JPS62100531A - Production of polyesterimide - Google Patents

Abstract

PURPOSE:A polyesterimide that is prepared by polycondensation reaction between bis(hydroxyphthalimide) and a dicarboxylic dihalide or between bis(phthalic ester) and organic diamine, thus showing clarity and heat resistance. CONSTITUTION:The polycondensation reaction, (A) between a bis(hydroxyphthalic imide) of formula I [R1 is 6-20C aromatic hydrocarbon or its halogenated derivative, alkylene, formula II (X is O, CO, S; m is 0, 1) and a dicarboxylic dihalide of formula III (R2 is R1, Y, Z are halogen), e.g., in an organic solvent under substantially anhydrous conditions, or (B) between a bis(ester-phthalic anhydride) of formula IV and an organic diamine of formula V in an organic solvent under substantially anhydrous conditions gives the objective polyesterimide bearing recurring units of formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel polymer having imide groups and a method for producing the same, and particularly to a novel polyesterimide and a method for producing the same.

(Prior art and its problems) Since polyimide has extremely excellent heat resistance, it is used in a wide range of applications, from the space and aircraft fields to general industrial applications such as 1M wire coating and 1 varnish for printed boards.

but. Conventional polyimides, such as Kapton (trademark; manufactured by DuPont), have had the disadvantage of poor transmittance to visible light and lack of transparency.

On the other hand, polycarbonate, saturated polyester, etc., which have excellent transparency, are used for applications such as liquid crystal display boards and Taiyo AI Ikegawa bar materials, but they are said to have inferior heat resistance compared to polyimide. There are drawbacks.

(Object of the Invention) An object of the present invention is to provide a polyesterimide that overcomes the drawbacks of conventional polyimides and has excellent transparency and heat resistance.

[Specific structure of the invention]

The first aspect of the present invention is an aromatic hydrocarbon group having a carbon atom or a halogenated derivative thereof; (b) an alkylene group having 2 to 8 carbon atoms;
polyorganosiloxane chain-terminated with alkylene groups or cycloalkylene groups having 2 to 20 carbon atoms, (C) m is O or an integer of 1, rl is 1 to
It is an integer of 5.

) is a divalent organic group selected from the group consisting of divalent groups represented by: ] This is a polyesterimide characterized by containing a repeating unit represented by the following.

The second invention of the present invention is to combine polyesterimide containing repeating units represented by general formula (I) with bis(hydroxyphthalimide) represented by general formula (wherein R2 is the same as the group defined above). , Y and 2 are any of F, (J, Br, [).

It is characterized by polycondensing bis(ester phthalic anhydride) represented by -, an organic diamine represented by the general formula % (in the formula, R1 is the same as the group defined above). This is a method for producing polyesterimide.

The polyesterimide of the present invention has good heat resistance and excellent transparency, has extremely high industrial value, and has a novel chemical structure.

The polyesterimide of the present invention is produced by the above-mentioned two types of production methods. In the method of obtaining by condensation, bis(hydroxyphthalimide) is
Bis(hydroxyphthalimide) described in Japanese Patent Application No. 60-55151 is used. This bis(hydroxyphthalimide) is 4-hydroxyphthalic anhydride and the general formula %
It is obtained by condensing an organic diamine represented by the formula % (R+ is the same as the group defined above) using a phenolic solvent or glacial acetic acid as a reaction solvent. Examples of the organic diamine include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylbroban, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4' -diaminodiphenylsulfone, 4゜4
'-Diamino diphenyl ether, 1.5-diaminonaphthalene, 3.3'-dimethylbenzidine, 3.3'-
Dimethoxybenzidine, 2,4-bis(β-amino-t
-butylphenyl)1-luene, bis(p-β-amino-1-butylphenyl)ether, and the like.

In this reaction, 1 mole of organic diamine is used per 2 moles of 4-hydroxyphthalic anhydride, but good results can also be obtained with 0.8 to 1.2 moles of organic diamine. . As a reaction solvent, a phenolic solvent or glacial acetic acid can be used as a solvent. As the phenolic solvent, o-, p-, m-cresol and mixtures thereof can be used, and G can be used in an amount of 1 to 2 parts by weight or more per 1 part by weight of the total reactants. The reaction temperature is preferably about 100 to 140°C. Furthermore, in order to facilitate the removal of reaction water during the production of bis(hydroxyphthalimide), a nonpolar solvent with a low point such as benzene, chlorobenzene, toluene, etc. can also be used as an azeotrope forming agent.

The reaction time ranges from about 20 minutes to about 2 hours depending on factors such as the type of organic diamine, the degree of stirring, and the temperature. When using glacial acetic acid as a solvent, reflux 10 parts by weight of glacial acetic acid per 1 part by weight of all reactants for 1 hour to 1 hour.
It is enough to react for about 5 hours. Specific examples of bis(human[14-siphthalimide) obtained in such a condensation reaction include 1,3-dos(4-hydroxyphthalimide)benzene, 1,4-bis(4-hydroxyphthalimide), and -hydroxyphthalimide)benzene, etc.

Further, as the dicarboxylic acid dihalide, basically all conceivable dicarboxylic acid dihalides can be used, and all dicarboxylic acid dihalides defined by the above formula (nl) can be used. Specifically, terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, phenylsuccinic acid, benzylsuccinic acid, oxy(noric acid, malonic acid, succinic acid, glutaric acid,
Examples include halides of dicarboxylic acids such as methylsuccinic acid and adipic acid.

The condensation reaction between bis([nitroxyphthalimide) represented by general formula (II)] and dicarboxylic acid dihalide represented by general formula (III) F is carried out in an organic solvent under substantially anhydrous conditions 1. Examples of this organic solvent include N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.
, N-dimethylacetamide, and other amide solvents, and these solvents are used after being thoroughly dried. Further, in order to remove hydrogen halide generated as the reaction progresses, a tertiary amine such as pyridine or triethylamine can be present in the reaction system. In this reaction, substantially 1 mol of dicarboxylic acid dihalide is used per 1 mol of bis(hydroxyphthalimide).

A reaction temperature of 20 to 50°C is sufficient, and the reaction time varies depending on the type of reactants, temperature and degree of stirring, etc.
The time range is from 0 minutes to about 30 hours.

After the reaction is completed, the polyesterimide can be isolated by adding a precipitation solvent such as methanol to the reaction mixture and separating the resulting precipitate in a furnace.

Also, on the right is a journal article about methods using solvents.
of Polymer Science (JO ■ “0a1 of P
Olymer 5science)'s X [-volume, 399
(1959) may be used.

Specifically, this is a method in which bis(hydroxyphthalimide) represented by general formula (II) is dissolved in an aqueous alkali solution, and dicarboxylic acid dihalide represented by general formula (Ilr) dissolved in an organic solvent is added thereto for polymerization.

Next, in the second production method, as the bis(ester phthalic anhydride) represented by the general formula <IV), for example, 4'-, drooxyphthalic anhydride and the general formula (II[
A product produced by condensation with a dicarboxylic acid dihalide represented by the formula is used. As the dicarboxylic acid dihalide here, the same ones as exemplified above can be used. The condensation reaction to obtain this bis(ester phthalic anhydride) consists essentially of 4-hydroxy phthalic anhydride 2
1 mole of dicarboxylic acid dihalide per mole is used, but good results can also be obtained with an amount of dicarboxylic acid dihalide of 0.8 to 1.2 cells.

Various solvents can be used as the reaction solvent, such as benzene, acetyl-2-lyl, N-methyl-2-pyrrolidone, and the like. Further, when a tertiary amine is added to remove hydrogen halide generated as the reaction progresses, the progress of the reaction is accelerated. Suitable tertiary amines include pyridine and triethylamine.

A reaction temperature of 20 to 50°C is sufficient, and a reaction time of about 5 to 20 hours, although it varies depending on the type of reactants, reaction temperature, etc. After the reaction is completed, a precipitation solvent such as water or methanol is added to the reaction mixture, and the precipitate is separated into seven separate units to obtain bis(ester phthalic anhydride) represented by the general formula (IV).

In addition, as the organic diamine represented by the general formula (V) used in the second production method, basically all conceivable organic diamines can be used, and all organic diamines defined by the general formula (V) can be used. It is possible. For example, m-phenylenediamine, p-phenylenediamine, 4,4'
-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzine and the like.

The polymerization reaction between the diamine (ester phthalic anhydride) of the general formula (IV) and the organic diamine of the general formula (V) can be carried out in the same manner as a normal polyimide polymerization method. For example, by reacting in an organic solvent such as dimethylace-1-amide under substantially anhydrous conditions at 20 to 50°C for 0.5 to 30 hours, an intermediate polyamic acid having a repeating unit represented by the general formula is obtained. , and then by a conventional dehydration cyclization method, 200 to 30
The desired polyesterimide can be obtained by heating at 0° C. for 1 to 5 hours.

〔Example〕

The polyesterimide of the present invention and the method for producing the same will be explained in detail below using Examples. However, these Examples are only for illustrating the practice of the present invention, and are not intended to limit the scope of the present invention.

(Example 1) 4.4'-bis(4-hydroxyphthalimide)diphenylsulfone 540Ing(1+not), terephthalic acid dichloride 202Ir! g (1111 mol)
Dissolved in 10d of dehydrated N-methyl-2-pyrrolidone.
I let it happen. Add 1581 ftg (2 m m ) of pyridine to this solution.
ol) was added thereto, and the mixture was stirred at room temperature for 15 hours under a nitrogen atmosphere.

After the reaction was completed, the reaction mixture was poured into 100 d of methanol to obtain a white solid. Separate this solid from house to house, water,
Thoroughly wash with methanol and acetone and heat at 100°C under reduced pressure.
for 5 hours and the corresponding polyesterimide 480
mg (yield 72%).

This one has an infrared absorption spectrum of 1775 e
There is a CO group absorption characteristic of imide groups at Since the values almost matched, it was confirmed that it was the target compound.

(Example 2) 1 cum of sodium hydroxide 0.40Q (10m mol)
4,4'-bis(4-hydroxyphthalimide)diphenylsulfone 2.70μ (5mn+
O+) was added and dissolved. To this, 0.290 g of sodium lauryl sulfate (is
mol ) of benzene solution was added thereto, and the mixture was vigorously stirred at room temperature for 1 hour. 500 d of reaction mixture containing white solid
When poured into acetone, a white solid precipitated. Remove this solid) separately, wash thoroughly with water and acetone, and remove under reduced pressure.
After drying at 00°C for 5 hours, 2.24 g (yield: 67%) of the corresponding polyesterimide was obtained. The infrared absorption spectrum of this product showed all the same absorption spectra as the compound of Example 1, confirming that it was the same polyesterimide.

(Example 3) 2.70q (5 mmol) of 4,4'-bis(4-hydroxyphthalimido)diphenylsulfone was added to 150 me of an aqueous solution of 0.40 g (10 mmol) of sodium hydroxide.
) was added and dissolved. Add to this 10d of an aqueous solution of 0.29g (1a mol) of sodium lauryl sulfate, and 7d of a benzene solution of 1.01g (5n+1ol) of isophthalic acid dichloride. M was added and stirred vigorously at room temperature for 1 hour. When the reaction mixture containing a white solid was poured into 500 m of acetone, a white solid was precipitated. This solid was divided into 7 houses,
Wash thoroughly with water and acetone, dry at 100°C under reduced pressure for 5 hours, and remove 2.01g of the corresponding polyesterimide (
A yield of 60% was obtained.

This substance has an infrared absorption spectrum of 1775 C
! There is a CO group absorption characteristic of imide groups at R-' and 1720a+-', no absorption of OH group near 3300α-1, and as shown in Table 1, the measured values and calculated values in elemental analysis. It was confirmed that the compound was the target compound because they were almost identical.

(Example 4) m01) represented by the following formula and 4,4'-diaminodiphenylsulfone 24
A mixture of 8Rg (In mol) and 5g of distilled dimethylacetamide was reacted for 24 hours at room temperature under a nitrogen atmosphere. When the reaction mixture was poured into 100 d of methanol, a white solid was precipitated. This solid was separated, thoroughly washed with water and acetone, and dried at 100°C under reduced pressure for 5 hours.
Next, the mixture was heated at 250° C. for 2 hours to obtain 550 Ing (yield: 82%) of the corresponding polyesterimide.

Since this product showed all the same absorption spectra as the compound of Example 1 in the infrared absorption spectrum, it was confirmed that it was the same polyesterimide.

(Example 5) Bis(ester anhydride 458JI9 (lsmo
l) and 4,4'-diaminodiphenylsulfone 248I
A mixture of Itg (1 mmol) and distilled dimethylacetamide 5Q was reacted for 24 hours at room temperature under nitrogen atmosphere. When the reaction mixture was poured into methanol 100++d, a white solid was precipitated. Separate this solid from house to house, water,
The product was thoroughly washed with acetone, dried under reduced pressure at 100° C. for 5 hours, and then heated at 250° C. for 2 hours to obtain 503 IItg (yield 75%) of the corresponding polyesterimide.

Since this product showed all the same absorption spectra as the compound of Example 3 in the infrared absorption spectrum, it was confirmed that it was the same polyesterimide.

(Examples 6 to 10) Various bis(
The same operation as in Example 1 was carried out using hydroxyphthalimide) to obtain the polyesterimide shown in Table 1.

Moreover, the identification of the compound was performed in the same manner as in Example 1. Table 1 shows the yield, infrared absorption spectrum data, and elemental analysis values.

(Examples 11 to 15) Various bis(
The same operation as in Example 3 was carried out using hydroxyphthalimide) to obtain the polyesterimide shown in Table 1.

Moreover, the identification of the compound was performed in the same manner as in Example 3. Table 1 shows the yield, infrared absorption spectrum data, and elemental analysis values. Furthermore, the thermal decomposition temperatures of polynisderimides obtained in Examples 11 to 15 are shown. Further, the light transmittance of the polyesterimide obtained in Example 4 is compared with that of a conventional product and is shown in the drawing. In the drawings, curve 1 shows the transmittance of the polyesterimide obtained in Example 4 (q), and curve 2 shows the transmittance of conventional polyimide (Kapton, manufactured by DuPont).

As shown in Table 1, the polyesterimide of the present invention has a thermal decomposition temperature of 400° C. or higher and has excellent heat resistance. Furthermore, as shown in the drawings, it can be seen that the light transmittance is significantly superior to that of conventional polyimide.

〔Effect of the invention〕

As explained above, the polyesterimide of the present invention is
It has excellent heat resistance and transparency, and has the advantage that it can be used for liquid crystal display boards, solar cell cover materials, etc.

[Brief explanation of drawings]

The drawing is a graph showing the light transmittance of the polyesterimide of the present invention and the conventional polyimide.

Claims (3)

[Claims] (1) A polyesterimide characterized by containing a repeating unit represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms or a halogenated derivative thereof, (b) an alkylene group, a carbon atom is a polyorganosiloxane chain-stopped with 2 to 8 alkylene groups or a cycloalkylene group having 2 to 20 carbon atoms, (c) the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, one member selected from the group consisting of -S- and -CnH_2n-, m is an integer of 0 or l , n is an integer of 1 to 5.) is a divalent organic group selected from the group consisting of divalent groups represented by: ] (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms or a halogenated derivative thereof, (
b) alkylene groups, polyorganosiloxanes chain-terminated with alkylene groups having 2 to 8 carbon atoms or 2 to 2
Cycloalkylene group with 0 carbon atoms, (c) following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X is -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas) , tables, etc. ▼, one member selected from the group consisting of -S- and -CnH_2n-, m is an integer of 0 or l, n is an integer of 1 to 5.) A divalent group represented by A divalent organic group selected from the group consisting of ] Bis(hydroxyphthalimide) represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. derivatives, (
b) alkylene groups, polyorganosiloxanes chain-terminated with alkylene groups having 2 to 8 carbon atoms or 2 to 2
Cycloalkylene group with 0 carbon atoms, (c) following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X is -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas) , tables, etc. ▼, one member selected from the group consisting of -S- and -CnH_2n-, m is an integer of 0 or l, n is an integer of 1 to 5.) A divalent group represented by A divalent organic group selected from the group consisting of In addition, Y and Z are F, Cl, Br, I
Either. ] A polyester represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are the same as the above groups.) Method for producing imide. (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_2 is (a) an aromatic hydrocarbon group having 6-20 carbon atoms or a halogenated derivative thereof, (
b) alkylene groups, polyorganosiloxanes chain-terminated with alkylene groups having 2 to 8 carbon atoms or 2 to 2
Cycloalkylene group with 0 carbon atoms, (c) following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X is -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas) , tables, etc. ▼, one member selected from the group consisting of -S- and -CnH_2n-, m is an integer of 0 or l, n is an integer of 1 to 5.) A divalent group represented by A divalent organic group selected from the group consisting of ] Bis(ester phthalic anhydride) represented by the general formula H_2N-R_1-NH_2 [wherein R_1 is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms or a halogenated derivative thereof, (
b) alkylene groups, polyorganosiloxanes chain-terminated with alkylene groups having 2 to 8 carbon atoms or 2 to 2
Cycloalkylene group with 0 carbon atoms, (c) following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X is -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas) , tables, etc. ▼, one member selected from the group consisting of -S- and -CnH_2n-, m is an integer of 0 or l, n is an integer of 1 to 5.) A divalent group represented by A divalent organic group selected from the group consisting of ] A method for producing polyester imide represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1 and R_2 are the same as the above groups) .