JPH01292034A - Production of poly(amidobenzoxazole) resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin having high molecular weight and excellent heat-resistance, processability and flexibility, by reacting a specific aromatic diamine with an aromatic dicarboxylic acid dihalide in an organic solvent and cyclizing the resultant aromatic polyamide resin. CONSTITUTION:The objective resin of formula IV can be produced by reacting an aromatic diamine of formula I (R1 is univalent organic silicon; R2 is H or univalent organic silicon) [e.g., 2,4-bis(trimethylsilylamino)- trimethylsiloxybenzene] with an aromatic dicarboxylic acid dihalide of formula II (R is bivalent aromatic group; Y is halogen) (e.g., isophthaloyl dichloride) in an organic solvent (e.g., DMF) preferably at -20-+50 deg.C to obtain an aromatic polyamide resin of formula III (n is 5-200) and cyclizing the obtained resin by heating preferably at 150-300 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel method for producing aromatic poly(amidobenzoxazole) resins.

[Conventional technology]

Conventionally, some aromatic polybenzoxazoles have been successfully obtained with a high degree of polymerization, and have been improved in mechanical properties such as tensile strength, bending strength, impact strength, heat distortion temperature,
It is known to have excellent properties such as thermal properties such as thermal decomposition and solvent resistance to various solvents. However, since these benzoxazoles have poor moldability, a method has been adopted in which they are molded in an intermediate stage, that is, in a soluble polyamide state, and then an oxazole ring is formed.

This oxazole ring formation method of polybenzoxazole is described, for example, by Macromol, Chem, 83.1
67 (1965), Japanese Patent Publication No. 42-19271, etc.

In general, the influence of molecular weight is important in determining the properties of polymer resins. If the degree of polymerization is low and the molecular weight is small, the viscosity and flexibility will be insufficient, resulting in a thin film. Tabata is the processing of J-fiber and molded products. Furthermore, even if processed, sufficient properties such as strength and heat resistance cannot be obtained. Conventionally known polybenzoxazole with a high degree of polymerization exhibits excellent thermal stability with a thermal decomposition initiation temperature of 400 C or higher, but on the other hand, it is completely inferior in processability. Conventionally, specific compounds have often been used as diamine components and dicarboxylic acid cybaride components in order to improve processability; examples thereof include, for example, JP-A-62-283127.

However, by these methods, polybenzoxazole having sufficient processability and flexibility cannot be obtained.

Further, as a method for producing poly(amidebenzoxazole) resin, which is the object of the present invention, for example, US Pat.
No. 322723, etc., but the raw materials are 2, 4-
It has been difficult to obtain high molecular weight polymers because diaminophenol is difficult to purify and has poor reactivity.

[Problem to be solved]

In order to solve the molding difficulties of polybenzoxazole, such as its processability and flexibility, the present inventors have developed an aromatic poly(polybenzoxazole), which has a sufficiently high molecular weight, high heat resistance, and excellent processability and flexibility.
As a result of our earnest efforts to obtain a resin (amidobenzoxazole), we have achieved the present invention. [Means for solving the problems] The present invention is based on the general formula R3 is hydrogen or 1
represents a valent organosilicon group. ) and the general formula (wherein, R is a divalent aromatic group and Y is a halogen).
One or more aromatic dicarboxylic acid civalides represented by are reacted in an organic solvent to produce an aromatic polyamide resin represented by the general formula, and then,
The polyamide resin is subjected to a cyclization reaction to convert it into an aromatic poly(amidebenzoxazole) represented by the general formula (wherein R is a divalent aromatic group and n is an integer from 5 to 200). This is a method for producing poly(amidebenzoxazole) resin characterized by the following.

The aromatic polyamide resin represented by the above general formula 1 is produced by the reaction between the aromatic diamine represented by the above general formula (I) and one or more aromatic dicarboxylic acid civalides represented by the above general formula (n). Manufactured. Examples of the organosilicon groups R1 and Rt of the aromatic diamine of general formula (I) include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, etc. Specific examples include 2,4-bis (trimethylsilylamino)-
Trimethylsiloxybenzene 2,5-bis(trimethylsilylamino)-trimethylsiloxybenzene and the like are effective.

