JPH04226532A - Polyamide resin, its production, 5-acyloxy-isophthalic acid and its production - Google Patents

Abstract

PURPOSE:To obtain a polyamide resin having excellent heat-resistance, solubility in organic solvent, film-forming property, etc., and suitable as an electronic insulation material by using an aromatic diamine and a 5-acyloxyisophthalic acid (derivative) as starting materials. CONSTITUTION:A polyamide resin composed of the recurring unit of formula III and having a reduced viscosity of 0.2-5/g can be produced by the polycondensation reaction of an aromatic diamine of formula I (e.g. m- tolylenediamine) and a 5-acyloxyisophthalic acid (derivative) of formula II (R is 1-30C straight or branched-chain alkyl) (e.g. 5-hydroxyisophthalic acid hexanoate). The 5-acyloxyisophthalic acid of formula V (X is hydroxyl, etc.) or formula VII (R is n-C5H22, etc.) is produced by reacting 5-hydroxyisophthalic acid of formula IV with a carboxylic acid (derivative) of formula V (X is hydroxyl, etc.) or formula VI.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new polyamide resin and a method for producing the same, as well as 5-acyloxyisophthalic acid and a method for producing the same.

0002

[Prior Art] Fully aromatic polyamides synthesized from aromatic diamines and aromatic dicarboxylic acids have excellent heat resistance and electrical and mechanical properties, and are used as electrical insulating materials, high-temperature materials, and certain types of materials. It is used in a wide range of industrial materials, including materials for protective clothing.

0003

However, the above-mentioned aromatic polyamides have poor solubility in ordinary organic solvents, which is extremely inconvenient when forming fibers, films, coatings, etc. Further, since the aromatic polyamide has a high melting point and high crystallinity, injection molding or extrusion molding is virtually impossible. The present invention relates to a polyamide resin that has excellent heat resistance, solubility in organic solvents, film formability, and mechanical properties, and has good moldability in injection molding, extrusion molding, etc., a method for producing the same, and 5-acyloxyisophthalic acid and a method for producing the same. It provides:

0004

[Means for Solving the Problems] The present invention provides general formula (I)

[Formula 9] (wherein, Ar represents a divalent residue of an aromatic diamine excluding the amino group, and R represents a straight or branched alkyl group having 1 to 30 carbon atoms) The present invention relates to a polyamide resin having repeating units.

[0005] The present invention also provides general formula (II)

embedded image H2N-Ar-NH2
(II) (wherein Ar is the same as in general formula (I)), an aromatic diamine represented by general formula (III)

embedded image (wherein R represents the same as in general formula (I),
X is a hydroxy group, a halogen atom, or a carbon atom number of 1 to
The present invention relates to a method for producing a poamide resin having a repeating unit represented by the general formula (I), which is characterized by polycondensation with 5-acyloxyisophthalic acid represented by (4) representing an alkoxy group or a derivative thereof.

The present invention also provides general formula (IV)

[Chem.12
] (wherein, R is n-C5H11, n-C11H23 or n
5-acyloxyisophthalic acid represented by -C17H35).

The present invention also provides general formula (V)

5-hydroxyisophthalic acid represented by the general formula (VI
)

[Chemical formula 14] R'-COX
(VI) (wherein R' is the general formula (IV)
(X represents a hydroxy group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms) or general formula (VII)

[Chemical formula 15] (R-C'O)2O
General formula (IV) characterized by reacting with a carboxylic acid represented by (VII) (wherein R' is the same as above) or a derivative thereof

This invention relates to a method for producing 5-acyloxyisophthalic acid represented by the formula (wherein R' is the same as defined above).

The polyamide resin of the present invention has the general formula (
It has a repeating unit represented by I). The number of carbon atoms in the straight chain or branched alkyl group R in general formula (I) is 1 to 30, preferably 6 to 18, and more preferably 10 to 18. When it exceeds 30, heat resistance decreases. As the alkyl group,
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert
-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethyl-hexyl group,
Examples include nonyl group, decyl group, undecyl group, dodecyl group, heptadecyl group, octadecyl group, eicosyl group, docosyl group, and triacontyl group.

Ar in the general formula (I) is a divalent residue of an aromatic diamine excluding the amino group. Examples of diamines include those listed above.

