JPH11255723A - Aromatic dicarboxylic acid-based derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having a triphenylamine skeleton, useful as a raw material for a heat-resistant resin having excellent heat resistance, mechanical characteristics, moldability and, soluble in an organic solvent. SOLUTION: This compound is an aromatic dicarboxylic acid compound of formula I or an aromatic dicarboxylic acid compound of formula II (X is a halogen). The compound of formula I is obtained by reacting aniline or an N-silylated aniline with p-fluorobenzonitrile in the presence of cesium fluoride to give dicyanotriphenylamine of formula III and reacting the compound in the presence of an acid or a base so as to hydrolyze the cyano group into carboxyl group. The compound of formula II can be obtained by synthesizing the compound of formula I and reacting the compound with a halide so as to replace the hydroxyl of the carboxyl group with a halogen. A polyamide resin of formula IV (Ar is a bifunctional aromatic group; (n) is an integer of 10-200) can be synthesized by using the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aromatic dicarboxylic acid compound and a method for producing the same. More specifically, the present invention relates to an aromatic dicarboxylic acid compound having a triphenylamine skeleton, an aromatic polyamide resin derived therefrom having excellent heat resistance, mechanical properties and moldability, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally aromatic polyimides, polyamides, polyazomethines, and the like have excellent heat resistance and excellent mechanical properties, and have been widely used as industrial materials. Insoluble in the solvent,
There were many problems with its moldability. Among such resins, polyimides and polyamides produced from diaminotriphenylamine as a raw material are known to be soluble in organic solvents (for example, Yoshiyuki Oishi et al., J. Polym, Sci., P
art A, Polym. Chem., 28, 1763 (1990): J. Polym, Sc
i., Part A, Polym. Chem., 301, 1027 (1992), etc.). Therefore, by using a dicarboxylic acid having a triphenylamine skeleton and its derivative instead of the diaminotriphenylamine, it is expected to obtain a heat-resistant resin that is soluble in an organic solvent, that is, excellent in moldability. However, such dicarboxylic acid compounds and heat-resistant resins derived therefrom are not currently known.

[0003]

PROBLEM TO BE SOLVED BY THE INVENTION The present invention relates to a novel aromatic dicarboxylic acid which is excellent in heat resistance and mechanical properties and which is a raw material of a heat-resistant resin which is excellent in moldability and can be dissolved in an organic solvent, especially An object of the present invention is to provide a novel dicarboxylic acid compound having a triphenylamine skeleton and a heat-resistant polyamide resin which is a derivative thereof, and a method for producing the same.

[0004]

According to the present invention, as a result of diligent studies on a method for obtaining such a novel aromatic dicarboxylic acid derivative, dicyanotriphenylamine is used as a raw material, and this is hydrolyzed. Have been achieved.

That is, the present invention relates to (1) an aromatic dicarboxylic acid compound represented by the general formula (I).

The present invention also relates to (2) an aromatic dicarboxylic acid compound represented by the general formula (II). (X in the formula represents a halogen atom)

Further, the present invention relates to (3) an aromatic dicarboxylic acid represented by the above general formula (I) or the above general formula (II) using a dicyanotriphenylamine represented by the general formula (III) as a raw material. The present invention relates to a method for producing an aromatic dicarboxylic acid compound, which comprises deriving a compound.

Further, the present invention relates to (4) a polyamide resin represented by the general formula (IV) derived from an aromatic dicarboxylic acid represented by the general formula (I). (In the formula, Ar represents a divalent aromatic group, and n represents an integer of 10 to 200.)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The present invention is an aromatic dicarboxylic acid compound represented by the following general formula (I) or (II).

[0010]

[0011] (X in the formula represents a halogen atom)

The aromatic dicarboxylic acid compound of the present invention can be produced using dicyanotriphenylamine represented by the following general formula (III) as a raw material. This general formula (I
The dicyanotriphenylamine represented by II) is
The compound can be easily produced by reacting aniline or N-silylated aniline with p-fluorobenzonitrile in the presence of cesium fluoride.

[0013]

The production of the aromatic dicarboxylic acid compound represented by the general formula (I) or the general formula (II) is carried out according to the general formula (III)
Using dicyanotriphenylamine represented by
It is performed in a one-step or two-step process. Hereinafter, a description will be given using a representative example.

The dicarboxylic acid compound represented by the general formula (I) is obtained by reacting a dicyanotriphenylamine represented by the general formula (III) in the presence of an acid or a base to hydrolyze a cyano group, Obtained by generating a carboxyl group. As the acid used for this reaction, an aqueous solution of hydrogen chloride, hydrogen bromide, sulfuric acid, acetic acid, formic acid or the like is preferable. Further, as the base used in this reaction, sodium hydroxide, potassium hydroxide, barium hydroxide and the like are preferable, and as the solvent, water or an alcoholic solvent such as methanol or ethanol, and ethylene glycol,
Ether solvents such as diethylene glycol and ethylene glycol monoethyl ether are used. The reaction temperature is suitably from 0 to 250 ° C, but is economically from 0 to 100 ° C.
A temperature range of ° C. is preferred. The reaction time varies depending on the type and amount of the reagent used, the type of the solvent, the reaction temperature, and the like, but it is generally preferable to carry out the reaction for tens of minutes to several days.

The dicarboxylic acid halide represented by the general formula (II) is prepared by producing a dicarboxylic acid compound represented by the general formula (I), and then reacting the compound with a halide.
It can be obtained by halogen substitution of the hydroxyl group of the carboxyl group.

The dicarboxylic acid compound of the general formula (I) thus obtained can be used as a raw material for various polymer compounds. Further, the compound of the general formula (I) can be easily derived by reacting the compound of the general formula (I) with a halide such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride, and phosphorus tribromide. .

The polyamide resin represented by the general formula (IV) of the present invention can be derived from an aromatic dicarboxylic acid represented by the general formula (I). The polyamide resin represented by the general formula (IV) is obtained by reacting the aromatic dicarboxylic acid and the aromatic diamine compound represented by the general formula (I) in the presence of an activator at 20 to 200 ° C. for several minutes to several days. By reacting, it can be easily produced.

In the present reaction, a phosphorus compound is preferably used as an activator. For example, a combination of triphenyl phosphite, pyridine, lithium chloride, a combination of triphenylphosphine and hexachloroethane,
A combination of phosphorus oxychloride and pyridine, or a phosphoric anhydride or a phosphoric ester is used alone. A case in which a triphenyl phosphite-pyridine system which is a typical activator is used will be described. When another activator is used, a slight change in conditions may be required. The amount of triphenyl phosphite used in this reaction is
For diamine compounds or dicarboxylic acid compounds,
Although it is 2 to 10 moles, the use of 2 to 3 moles is economically preferable. The amount of pyridine to be used is usually twice as much as the diamine compound, but it can be used as a substantial solvent. In addition, as a solvent used in this reaction, N, N-dimethylformamide, N,
N-dimethylacetamide, N-methyl-2-pyrrolidone,
Aprotic polar solvents such as 1,3-dimethyl-2-imidazolidone and pyridine are preferred.

In this method, the molecular weight of the polyamide resin represented by the general formula (IV) is limited by the charged amounts of the diamine compound and the dicarboxylic acid compound. The polyamide resin represented by IV) can be produced.

The reason for limiting the degree of polymerization n to an integer of 10 to 200 in the polyamide resin represented by the general formula (IV) is that when n is less than 10, the mechanical properties and This is because heat resistance is not sufficient, and if n exceeds 200, solubility in an organic solvent is deteriorated.

The properties of the polyamide resin represented by the general formula (IV) produced as described above vary depending on the kind of the diamine component used. The polyamide resin represented by the above general formula (IV) is all or part of an organic solvent such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and tetrahydrofuran. It is soluble in Using these solvents, a pale yellow transparent cast film can be produced. The tensile strength, elongation at break, and tensile modulus of this film are 90-145 MPa, 5-9%, 2.7-
4.2 GPL with good mechanical properties. Also, 250-
It has a high glass transition temperature of around 350 ° C., has no noticeable weight change even when heated to around 400 ° C., and has high heat resistance.

As an example, a polyamide obtained by a polymerization reaction of 4,4′-diaminotriphenylamine and 4,4′-dicarboxytriphenylamine of the present invention is:
Dissolves in a polar solvent such as dimethylsulfoxide, N, N'-dimethylformamide, NMP to give a yellow clear cast film. The tensile strength, elongation at break, and initial tensile modulus of this film were 131 MPa and 9, respectively.
3%, 3.4 GPa and excellent mechanical properties. Further, the glass transition temperature is as high as 304 ° C., and the 10% weight loss temperatures in air and nitrogen are 510 ° C. and 530 ° C., respectively, indicating high heat resistance.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 1.47 g (5 mmol) of 4,4'-dicyanotriphenylamine
Then, 13 g of a 50 wt% aqueous solution of potassium hydroxide and 35 ml of methanol were added thereto, and the mixture was reacted under reflux for 6 hours. The solution was poured into 500 ml of distilled water, 5% diluted hydrochloric acid was added dropwise to the aqueous solution, and the aqueous solution was adjusted to pΗ6 to precipitate a white powder. This powder was separated by filtration, washed well with distilled water, and dried at 80 ° C. under reduced pressure. The crude product was washed with diethyl ether and recrystallized from methanol to obtain colorless crystals. The product was 4,4'-dicarboxytriphenylamine. The yield after purification was 1.48 g (8
9%) and the melting point was 308-310 ° C. Also,
Physical properties of this compound were as follows. IR (KBr): 1686 cm ^-1 (C = O) ¹ H-NMR (CDCl ₃ ): 7.05 ppm (d, 4H, J = 8.75 Hz, phenylene), 7.14 ppm (d, 2H, phenyl), 7.24 ppm ( (t, 1H, phenyl), 7.42 ppm (t, 2H, phenyl), 7.85 ppm (d, 4H, J = 8.78H
z, phenylene) ¹³ C-NMR (CDCl ₃ ): 122.2 ppm, 124.7 ppm, 125.6 pp
m, 126.6ppm, 130.2ppm, 131.1ppm, 145.7ppm, 150.4pp
m, 166.9 ppm (C = O) Elemental analysis value (C ₂₀ H ₁₅ NO ₄ ) Calculated value (%) C: 72.06 Η: 4.54 N: 4.20 Actual value (%) C: 71.77 Η: 4.56 N: 4.16

Example 2 11.2 g of 4,4'-dicarboxytriphenylamine (34 m
mol), 50 ml of thionyl chloride and several drops of N, N-dimethylformamide were added, and the mixture was reacted at 65 ° C. for 24 hours. From the resulting clear solution, unreacted thionyl chloride was removed under reduced pressure to obtain a red solid. This is vacuum distilled twice (200 ° C
/0.1 Torr). The product was 4,4'-bis (chloroformyl) triphenylamine hydrochloride. The yield after purification was 5.8 g (42%), mp 18
4-185 ° C. The physical properties of this compound were as follows. ^{IR (KBr): 1765cm -1 (} C = O), 1726cm -1 (C = O) 1 H-NMR (CDC1 3): 7.05-7.20ppm (m, 7H, phenylene and phenyl), 7.38ppm (t, 2H, phenyl), 8.02ppm (d, 4H, J
= 8.85 Hz, phenylene) Elemental analysis (C ₂₀ H ₁₄ Cl ₃ NO ₂ ) Calculated (%) C: 59.07 H: 3.47 N: 3.44 Actual (%) C: 59.26 H : 3.26 N: 3.62

Example 3 0.688 g (2.5 mmo) of 4,4'-diaminotriphenylamine
l) and 0.833 g of 4,4-dicarboxytriphenylamine
(2.5 mmol) was added and dissolved in 5 ml of N-methyl-2-pyrrolidone. Next, 1.25 ml of pyridine, 1.35 ml of triphenyl phosphite and 0.25 g of lithium chloride are added in this order. The mixture was stirred at 110 ° C. for 12 hours while flowing dry nitrogen gas. After the reaction, the viscous solution was gradually poured into 500 ml of methanol to precipitate a polymer. The precipitated polymer was separated by filtration and washed with hot methanol. The polymer was filtered off again and dried at 100 ° C. under reduced pressure. The yield is 1.4
2 g (99%). As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit. (Ar in formula is a divalent aromatic radical, n is an integer of 10 to 200.) IR ^{Film): 1654cm -1 (C = O} ) Elemental analysis _{(C 38 Η 28 N 4 O} 2) calculated Value (%) C: 79.70 H: 4.93 N: 9.78 Actual value (%) C: 79.40 H: 4.80 N: 9.53

The properties of this polymer are shown below. 1. 1. Intrinsic viscosity (ηinh): 2.36 dL / g (concentration: 0.5 g / dL, in N-methyl-2-hydroxylithone at 30 ° C.) Glass transition temperature (differential scanning calorimetry): 304 ° C. 3.10% weight loss temperature (thermobalance measurement): 510 ° C. (in air), 530 ° C. (in nitrogen) The polyamide resin is dimethyl sulfoxide, N, N-
Dimethylformamide, N, N-dimethylacetamide,
A pale yellow, transparent cast film that was soluble in an organic solvent such as N-methyl-2-pyrrolidone (NMP) was prepared from the NMP solution. The tensile strength, elongation at break, and tensile modulus of the film were 131 MPa, 9.3%, and 3.4 GPa, respectively.

REFERENCE EXAMPLE 1 6.07 g of cesium fluoride was placed in a flask purged with nitrogen gas.
(40 mmol) and sufficiently dried with a drier. next,
1.86 g (20 mmol) of aniline, N-methyl-2-pyrrolidone
(NMP) 50 ml, p-fluorobenzonitrile 4.84 g
(40 mmol) was added and reacted at 160 ° C. for 24 hours. NMP as a solvent was distilled off under reduced pressure, and the obtained residue was poured into distilled water, and the precipitate was separated by filtration. The crude product was dried at 80 ° C. under reduced pressure, distilled under reduced pressure (220 ° C./0.1 Torr), and recrystallized with ethanol to obtain colorless powdery crystals. The product was 4,4'-dicyanotriphenylamine. The yield after purification is 2.
13g (36%), mp 191-192 ° C. The physical properties of this compound were as follows. IR (KBr): 2221 cm ^-1 (CN) ¹ H-NMR (CDCl ₃ ): 7.11 ppm (d, 4H, J = 8.82 Hz, phenylene), 7.13 ppm (d, 2H, phenyl), 7.26 ppm (t, 1H, phenyl), 7.40 ppm (t, 2H, phenyl), 7.52 ppm (d, 4Η, J = 8.64H
z, phenylene) ¹³ C-NMR (CDCl ₃ ): 105.8 ppm, 118.8 ppm (CN), 122.8
ppm, 126.5 ppm, 126.9 ppm, 130.3 ppm, 133.5 ppm, 145.0
ppm, 150.1 ppm Elemental analysis value (C ₂₀ H ₁₃ N ₃ ) Calculated value (%) C: 81.33 Η: 4.44 N: 14.23 Actual value (%) C: 81.37 H: 4.46 N: 14.35

Reference Example 2 30.4 g of cesium fluoride was placed in a flask purged with nitrogen gas.
(0.2 mol) and sufficiently dried with a dryer. next,
16.5 g (0.1 mol) of N-trimethylsilylaniline, 200 ml of N-methyl-2-pyrrolidone (NMP) and 24.2 g (0.2 mol) of p-fluorobenzonitrile were added.
Allowed to react for hours. The solvent NMP was distilled off under reduced pressure, and the obtained residue was poured into distilled water, and the precipitate was separated by filtration. The crude product is dried under reduced pressure at 80 ° C. and distilled under reduced pressure (220 ° C./0.1 Torr).
Thereafter, recrystallization was performed with ethanol to obtain colorless crystals. The product was 4,4'-dicyanotriphenylamine. The yield after purification was 16.7 g (57%), mp 191.
１９192 ° C. The physical properties of this compound were as follows. IR (KBr): 2221 cm ^-1 (CN) ¹ H-NMR (CDCl ₃ ): 7.11 ppm (d, 4H, J = 8.82 Hz, phenylene), 7.13 ppm (d, 2H, phenyl), 7.26 ppm (t, 1H, phenyl), 7.40 ppm (t, 2H, phenyl), 7.52 ppm (d, 4Η, J = 8.64H
z, phenylene) ¹³ C-NMR (CDCl ₃ ): 105.8 ppm, 118.8 ppm: (CN), 122.
8ppm, 126.5ppm, 126.9ppm, 130.3ppm, 133.5ppm, 145.
0 ppm, 150.1 ppm Elemental analysis value (C ₂₀ H ₁₃ N ₃ ) Calculated value (%) C: 81.33 Η: 4.44 N: 14.23 Actual value (%) C: 81.38 H: 4.45 N: 14.38

[0030]

The present invention provides an aromatic dicarboxylic acid compound represented by the general formulas (I) and (II), a polyamide resin derived therefrom, and an advantageous method for producing the same. Whereas heat-resistant resins such as wholly aromatic polyamides and polyesters produced from many conventional aromatic dicarboxylic acid compounds as raw materials have low solubility in organic solvents, molding was difficult. The heat-resistant resin produced using the aromatic dicarboxylic acid compound as a raw material is soluble in an organic solvent, is easy to mold, and has excellent heat resistance, electrical properties,
Since it has mechanical properties, it has great value as an industrial material.

Claims (4)

[Claims] 1. An aromatic dicarboxylic acid compound represented by the general formula (I). 2. An aromatic dicarboxylic acid compound represented by the general formula (II). (X in the formula represents a halogen atom) 3. An aromatic dicarboxylic acid compound represented by the general formula (I) or the general formula (II) is derived from a dicyanotriphenylamine represented by the general formula (III) as a raw material. For producing an aromatic dicarboxylic acid compound. 4. A polyamide resin represented by the general formula (IV) derived from an aromatic dicarboxylic acid represented by the general formula (I). (In the formula, Ar represents a divalent aromatic group, and n represents an integer of 10 to 200.)