield. Since a highly pure amide group-containing tetracarboxylic dianhydride has been obtained once through a supersaturated state, a solvent with low solubility is then added to further precipitate the amide group-containing tetracarboxylic dianhydride from the system. Even if this is the case, there is little reduction in chemical purity. Examples of the solvent having low solubility of the amide group-containing tetracarboxylic dianhydride include hydrocarbon organic solvents such as n-heptane, hexane, pentane, and toluene, and these can be preferably used.

  The separation and purification of the amide group-containing tetracarboxylic dianhydride obtained by the amidation reaction will be described. After completion of the reaction, the precipitate is filtered off and washed with a solvent having a lower solubility of the amide group-containing tetracarboxylic dianhydride than the reaction solvent, so that impurities, by-products, salts formed with deoxidizer and hydrochloric acid, etc. Can be removed. Finally, the product is vacuum-dried at 30 to 160 ° C. for 1 to 24 hours, whereby a highly purified amide group-containing tetracarboxylic dianhydride can be obtained. In consideration of the drying speed, it is desirable to vacuum dry at 120 ° C. or higher.

  The amide group-containing tetracarboxylic dianhydride obtained after the precipitation operation is added to a solvent having a lower solubility than the reaction solvent, heated and then separated by filtration, whereby a higher purity amide group-containing tetracarboxylic dianhydride is obtained. You can also get things. Further, by this operation, the amide group-containing tetracarboxylic acid opened by the amide group-containing tetracarboxylic dianhydride can be reclosed. As the solvent used in the heating operation, various solvents can be used as long as the solubility of the amide group-containing tetracarboxylic dianhydride is lower than that of the reaction solvent, but ethyl acetate, tetrahydrofuran (THF), 1,4- Dioxane, picoline, pyridine, acetone, chloroform, toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane, N-methyl-2-pyrrolidone, N, N-dimethylacetamide (hereinafter referred to as DMAc), N, N-diethyl Acetamide, N, N-dimethylformamide (hereinafter referred to as DMF), hexamethylphosphoramide, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2 -Aprotic solvent such as -methoxyethyl) ether, Protic solvents such as n-heptane, hexane, pentane, phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p-chlorophenol, acetic acid, acetic anhydride, toluene, etc. Can be preferably used. These solvents may be used alone or in combination of two or more. In particular, it can be purified efficiently by heating in a mixed solvent of acetic anhydride and toluene followed by filtration.

  The amide group-containing tetracarboxylic dianhydride produced by the production method of the present invention can be used for polymerization of various polyimides.

  Hereinafter, although an experimental example of the present invention will be shown and described, the present invention is not limited to this. The physical property values in the following examples were measured by the following methods.

<HPLC>
Analysis was performed using WATERS2690, and WATERS996 was used as a detector. DAISOPAK SP-200-5-ODS-BP 250 mm × 4.6 mm was used as the column, and DAISOPAK SP-200-5-ODS-BP 35 mm × 4.6 mm was used as the precolumn. The column temperature was set to 40 ° C., the detection wavelength was set to 254 nm, and the flow rate was set to 1 ml / min. The eluent is methanol / distilled water / trifluoroacetic acid = 600/400/1 (volume ratio). The sample was dissolved in methanol and adjusted by stirring for 30 minutes so that the concentration was about 0.05 wt%. The detection wavelength was 254 nm and the chemical purity was determined from the absorbance.

<Infrared absorption spectrum>
The infrared absorption spectrum of the tetracarboxylic dianhydride of the present invention was measured by the KBr method using a Fourier transform infrared spectrophotometer (FT-IR5300 manufactured by JASCO Corporation). Further, an infrared absorption spectrum of the polyimide thin film (5 μm thickness) of the present invention was measured by a transmission method.

<NMR>
A ¹ H-NMR spectrum of tetracarboxylic dianhydride was measured in deuterated dimethyl sulfoxide using a JEOL NMR spectrophotometer (ECP400).