Aromatic dicarboxylic acid dino-
Examples of the ride include inphthalic acid dichloride, isophthalic acid dibromide, isophthalic acid diiodide, terephthalic acid dichloride, 4,4'-biphenyldicarboxylic acid dichloride, diphenyl ether-4,4'-dicarboxylic acid dichloride, and benzophenone-4,4'-dicarboxylic acid dichloride. Acid dichloride, diphenylsulfone-4,4'-dicarboxylic acid dichloride, inpropylidene diphenyl-
Examples include 4,4'-dicarboxylic acid dichloride, hexafluoroisopropylidene diphenyl-4,4'-dicarboxylic acid dichloride, and naphthalene-2,6-dicarboxylic acid dichloride. These may be used alone or in combination of two or more.

In this method, the molecular weight of the poly(amidebenzoxazole) resin represented by the general formula is determined by the combination of the diamine compound represented by the general formula (I) and one or more dicarboxylic acid civalides represented by the general formula (■). It is possible to produce a high molecular weight aromatic poly(amidebenzoxazole) resin by using equimolar amounts of these reaction components, which are influenced by the charging ratio.

In the present invention, the reaction between the aromatic diamine compound represented by the general formula (1) and one or more aromatic dicarboxylic acid dino-lides represented by the general formula (It) is carried out in an organic solvent with a substantially anhydrous under conditions of approximately -30C to 10
0C1 preferably about -207? The reaction is carried out for several minutes to several hours at a solvent temperature of 50C.

As the organic solvent that can be used in this method, a wide variety of generally known non-aqueous organic solvents can be used.

Specifically, N,N-dimethylformamide, N.

Nitrogen solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolitone,
Benzene, toluene, anisole, diphenyl ether, benzene solvents such as nitrobenzene, chloroform,
Examples include halogenated hydrocarbons such as carbon tetrachloride and trichloroethane, sulfur solvents such as dimethylsulfoxide and tetramethylsulfone, and ether solvents such as tetrahydrofuran, but are not limited to these.

The production of the poly(amide benzoxazole) resin represented by the general formula (It) from the polyamide resin represented by the general formula (It) is carried out in a suitable trench for several seconds to several hours, and for about 1 hour to 2 hours.
4 hours at a temperature of 100C to 500C, preferably about 1
50t? This is done by heating from 300C to 300C. When R2 of the polyamide resin represented by the general formula (1) is hydrogen, the reaction can be carried out at a low temperature in the presence of a dehydrating agent such as polyIJ acid.

The yield of general formula (5), which is the final product based on general formula (1) and general formula (Tl), is about 90 to
The number is extremely high at 98.

〔Effect of the invention〕

The present invention provides an effective method for producing an aromatic poly(amidebenzoxazole) resin represented by the general formula.

The resin obtained by the present invention is a resin containing an amide bond and an oxazole ring between molecules, and has good properties such as heat resistance, weather resistance, mechanical strength, and electrical properties, and has good processability and flexibility. It is an excellent industrial material with excellent moldability and moldability.

The present invention provides an advantageous method for producing a resin having a sufficiently higher molecular weight than conventional resins having oxazole rings, and has high industrial utility value.

〔Example〕

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

Example-1 2,4-bis(trimethylsilylamino)-trimethylsiloxybenzene was placed in a three-necked flask with a capacity of 5011.
．． 851? (2,5mmo,,e), N-methyl-
2-pyrrolidone5. Oml was taken and dissolved with stirring under a nitrogen gas atmosphere.

After cooling this solution to 115 tll with ice and salt, add 0.508 P of isophthalic acid dichloride (2.5 mmol
-6) was added. After stirring this for 6 hours, the solution was poured into a large amount of methanol to obtain a polyamide resin precipitate. The intrinsic viscosity of the produced resin is 1.49 (0.5f/di
dimethylacetamide, 30C).

As a result of infrared absorption spectrum and elemental analysis, it was confirmed that it was a) 4-product.

Infrared absorption spectrum 1655rm-' (C=0) origin analysis CHN Calculated value (correspondence) 66.14 3.96 11.02 Actual value (Qb) 65.25 3.89 10.83 Then, this polyamide resin was treated with dimethylacetamide. A film was formed by dissolving the solution in water and spreading it on a glass plate.

This film was heat-treated at a reduced pressure of 280 to 300 C for 15 hours to obtain a transparent and strong film.

As a result of infrared absorption spectrum (film transmission method) and elemental analysis, it was confirmed that it was a poly(amide benzoxazole) resin represented by the following formula, and the infrared absorption spectrum was 1660 m''''' (C=O) 1620 CrrI-'
(C=N) Elemental analysis CHN Calculated value (%) 71.18 3.41 11.86 Actual value (correspondence) 69.93 3.35 11.73.

