JP2666457B2 - Alicyclic tetracarboxylic acids and derivatives thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to raw materials such as polyimide and water-soluble polyester, a plasticizer of polyvinyl chloride, a curing agent of epoxy resin,
In addition, the present invention relates to a novel alicyclic tetracarboxylic acid and a derivative thereof which can be used in a wide variety of fields.

[Prior Art] Generally, tetracarboxylic acid is useful as a polyimide raw material, and the main tetracarboxylic acids that have been widely used in the past include aromatic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, and biphenyltetracarboxylic acid. 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 from aromatic tetracarboxylic acids as raw materials are excellent in heat resistance,
There is a problem that workability is extremely poor, such as being completely insoluble in a solvent or not melting below the decomposition temperature.On the other hand, polyimide resins made from aliphatic tetracarboxylic acids have poor solubility in solvents. Is excellent, but has a problem that its heat resistance is inferior to that of a polyimide resin based on aromatic tetracarboxylic acids.

Against this background, there has been a demand for the development of tetracarboxylic acids which are excellent in solvent solubility and give polyimide resins having excellent heat resistance. To date, methyldichlorooctenetetracarboxylic acids (Japanese Patent Application Laid-Open No. 61579
JP-A-60-61582), 3,5,6-tricarboxy-2-carboxymethylnorbornanes (JP-A-60-61582)
-104091), bicyclo [2.2.1] heptane-2,3,
5,6-tetracarboxylic acids (JP-A-63-57557 and JP-A-63-57589) have been proposed. These are alicyclic tetracarboxylic acids having a rigid structure.

However, conventional alicyclic tetracarboxylic acids are:
In terms of various properties such as solubility, fusibility, water absorption and heat resistance, it does not give a polyimide resin having sufficient physical properties.

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

That is, the present invention provides an alicyclic tetracarboxylic acid represented by the following general formula (I-1) or (II) and a derivative thereof, and an alicyclic tetracarboxylic acid represented by the following general formula (I-2) It is intended to provide a derivative of a tetracarboxylic acid (hereinafter, these are collectively referred to as “tetracarboxylic acids”).

(Wherein, R ^{1 to} R ⁴ may be the same or different, and represent an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms.) In R ^{1 to} R ⁴ in -2), examples of the aliphatic hydrocarbon group having 1 to 25 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, cyclopentyl, cyclohexyl, allyl, and homoallyl. Group, cyclopentenyl group, cyclohexene group, propargyl group, and the like.Examples of the aromatic hydrocarbon group having 6 to 25 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a cinnamyl group, and a naphthyl group. Can be.

Among the tetracarboxylic acids of the present invention, the compound represented by the general formula (I-
The derivative of the alicyclic tetracarboxylic acid represented by 2) is obtained by adding a compound represented by the following general formula (III) (hereinafter, referred to as “compound (III)”) to carbon monoxide and an alcohol in the presence of a palladium catalyst. Can be produced by reacting

As the palladium catalyst that can be used here,
Palladium chloride, palladium nitrate, potassium tetrachloroparadate, palladium inorganic acid salts such as palladium sulfate, palladium organic acid salts such as palladium acetate and palladium propionate, and supported on carriers such as palladium carbon, palladium silica and palladium alumina Metal palladium is mentioned. This palladium catalyst is generally used in the range of 0.0001 to 0.1 mol per 1 mol of compound (III).

In carrying out this reaction, it is usually preferable to use a reoxidizing agent of a palladium catalyst in combination. As the reoxidizing agent, a copper compound, an iron compound and the like are used. For example, cupric chloride, cupric nitrate, cupric sulfate, cupric acetate, ferric chloride, ferric nitrate and the like are used. Can be mentioned. Also,
It is also possible to use a Wacker reaction by using oxygen gas and the above-mentioned copper compound as a reoxidizing agent. The amount of the copper compound or iron compound to be used is generally 0.1 to 12 mol, per 1 mol of compound (III).

As the alcohol used in this reaction, for example,
Methanol, ethanol, propanol, butanol,
Aliphatic alcohols such as cyclopentanol, cyclohexanol, allyl alcohol, homoallyl alcohol, cyclopentenyl alcohol, cyclohexenyl alcohol, and propargyl alcohol, benzyl alcohol, cinnamyl alcohol, naphthyl alcohol, etc. may be used alone or in combination of two or more. Can be used
Of the above, aliphatic alcohols, especially methanol, are preferred. The amount of these alcohols used depends on the compound (II
I) 4 mol or more, preferably 4 mol, per 1 mol
~ 400 moles.

The carbon monoxide used in this reaction is not limited to pure carbon monoxide, but may be, for example, an inert gas such as argon or nitrogen containing carbon monoxide at a concentration of 10% by volume or more. As a method of supplying carbon monoxide to the reaction system, a method of introducing into the reaction solution by pressurization, a method of introducing into the reaction solution while bubbling at normal pressure, or simply bringing the reaction solution into contact with the surface of the reaction solution at normal pressure And the like.