<DSC>
The melting point and melting curve of tetracarboxylic dianhydride were measured using a differential scanning calorimeter (DSC3100) manufactured by Bruker Ax in a nitrogen atmosphere at a heating rate of 5 ° C./min.

Example 1
An amide group-containing tetracarboxylic dianhydride (hereinafter referred to as TATFMB) represented by the formula (1) was synthesized from TFMB and trimellitic anhydride chloride. Solution 44 was prepared by adding 42.44 g (201.54 mmol) of trimellitic anhydride chloride to a separable flask and adding 84.79 g of ethyl acetate to dissolve. On the other hand, 29.34 g (91.62 mmol) of TFMB was placed in another separable flask, and 88.02 g of ethyl acetate and 10.65 g of propylene oxide as a deoxidizer were added and dissolved to prepare Solution B.

  The reaction vessel was prepared in a thermostatic bath so as to be 10 ° C., and the solution B was added dropwise to the solution A over 1 hour. At the end of dropping, the system was uniform despite exceeding the solubility limit, and further, stirring was continued for 30 minutes to precipitate crystals. Thereafter, the temperature was raised so that the internal temperature became 20 ° C., and aging was performed for 2 hours. Thereafter, 129.68 g of n-heptane was added to the reaction vessel, and the mixture was stirred for 1 hour and then filtered to obtain a white product. By-product was removed by washing this white product with a mixed solution of 84.79 g of ethyl acetate and 58.68 g of n-heptane, and dried in a vacuum oven at 120 ° C. to obtain 54.66 g of crude crystals. (Yield 89.25%).

  This was added to a mixed solvent of 50.08 g of acetic anhydride and 497 g of toluene, heated to 110 ° C. and stirred for 3 hours. The reaction vessel was cooled to 10 ° C., white crystals were filtered off, washed with 50.01 g of toluene, and dried in an oven at 120 ° C. for 12 hours to obtain 49.19 g of the target TATFMB (total) Yield 80.33%).

  The chemical purity of the obtained TATFMB is shown in Table 1.

The product was confirmed by FT-IR and NMR.
FT-IR: 3378 cm −1 (amide group NH stretching vibration), 3108 cm −1 (aromatic C—H stretching vibration), 1858 cm −1, 1782 cm −1 (acid anhydride group C═O stretching vibration), 676 cm −1 (Amido group C = O stretching vibration)
1H-NMR: δ 11.06 ppm (s, NH, 2H), δ 8.65 ppm (s, on phthalimide, 3-position CaromH, 2H), δ 8.37 ppm (on phthalimide, 5- and 6-position CaromH, 4H), δ 7.46 ppm (D, 6 and 6'-position CaromH, 2H on central biphenyl), δ 8.13 ppm (d, on central biphenyl, 5 and 5'-position CaromH, 2H), δ 8.27 ppm (s, on central biphenyl, 3 and 3 'Position CaromH, 2H)
DSC: melting point 267 ° C.

(Example 2)
The synthesis was performed in the same manner as in Example 1 except that the temperature of the reaction vessel was −20 ° C. It was uniform at the end of dropping and formed a supersaturated state as in Example 1. Subsequent purification was carried out in the same manner as in Example 1 to obtain 49.02 g of TATFMB (yield 80.05%).

  The chemical purity of the obtained TATFMB is shown in Table 1.

(Example 3)
Each step was performed in the same manner as in Example 1 except that 129.68 g of n-heptane was added and the step of stirring for 1 hour was not performed. As a result, 42.32 g of TATFMB was obtained (yield 69.11%). .

  The chemical purity of the obtained TATFMB is shown in Table 1.

(Comparative Example 1)
Solution 37 was prepared by adding 19.37 g (91.98 mmol) of trimellitic anhydride chloride to a separable flask and adding 58.12 g of ethyl acetate to dissolve. On the other hand, 14.38 g (44.91 mmol) of TFMB was placed in another separable flask, and 53.25 g of ethyl acetate and 44.73 g of heptane and 5.219 g of propylene oxide as a deoxidizer were added and dissolved to prepare solution B. .

