JPH01161021A - New polyamic acid or ester thereof and preparation thereof and new polyimide and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a polyamic acid (or ester thereof) providing at low temp. a polyimide having excellent transparency, heat resistance and mechanical characteristics, by reacting a specified compd. with a diamine. CONSTITUTION:Dicyclohexyl-3,4,3',4'-tetracarboxylic acid is obtd. by hydrogenating tetramethyl ester of biphenyl-3,4,3',4'-tetracarboxylic acid in the presence of an Rh catalyst and carrying out acid or alkali hydrolysis and acid deposition. A compd. (A) of formula I (wherein R3-4 are each independently O, two OH groups or OH group and alkoxy group) is prepared by dehydrating the obtained acid by heating or with acetic anhydride, if necessary, and then esterifying it with an alcohol, if necessary. A polyamic acid (or ester thereof) contg. structural units of formula III-V (wherein R1 is H, a monovalent hydrocarbon group) is obtd. by adding a dianhydride component among the component A into a soln of a diamine (B) of formula II (wherein R2 is a divalent group) in a solvent such as N-methyl-2-pyrrolidone, stirring and reacting at 80 deg.C or lower, converting the carboxyl groups into acyl chloride groups with thionyl chloride, if necessary, and esterifying it with an alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel polyamic acid or polyamic acid ester and a method for producing the same, and a novel polyimide and a method for producing the same.

(Prior Art) Conventionally, polyimide is generally produced by reacting diamine and tetracarboxylic dianhydride in a solvent to produce polyamic acid.
It is obtained by dehydration and ring closure, or by reacting diisocyanate and tetracarboxylic dianhydride to directly produce polyimide.

The properties of the polyamic acid and polyimide thus obtained are similar to those used in diamines and diisocyanates.

Determined by the selection of tetracarboxylic dianhydride, etc., and the combination of these, those with excellent heat resistance, those with high flexibility,
Nine different types are known, including those with excellent solubility.

Among them, polyimide using aromatic tetracarboxylic dianhydride as the tetracarboxylic dianhydride has excellent heat resistance and mechanical properties.

The temperature for producing polyimide requires a temperature of 300° C. or higher, and the resulting polyimide has a colored appearance.

On the other hand, polyimide has come to be applied in various fields,9 for example, in the field of optical devices such as alignment films for liquid crystal display elements. However, polyimides using the above-mentioned aromatic tetracarboxylic dianhydride have low transparency, and the liquid crystal display element itself has poor heat resistance, so it cannot be used because the element itself decomposes during the polyimidation process. is difficult.

For this reason, aliphatic tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic dianhydride are used as tetracarboxylic dianhydrides that can be polyimidized at low temperatures and the resulting polyimide has good transparency. dianhydride or 1
．． Alicyclic tetracarboxylic dianhydrides such as 2.4.5-cyclohexyltetracarboxylic dianhydride and 1,2,3,4-cyclohentanetetracarboxylic dianhydride are known. .

(Problems to be Solved by the Invention) Conventionally known polyimides using aliphatic tetracarboxylic dianhydrides have a drawback of extremely low heat resistance.

Also, 1, 2.4.5 which is an alicyclic tetracarboxylic acid
- It was confirmed that polyimide using cyclohexyltetracarboxylic dianhydride has a higher glass transition temperature and thermal decomposition initiation temperature than aliphatic tetracarboxylic dianhydride, but is extremely brittle. Alternatively, 1,2,3,4-cyclopentanetetracarboxylic dianhydride does not increase the degree of polymerization of polyamic acid, and only a very brittle polyimide can be obtained.

The present invention solves the conventional problems and converts polyimide at low temperature,
The purpose of the present invention is to provide a polyimide that has good transparency, heat resistance, and mechanical properties.

(Means for solving the problem) The first invention is based on the following general formula [1], (n) straddle (LI
The present invention relates to a novel polyamic acid or polyamic acid ester containing a structural unit represented by D.

(In the formulas of the above CD, (It) and [■1], R1 represents a hydrogen atom or a monovalent hydrocarbon group, and R.2 represents all divalent Q groups) The second invention is based on the general formula [■] (In the formula, & and 几4 are each independently an oxygen atom.

A compound represented by two hydroxyl groups or a hydroxyl group and an alkoxyl group) is reacted with a diamine represented by the general formula [v] 82N--NH2CVI (wherein r Rs represents a divalent group). The following general formula CI),
The present invention relates to a method for producing a novel polyamic acid or polyamic acid ester containing a structural unit covered with [:■] or [■].