This reaction is usually performed in the presence of a solvent. Examples of the solvent include 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 (II)
The alcohol itself to be reacted with I) can be used as a solvent. The reaction temperature of this reaction is -80 to 100 ° C, the reaction pressure is normal pressure to 50 kg / cm ² , and the reaction time is suitably 1 to 72 hours.

Among the tetracarboxylic acids of the present invention, the compound represented by the general formula (I-
The alicyclic tetracarboxylic acid represented by 1) (hereinafter simply referred to as “tetracarboxylic acid”) can be produced by hydrolyzing the derivative obtained as described above.

This hydrolysis can be performed with high efficiency by, for example, a method using an acid catalyst or a base catalyst. Here, examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid;
Organic acids such as p-toluenesulfonic acid, formic acid, and trifluoroacetic acid can be used, and alkali compounds such as sodium hydroxide and potassium hydroxide are used as the base catalyst. This hydrolysis is generally performed in the presence of a solvent, and as the solvent, water or a mixed solvent of water and a hydrophilic organic solvent such as methanol, acetone, and tetrahydrofuran is used. 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 room temperature to 120 ° C.

Among the alicyclic tetracarboxylic acids of the present invention, the alicyclic tetracarboxylic anhydride represented by the general formula (II) (hereinafter, referred to as “tetracarboxylic anhydride”) is obtained by heat treating the tetracarboxylic acid. Or by a dehydration treatment.

For this heat treatment, a method of heating the tetracarboxylic acid at a temperature of, for example, 120 to 250 ° C. under reduced pressure or an inert gas is used. This heat treatment can be performed in a solvent inert to tetracarboxylic acid, for example, diethylbenzene, tert-amylbenzene and the like.

As the dehydration treatment, a method of reacting an acid anhydride for dehydration such as acetic anhydride is typical. The acid anhydride for dehydration is usually 2 mol or more per 1 mol of tetracarboxylic acid,
The method is preferably used in an amount of 10 mol or more, for example, in a solvent composed of an aromatic hydrocarbon compound such as benzene or toluene, or without a solvent.

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

The tetracarboxylic acid or tetracarboxylic anhydride of the present invention is converted into a polyamic acid (hereinafter, simply referred to as “polyamic acid”) by reacting with a diamine, and then the polyamic acid is dehydrated to obtain the following general formula (IV) ) (Hereinafter simply referred to as “polyimide”).

(In the formula, R ⁵ represents a divalent organic group.) As R ⁵ in the general formula (IV), for example, (Wherein X ₁ , X ₂ , X ₃ and X ₄ may be the same or different, and —H, —CH ₃ or —OCH ₃ , Y is —CH ₂ , —C ₂ H ₄ —,
-O-, -S-, —SO ₂ — or —CONH—, n represents 0 or 1), an aromatic group represented by — (CH ₂ ) _n — (n = 2 to 20), And a C2-20 aliphatic or alicyclic group.

Examples of the diamine used here include paraphenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, benzidine, 4,4'-diaminodiphenylsulfide, and 4,4'-diamino. Phenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,
3'-dithimer-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, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis ( 3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydro-
Anthracene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl , 2,2'-dichloro-4,4-diamino-5,5'-
Aromatic diamines such as dimethoxybiphenyl and 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,1'-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylene Diamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4'-dimethylheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methano Indylene dimethylene diamine, tricyclo (6,2,1,0
^2.7 )-an aliphatic or cycloaliphatic diamine such as undecylenedimethyldiamine, and (Wherein, R is an alkyl group such as a methyl group, an ethyl group, or a propyl group having 1 to 12 carbon atoms, an alicyclic group such as a cyclohexyl group, or an aromatic group such as a phenyl group, m is an integer of 1 to 3, n represents an integer of 1 to 20.) and the like.

These diamines may be used in combination of two or more.

R ⁵ in the general formula (IV) is a residue of these cyamines.

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

The resulting organic solvent solution of the polyamic acid is used as it is, or the polyamic acid is recovered from the organic solvent solution by an ordinary method, purified if necessary, then dissolved again in the organic solvent, and in the presence of an organic carboxylic acid anhydride. And optionally 3
An imidation reaction is performed by adding a tertiary amine.

In the present invention, as the organic solvent at the time of the imidization reaction, for example, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphortriamide and the like Polar solvents are used.

