JPH02235842A - Alicyclic tetracarboxylic acid and derivative thereof - Google Patents

Abstract

NEW MATERIAL:An alicyclic tetracarboxylic acid expressed by formula I or II (R<1> to R<4> may be same or different and H or hydrocarbon group) and derivatives thereof. USE:Useful in wide fields of a raw material for polyimides, water-soluble polyesters, etc., plasticizer for polyvinyl chloride, curing agent for epoxy resins, etc. PREPARATION:A compound expressed by formula III is reacted with carbon monoxide and an alcohol in the presence of a palladium catalyst to afford the compound expressed by formula I. A reoxidizing agent of the palladium catalyst is further preferably used for the above-mentioned reaction. A copper or iron compound is used as the reoxidizing agent and the amount thereof used is 0.1-12mol based on 1mol compound expressed by formula III. The amount of the aforementioned catalyst used is within the range of 0.0001-0.1mol. The alcohol is especially preferably methanol and the amount thereof used is 4-400mol. The reaction temperature is within the range of -80 to 100 deg.C.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is a novel material that can be used in a wide range of fields as raw materials for polyimides, water-soluble polyesters, plasticizers for polyvinyl chloride, curing agents for epoxy resins, etc. The present invention relates to alicyclic tetracarboxylic acids and derivatives thereof.

[Prior art] Tetracarboxylic acids are generally useful as polyimide raw materials, and the main tetracarboxylic acids that have been widely used include pyromellitic acid, penzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, etc. Aromatic tetracarboxylic acids are known, and aliphatic tetracarboxylic acids include butanetetracarboxylic acid, 5-
(2,5-dioxotetrahydro-3-furanyl)-
3-methyl-3-cyclohexene-1,2-dicarboxylic acid and the like are known.

[Problems to be solved by the invention] However, although polyimide resins obtained using aromatic tetracarboxylic acids as raw materials have excellent heat resistance, they are completely insoluble in solvents or do not melt below the decomposition temperature. It has the problem of extremely poor workability, such as
On the other hand, polyimide resins made from aliphatic tetracarboxylic acids have excellent solubility in solvents, but
It has a problem of inferior heat resistance compared to polyimide resins made of aromatic tetracarboxylic acids.

Against this background, there has been a demand for the development of tetracarboxylic acids that provide polyimide resins with excellent solvent solubility and excellent heat resistance. 615
No. 79, JP-A No. 60-61582), 3.
5. 6-tricarboxy-2-carboxymethylnorbornanes (JP-A-60-104091), bicyclo[2. 2. 1) Hebutane-2. 3,
5. 6-tetracarboxylic acids (JP-A-63-5
7557, Japanese Unexamined Patent Publication No. 63-57589), etc. have been proposed. These are alicyclic tetracarboxylic acids with a rigid structure.

However, conventional alicyclic tetracarboxylic acids do not provide polyimide resins that still have sufficient physical properties in terms of solubility, fusibility, water absorption, heat resistance, and other properties.

[Means for Solving the Problems] The present invention has been made based on the above circumstances, and is useful as a raw material for obtaining a polyimide resin having suitable characteristics, or an intermediate thereof, for example. The present invention provides novel alicyclic tetracarboxylic acids and derivatives thereof.

That is, the present invention provides the following general formula (I) or general formula (
The present invention provides alicyclic tetracarboxylic acids represented by II) and derivatives thereof (hereinafter collectively referred to as "tetracarboxylic acids").

(In the formula, R1 to R4 may be the same or different, and represent a hydrogen atom or a hydrocarbon group.)
C In R1 to R4 in the general formula (I), the hydrocarbon group includes a methyl group, an ethyl group, a probyl group, an isopropyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, an allyl group, a pomoallyl group, and a cyclopentenyl group. , aliphatic hydrocarbon groups having 1 to 25 carbon atoms such as cyclohexenyl group, cinnamyl group, and propargyl group; and aliphatic hydrocarbon groups having 6 to 25 carbon atoms such as phenyl group, tolyl group, xylyl group, and naphthyl group.
25 aromatic hydrocarbon groups may be mentioned.