  The reaction vessel was prepared in a thermostatic bath so as to be 10 ° C., and the solution B was added dropwise to the solution A over 1 hour. White crystals were precipitated from the time of dropping and did not become supersaturated. Thereafter, the temperature was raised so that the internal temperature became 20 ° C., and aging was performed for 2 hours. Thereafter, 46.01 g of n-heptane was added to the reaction vessel, and the mixture was stirred for 1 hour and then filtered to obtain a white product. By-product was removed by washing this white product with a mixed solution of 41.56 g of ethyl acetate and 28.76 g of n-heptane, followed by drying in a vacuum oven at 120 ° C. to obtain 26.67 g of crude crystals. (Yield 88.85%).

  This was added to a mixed solvent of 24.55 g of acetic anhydride and 243 g of toluene, heated to 110 ° C., and heated and stirred for 3 hours. The reaction vessel was cooled to 8-12 ° C., white crystals were filtered off, washed with 24.50 g of toluene, and dried in an oven at 120 ° C. for 12 hours to obtain 23.90 g of the desired TATFMB. (Total yield 79.63%).

  The chemical purity of the obtained TATFMB is shown in Table 1.

(Comparative Example 2)
Synthesis was performed in the same manner as in Comparative Example 1 except that 44.73 g of toluene was used instead of 44.73 g of heptane. At that time, white crystals had already been deposited at the end of dropping. Subsequent purification operations were carried out in the same manner as in Comparative Example 1. As a result, 13.52 g of the target TATFMB was obtained (yield 45.05%).

Claims (10)

  In a method for producing an amide group-containing tetracarboxylic dianhydride by amidating a dicarboxylic acid anhydride-containing acid chloride and a diamine in a solution, a reaction solution of the amide group-containing tetracarboxylic dianhydride as the reaction proceeds Forming a supersaturated state, and then depositing an amide group-containing tetracarboxylic dianhydride, a method for producing an amide group-containing tetracarboxylic dianhydride.   The method for producing an amide group-containing tetracarboxylic dianhydride according to claim 1, wherein the amidation reaction is performed at -50 ° C or higher and 40 ° C or lower.   The method for producing an amide group-containing tetracarboxylic dianhydride according to any one of claims 1 and 2, wherein a solvent constituting the reaction solution contains ethyl acetate.   The method for producing an amide group-containing tetracarboxylic dianhydride according to any one of claims 1 to 3, wherein the dicarboxylic anhydride-containing acid chloride has an aromatic ring.   5. The method for producing an amide group-containing tetracarboxylic dianhydride according to claim 4, wherein the dicarboxylic anhydride-containing acid chloride is trimellitic anhydride chloride.   The method for producing an amide group-containing tetracarboxylic dianhydride according to any one of claims 1 to 5, wherein the diamine is an aromatic diamine or an aliphatic diamine.   The method for producing an amide group-containing tetracarboxylic dianhydride according to claim 6, wherein the diamine is 2,2'-bis (trifluoromethyl) benzidine.   The amide group-containing tetracarboxylic acid diester according to any one of claims 1 to 7, wherein a solvent having a lower solubility of the amide group-containing tetracarboxylic dianhydride than the reaction solvent is added after the amidation reaction. Method for producing anhydride.   The amide group-containing tetracarboxylic acid according to any one of claims 1 to 8, which comprises a step of adding the precipitated amide group-containing tetracarboxylic dianhydride to a solvent having a lower solubility than the reaction solvent and heating it, followed by filtration. Method for producing acid dianhydride.   The amide group according to any one of claims 1 to 9, wherein a concentration of the amide group-containing tetracarboxylic dianhydride is 0.15 mmol / ml or more when a supersaturated state is formed in the amidation reaction. A method for producing a containing tetracarboxylic dianhydride.