The reaction ratio of the tetracarboxylic acid or the tetracarboxylic anhydride to the diamine is preferably performed in equimolar amounts, but the ratio of these monomers may be slightly changed 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 mol of a diamine per 1 mol of tetracarboxylic acid or tetracarboxylic anhydride. Further, the molecular weight of the polyamic acid can be adjusted by adding a monoamine or a dicarboxylic anhydride. The reaction temperature for producing the polyamic acid is usually 50 to 300 ° C when using tetracarboxylic acid, preferably 100 to 250 ° C,
When using tetracarboxylic anhydride, the temperature is 0 to 100 ° C. In general, it is preferable to use tetracarboxylic acid anhydride between tetracarboxylic acid and tetracarboxylic acid anhydride, which facilitates production of a polyamic acid soluble in an organic solvent.

In addition, as an organic solvent when reacting a tetracarboxylic acid or a tetracarboxylic anhydride with a diamine, alcohols that are general organic solvents other than the polar solvent,
Phenols, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene 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, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like can also be used.

In particular, when a mixture of the above-mentioned polar solvent and a general organic solvent is used, it becomes easy to obtain a high molecular weight polyamic acid. For example, when a tetracarboxylic anhydride and a diamine are reacted with a solvent of acetone / dimethylformamide = about 7/3 (volume ratio), the reaction system becomes uniform, and it becomes particularly easy to obtain a high molecular weight poamic acid.

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

The intrinsic viscosity (0.5 g / dl, in a polar solvent, 30 ° C.) of the polyamic acid thus obtained is preferably 0.2 to 10
dl / g.

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

The boiling point of the organic carboxylic anhydride used in the present invention,
The temperature is preferably 250 ° C. or lower. If the boiling point of the organic carboxylic acid anhydride exceeds 250 ° C, the organic carboxylic acid anhydride is not removed at the same time in the step of removing the solvent by heating during film formation, and remains in the film, adversely affecting the physical properties and the like. give.

Such organic carboxylic acid anhydrides include, for example,
Acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride and the like are used. Mixed acid anhydrides of these organic carboxylic acids, for example, acid anhydrides obtained from acetic acid and propionic acid can also be used.

The amount of the organic carboxylic anhydride to be added is preferably 0.2 to 20 moles per mole of the repeating structural unit of the polyamic acid. When the molar ratio is less than 0.2 times, the progress of the imidation reaction becomes slow.

In the present invention, in order to promote the imidation reaction,
If desired, a tertiary amine can be added as a catalyst. The tertiary amine not only promotes the imidization reaction but also has an effect of suppressing a decrease in solution viscosity of the obtained polyimide compound.

The tertiary amine used in the present invention is preferably one having a boiling point of 250 ° C. or lower for the same reason as the mixing of the organic carboxylic acid anhydride. For example, aliphatic tertiary amines such as triethylamine, tripropylamine and tributylamine; N, N-
Aromatic tertiary amines such as dimethylaniline, pyridine,
Heterocyclic compounds such as 2-methylpyridine, N-methylimidazole and quinoline are exemplified.

The amount of the tertiary amine to be added is preferably not more than 20 times the mole of the repeating unit of the polyamic acid. If the molar ratio exceeds 20 times, the solubility of the polyamic acid in an organic solvent tends to decrease.

In the present invention, the imidization reaction is a heat treatment of the organic solvent solution of the polyamic acid obtained in the reaction as it is, or after the generated polyamic acid is recovered, purified if necessary, and used for the production of polyamic acid. This is carried out by heat-treating a redissolved substance in the same or different organic solvent as the solvent. The reaction temperature of the imidation reaction is preferably 60 to
The temperature is 200 ° C, particularly preferably 100 to 170 ° C. If the temperature is lower than 60 ° C., the progress of the imidization reaction is delayed.

The order of adding the organic carboxylic acid anhydride and the tertiary amine may be any order, or they may be mixed and then added.

The intrinsic viscosity of the polyimide thus obtained (0.5 g
/ dl, 30 ° C. in a polar solvent) is usually 0.15 to 8 dl / g, preferably 0.3 to 4 dl / g.

The polyimide obtained in this manner is a glass plate, a substrate such as a metal plate, after casting an organic solvent solution of the reacted polyimide, an organic solvent by a method such as heating, an organic carboxylic anhydride. A film can be formed by removing the tertiary amine. Also, after recovering the polyimide from the organic solvent solution of the polyimide after the reaction,
It can be redissolved in an organic solvent and then formed into a film by the above method. Examples of the organic solvent used for the re-dissolution include, in addition to the polar solvent described above, a solvent for dissolving the polyimide, for example, a phenol-based solvent such as meta-cresol.

The polyimide obtained using the tetracarboxylic acid or tetracarboxylic anhydride of the present invention has excellent heat resistance, mechanical properties, electrical properties, chemical resistance properties, etc., and also has excellent workability in film production, and Less shrinkage,
It is useful for films, adhesives, paints, etc. used at high temperatures, and specifically for printed wiring boards, flexible printed wiring boards, surface protection films for semiconductor integrated circuit devices, coating materials for enameled wires, various laminates, etc. It can be used for a wide range of applications as an electrical insulating material.

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

Example 1 16.2 g (0.10 mol) of compound (III), 110.4 g of cupric chloride
(0.82 mol), 5 g of palladium on carbon 3.1 g (0.00029mo
l) and methanol (300 ml) were charged into a reaction vessel, vigorously stirred at room temperature while introducing carbon monoxide, and reacted for 4 hours. After removing carbon monoxide from the system, the reaction solution was filtered, and the filtrate was filtered. After concentration, add 100 ml of chloroform and 100 ml of water.
And washed. Further, after washing the chloroform layer with a saturated aqueous solution of sodium hydrogencarbonate, the chloroform layer is concentrated, and the residual solid content is recrystallized from ethanol to give a compound having the following structure and a molecular weight of 394 and a melting point of 146 to 147 ° C. 22.9 g 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, suspended in 30 ml of methanol, and then suspended in hydrochloric acid (40 m 2).
l) and water (30 ml) were added and reacted at 50 ° C. for 48 hours. Thereafter, the solvent was distilled off and concentrated to obtain 8.12 g of a compound having the following structure and a melting point of 198 ° C, and the infrared absorption spectrum of the obtained compound was measured. The chart is shown in FIG.

Example 3 (1) 10 g (0.03 mol) of the compound obtained in Example 2 was added to 10
It was dissolved in 0 ml of acetic anhydride and reacted under reflux for 6 hours. After allowing to cool, the precipitated white solid was washed with anhydrous ether to give a compound having a molecular weight of 303 (M ⁺ 1) and a melting point of 30 having the following structure.
7.8 g of compound at 5-306 ° C were obtained. The obtained compound was measured for infrared absorption spectrum. The chart is shown in FIG.

Test Example 1 10.01 g of 4,4'-diaminodiphenyl ether (0.05mo
l) was dissolved in 100.52 g of anhydrous N-methylpyrrolidone,
In this solution, 15.12 g (0.05 mol) of the compound obtained in Example 3 was added.
l) and stirred under a nitrogen atmosphere for 4 hours at room temperature,
A viscous polyamic acid solution of N-methylpyrrolidone was obtained. The intrinsic viscosity [η] (30 ° C., in N-methylpyrrolidone) of this polyamic acid was 0.80 dl / g. This polyamic acid solution is cast on a glass plate, and is heated at 120 ° C for 1 hour at 200 ° C.
For 3 hours, to obtain a polyimide having the following repeating structural units and an intrinsic viscosity [η] (30 ° C., in N-methylpyridone) of 0.58 dl / g.

Confirmation of the imide bond was confirmed by infrared absorption spectrum
Disappearance of absorption of NH around 1540 cm ^-1 that polyamic acid has,
And 1750-1780 derived from a new imidocarbonyl group
It was confirmed by the absorption near. Table 1 shows the 5% heat loss temperature and thermal decomposition temperature of the obtained polyimide.

Test Example 2 In Test Example 1, 9.9% of 4,4′-diaminodiphenylmethane was used instead of 4,4′-diaminodiphenylether.
The reaction was conducted in the same manner as in Test Example 1 except that 1 g (0.05 mol) was used and the amount of anhydrous N-methylpyrrolidone was changed to 100.12 g. C., in N-methylpyrrolidone) of 0.42 dl / g. Table 1 shows the 5% heat loss temperature and thermal decomposition temperature of the obtained polyimide.

Test Example 3 In Test Example 1, 20.52 g (0.05 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was used in place of 4,4′-diaminodiphenyl ether.
The reaction was carried out in the same manner as in Test Example 1 except that the amount of anhydrous N-methylpyrrolidone was changed to 142.56 g, and the following repeating structural units were obtained, and the intrinsic viscosity [η] was 30 ° C. in N-methylpyrrolidone). 0.91 dl / g of polyimide was obtained. Table 1 shows the 5% heat loss temperature and thermal decomposition temperature of the obtained polyimide.

[Effect of the Invention] The alicyclic tetracarboxylic acids of the present invention are useful as a raw material for providing a polyimide excellent in solubility, low water absorption, heat resistance and the like.

[Brief description of the drawings]

FIG. 1 shows an infrared absorption spectrum of the compound obtained in Example 1, FIG. 2 shows a nuclear magnetic resonance spectrum of the compound obtained in Example 1, and FIG. FIG. 4 is a diagram showing an infrared absorption spectrum of the compound obtained in Example 3. FIG.

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (I-1) or (II)
And an alicyclic tetracarboxylic acid represented by the formula: 2. An alicyclic tetracarboxylic acid derivative represented by the following general formula (I-2). (In the formula, R ^{1 to} R ⁴ may be the same or different, and represent an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms.)