Tet of the present invention. Among the lacarboxylic acids, derivatives of alicyclic tetracarboxylic acids in which R1 to R4 in general formula (1) are hydrocarbon groups (hereinafter simply referred to as "derivatives") are compounds represented by the following general formula (m) ( Hereinafter, "compound (
It can be produced by reacting carbon monoxide and alcohol in the presence of a palladium catalyst.

Palladium catalysts that can be used here include palladium chloride, palladium nitrate, potassium tetrachloride, palladium inorganic acid salts such as palladium sulfate, palladium organic acid salts such as palladium acetate and palladium propionate, and palladium on carbon. Examples include metal palladium supported on a carrier such as palladium silica and palladium alumina. This palladium catalyst is usually 0.0001 to 0.00% per mole of compound (■).
It is used in a range of 1 mol.

In carrying out this reaction, it is usually preferable to use a palladium-catalyzed reoxidizing agent in combination. Copper compounds, iron compounds, and the like are used as the reoxidizing agent, such as cupric chloride, cupric nitrate, cupric sulfate, cupric acetate, ferric chloride, and ferric nitrate. can be mentioned. It is also possible to utilize Wacker reaction using oxygen gas and the copper compound as a reoxidizing agent. The amount of these copper compounds or iron compounds to be used is usually in the range of 0.1 to 12 mol per 1 mol of compound (■).

Examples of alcohols used in this reaction include methanol, ethanol, propanol, butanol, cyclopentanol, cyclohexanol, allyl alcohol, homoallyl alcohol, cyclopentenyl alcohol, cyclohexenyl alcohol, cinnamyl alcohol, propargyl alcohol, etc. These aliphatic alcohols, benzyl alcohol, naphthyl alcohol, etc. can be used alone or in combination of two or more kinds, and among the above aliphatic alcohols, methanol is particularly preferred. The amount of these alcohols used is usually 4 mol or more, preferably 4 to 400 mol, per 1 mol of compound (■).
It is a mole.

The carbon monoxide used in this reaction is not only pure carbon monoxide, but may also be an inert gas such as argon or nitrogen containing carbon monoxide at a concentration of 10% by volume or more. In addition, methods for supplying carbon monoxide to the reaction system include introducing it into the reaction solution under pressure, introducing it into the reaction solution while bubbling at normal pressure, and simply bringing it into contact with the surface of the reaction solution at normal pressure. Examples include methods.

This reaction is usually carried out in the presence of a solvent, such as hydrocarbon compounds such as n-hexane and cyclohexane, ether compounds such as tetrahydrofuran and dimethoxyethane, and halogenated hydrocarbons such as methylene chloride and chloroform. Compound (m) can be used
The alcohol itself to be reacted with can also be used as a solvent.

The appropriate reaction temperature for this reaction is -80 to 100°C, the reaction pressure is normal pressure to 50 kg/cj, and the reaction time is 1 to 72 hours.

Among the tetracarboxylic acids of the present invention, alicyclic tetracarboxylic acids in which R1 to R4 in general formula (I) are hydrogen atoms (hereinafter simply referred to as "tetracarboxylic acids") are derivatives obtained as described above. It can be produced by hydrolyzing.

This hydrolysis can be carried out with high efficiency, for example, by a method using an acid catalyst or a base catalyst. Here, as the acid catalyst, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, p
- Organic acids such as toluenesulfonic acid, formic acid, and trifluoroacetic acid can be used, and as base catalysts,
Alkaline compounds such as sodium hydroxide and potassium hydroxide are used. This hydrolysis is generally carried out in the presence of a solvent, and the solvent used is water or a mixed solvent of water and a hydrophilic organic solvent such as methanol, acetone, or tetrahydrofuran. The amount of the acid catalyst or base catalyst used in this hydrolysis is usually 0.0001 to 0.4 mol per 1 mol of the derivative, and the reaction temperature is suitably from room temperature to 120°C.