[0010] The polyamide resin having a repeating unit represented by the general formula (I) has a reduced viscosity of 0.2 to 5.0 dl at 30°C of a solution obtained by dissolving 0.2 g of the resin in dimethylformamide to make 100 ml. /g is preferred. If this viscosity is too low, the mechanical strength of the resin tends to decrease, and if it is too high, the solubility of the resin in organic solvents tends to be poor.

[0012] In this specification, reduced viscosity (ηS
P/c) is determined by the following equation. ηSP/c=(η/η0-1)/c (where η and η0 represent the viscosity of the solution and the viscosity of the solvent, respectively, and the viscosity of the solution and solvent when measured using an Ubbelohde dilution capillary viscometer. When the flow times are t and t0, respectively, η/η0=t/t0, and c is the resin concentration of the solution (g/dl))

The polyamide resin of the present invention has N-methyl-
It dissolves well in polar solvents such as 2-pyrrolidone, dimethylacetamide, and dimethylformamide.

In the polyamide resin of the present invention, for example, the aromatic diamine of the general formula (II) is combined with 5 of the general formula (III).
- Can be produced by polymerizing with acyloxyisophthalic acid or its derivatives.

Examples of the aromatic diamine of general formula (II) include m-tolulenediamine, m-phenylenediamine, p-phenylenediamine, 5-chloro-m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether-4
, 4'-benzidine, 4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2, 2'-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylsulfone, 4,4'-
Diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 3,3'-diaminobiphenyl,
1,3-bis(4-aminophenoxy)benzene, 1,
3-bis(3-aminophenoxy)benzene, 1,4-
Bis(4-aminophenoxy)benzene, 4,4'-[
1,3-phenylenebis(1-methylethylidene)],
4,4'-[1,4-phenylenebis(1-methylethylidene)], 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-methyl-
4-(4-aminophenoxy)phenyl]propane, 2
, 2-bis[3-chloro-4-(4-aminophenoxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, bis[4-(4-aminophenoxy)phenyl] ]Methane, 3,3'-dimethoxy-4,4'-diaminbiphenyl, bis[4-(4
-aminophenoxy)phenyl]sulfone, bis[4-
(3-aminophenoxy)phenyl]sulfone, 2,2
-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-
(aminophenyl)fluorene, etc.

In addition to the aromatic diamines mentioned above, aliphatic diamines such as hexamethylene diamine and ethylene diamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminophenyl) A siloxane diamine such as tetramethyldisiloxane may be used in combination as a diamine component, but in this case, it is preferably used in an amount of 30 mol % or less based on the total diamine. If there are too many of these, heat resistance tends to decrease.

5-acyloxyisophthalic acid or its derivative represented by the above general formula (III)
Examples of the acyloxyisophthalic acid include 5-hydroxyisophthalic acid hexanoate, 5-hydroxyisophthalic acid dodecanoate, and 5-hydroxyisophthalic acid octadecanoate. Examples of derivatives of these 5-acyloxyisophthalic acids include dihalides such as dichloride and dibromide, and diesters such as dimethyl ester and diethyl ester. The number of carbon atoms in the alkoxy group in the diester must be 1 to 4. When the number of carbon atoms is more than 4, reactivity decreases.

5-acyloxyisophthalic acid represented by the above general formula (III) can be easily obtained, for example, by reacting 5-hydroxyisophthalic acid and an alkyl acid chloride in the presence of pyridine or the like. The 5-acyloxyisophthalic acid thus obtained can be converted into an acid derivative such as a halide or diester according to a known method.

Some of the 5-acyloxyisophthalic acids represented by the general formula (III) and their derivatives are 5-acyloxyisophthalic acids represented by the general formula (IV).

Although the method for producing 5-acyloxyisophthalic acid represented by the general formula (IV) is not particularly limited, the following preparation method is preferred. That is, formula (V)

[
17] In the presence of a base such as pyridine, 5-hydroxyisophthalic acid represented by general formula (VI)

[Chemical formula 18] R'-COX
(VI) (wherein R' is the general formula (IV)
(X represents a halogen atom), or a carboxylic acid halide represented by the general formula (VII
)

[Chemical formula 19] (R'-CO)2O
(VII) (wherein R' is the same as in general formula (IV)), etc., by reacting with a 5-acyloxyisophthalate represented by general formula (IV). Acid can be obtained.

[0021] Furthermore, formula (V)

In the presence of an acid catalyst such as sulfuric acid or a dehydrating agent such as DCC, 5-hydroxyisophthalic acid represented by the general formula (VII
)

[Chemical formula 21] R'-COX
(VII) (wherein R' is the general formula (IV
), where X represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms), by reacting with a carboxylic acid or an ester thereof, the general formula (
5-acyloxyisophthalic acid represented by IV) can be obtained.

As the dicarboxylic acid component, the above general formula (I
II) together with 5-acyloxyisophthalic acid or its derivatives, terephthalic acid, isophthalic acid, 4
, 4'-diphenyl ether dicarboxylic acid, 4,4'-
Aromatic dicarboxylic acids such as diphenylcarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid may be used. These are preferably used in an amount of 50 mol % or less based on the total carboxylic acid components. If these amounts are too large, the solubility in organic solvents tends to decrease. In addition, as a dicarboxylic acid component, aliphatic dicarboxylic acids such as adipic acid and sebacic acid are added at 5% of the total carboxylic acid component.
It may be used in an amount of 0 mol% or less. Too much aliphatic dicarboxylic acid tends to reduce heat resistance.

[0023] The aromatic diamine represented by the above general formula (II) and the 5-acyloxyisophthalic acid represented by the above general formula (III) or a derivative thereof are polycondensed,
This polycondensation method is not particularly limited, and for example, a low temperature polycondensation method, a direct polycondensation method, an active ester method, etc. can be employed.

When employing the low temperature polycondensation method, preferably the dihalide of 5-acyloxyisophthalic acid represented by the general formula (III) is added to 1 equivalent of the aromatic diamine represented by the general formula (II). Use 0.9 to 1.2 equivalents,
In the presence of an acid acceptor such as triethylamine or a 1,2-epoxide such as propylene oxide, styrene oxide, or cyclohexene oxide, in a non-reactive polar solvent such as N-methyl-2-pyrrolidone or dimethylacetamide at minus 10-odd degrees Celsius. The reaction can be carried out within a range from 1 to reflux temperature of the organic solvent used.

[0025] Furthermore, when employing the direct polycondensation method,
Aromatic diamine represented by general formula (II) and general formula (I
5-acyloxyisophthalic acid represented by II) is used in an equivalent or approximately equivalent amount, triphenyl phosphite,
The reaction can be carried out in a phosphorus catalyst such as phosphorus trichloride or condensed phosphoric acid ester, and pyridine or a non-reactive polar solvent similar to those mentioned above at a temperature ranging from room temperature to the reflux temperature of the organic solvent used. In this case, the phosphorus catalyst is used in an amount equivalent to or approximately equivalent to the diamine, and the pyridine or organic solvent is preferably used in an amount of 10 mol % or more based on the dicarboxylic acid or aromatic diamine.

When the active ester method is employed, benzotriazyl ester is produced by reacting the dihalide of 5-acyloxyisophthalic acid represented by the general formula (III) with 1-hydroxybenzotriazole,
This ester and the aromatic diamine represented by the above general formula (II) can be used in equivalent or nearly equivalent amounts and reacted at room temperature or higher in a non-reactive polar organic solvent similar to that described above. .

[0027] The reaction solution obtained by either method is poured into a large excess of a lower alcohol such as methanol, a solvent that is compatible with the above organic solvent such as water, and is a poor solvent with respect to the resin, to precipitate. can get things. The polyamide resin of the present invention can be recovered by filtering this and drying it.

The polyamide resin of the present invention has aliphatic side chains, and due to its bulk, it has much better solubility in organic solvents than conventional aromatic polyamides, and is resistant to other solvents. Like soluble resins, it can be formed into films, coatings, etc. by the casting method, and these films and coatings exhibit excellent heat resistance and excellent mechanical properties, making them useful as electronic insulating materials and heat-resistant adhesives. It is suitable for use as an agent, liquid crystal alignment film material, and high temperature material.

[0029]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples.

Example 1 20 g of 5-hydroxyisophthalic acid (0.11 m
mol) and dissolved in 100 ml of pyridine. While stirring, be careful not to generate heat, add 22.2 g of hexanoyl chloride.
(0.17 mol) was added dropwise. After stirring for 1 hour, 20 ml of methanol was added to stop the reaction. The reaction solution was poured into 600 ml of cooled 2N hydrochloric acid, and extracted with diethyl ether. The organic layer was washed with 2N hydrochloric acid and saturated brine, and the solvent was distilled off under reduced pressure to obtain a white solid. Purified by recrystallization (methanol) to give white needle-like crystals of 5-
Hydroxyisophthalic acid hexanoate was obtained.

Yield: 20.1g Yield: 65.6
%mp (°C) 225-229 1H-NMR (60MHz, DMSO-d6) 0.7-
2.0 (br, 9H), 2.66 (t, 2H, J=6.
6Hz), 7.98 (s, 2H), 8.52 (s, 1H
) 1R (KBr, cm-1) 3082, 2962, 29
35, 2862, 2675, 2565, 1757, 16
95, 1466, 1410, 1319, 1277, 12
21,920,754

Example 2 Hexanoyl chloride 22.2g (0
．． 17 mol) instead of dodecanoyl chloride 28.8 g
The same operation as in Example 1 was performed except that (0.13 mol) was used to obtain 5-hydroxyisophthalic acid dodecanoate in the form of white needle-like crystals.

Yield: 31.2g Yield: 78.0
%mp (°C) 165-167 1H-NMR (60MHz, DMSO-d6) 0.7-
2.0 (br, 21H), 2.5-2.8 (br, 2H
), 7.92 (s, 2H), 8.40 (s, 1H) 1R
(KBr, cm-1) 2920, 2850, 2658,
2548, 1767, 1714, 1468, 1406,
1298, 1267, 1238, 1141, 743

0
Example 3 5-hydroxyisophthalic acid 15.0g (0.082m
ol), hexanoyl chloride 22.2g (0.17mol
) instead of octadecanoyl chloride 37.4g (0.1
The same operation as in Example 1 was performed except that 2 mol) was used to obtain 5-hydroxyisophthalic acid octadecanoate in the form of white needle-like crystals.

Yield: 32.5g Yield: 88.0
%mp (°C) 144-148 1H-NMR (60MHz, DMSO-d6) 0.6-
1.9 (br, 33H), 2.5-2.8 (br, 2H
), 7.97 (s, 2H), 8.46 (s, 1H) 1R
(KBr, cm-1) 2918, 2850, 2673,
2563, 1767, 1716, 1468, 1304,
1146

Example 4 2.85 g (14.3 mmol) of 4,4'-diaminodiphenyl ether, 5
-Hydroxyisophthalic acid hexanoate 4.00g (
14.3 mmol), triphenyl phosphite 8.8
g (28.3 mmol), pyridine 4.5 g (57.0
mmol) and lithium chloride 0.5 g (11.8 mmol)
1), and 40 ml of N-methyl-2-pyrrolidone was added. After stirring at room temperature for 10 minutes to dissolve, the temperature was raised and 11
The reaction was carried out at 0°C for 2.5 hours. It was cooled to room temperature and poured into 400 ml of methanol. The resulting precipitate was filtered off, washed with methanol, and dried at 100°C overnight. Table 1 shows the reduced viscosity, yield, organic solvent solubility, and glass transition temperature, which is an index of the heat resistance after film production, of the polyamide resin thus obtained.

Further, the infrared absorption spectrum (reflection method) of the above polyamide resin is shown in FIG. As is clear from FIG. 1, absorption of the carbonyl of the amide bond was observed at 1653 cm-1 and absorption based on N-H stretching vibration was observed at 3309 cm-1, confirming that an amide bond was formed.

Example 5 2.85 g (1
4.17 g (14.3 mmol) of 1,4-bis(4-aminophenoxy)benzene instead of
The same operation as in Example 4 was performed except that . The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG.

Example 6 2.85 g (1
4.3 mmol) instead of 4,4'-bis(4-aminophenoxy)biphenyl 5.26 g (14.3 mmol)
The same operation as in Example 4 was performed except that 1) was used. The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG.

Example 7 4.00 g of 5-hydroxyisophthalic acid hexanoate
(14.3 mmol) instead of 5-hydroxyisophthalic acid dodecanoate 5.21 g (14.3 mmol)
The same operation as in Example 4 was performed except that . The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG.