Example-2 Instead of isophthalic acid dichloride, the same amount of terephthalic acid dichloride (0.508 y-(2.5 mmnA
) was used, but the reaction was carried out in the same manner as in Example 1 to obtain a polyamide resin.

The intrinsic viscosity was 1.40 (0.5 f/di N-methyl-2-pyrrolidone, 30C). As a result of infrared absorption spectrum and elemental analysis, it was confirmed that it has the following structure.

This resin was dissolved in N-methyl-2-pyrrolidone, formed into a film on a glass plate, and subjected to the same heat treatment as in Example-1.

From the elemental analysis results and infrared absorption spectrum of the obtained resin, poly(amidebenzoxazole) with the following structure was found.
It was confirmed that it was resin.

The glass transition temperature of this resin is 301C1 tensile strength is 11
4 MPa, and the initial elastic modulus was 3.0 GPa.

Example 3 A polyamide resin was obtained by carrying out the reaction in the same manner as in Example 1, except that the same amount of tetrahydrofuran was used as a solvent instead of N-methyl-2-pyrrolidone.

The intrinsic viscosity was 0.73 (0.5%/d/dimethylacetamide, 30C). As a result of infrared absorption spectrum and elemental analysis, it was confirmed that the resin had the same structure as Example-1. This polyamide resin was dissolved in dimethylacetamide and subjected to the same heat treatment as in Example-1. As a result of infrared absorption spectrum and elemental analysis of the obtained resin, it was confirmed that it was a poly(amidobenzoxazole) resin having the same structure as in Example-1.

Example-4 Instead of inphthalic acid dichloride, 0.63 of naphthalene-2,6-dicarboxylic acid dichloride, which has an equimolar proportion thereto, was used.
A polyamide resin was obtained by carrying out the reaction in the same manner as in Example-1 except that 3f (2.5mmo, 6) was used. Intrinsic viscosity is 1.58 (0.5f/dl concentrated sulfuric acid,
30C).

The structure was confirmed by infrared absorption spectrum and elemental analysis.

Film molding was performed by spreading a reaction solution containing a polyamide resin on a glass plate as it was.

This film was heat-treated at 280 to 300C for 15 hours under reduced pressure, and as a result of infrared absorption spectrum and elemental analysis of the resulting resin, it was confirmed that it was a poly(amidebenzoxazole) resin with the following structure.

The glass transition temperature of this resin was 2870, the tensile strength was 105 MPa, and the initial elastic modulus was 3.0 GPa.

Example-5 Instead of isophthalic acid dichloride, an equimolar amount of diphenyl-4,4'-dicarboxylic acid dichloride 0.6
A polyamide resin was obtained by carrying out the reaction in the same manner as in Example-1 except that 98 f (2.5 mmo-g) was used. The intrinsic viscosity was 2.23 (0.5 f/di concentrated sulfuric acid, 30C).

The structure was confirmed by infrared absorption spectrum and elemental analysis.

Film molding was also carried out according to Example-4.

As a result of infrared absorption spectrum and elemental analysis, it was confirmed that it was a poly(amidobenzoxazole) resin with the structure.

The glass transition temperature of this resin was 285''C, the tensile strength was 120 MPa, and the initial elastic modulus was 3.50 Pa.

Example-6 The same method as Example-1 was used, except that an equimolar amount of diphenyl ether-4,4'-dicarboxylic acid dichloride 0.738 F (2,5 mmo-6) was used instead of isophthalic acid dichloride. A reaction was carried out to obtain a polyamide resin. The intrinsic viscosity was 0.83 (0.5%/#dimethylacetamide, 30C).

The structure was confirmed by infrared absorption spectrum and elemental analysis.

Next, this polyamide resin was dissolved in dimethylacetamide and spread on a glass plate to form a film.

This film was heat-treated at 280 to 300C for 15 hours under reduced pressure. As a result of infrared absorption spectrum and elemental analysis of the obtained resin, it was confirmed that it was a poly(amidebenzoxazole) resin having the following structure.

Example 7 A polyamide resin was obtained by carrying out the reaction in the same manner as in Example 1 except that 0.858 t (2.5 mmoA) of acid dichloride was used. Intrinsic viscosity is 0.82 (0.5%
/d! The structure was confirmed to be dimethylacetamide (30C) as a result of infrared absorption spectrum and elemental analysis.

Next, this polyamide resin was treated in the same manner as in Example-1 to obtain a film.

As a result of infrared absorption spectrum and elemental analysis of this film, it was confirmed that it was a poly(amide benzoxazole) resin with the following structure.

The glass transition temperature of this resin was 300C.