Among the alicyclic tetracarboxylic acids of the present invention, the alicyclic tetracarboxylic anhydride (
The tetracarboxylic acid anhydride (hereinafter referred to as "tetracarboxylic anhydride") can be obtained by subjecting the tetracarboxylic acid to heat treatment or dehydration treatment.

This heat treatment is performed under reduced pressure or inert gas.
A method is used in which tetracarboxylic acid is heated, for example, at a temperature of 120 to 250°C. This heat treatment can be carried out in a solvent inert to the tetracarboxylic acid, such as diethylbenzene or tert-amylbenzene.

In addition, a typical dehydration treatment is a method in which a dehydrating acid anhydride such as acetic anhydride is applied, and the dehydrating acid anhydride is usually 2 moles or more, preferably 10 moles or more, per 1 mole of tetracarboxylic acid. Examples of the above methods include methods in which the reaction is carried out in a solvent consisting of an aromatic hydrocarbon compound such as benzene and toluene, or in the absence of a solvent.

The tetracarboxylic acids of the present invention can also be purified by recrystallization or the like.

The tetracarboxylic acid or tetracarboxylic anhydride of the present invention can be reacted with a diamine to produce a polyurethane. After making the polyamic acid (hereinafter simply referred to as "boriamic acid"), by dehydrating the polyamic acid, the following general formula (IV) is obtained.
Polyimide having a repeating structural unit represented by (hereinafter simply referred to as "polyimide") can also be used.

(In the formula, R5 represents a divalent organic group.) The above general formula (I
R5 in V) is, for example, an aromatic group represented by (X1 n represents 0 or 1), (CH2
) (n=2 to 20), n CH3 ζ − (CH2)3 −C one (CH2)3 −CH
3 (where x, x2, X3 and X4 may be the same or different, -H, -CH3 or -OCH3, Y is -C
Examples include aliphatic groups or alicyclic groups having 2 to 20 carbon atoms represented by H2, -C2H4- 101-S- CH3 I CF3 .

The diamines used here include paraphenylene diamine, metaphenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4.4'-diaminodiphenylsulfone, 4.
4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dithymel-4,4'-diaminobiphenyl, 3,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 3.3'-
Diaminobenzophenone, 3.4'-diaminobenzophenone, 4.4'-diaminobenzophenone, 2
,2-bis(4-(4-aminophenoxy)phenyl)
Propane, bis(4-(4-aminophenoxy)phenyl)sulfone, 1,4-bis(4-aminophenoxy)
Benzene, l,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 9,9-bis( 4-aminophenyl)
Fluorene, 4.4'-methylenebis(2-chloroaniline), 2.2',5.5'tetrachloro-4.
4'-diaminobiphenyl, 2,2'-dichloro 4,
4-diamino-5,5'-dimethoxybiphenyl, 3.
Aromatic diamines such as 3'-dimethoxy-4,4'-diaminobiphenyl, 1,1'-methaxylylene diamine, 1,3-brobanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, hebutylene diamine, etc. Methylene diamine, octamethylene diamine, nonamethylene diamine, 4.4'-dimethylbutamethylene diamine, 1,4-diaminoxyhexane, isophorone diamine, tetrahydride pentadienyl diamine, hexahydride-4.7- Methanoindani dimethylenediamine, tricyclo(6.2.1.0
2.7) Aliphatic or alicyclic diamines such as undecylendimethyldiamine, and (wherein R is an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, or a probyl group, or an alicyclic group such as a cyclohexyl group) group group or aromatic group such as phenyl group, m is 1 to 3
An integer, n represents an integer of 1 to 20. ) and the like are diaminoorganosiloxanes.

Moreover, two or more types of these diamines can also be used in combination.