(CI'll above, [1:11) and [IIl Okishikichu +
R1 is a hydrogen atom or a monovalent hydrocarbon group, & is a divalent group) The third invention is a structure represented by the general formula ["W] (in the formula 1 & represents a divalent group) This invention relates to a novel polyimide containing units.

The fourth invention is based on the following general formula [1], [ff] or [m]
The present invention relates to the production of a novel polyimide containing a structural unit represented by the following general formula CM, which is characterized in that a novel polyamic acid or polyamic acid ester containing a structural unit represented by the formula CM is ring-closed by dehydration or dealcoholization.

(in the formulas of [139 Kuguchi, [Kawa] and [VI] above, p 1
%s is.

Hydrogen atom or monovalent hydrovalent group, l (2 indicates a divalent group) The following two aspects of the present invention will be described in detail.

The novel polyamic acid or polyamic acid ester of the present invention containing a structural unit represented by the general formula CI], I:u] or [[Il] is a compound represented by the general formula [■],
It is obtained by reacting a diamine represented by general formula [v] in a solvent. The compound represented by the general formula [IV] is a new compound, biphenyl-3 as shown in the following formula.
, 4,3', 4'-tetracarboxylic acid.

In other words, biphenyl-&4.314'-tetracarboxylic acid tetramethyl ester was hydrogenated in the presence of a rhodium catalyst to form dicyclohexy/9-3.4. a;
4'-tetracarboxylic acid tetramethyl ester.

Thereafter, dicyclohexyl-34,W 4'-tetracarboxylic acid is obtained by acid hydrolysis or alkali hydrolysis and acid precipitation. Thereafter, if necessary, dehydration and ring closure are performed with heating or acetic anhydride to dicyclohexyl-3,4,
3: Can be 4'-tetracarboxylic dianhydride. Furthermore, this product was reacted with alcohol to dichlorohexyl and 4. It can be a λ'4'-tetracarboxylic acid diester.

General formula (11, (It) and [111) in the novel polyamic acid or polyamic acid ester containing the structural unit represented by the general formula C1), (n) or [■] of the present invention
The divalent group represented by R2 corresponds to the diamine z of the general formula [■] which is reacted with the compound represented by the general formula [IV]. That is, it depends on the type of diamine. Therefore, general formula (1'), [[I) or [■
] via a novel polyamic acid or polyamic acid ester containing a structural unit represented by the general formula CVT' ] Determined by the type of diamine.

Examples of the diamine represented by the general formula [■] used in the present invention include 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylmethane.

4.4'-diaminodiphenylsulfone, 4.4'-diaminodiphenyl sulfide, pentedine, metaphenylenediamine, paraphenylenecyabane.

2.2-bis(4-aminophenyl)propane, diaminobenzophenone, 1.5-diaminonaphthalene, 2.
6-diaminonaphthalene, 1.3-bis(4-aminophenoxy)benzene, 1.4-bis(4-aminophenoxy)benzene, 4.4'-di(4-aminophenoxy)diphenylsulfone, 4.4' -di(3-aminophenoxy)diphenylsulfone.

2-bis(4-(4-aminophenoxy)phenyl)
Aromatic diamine compounds such as propane, 9th general formula [■
] Cyabanosiloxane.

(In the formula, 1 (3 is a divalent hydrocarbon group, R4 is a monovalent hydrocarbon group, and 2m is an integer of 1 or more), for example.

H3CHs II CaHs　C5Hs Compounds such as the following can also be used.

In producing the novel polyamic acid or polyamic acid ester and polyimide of the present invention.

For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylenesulfone, p-chlorophenol, I)-7'
Solvents such as romophenol and 2-10-4-hydroxytoluene are used.

In carrying out the present invention, in the case of a novel polyamic acid containing a structural unit represented by the general formula [11, (n) and/or (II)], it is preferable to first use a diamine represented by the general formula [■]. After dissolving in the above inert solvent, dicyclohexyl-3,4, ¥4'-tetracarboxylic dianhydride, which is one of the compounds represented by the general formula [■], is added, preferably about Stir while maintaining the temperature at 80° C. or lower, especially around room temperature or lower. As a result, the reaction proceeds quickly, and the viscosity of the reaction system gradually increases.
Polyamic acid is produced. After the reaction was completed, in addition to the solvent used in the 9 reactions, diethylene glycol monomethyl ether was added to adjust the viscosity of the polyamic acid varnish.

Cellosolve solvents such as diethylene glycol monoethyl ether and ethylene glycol monobutyl ether can be added.

To obtain a novel boriabatic acid ester containing a structural unit represented by the general formula CI], [:[] or [l1l).

A method in which the carboxylic acid group of the polyamic acid synthesized by the above method is made into an acid chloride using thionyl chloride, etc., and then reacted with an alcohol such as methanol or ethanol, or dicyclohexyl-a, 4.3', 4'
- Tetracarboxylic acid etc. esterified via acid chloride as above, or dicyclohexyl-3
,4,3? It can be obtained by, for example, a method in which 4'-tetracarphonic dianhydride or the like is ring-opened with alcohol to form a diester, and then reacted with a diamine compound in a solvent.

When R1 in the general formulas [1), (n) and CII[) is a monovalent hydrocarbon group, 几1 corresponds to the alcohol used when obtaining the above polyamic acid ester.

That is, the portion obtained by removing the hydroxyl group from the alcohol is R+. To convert this polyamic acid or polyamic acid ester into polyimide.

Heat treatment is preferably carried out at a temperature of 100 to 300°C for 30 minutes to 5 hours. In this way, in the case of elliplyamic acid, it is dehydrated and ring-closed, and in the case of polyamic acid ester, it is dealcoholized and ring-closed to obtain a novel polyimide containing a structural unit represented by the general formula (Vl). For this dehydration, ring closure, dealcoholization, and ring closure reactions, acetic anhydride, phosphoric acid, or the like may be used as a dehydrating agent or dealcoholization agent. At this time, organic metals such as dibutyltin silaurylate and triethylamine,
It is also possible to use amine catalysts. As a result, the reaction progresses and the viscosity of the reaction system increases.

Polyimide is produced.

(Example) The present invention will be explained below with reference to nine examples.

Reference example Synthesis example of dicyclohexyl-3,4,3ζ4'-tetracarboxylic acid and its dianhydride (1) Production of dicyclohexyl-3,4,3ζ4'-tetracarboxylic acid tetramethyl ester By electromagnetism Biphenyl 3.43:4/in a 500ml autoclave with a vertical stirring device (5E-50 electromagnetic vertical stirring autoclave manufactured by Hanshita Kagaku Kiki ■)
-Tetracarboxylic acid tetramethyl ester 38.69 (
0,100 mol), 193 g of tetrahydrofuran, and 3.869 g of a catalyst (manufactured by Nippon Engelhard Co., Ltd.) consisting of 5% rhodium supported on activated carbon, and the hydrogen pressure was 30 k.
The hydrogenation reaction was carried out at a reaction temperature of 100°C. Hydrogen consumption stopped after a reaction time of 3.5 hours, and the amount of consumed hydrogen calculated from the amount of decrease in hydrogen pressure in the pressure accumulator at that time was theoretical. It was 98.8% of the amount of hydrogen consumed (0.60 mol).

After removing the activated carbon-supported rhodium catalyst in the reaction solution by r-filtration, the molten tetrahydrofuran was removed by evaporation, and white wax-like dicyclohexyl-3,
36.879 (0,0925 mol) of 4,3ζ4'-tetracarboxylic acid tetramethyl ester was obtained. IH-N
As a result of analysis using a M-ring (Hitachi Model R-250 Nuclear Magnetic Resonance Spectrometer manufactured by Hitachi, Ltd.), no benzene nuclear hydrogen or hydrogen attached to carbon-carbon double bonds were found, indicating that the hydrogenation reaction was complete. I understand.

(21dicyclohexyl-3,4,:3:4'-fto5
Production of Carboxylic Acid 29.99 (0,075 mol) of dicyclohexyl-3,4,3,'4'-tetracarboxylic acid tetramethyl ester was placed in a 11 eggplant-shaped flask equipped with a drain tube.

After adding 200g of methanol to this to make a homogeneous solution,
Add 200ge of 10% sodium hydroxide solution.

It was placed in a 100°C oil bath and refluxed for 6 hours. After this, methanol was distilled off by evaporation and concentrated until the volume of the 9 reaction liquid was 1409, and 36%
48 ml of hydrochloric acid was added to prepare 1) Hl. At pH 4 to 5, the liquid became cloudy, and at pH 1, fine white powder precipitated. The precipitate was removed by filtration, then washed with water and dried, 17.
89 white fine powder crystals of dicyclohexyl-3,4,3
,'4'-tetracarboxylic acid (0.052 mol) was obtained.

Infrared absorption spectrum of this crystal (measured by KBr method using Hitachi Model 260-30 infrared spectrophotometer manufactured by Hitachi, Ltd.)
is shown in Figure 1. The IH-NMR spectrum is shown in FIG. In Figure 2, the absorption at 2.50 ppm is the solvent d6-
Absorption based on dimethyl sulfoxide, 3.35
The ppm absorption is due to water contained in the solvent. In absorption excluding these two, 11.95ppm
The absorption based on the carboxyl group proton of 0.87
The integrated intensity ratio of absorption based on ~3.00 ppm cyclohexane ring protons is 29:132 (former: latter).
= 4:18.2), which agreed with the theoretical value.

In addition, the melting point of this crystal is 219-222°C, and the result of two-element analysis is 56.24% carbon and 6.53% hydrogen, which matches the calculated value of 56.1.3% carbon and 6.48% hydrogen. did.

(3) Production of dicyclohexyl-3,4,4'-tetracarboxylic dianhydride 300 ml with cooling tube attached! In an eggplant-shaped flask, add 1 dicyclohexyl-3,4,4'-tetracarboxylic acid.
5.0 (0,044 mol) and 180 g of acetic anhydride were placed in an oil bath at 150° C. and refluxed for 1 hour.

After this, when hot filtration was performed and the P solution was allowed to cool,
White crystals precipitated. The crystals were taken out by filtration and dried at a pressure of 30 mmHg and a temperature of 100° C. for 2 hours, and the amount of crystals was 10.89 (0,035 mol).

The melting point of the crystal is 231 to 234°C, and as a result of two-element analysis, it is 62.59% carbon and 6.01% hydrogen.

This was in good agreement with the theoretical values of 62.74% carbon and 5.92% hydrogen.

The infrared absorption spectrum of this crystal is shown in FIG.

The IH-NMR spectrum is shown in FIG. In FIG. 4, it can be seen that there is no absorption of carboxylic acid protons in a low magnetic field of 10 to 131)I)m, indicating that it is an anhydride.

Example 1 20 equipped with thermometer, stirrer and calcium chloride tube
4,4'-diaminodiphenyl ether 110149 (60 mmol) and 70.92 g of N-methyl-2-pyrrolidone as a reaction solvent were placed in a 0 mJ three-necked flask and dissolved with stirring at room temperature. In addition to this, dicyclohexyl-λ4 synthesized in the reference example. 18.3799 (60 mmol) of 4'-tetracarboxylic dianhydride was added, and stirring was continued for 8 hours at room temperature.

During this period, the viscosity of the polyamic acid reaction solution increased with the passage of 9 reaction hours, and the viscosity reached 86 boads at 25° C. after 8 hours of stirring. Then, this reaction solution was diluted with 8
After heating (kucking) at 0° C. for about 5 hours to adjust the viscosity to 15 poise, it was applied onto a glass plate and dried, and a portion of this polyamic acid was collected. The infrared absorption spectrum of this polyamic acid (measured by the KBr method using a Hitachi Model 270-50 infrared spectrophotometer manufactured by Hitachi, Ltd.) is shown in FIG.

Next, 2 coats of polyamic acid were coated on the glass plate and dried.
When the film was heat-treated at 50° C. for 1 hour and peeled off from the glass plate, a polyimide film with a thickness of 35 μm and good transparency was obtained. Collect a part of this polyimide film,
FIG. 6 shows an infrared absorption spectrum measured in the same manner as above. Also.

The Tg (glass transition temperature) of this product is
Measured using a 910 differential scanning calorimeter: 244°C
Met. Next, this polyimide film was evaluated by the test method shown below. The results are shown in Table 1.

Test method (1) Thermal decomposition temperature Using the above film 10,
The temperature was measured using a 10-type DEC) in an air stream at a temperature increase rate of 5° C./min, and the temperature at which the weight decreased by 5% was defined as the thermal decomposition temperature.

(2) Using a transmittance spectrophotometer (Hitachi Model 200-20 double beam spectrophotometer manufactured by Hitachi, Ltd.) at a wavelength of 700 nm, 6
The visible light transmittance at 00 nm and 500 nm was measured.

Example 2 4.4'-di(3-aminophenoxy)diphenylsulfone 19.4639 (45 mmol), dicyclohexyl-3,4,x 4'-tetracarboxylic dianhydride 13
．． A polyamic acid solution and a polyimide film were prepared in the same manner as in Example 1 using 7849 (45 mmol) and N-methyl-2-pyrrolidone 77.589, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. It is also shown in .

Comparative Example 1 4.4'-diaminodiphenyl ether 8.0109 (
40 mmol), pyromellitic dianhydride 8.7259
(40 mmol), N-methyl-2-pyrrolidone 94.
839 was used in the same manner as in Example 1, a polyamic acid solution was obtained, heat treated at 350°C for 1 hour to produce a polyimide film, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
It is also shown in .

Comparative Example 2 4.4'-diaminodiphenyl ether 15.018g
(75 mmol), 1,2,3,4-butanetetracarboxylic dianhydride 14.8609 (75 mmol) and N
Example 1 using 69.72 g of -methyl-2-pyrrolidone
A polyamic acid solution and a polyimide film were prepared in the same manner as in Example 1, and the results were also shown in Table 1.

Comparative example 3 Journal of Organic Chemistry (J.

Org, Cherr+,) Volume 31, Page 3438 (19
1, 2, 4.5-7 by the method described in 1966).
Clohexanetetracarboxylic acid was synthesized and dehydrated and ring-closed using acetic anhydride to obtain 1,2,4.5-cyclohexanetetracarboxylic dianhydride. This acid anhydride 1
5.6929 (70 mmol) and 4,4'-diaminodiphenyl ether 14.0179 (70 mmol)
A polyamic acid solution was prepared in the same manner as in Example 1 using 69.3219 and N-methyl-2-pyrrolidone. Next, a polyamic acid solution was applied to a glass plate in the same manner as in Example 1, and after drying, heat treatment was performed at 250'C for 1 hour. When the coating film cracked into flakes, a film could not be formed. .

(Effects of the Invention) The novel polyamic acid or polyamic acid ester according to the first invention or obtained by the second invention is polyimidized at low temperature according to the fourth invention to provide a novel polyimide according to the third invention. Such polyimides have transparency,
Use materials with good heat resistance and mechanical properties.

[Brief explanation of the drawing]

Figure 1 shows dicyclohexyl-3 in Reference Example (2),
4,3; Infrared absorption spectrum of 4'-tetracarboxylic acid, Figure 2 shows dicyclohexyl- in Reference Example (2).
3,4,3: 'H-NMR of 4-tetracarboxylic acid
The spectrum, Figure 3 is the infrared absorption spectrum of synchlohexyl-3,4,4'-tetracarboxylic dianhydride in Reference Example (3), and Figure 4 is the infrared absorption spectrum of dicyclohexyl-3,4'-tetracarboxylic dianhydride in Reference Example (3). , 4, IH-NMR spectrum of 4'-tetracarboxylic dianhydride. x Infrared absorption spectrum of polyamic acid obtained by reacting 4'-tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether. The figure shows the infrared absorption spectrum of the polyimide obtained. Agent Patent Attorney Kunihiko Wakabayashi

Claims (1)

[Claims] 1. A novel polyamic acid or polyamic acid ester containing a structural unit represented by the following general formula [I], [II] or [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formulas [I], [II], and [III] above, R_1 represents a hydrogen atom or a monovalent hydrocarbon group, and R_2 represents a divalent group. )2.General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[IV] (In the formula, R_3 and R_4 each independently represent an oxygen atom,
Reacting a compound represented by two hydroxyl groups or a hydroxyl group and an alkoxyl group with a diamine represented by the general formula H_2N-R_2-NH_2[V] (wherein R_5 represents a divalent group). Characterized by the following general formula [I]
A method for producing a novel polyamic acid or polyamic acid ester containing a structural unit represented by , [II] or [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] (Above [I], [II] and [ III], R_1 is a hydrogen atom or a monovalent hydrocarbon group, and R_2 is a divalent group) 3. General formula [VI] ▲ Numerical formulas, chemical formulas, tables, etc. , R_2 represents a divalent group). 4. A novel polyamic acid or polyamic acid ester containing a structural unit represented by the following general formula [I], [II] or [III] is subjected to a dehydration or dealcoholization reaction to cause ring closure. ] A method for producing a novel polyimide containing a structural unit represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ II ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ III ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ VI] (In the formulas [I], [II], [III] and [VI] above, R
_1 represents a hydrogen atom or a monovalent hydrocarbon group, R_2 represents a divalent group)