JPH01185324A - New copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a copolymer excellent in heat resistance and moldability and high in the mechanical strengths and modulus of a molding, by reacting a p-acyloxybenzoic acid with a diacyloxy compound, a dicarboxylic acid and a diimidodicarboxylic acid. CONSTITUTION:A p-acyloxybenzoic acid of formula I (wherein R<1> is a 1-5C alkyl) is reacted with a diacyloxy compound of formula II (wherein Ar is formu la III, IV or the like, R<2> and R<3> are each a 1-5C alkyl), a dicarboxylic acid of formula I and a diimidodicarboxylic acid of formula VI to obtain the purpose copolymer. In formula VI, X<1> and X<3> are each a halogen atom, a 1-4C alkyl, a 1-4C alkoxyl, a phenyl or a cyclohexyl, X<2> and X<4> are each H, a halogen atom, a 1-4C alkyl, a 1-4C alkoxyl, a phenyl or a cyclohexyl, and n is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel copolymer and a method for producing the same. More specifically, the present invention relates to electronic/electrical equipment,
A new wholly aromatic polyester copolymer that is suitable as a material for machine parts, films, fibers, etc. and has excellent properties such as excellent heat resistance and moldability, as well as high mechanical strength and elastic modulus of molded products. It relates to coalescence and its manufacturing method.

[Conventional technology]

Conventionally, polyesters such as polyethylene terephthalate have been known to have various structures, and because they have excellent mechanical properties, temperature properties, and electrical properties, they are used for example in electronics, electrical equipment, mechanical parts, and films. ,
It is widely used as a material such as fibers.

As described above, polyester is used for a variety of applications, but as its applications have expanded in recent years, there has been a demand for products with better properties, especially those with high heat resistance, high mechanical strength, and elastic modulus. It started to be done.

As a wholly aromatic polyester thermoplastic polymer having high heat resistance, high strength, and high elastic modulus, wholly aromatic polyester consisting of repeating units represented by -+-0-8r-0-+-1 and is known. (Japanese Patent Publication No. 47-47870).

[Problem to be solved by the invention]

However, although the fully aromatic polyester mentioned above has high heat resistance, it is still unsatisfactory in terms of mechanical strength and elastic modulus, and its molding temperature is high, making it difficult to mold using a general-purpose injection molding machine. It has its drawbacks. For this reason, attempts have been made to introduce various copolymer components, but at present it has not been possible to satisfy all of heat resistance, moldability, and mechanical properties.

Under these circumstances, the purpose of the present invention is to develop a wholly aromatic polyester co-polyester which has excellent properties such as not only excellent heat resistance and moldability, but also high mechanical strength and elastic modulus of molded products. The purpose is to provide a polymer.

[Means to solve the problem]

The present inventors have conducted intensive research to develop a wholly aromatic polyester copolymer having the above-mentioned excellent properties. The inventors have discovered that the objective can be achieved by introducing a copolymer component with a specific structure into a copolymer consisting of repeating units represented by group polyesters, and have completed the present invention based on this knowledge.

In other words, the invention of claim 1 comprises (A) a repeating unit represented by the formula %, (B) a repeating unit represented by the general formula %, and (C) a repeating unit represented by the formula %. and (D) General formula (in the formula, X' and x3 are each a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or a cyclohexyl group, and are the same) x2 and X4 are each hydrogen, halogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms) L4
, phenyl group, or cyclohexyl group, which may be the same or different, and n is 0 or 1. ) A novel copolymer consisting of repeating units represented by:

The novel copolymers of the present invention have the formulas (A), (B), (
It is necessary to have repeating units represented by C) and (D) as main constituents, and the invention of claim 2 is a novel copolymer of the invention of claim 1 that contains repeating units of these repeating units. This provides a copolymer with a more preferable content ratio. That is, in order for the copolymer to have high mechanical strength and elastic modulus, as well as good heat resistance and moldability, on a molar basis, A/(B + C
+I)) is preferably 30/70 to 80/20. If the amount of repeating unit (A) is more than this range, moldability may be impaired. If the amount is less than this range, the mechanical strength of the molded product may decrease. Further, it is desirable that B/(C+D) is 60/40 to 40/60, preferably 50,150. Outside this range, it may be difficult to produce a polymer with a high degree of polymerization. Moreover, it is preferable that C/D exists in the range of 50150-90/10. If the amount of the repeating unit (D) is more than this range, polymerization may become difficult, and if it is less than this range, the objectives of the present invention, such as improving mechanical strength and elastic modulus, may not be achieved. be.

In the repeating unit (B), Ar is a p-phenylene group, or
Regarding the repeating unit (C), those having a p-phenylene group and those having an m-phenylene group are para/
It is desirable that they are mixed in a meta ratio of 90/10 to 50,150. If the number of repeating units having p-phenylene groups exceeds this range, moldability may be impaired.

Furthermore, if the amount is less than this range, the mechanical strength of the molded product may decrease.

The polymer of the present invention can be produced, for example, according to the production method according to claim 3, in the form % formula % (1) (where R1 is an alkyl group having 1 to 5 carbon atoms).

p-acyloxybenzoic acid represented by -form % formula %) (the total in the formula has the same meaning as above, R2 and R3 are each an alkyl group having 1 to 5 carbon atoms, and are the same) There may be one or different.

), a dicarboxylic acid represented by the formula, and a diimide dicarboxylic acid represented by the general formula (in the formula, ×1, X3, X2, X', and n have the same meanings as above) It can be produced by reacting with an acid.

The p-acyloxybenzoic acid represented by the -format (T) is, for example, p-hydroxybenzoic acid and the -format R'C0
It can be obtained by reacting a carboxylic acid represented by 0H (wherein R1 is an alkyl group having 1 to 5 carbon atoms) or a reactive derivative thereof, such as an acid anhydride, acid chloride, or ester of the carboxylic acid. Examples of the p-acyloxybenzoic acid include p-acetoxybenzoic acid, p-propionyloxybenzoic acid, p-butyryloxybenzoic acid, and among these, p-acetoxybenzoic acid is particularly preferred.

The cyasiloxy compounds represented by the above-mentioned form (II) include, for example, hydroquinone, resorcinol, 4°4'-biphenol, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,
4'-dihydroxydiphenylsulfone, 4.4'-
Dihydroxy compounds such as dihydroxyhensiphenone, 4,4'-dihydroxydiphenylmethane, and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) are converted into -format R2C00H (where R2 is an alkyl group having 1 to 5 carbon atoms). ), or a carboxylic acid represented by the -format R'C00H (where R3 is an alkyl group having 1 to 5 carbon atoms), or a reactive derivative thereof. . As this siasyloxy compound, diacetates of the above-mentioned dihydroxy compounds are preferably used. Among these, 1,4-diacetoxybenzene and 4,4'-diacetoxydiphenyl are particularly preferred.

As the dicarboxylic acid represented by the formula (I[I), terephthalic acid and isophthalic acid are preferably used.

The diimidodicarboxylic acid represented by the above-format (IV) is, for example, trimellitic anhydride and -form (XI in the formula,
X2, x3, X4, and n have the same meanings as above. ) is obtained by reacting with an aromatic diamino compound represented by: under heating.

xl and Examples include groups.

As X2 and ×4, for example, a hydrogen atom, a chlorine atom,
Examples include fluorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, 1so-propyl group, various butyl groups, methoxy group, ethoxy group, phenyl group, and cyclohexyl group.

Examples of the diimidodicarboxylic acids include 1.4-bis[(4-carboxy)phthalimido]-2-chlorobenzene, 1.4-bis[(4-carboxy)phthalimido]-2-methylhenzene, and 1.4-bis[(4-carboxy)phthalimido]-2-methylhenzene. (4-carboxy)phthalimido)-2,5-dimethylbenzene, 4
,4'-bis[(4-carboxy)phthalimide]-3
, 3'-dimethyldiphenyl, and 4,4'-bis[
(4-carboxy)phthalimido)-3,3'-dimethoxydiphenyl and the like are preferably used.

In the production method according to claim 3, the copolymer of the present invention is produced by reacting the four components of p-acyloxybenzoic acid, cyasyloxy compound, dicarboxylic acid, and diimidodicarboxylic acid. is preferably carried out in two stages.

To explain one preferred example of producing the copolymer through this two-stage reaction, first, in the first stage,
A raw material mixture containing each raw material in a desired ratio is reacted by heating separately for 1 to 2 hours at normal pressure, preferably at a temperature in the range of 200 to 300°C, to perform decarboxylation, followed by a second reaction. In the stage, under reduced pressure, preferably 280 to 35
The transesterification reaction is carried out by heating at a temperature in the range of 0°C for about 1 to 8 hours.

This reaction is preferably carried out in an inert gas atmosphere such as argon. Although it can be carried out without using a catalyst, sodium acetate, antimony oxide, etc. may be added as a catalyst to promote the polymerization reaction. Further, although it is usually not necessary to use a solvent, a solvent inert to the reaction may be used if desired.

In addition, the novel copolymer of the invention of claims 1 and 2 is prepared according to the production method of claim 4, and instead of the diimide dicarboxylic acid, its precursor (Xl, X2, X3, X4, and n has the same meaning as above.), and this is expressed by the -form % expression %() (R1 in the formula has the same meaning as above).
Reacting p-acyloxybenzoic acid with a cyasyloxy compound represented by -formation% formula % (Ar, R2, and R3 in the formula have the same meanings as above) and a dicarboxylic acid represented by the formula. It can also be manufactured by In this case, the reaction is preferably carried out in two stages.

To explain one preferred example of producing the copolymer by this two-step reaction, first, in the first stage, a raw material mixture containing each raw material in a desired ratio is heated at normal pressure, preferably at 200 to 300 The temperature is raised to 0.degree. C. and kept at that temperature for 1 to 2 hours for reaction to effect dehydration and decarboxylation. Subsequently, in the second stage, under reduced pressure, preferably 28
The transesterification reaction is carried out by heating at a temperature in the range of 0 to 350°C for about 1 to 8 hours.

The diimidodicarboxylic acid precursor described above can be obtained by reacting trimellitic anhydride and the aromatic diamino compound represented by the above-mentioned formula (V) at room temperature.

Examples of the diimide dicarboxylic acid precursor include 2.
5-bis((2,5-dicarboxyphenyl)penzamide to 1-chlorohenzene, 2゜5-bis((2,5
-dicarboxyphenyl)benzamide]-1-methylbenzene, 2.5-bis[(2,5-dicarboxyphenyl)penzamide)-14-dimethylbenzene, 4.
Examples include 4'-bis((2,5-dicarboxyphenyl)penzamide)-3,3'-dimethyldiphenyl.

The invention as set forth in claim 5 provides a method for carrying out the synthesis of diimide dicarboxylic acid and the polymerization reaction in one pot in the production method as set forth in claim 4. in this case,
First, trimellitic anhydride, an aromatic diamine represented by the general formula, and a solvent are charged into a reaction vessel, and are mixed at room temperature to react to form a diimide dicarboxylic acid precursor of the formula (Vl).

This is then combined with p-acyloxybenzoic acid represented by the general formula and -forming R2CO
O-8r-OCOR3(II) (wherein xl, X2
, X3, x4, n, Ar, R', R2, and R3 have the same meanings as above. ) and the dicarboxylic acid represented by the formula were added, and the mixture was heated under normal pressure to 200 to 3
The temperature is raised to 00°C and maintained at this temperature for about 1 to 2 hours to perform solvent removal, dehydration, and decarboxylation reactions. Continuing, as the second stage reaction, under reduced pressure, 2
The novel copolymer of the present invention is produced by carrying out the transesterification reaction at a temperature of 80 to 350"C for about 1 to 8 hours.

Solvents used in this method include methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide, dimethylacetamide, and the like.

Further, the manufacturing methods according to claims 4 and 5 are also preferably carried out in an inert gas atmosphere such as argon. Although it can be carried out without using a catalyst, sodium acetate, antimony oxide, etc. may be added as a catalyst to promote the polymerization reaction.

The novel copolymer obtained by the present invention is useful for producing various molded products and has sufficient strength in fissuring.

The novel copolymers of this invention can be made into useful products using conventional conventional methods and conventional equipment.

For example, fibers can be formed by conventional melt spinning techniques and injection molded using conventional conventional equipment and techniques.

The novel copolymers of the present invention may also contain fillers, pigments, glass fibers, carbon fibers, antioxidants, stabilizers, plasticizers, lubricants and other additives.

EXAMPLES The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Production Example 1 1 Summer of Diimide Dicarbonate In a flask with an internal volume of 11 equipped with a stirrer, a reflux condenser, and an argon gas blowing tube, 7 mL of trimellitic anhydride was added.
Add 6.8 g (0.4 mol), 28.5 g (0.2 mol) of 1,4-diamino-2-chlorobenzene, and 500 ml of dimethylacetamide as a solvent, and cool at room temperature while blowing argon gas until a homogeneous solution is obtained. It was stirred with

Next, the temperature was raised to 170°C and reaction was carried out for 8 hours with stirring. The obtained product was poured into water in Step 3, and the precipitate was collected by filtration and washed with water and methanol, respectively, to obtain 95.2 g of pale red crystals.

The melting point of the obtained compound was 390°C, 270-3
It exhibited liquid crystallinity in a temperature range of 90°C.

The results of elemental analysis were as follows.

(Measured value) (Theoretical value) Carbon 58.6% 58.7% Hydrogen 2.2% 2.2% Oxygen 26.2% 26.1% Nitrogen 5.6% 5.7% Chlorine 7.4% 7 .3% In addition, infrared absorption spectrum 1H analysis of this compound revealed absorption by Hensen's ring at 1580 cm-' and 1490 cm-', absorption by carbonyl group at 1650 cm-', 1780-1680c+n-' and 7
Absorption due to imide group was observed at position 20c+n-'. From the above, this compound was recognized to have the structure shown below.

Production Example 2 Li Notice of Diimide Dicarbonate - Instead of 1,4-diamino-2-chlorobenzene in Production Example 1, 1,4-diamino-2-methylbenzene.2
84.6 g of white crystals were obtained in the same manner as in Production Example 1 except that 39.0 g (0.2 mol) of the hydrochloride was used.

This compound had a melting point of 410°C, and the elemental analysis values were as follows.

(Measured value) (Theoretical value) Carbon 63.9% 63.8% Hydrogen 2.9% 3.0% Oxygen 27.0% 27.2% Nitrogen 6.2% 6.0% Also, the infrared rays of this compound The absorption spectrum analysis results are
It was the same as Production Example 1.

From the above, this compound was recognized to have the following structure.

Production Example 3 1' of Diimide Dicarbonate In place of 1,4-diamino-2-chlorobenzene in Production Example 1, 27.2 g (0.2 mol) of 1,4-diamino-2,5-dimethylbenzene was used. ) was used, except that Production Example 1 was used.
In the same manner as above, 94.3 g of white crystals were obtained.

This compound had a melting point of 420°C, and the elemental analysis values were as follows.

(Measured value) (Theoretical value) Carbon 64.4% 64.4% Hydrogen 3.2% 3.3% Oxygen 26.5% 26.5% Nitrogen 5.9% 5.8% Also, the infrared rays of this compound The absorption spectrum analysis results are
It was the same as Production Example 1.

From the above, this compound was recognized to have the following structure.

Production Example 4 42.4 g (0.2 mol) of 4,4'-diamino-3,3'-dimethyldiphenyl was used instead of 1,4-diamino-2-chlorobenzene in Production Example 1. 108.2 g of white crystals were obtained in the same manner as in Production Example 1, except that 108.2 g of white crystals were obtained.

This compound had a melting point of 430°C, and the elemental analysis values were as follows.

(Measured value) (Theoretical value) Carbon 68.4% 68.6% Hydrogen 3.6% 3.6% Oxygen 22.9% 22.8% Nitrogen 5.1% 5.0% Also, the infrared rays of this compound The absorption spectrum analysis results are
It was the same as Production Example 1.

From the above, this compound was recognized to have the following structure.

Production Example 5 Diimide dicarboxylic acid 48.8 g (0.2 mol) of 4,4'-diamino-3,3'-dume-1-oxydiphenyl in place of 1,4-diamino-2-chlorobenzene in Production Example 1 107.4 g of white crystals were obtained in the same manner as in Production Example 1 except that 107.4 g of white crystals were used.

The melting point of this compound was 450°C, and the elemental analysis values were as follows.

(Actual value) (Theoretical value) Carbon 64.9% 64.9% Hydrogen 3.3% 3.4% Oxygen 27.0% 27.0% Nitrogen 4.8% 4.7% Also, the infrared rays of this compound The absorption spectrum analysis results are
It was the same as Production Example 1.

From the above, this compound was recognized to have the following structure.

Production Example 6 Diimide dicarbonate 76% of trimellitic anhydride was placed in a flask with an internal volume of 11 equipped with a stirrer, a reflux condenser, and an argon gas blowing tube.
．． 8 g (0.4 mol), 28.5 g (0.2 mol) of 1,4-diamino-2-chlorobenzene, and 500 mf of methanol as a solvent were added, and the mixture was stirred at room temperature for 3 hours while blowing argon gas. The generated precipitate was collected by filtration to obtain 97.5 g of white crystals.

It was found that the obtained compound undergoes a dehydration reaction when heated above 100°C. The melting point of the dehydrated product is 390
It exhibited liquid crystallinity in the range of 270 to 390°C.

The results of elemental analysis were as follows.

(Actual measurements) (Theory (i) Carbon 54.8% 54.7% Hydrogen 2.8% 2.9% Oxygen 30.5%, 30.4% Nitrogen 5.2% 5.3% Chlorine 6.7 % 6.7% Also, according to infrared absorption spectrum analysis of this compound, 1
Absorption due to Hensen's ring was observed at the 580 cm-' and 1490 ctn-1 positions, absorption due to the carbonyl group at the 1650 cm-' position, and absorption due to the amide group at the 1690 cm-' position.

From the above, this compound was recognized to have the structure shown below.

Example 1 P-
Acetoxybenzoic acid 108. Og (0,60 mol L
4,4'-diacetoxydiphenyl 54゜0g (0,2
0 mole), terephthalic acid 19.9 g (0°12 mole),
8.3 g (0.05 mol) of isophthalic acid, and 14.7 g (0.05 mol) of 1,4-bis[(4-carboxy)phthalimide: 1-2-chlorobenzene obtained by repeating Production Example 1 above.
g (0.03 mol) and heated at 280° under an argon stream.
The temperature was raised to C. and stirring was continued for 1 hour, during which time the acetic acid produced was distilled off.

Next, the pressure inside the reactor was reduced to 1Qmmllg, and the temperature was increased to 300°C.
The temperature was raised to 350°C for 1 hour, then the pressure was reduced to 11 g of 1H+ml, the temperature was raised to 350°C, and the reaction was allowed to proceed for 2 hours. The thus obtained copolymer had a reduced viscosity (77 SIl/C) of 0.68 dj2/g at 60°C in a solution having a concentration of 0.2 g/dff using pentafluorophenol as a solvent. In addition, this copolymer was heated at 300°C under a polarizing microscope.
It showed liquid crystallinity. Infrared absorption spectrum analysis of this copolymer revealed that 158OCT11-' and 1,49
Absorption by benzene ring at 0 cm-' position, 1650
Absorption by carbonyl group at cm-' position, 1780~
Absorption due to imide groups was observed at 1680 cm-' and 720 cm-' positions. From the above, it was recognized that this copolymer consisted of the following repeating units.

This polymer was injection molded at 330°C, and the resulting test piece was subjected to a bending test according to JIS-7203. The results are shown in the attached table.

Example 2 P-
Acetoxybenzoic acid 72.0 g (0.40 mol L 4,
81.0 g (0.30 mol) of 4'-diacetoxydiphenyl, 29.8 g (0.18 mol) of terephthalic acid, 16.6 g (0.10 mol) of isophthalic acid, and obtained by repeating the above Production Example 2. 9.42 g of 1,4-bis[(4-carboxy)phthalimide]-2-methylhenzene (
0.02 mol) was added, the temperature was raised to 280°C under an argon stream, and stirring was continued for 1 hour, during which time the acetic acid produced was distilled off.

Next, the pressure inside the reactor was reduced to lQmmHg, the temperature was raised to 300°C, and the pressure was continuously reduced to lmmHg to 350°C for 1 hour.
The temperature was raised to °C and the reaction was carried out for 2 hours. The copolymer thus obtained had a reduced viscosity (77311/C) of 0.12 dl/g at 60°C in a solution with a concentration of 0.2 g/dffi using pentafluorophenol as a solvent.

This copolymer also exhibited liquid crystallinity at 300°C under a polarizing microscope. Infrared absorption spectrum analysis of this copolymer revealed that 1580cm-' and 1490c++r'
Absorption by benzene ring at position, absorption by carbonyl group at position 1650c+c', 1780-1680c+
Absorption due to imide groups was observed at positions I+-' and 720 cm-'. From the above, it was recognized that this copolymer consisted of the following repeating units.

This polymer was injection molded at 330°C, and the resulting test piece was subjected to a bending test according to JIS-7203. The results are shown in the attached table.

Example 3 P-
Acetoxybenzoic acid 108. Og (0,60 mol L
4,4'-diacetoxydiphenyl 54゜0g (0,
20 mol), terephthalic acid 16.6g (0°10 mol)
, 8.3 g (0.05 mol) of isophthalic acid, and 1,4-bis((4-carboxy)phthalimide)-2゜5-dimethylbenzene 2 obtained by repeating Production Example 3 above.
4.2 g (0.05 mol) was added and heated under an argon stream for 2 hours.
The temperature was raised to 80°C, stirring was continued for 1 hour, and the acetic acid produced during this time was distilled off. Next, the inside of the reactor was set to 10 mmHg.
The pressure was reduced to
The pressure was reduced to mmHg, the temperature was raised to 350°C, and the reaction was carried out for 2 hours. The thus obtained copolymer had a reduced viscosity [ηsp/c] of 0.85 dj2/g at 60°C in a solution having a concentration of 0.2 g/dj2 using pentafluorophenol as a solvent. Furthermore, this copolymer exhibited liquid crystallinity at 30σ°C under a polarizing microscope. Infrared absorption spectrum analysis of this copolymer revealed that 1580
Absorption by the benzene ring at the positions cm-1 and 1490 cyn-', absorption by the carbonyl group at the position 1650CTl-', 1780-1680 cm-' and 720 cm
Absorption due to imide group was observed at the -' position. From the above, it was recognized that this copolymer consisted of the following repeating units.

+o@-co ”)o, 6o (A')÷
Co<E giant Σco+. 1o (C) This polymer was injection molded at 330°C, and the resulting test piece was subjected to a bending test according to JIS-7203. The results are shown in the attached table.

Example 4 P-
Acetoxybenzoic acid 108.0 g (0.60 mol)
, 4.4'-diacetoxydiphenyl 54゜0g (0
, 20 mol), 16.6 g (0°10 mol) of terephthalic acid, 8.3 g (0.05 mol) of isophthalic acid, and 4,4'-bis[(4-
Carboxy)phthalimide]-3゜3'-dimethyldiphenyl 2B, (Ig (0.05 mol) was added, the temperature was raised to 280°C under an argon stream, and stirring was continued for 1 hour to remove the acetic acid produced during this time. was distilled off.Next, the pressure inside the reactor was reduced to lommHH, the temperature was raised to 300°C, and the reaction was continued for 1 hour, and then the pressure was reduced to 1mmHg, the temperature was raised to 350°C, and the reaction was carried out for 2 hours. The copolymer obtained by
Reduced viscosity at 60°C of a solution of concentration [ηsp/c)
was 0.65 dl/g. In addition, this copolymer is
It exhibited liquid crystallinity at 300°C under a polarizing microscope. Infrared absorption spectrum analysis of this copolymer revealed that 153
Absorption by benzene ring at Qcm-' and 1490cm-' positions, absorption by carbonyl group at 1650cm-' position, 1780-1680cm-' and 720cm-'
Absorption due to imide group was observed at position 1. From the above, it was recognized that this copolymer consisted of the following repeating units.

This polymer was injection molded at 330°C, and the resulting test piece was subjected to a bending test according to JIS-7203. The results are shown in the attached table.

Example 5 P-
Acetoxybenzoic acid 108.0 g (0.60 mol)
, 4.4'-diacetoxydiphenyl 54゜0g (0,
20 mol), terephthalic acid 16.6g (0°10 mol)
, 8.3 g (0.05 mol) of isophthalic acid, and 29.6 g (29.6 g) of 4,4'-bis[(4-carboxy)phthalimide]-3°3'-dimethoxydiphenyl obtained by repeating the above Production Example 5 ( 0.05 mol) was added, the temperature was raised to 280"C under an argon stream, and stirring was continued for 1 hour.
Acetic acid produced during this time was distilled off. Next, the inside of the reactor is
The pressure was reduced to 0 mmHg and the temperature was raised to 300°C for 1 hour, and then the pressure was reduced to 1 mmHg and the temperature was raised to 350°C for 2 hours. The copolymer thus obtained was prepared at a rate of 0.2 g/dffi using pentafluorophenol as a solvent.
Reduced viscosity at 60°C of a solution of concentration [ηsp/c]
was 0.75 d1/g. In addition, this copolymer is
It exhibited liquid crystallinity at 300°C under a polarizing microscope. Infrared absorption spectrum analysis of this copolymer revealed that 158
Absorption by benzene ring at 0 cm-' and 1490c+n-' positions, absorption by carbonyl group at 1650 cm-' position, 1780-1680 cm-' and 720 cm
Absorption due to imide group was observed at the - position. From the above, it was recognized that this copolymer consisted of the following repeating units.

This polymer was injection molded at 330°C, and the resulting test piece was subjected to a bending test according to JIS-7203. The results are shown in the attached table.

Example 6 P-
Acetoxybenzoic acid 108.0 g (0.60 mol>, 4
．． 4'-Diacetoxydiphenyl 54゜0g (0,2
0 mol), terephthalic acid 16.6g (0°10 mol),
8.3 g (0.05 mol) of isophthalic acid, and 28.3 g (0.05 mol) of 2,5-bis((2,5-dicarboxyphenyl)penzamide)-1-chlorohenzene obtained by repeating Production Example 6 above. The temperature was raised to 280°C over 1 hour under an argon stream, and stirring was continued for another 1 hour to distill off the acetic acid and water produced during this time.Next, the inside of the reactor was heated to 10 mmHH. Reduce pressure to 300°
The temperature was raised to C for 1 hour, and the pressure was then reduced to 1 mmHg.
The temperature was raised to 50°C and the reaction was carried out for 2 hours. The thus obtained copolymer had a reduced viscosity [77sI)/C) of 0.70 dn/g at 60'C in a solution having a concentration of 0.2 g/dβ using pentafluorophenol as a solvent.

This copolymer also exhibited liquid crystallinity at 300'C under a polarizing microscope. Infrared absorption spectrum analysis of this copolymer revealed that 1580 cm-' and 149OCT11
Absorption by benzene ring at position -', 1650 cm-'
Absorption by carbonyl group at position 1780-1680
Absorption due to imide groups was observed at cm-' and 720 cm-' positions. From the above, it was recognized that this copolymer consisted of the following repeating units.

This polymer was injection molded at 330°C, and the resulting test piece was subjected to a bending test according to JIS-7203. The results are shown in the attached table.

Example 7 A solution of 19.2 g (0.10 mol) of trimellitic anhydride dissolved in 50 mN of methanol was charged into a reactor equipped with a stirring device and an argon gas introduction tube, and 7.13 g of 2゜5-diaminochlorohenzene was added. (0.05 mol) was added and stirred. The reaction solution was initially homogeneous, but after 30 minutes, a precipitate formed and it became a slurry. p after 1 hour
-acetoxybenzoic acid 108. Og (0,60 mol)
, 4.4'-diacetoxydiphenyl 54.0g (0,
20 mol), terephthalic acid 16.6 g (0.10 mol)
, and 8.3 g (0.05 mol) of isophthalic acid were added, and the temperature was raised to 280° C. over 1 hour under an argon gas flow. During this time, methanol, water, and acetic acid were distilled out. The reaction was continued at that temperature for an additional hour, and the acetic acid produced during this time was distilled off. Next, the temperature was raised to 350°C, the pressure inside the reactor was reduced to 1+nmHg, and the reaction was carried out for 2 hours to obtain a copolymer. The copolymer obtained in this way was prepared using pentafluorophenol as a solvent.
dI! , the reduced viscosity at 60 °C of a solution with a concentration of 77
St)/C) was 0.95 dffi/g. As a result of infrared absorption spectrum analysis of this copolymer, 1580c
Absorption by a benzene ring was observed at a position diagonal to ++r' and 1490 cm, absorption by a carbonyl group at a position of 1650 cm-', and absorption by an imide group at positions from 1780 to 1680 cm-' and 720 cm''.From the above, This copolymer was found to consist of the following repeating units.

This polymer was injection molded at 330°C, and the resulting test piece was subjected to a bending test according to JIS-'-7203. The results are shown in the attached table.

Comparative Example A reactor equipped with a stirring device and an argon gas inlet tube was equipped with p-
Acetoxybenzoic acid 108. Og (0,60 mol), 4
．． 4'-Diacetoxydiphenyl 54゜0g (0,20
mol), 24.9 g (0°15 mol) of terephthalic acid, and 8.3 g (0.05 mol) of isophthalic acid were added, the temperature was raised to 280°C over 1 hour under an argon stream, and the mixture was stirred for an additional 1 hour. Subsequently, acetic acid and water produced during this time were distilled off. Next, 1. Q mmflg
The pressure was reduced to 300℃, and the temperature was raised to 300℃ for 1 hour
The pressure was reduced to 11 g mm, the temperature was raised to 350°C, and the mixture was reacted for 2 hours. The copolymer thus obtained was 0.2 g/d I! in pentafluorophenol as a solvent.
, the reduced viscosity at 60°C of a solution with a concentration [ηsp/c
] was 0.70dj2/g.

This copolymer also exhibited liquid crystallinity at 300"C under a polarizing microscope. Infrared absorption spectrum analysis of this copolymer revealed that
Absorption due to the Hensen ring was observed at the position , and absorption due to the carbonyl group was observed at the 1650 cm-' position. From the above, it was recognized that this copolymer consisted of the following repeating units.

-+O@CO+o, b o (A) 1,000Φ
X) Leaves. , 20 (B) ÷ co @ c o ten. , 1s (c) This polymer was injection molded at 330°C, and the resulting test piece was subjected to a bending test according to JIS-7203. The results are shown in the attached table.

Table [Effects of the Invention] The new copolymer of the present invention not only has excellent heat resistance and moldability, but also has excellent properties such as high mechanical strength and elastic modulus of molded products.・Electrical equipment,
It is suitably used as a material for mechanical parts, films, fibers, etc., and can be manufactured using relatively easily available raw materials, so its industrial value is extremely large.

Claims (1)

[Claims] 1. Repeating unit represented by (A) formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ and (B) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Ar in the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. ) A repeating unit represented by (C) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A repeating unit represented by (D) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula X^1 and X^3 are each a halogen atom,
An alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or a cyclohexyl group, which may be the same or different, and X^2 and X^4 are each Hydrogen, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or a cyclohexyl group, which may be the same or different, and n is 0 or It is 1. ) A new copolymer consisting of repeating units represented by 2. Repeating units (A), (B), (C), and (D
) content is molar ratio A/(B+C+D) is 30/7
0 to 80/20, and B/(C+D) is 60/40 to
40/60 and C/D is 50/50 to 90/10. 3. p-acyloxybenzoic acid represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1 in the formula is an alkyl group having 1 to 5 carbon atoms) and the general formula R^2COO -Ar-OCOR^3 (Ar in the formula ▲ has a mathematical formula, chemical formula, table, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and R^2 and R^3 are each an alkyl group with 1 to 5 carbon atoms. , may be the same or different. ) A diacyloxy compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A dicarboxylic acid represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X^1 and X^ in the formula 3 is a halogen atom,
An alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or a cyclohexyl group, which may be the same or different, and X^2 and X^4 are each Hydrogen, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or a cyclohexyl group, which may be the same or different, and n is 0 or It is 1. ) is characterized by reacting with diimide dicarboxylic acid represented by (A) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (B) General formula ▲ Numerical formulas, chemical formulas, There are tables, etc. ▼ (Ar in the formula has the same meaning as above.) The repeating unit represented by formula (C) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The repeating unit represented by ( D) Repeating unit represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X^1, X^2, X^3, X^4, and n in the formula have the same meanings as above) A method for producing a novel copolymer having 4. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1 in the formula is an alkyl group having 1 to 5 carbon atoms.) p-acyloxybenzoic acid represented by the general formula R^2COO -Ar-OCOR^3 (Ar in the formula ▲ has a mathematical formula, chemical formula, table, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and R^2 and R^3 are each an alkyl group with 1 to 5 carbon atoms. , may be the same or different. ) A diacyloxy compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A dicarboxylic acid represented by the general formula (X^1 and X^3 in the formula are halogen atoms,
An alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or a cyclohexyl group, which may be the same or different, and X^2 and X^4 are each Hydrogen, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or a cyclohexyl group, which may be the same or different, and n is 0 or It is 1. ) is characterized by reacting with a diimide dicarboxylic acid precursor represented by (A) formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (B) general formula ▲ mathematical formula, There are chemical formulas, tables, etc. ▼ (Ar in the formula has the same meaning as above.) Repeating units represented by formula (C) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ , (D) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X^1, X^2, X^3, X^4, and n in the formula have the same meanings as above) A method for producing a novel copolymer having repeating units. 5. Diimide dicarboxylic acid represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. by preparing and reacting trimellitic anhydride with a diamine represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and a solvent. An acid precursor is formed, which is then converted into p-acyloxybenzoic acid represented by the general formula ▲Mathematical formula, chemical formula, table, etc.▼ and p-acyloxybenzoic acid represented by the general formula R^2COO-Ar-OCOR^3. and dicarboxylic acids represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (wherein, X^1, X^2, X^3, X^4, n, Ar,
R^1, R^2, and R^3 have the same meanings as above. ) The method for producing a novel copolymer according to claim 4, which comprises adding and reacting the copolymer.