Example 8 2.85 g (1
4.17 g (14.3 mmol) of 1,4-bis(4-aminophenoxy)benzene instead of
The same operation as in Example 7 was performed except that . The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG.

Example 9 4,4'-diaminodiphenyl ether 2.85g (1
4.3 mmol) instead of 4,4'-bis(4-aminophenoxy)biphenyl 5.26 g (14.3 mmol)
The same operation as in Example 4 was performed except that 1) was used. The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG.

Example 10 4.00 g of 5-hydroxyisophthalic acid hexanoate
(14.3 mmol) instead of 6.41 g (14.3 mmol) of 5-hydroxyisophthalic acid octadecanoate.
The same operation as in Example 4 was performed except that 1) was used. The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG.

Example 11 2.85 g (1
4.17 g (14.3 mmol) of 1,4-bis(4-aminophenoxy)benzene instead of
The same operation as in Example 10 was performed except that . The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG.

Example 12 2.85 g (1
4.3 mmol) instead of 4,4'-bis(4-aminophenoxy)biphenyl 5.26 g (14.3 mmol)
The same operation as in Example 4 was performed except that 1) was used. The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG.

[0046]

[Table 1]

[0047]

Effects of the Invention The polyamide resin using 5-acyloxyisophthalic acid, etc. of the present invention has excellent heat resistance, organic solvent solubility, film formability, and mechanical properties, and has excellent moldability in injection molding, extrusion molding, etc. Also good in electrical insulation materials, heat-resistant adhesives,
Suitable for liquid crystal alignment film materials, high temperature materials, etc.

[Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of the polyamide resin obtained in Example 4.

FIG. 2 shows an infrared absorption spectrum of the polyamide resin obtained in Example 5.

FIG. 3 shows an infrared absorption spectrum of the polyamide resin obtained in Example 6.

FIG. 4 shows an infrared absorption spectrum of the polyamide resin obtained in Example 7.

FIG. 5 shows an infrared absorption spectrum of the polyamide resin obtained in Example 8.

FIG. 6 shows an infrared absorption spectrum of the polyamide resin obtained in Example 9.

FIG. 7 shows an infrared absorption spectrum of the polyamide resin obtained in Example 10.

FIG. 8 shows an infrared absorption spectrum of the polyamide resin obtained in Example 11.

FIG. 9 shows an infrared absorption spectrum of the polyamide resin obtained in Example 12.

Claims (5)

[Claims] Claim 1: General formula (I) [Formula 1] (wherein, Ar represents a divalent residue of an aromatic diamine excluding the amino group, and R represents a linear or branched residue having 1 to 30 carbon atoms. A polyamide resin having a repeating unit represented by (representing a chain alkyl group). 2. The polyamide resin according to claim 1, wherein a solution obtained by dissolving 0.2 g of the polyamide resin in dimethylformamide to make 100 ml has a reduced viscosity of 0.2 to 5.0 dl/g at 30°C. [Claim 3] General formula (II) [Chemical formula 2] H2-Ar-NH2
(II) (wherein, Ar is the same as in general formula (I)), the aromatic diamine represented by general formula (III) [Chemical formula 3] (wherein, R is the same as in general formula (I)) shows the same thing as
X is a hydroxy group, a halogen atom, or a carbon atom number of 1 to
2. The method for producing a polyamide resin according to claim 1, wherein the polyamide resin is polycondensed with 5-acyloxyisophthalic acid represented by (4) representing an alkoxy group or a derivative thereof. 4. 5-acyloxyisophthalic acid represented by the general formula (IV): (wherein R' represents n-C5H11, n-C11H23 or n-C17H35). 5. General formula (VI) is added to 5-hydroxyisophthalic acid represented by general formula (V)
) [Chemical 6] R'-COX
(VI) (wherein R' is the same as in general formula (IV), X represents a hydroxy group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms) or the general formula (
VII) [Chemical formula 7] (R'-CO)2O (
VII) (wherein R' is the same as above) or a derivative thereof is reacted with the general formula (IV) [Chemical formula 8] (wherein R' is the same as above) A method for producing 5-acyloxyisophthalic acid (same as above).