R5 in the general formula (IV) is a residue of these diamines.

To obtain polyimide, first, a tetracarboxylic acid or tetracarboxylic acid anhydride and a diamine are reacted, usually in an organic solvent, to obtain an organic solvent solution of polyamic acid.

The obtained organic solvent solution of polyamic acid was used as it was.
Alternatively, polyamic acid is recovered from an organic solvent solution by a conventional method, purified if necessary, then dissolved in an organic solvent again, and imidized by adding a tertiary amine if desired in the presence of an organic carboxylic acid anhydride. Carry out the reaction.

In the present invention, as the organic solvent during the imidization reaction,
For example, polar solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphortriamide, etc. are used.

The reaction ratio of tetracarboxylic acid or tetracarboxylic acid anhydride and diamine is preferably carried out in equimolar terms;
The ratio of these monomers may be slightly varied as long as the desired polyamic acid is obtained. For example, in order to obtain a high molecular weight polyamic acid, it is preferable to use about 0.7 to 1.3 moles of diamine per 4 moles of tetracarboxylic acid or tetracarboxylic acid anhydride. Moreover, the molecular weight of the polyamic acid can also be adjusted by adding a monoamine or a dicarboxylic acid anhydride.

The reaction temperature when producing polyamic acid is usually 50 to 300°C when using a tetracarboxylic acid, preferably 100 to 250°C, and 0 to 100°C when using a tetracarboxylic anhydride. In general, it is preferable to use a tetracarboxylic acid anhydride as the tetracarboxylic acid and the tetracarboxylic anhydride, which facilitates the production of a polyamic acid that is soluble in an organic solvent.

In addition, in addition to the polar solvents mentioned above, general organic solvents such as alcohols, phenols, ketones, esters, lactones, Ethers, halogenated hydrocarbons, hydrocarbons such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, brobylene glycol,
1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, phenol, m
-Cresol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, 0-dichlorobenzene, hexane, hebutane, octane, benzene,
Toluene, xylene, etc. can also be used.

In particular, when the above polar solvent and a general organic solvent are mixed and used, it becomes easier to obtain a high molecular weight polyamic acid. For example, when a tetracarboxylic acid anhydride and a diamine are reacted using a solvent of acetone/dimethylformamide=7/3 (volume ratio), the reaction system becomes homogeneous, and a poamic acid having a particularly high molecular weight is easily obtained.

When a tetracarboxylic acid or a tetracarboxylic anhydride is reacted with a diamine using these general organic solvents, the produced polyamic acid is generally recovered and imidized again as a solution in the above polar solvent.

The intrinsic viscosity of the polyamic acid obtained in this way (0
．． 5g:/J, in a polar solvent at 30°C) is preferably 0
．． The amount is 2 to 10 rinsings/g.

The concentration of the organic solvent solution of polyamic acid used in the present invention is preferably 1 to 50% by weight, particularly preferably 1 to 50% by weight.
It is 30% by weight.

The boiling point of the organic carboxylic acid anhydride used in the present invention is 2
Preferably, the temperature is 50°C or less. If the boiling point of the organic carboxylic acid anhydride exceeds 250°C, the organic carboxylic acid anhydride will not be removed at the same time in the process of removing the solvent by heating during film formation, and will remain in the film.
Adversely affects physical properties, etc.

Examples of such organic carboxylic acid anhydrides include acetic anhydride, probionic anhydride, butyric anhydride, isobutyric anhydride,
Valeric anhydride and the like are used. Mixed acid anhydrides of these organic carboxylic acids, such as acid anhydrides obtained from acetic acid and brobionic acid, can also be used.

The amount of organic carboxylic acid anhydride added is preferably 0.2 to 20 moles per mole of repeating structural unit of polyamic acid. When the amount is less than 0.2 times the mole, the imidization reaction progresses slowly, and when it exceeds 20 times the mole, the solubility of the polyamic acid in the organic solvent decreases.

In the present invention, in order to promote the imidization reaction, a tertiary amine can be added as a catalyst if desired. In addition to promoting the imidization reaction, the tertiary amine also has the effect of suppressing a decrease in the solution viscosity of the resulting polyimide compound.

The tertiary amine used in the present invention preferably has a boiling point of 250°C or lower for the same reason as the organic carboxylic acid anhydride. For example, aliphatic tertiary amines such as triethylamine, tribubylamine, and tributylamine , N, N-
Aromatic tertiary amines such as dimethylaniline, pyridine,
Examples include heterocyclic compounds such as 2-methylpyridine, N-methylimidazole, and quinoline.

The amount of the tertiary amine added is preferably 20 times or less in mole per mole of repeating structural units of the polyamic acid. When the amount exceeds 20 times the mole, the solubility of polyamic acid in organic solvents tends to decrease.

In the present invention, the imidization reaction is carried out by heat-treating the organic solvent solution of polyamic acid obtained in the reaction as it is, or by collecting the produced polyamic acid, and then purifying it as necessary and using it for producing polyamic acid. This is carried out by redissolving the solvent in the same or different organic solvent and heat-treating it. The reaction temperature of the imidization reaction is preferably 60~
The temperature is 200°C, particularly preferably 100-170°C. 6
At temperatures below 0°C, the progress of the imidization reaction is delayed, and at temperatures below 200°C,
If it exceeds this, the molecular weight of the polyimide compound will decrease significantly.

The order of addition of organic carboxylic acid anhydride and tertiary amine is:
Either one may be added first, or the two may be mixed and then added.

The intrinsic viscosity of the polyimide thus obtained (0.
5g/df! , in a polar solvent at 30°C) is usually 0.1
5~8df! /g, preferably 0. 3~4dl/g
It is.

The polyimide thus obtained is produced by casting a solution of the reacted polyimide in an organic solvent onto a substrate such as a glass plate or a metal plate, and then applying the organic solvent, organic carboxylic acid anhydride, etc. by heating or other methods. A film can be formed by removing the tertiary amine and the tertiary amine. Alternatively, after the polyimide is recovered from the organic solvent solution of the polyimide after the reaction, it can be redissolved in the organic solvent and then formed into a film by the above method. Examples of the organic solvent used for this redissolution include, in addition to the above-mentioned polar solvents, solvents that dissolve polyimide, such as phenolic solvents such as metacresol.

The polyimide obtained using the tetracarboxylic acids of the present invention has excellent heat resistance, mechanical properties, electrical properties, chemical resistance properties, etc., and also has excellent workability during film production and has little shrinkage during film formation. It is useful for films, adhesives, paints, etc. that are used under high temperatures.Specifically, it is useful for printed wiring boards, flexible printed wiring boards, surface protection films for semiconductor integrated circuit elements, coatings for enameled electric wires, various laminates, etc. It can be used in a wide range of applications, including as an electrical insulating material.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Compound (III) 16. 2g (0.10mo
l), cupric chloride 110. 4g (0.82
mol), 5 weight palladium on carbon 3. 1g (
0. 00029 mol), and methanol 30
Pour 0ml into a reaction container, stir vigorously at room temperature while introducing carbon monoxide, react for 4 hours, remove carbon monoxide from the system, filter the reaction solution with P, concentrate the P solution, 100 ml of chloroform was added and washed with 100 ml of water. Furthermore, after washing this chloroform layer with a saturated sodium bicarbonate aqueous solution, the chloroform layer was concentrated and the remaining solid content was recrystallized from ethanol to obtain a compound having the following structure with a molecular weight of 394 and a melting point of 146-147°C. 22.9g was obtained. The infrared absorption spectrum and nuclear magnetic resonance spectrum of the obtained compound were measured. The charts are shown in FIGS. 1 and 2, respectively.

Example 2 10 g (0.025 mol) of the compound obtained in Example 1
) was placed in a reaction vessel and suspended in 30 ml of methanol, then hydrochloric acid (40 ml) and water (30 ml) were added.
The reaction was carried out at 50°C for 48 hours. Thereafter, the solvent was distilled off and concentrated, and a compound 8. having the following structure and a melting point of 198°C was obtained.
12 g was obtained, and the infrared absorption spectrum of the obtained compound was measured. The chart is shown in Figure 3.

Example 3 (1) 10 g of the compound obtained in Example 2 (0.0
3 mol) was dissolved in 100 ml acetic anhydride, and under reflux,
The reaction was allowed to proceed for 6 hours. After cooling, the precipitated white solid was washed with anhydrous ether to obtain the following structure with a molecular weight of 303 (M" 1.) and a melting point of 305-306°C.
7.8 g of the compound was obtained. The infrared absorption spectrum of the obtained compound was measured. The chart is shown in Figure 4.

Test Example 1 4,4'-diaminodiphenyl ether 10.01g
(0.05 mol) of anhydrous N-methylpyrrolidone 10
0. ! 15.12 g (0.05 mol) of the compound obtained in Example 3 was added to this solution, and the mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere. A solution was obtained. The intrinsic viscosity [η] (30° C., in N-methylpyrrolidone) of this polyamic acid was 0.80 clf/g. This polyamic acid solution was cast onto a glass plate and heated at 120°C for 1 hour.
By heating at 200°C for 3 hours, a polyimide having the following repeating structural unit and having an intrinsic viscosity [η] (30°C, in N-methylbibutene) of 0.58 d1/g was obtained.

The imide bond was confirmed by the disappearance of the NH absorption of polyamic acid near 1540 cm in the infrared absorption spectrum and the 17
Confirmed by absorption around 50 to 1780. Table 1 shows the 5% heating loss temperature and thermal decomposition temperature of the polyimide obtained.

II IIO
o Test Example 2 In Test Example 1, 4.4'-diaminodiphenyl methane 9. was used instead of 4.4'-diaminodiphenyl ether. Using 91 g (0.05 mol), the amount of anhydrous N-methylpyrrolidone used was 100.12 g.
The reaction was carried out in the same manner as in Test Example 1, except that the following repeating structural units were used, and the intrinsic viscosity [η] (30℃
A polyamide containing 0.42 N-methylpyrrolidone/g was obtained. Table 1 shows the 5% heating loss temperature and thermal decomposition temperature of the polyimide obtained.

Test Example 3 In Test Example 1, 2,2-bis[4-(4-aminophenoxy)phenyl]propane was used instead of 4,4'-diaminodiphenyl ether. 52g (0.
The reaction was carried out in the same manner as in Test Example 1, except that the amount of anhydrous N-methylpyrrolidone used was 142.56 g. - in methylpyrrolidone) is 0.
A polyimide having a concentration of 91 cle/g was obtained. Table 1 shows the 5% heating loss temperature and thermal decomposition temperature of the polyimide obtained.

Below is Table 1 in the margin [Effects of the Invention] The alicyclic tetracarboxylic acids of the present invention are useful as raw materials for producing polyimides with excellent solubility, low water absorption, heat resistance, and the like.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of the compound obtained in Example 1, Figure 2 shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1, and Figure 3 shows the nuclear magnetic resonance spectrum of the compound obtained in Example 2. FIG. 4 shows an infrared absorption spectrum of the compound obtained in Example 3. Patent applicant: Japan Synthetic Rubber Co., Ltd. Transmittance (%) Transmittance (%) Transmittance (%)

Claims (1)

[Claims] (1) Alicyclic tetracarboxylic acids represented by the following general formula (I) or general formula (II) and derivatives thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(I) (In the formula, R^1 to R^4 may be the same or different, and represent a hydrogen atom or a hydrocarbon group.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・・・・
...(II)