Example-8 2,4-bis(trimethylsilylamino)-trimethylsiloxypenze was added to a three-necked flask with a volume of 5 otnl.
1.70 f (5, Ommoβ), N-methyl-2-
10 ml of pyrrolidone was taken and dissolved with stirring under a nitrogen gas atmosphere. After cooling this solution with ice and salt to -15r, isophthalic acid dichloride o,5oB(2,smmoβ
), terephthalic acid dichloride 0.50854 (2.5m
mo1) was added.

After stirring this for 6 hours, the solution was poured into a large amount of methanol to obtain a polyamide resin precipitate.

The intrinsic viscosity of the resulting resin was 0.71 (0.5%/# concentrated sulfuric acid, 30C).

As a result of infrared absorption spectrum and elemental analysis, it was confirmed that the structure consists of two repeating units.

Next, this polyamide resin was subjected to the same treatment as in Example 1 to obtain a film.The results of the infrared absorption spectrum and elemental analysis of this film revealed that it was a poly(amidebenzoxazole) resin with a structure consisting of two repeating units. I confirmed that there is.

The glass transition temperature of this resin was 283C.

Example-9 Instead of terephthal or dichloride, use 1 and equimolar amount of diphenyl-4,4'-dicarboxylic acid dichloride 0.6
98! Except for using i' (2,5 mmo/ ),
The reaction was carried out in the same manner as in Example 8 to obtain a polyamide resin.

The intrinsic viscosity was 1.67 (0,591-/di concentrated sulfuric acid, 30C).

As a result of infrared absorption spectrum and elemental analysis, it was confirmed that it had a structure consisting of two repeating units.

This polyamide resin was then treated in the same manner as in Example 1 to obtain a strong film.

The infrared absorption spectrum and elemental analysis of the obtained resin confirmed that it was a poly(amidepenzoxal) resin having a structure consisting of the following two repeating units.

The glass transition temperature of this resin was 264C, the tensile strength was 114MPa, and the initial elastic modulus was 3.1GPa.

Example 10 A polyamide resin was obtained by carrying out the reaction in the same manner as in Example 8, except that 0.633 f (2.5 mmog) was used.

The intrinsic viscosity was 1.52 (0.5%/d+!! concentrated sulfuric acid, 30C).

As a result of infrared spectrum and elemental analysis, it was confirmed that the structure consists of two repeating units.

This resin was then treated in the same manner as in Example 1 to obtain a strong film.

It was confirmed from the infrared absorption spectrum and elemental analysis of the obtained resin that it was a compound with a structure consisting of the following two repeating units.

This poly(amidebenzoxazole) resin had a glass transition temperature of 269C, a tensile strength of 104 MPa, and an initial elastic modulus of 2.4 GPa.

Comparative Example-1 2,4-diaminophenol 5 mmoA and N-methyl-2-pyrrolidone 10 were placed in a 50 ml Mitsulo flask.
d was taken and dissolved with stirring under a nitrogen gas atmosphere.

After cooling this solution to -15C with ice and salt, 5 mmo-g of isophthalic acid dichloride was added. After stirring this for 6 hours, the solution was poured into a large amount of methanol to obtain a powdery precipitate of polyamide resin.

The intrinsic viscosity of this resin is 0.31 (0.5f/di
The mixture was finished with dimethylacetamide (30C).

This polyamide resin had an extremely low viscosity compared to the polyamide resin of Example-1, and could not be formed into a film.

The poly(amidebenzoxazole) resin obtained in the above example has a high intrinsic viscosity and a high glass transition temperature, and has excellent heat resistance. 1. These resins obtained have high tensile strength and elastic modulus, and therefore have excellent moldability and flexibility, and are of great industrial utility.

Patent applicant: Cosmo Oil Co., Ltd.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 represents a monovalent organosilicon group, and R_2 represents hydrogen or a monovalent organosilicon group.) Aromatic diamine represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R represents a divalent aromatic group and Y represents a halogen.)
One or more aromatic dicarboxylic acid dihalides represented by are reacted in an organic solvent to form the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) (In the formula, R is a divalent aromatic group. , R_2 is hydrogen or a monovalent organosilicon group, and n is an integer from 5 to 200.), and then the polyamide resin is subjected to a cyclization reaction to form the general formula ▲ , chemical formulas, tables, etc. ▼(IV) (In the formula, R is a divalent aromatic group, and n is an integer from 5 to 200.) Conversion to aromatic poly(amidebenzoxazole) A method for producing a poly(amidebenzoxazole) resin characterized by: