JPH055027A - Production of wholly aromatic polyester - Google Patents

Abstract

PURPOSE:To produce a wholly aromatic polyester having excellent mechanical characteristics and heat resistance, etc., and capable of carrying out melt forming without causing corrosion of production apparatus due to by-products by using a specific raw material and preferably specific catalyst. CONSTITUTION:A compound expressed by the formula I (Ar<51> and Ar<52> are phenyl; Ar<52> is phenylene) is used as an aromatic dicarboxylic acid component and simultaneously (A) an aromatic oxycarboxylic acid (preferably parahydroxybenzoic acid) expressed by formula II (R is H or phenyl; Ar'' is divalent aromatic hydrocarbon group) and (B) aromatic diol (e.g. hydroquinone) expressed by formula III (Ar<21> is aromatic group) and or the component B and (C) 4,4'-dihydroxydiphenyl ether expressed by formula IV (Ar<31> is phenylene) or the components A, B and C are used and a tin compound expressed by formula V (R<1> to R<4> are alkyl or aryl; X<1> and X<2> are hydroxy, alkoxy or aryloxy) is preferably used as a catalyst to produce the objective wholly aromatic polyester.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing wholly aromatic polyester, and more particularly to a method for producing melt-moldable wholly aromatic polyester.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION AND PROBLEMS OF THE INVENTION A wholly aromatic polyester such as paraoxybenzoic acid polyester generally has excellent properties such as heat resistance, but tends to have poor melt moldability. Therefore, various attempts have been made to improve the properties of such wholly aromatic polyesters.

For example, JP-A-55-94930 discloses a method for producing an aromatic polyester by a bulk polymerization method. In this method, a three-step polymerization method is adopted in producing polyester.

That is, the following general formulas (II) and (II
Compounds represented by I) and (IV); General formula

[0005]

[Chemical 2]

(Wherein R ¹ is a hydrogen atom, a benzyl group, a lower alkyl group, or a phenyl group), a general formula

[0007]

[Chemical 3]

(Wherein R ² is a hydrogen atom, a benzyl group, a lower alkyl group, or a phenyl group), and the general formula

[0009]

[Chemical 4]

A compound selected from the group consisting of compounds represented by the formula: wherein X is --O--, --S0--, --S-- and --CO--, and m and n are integers of 0 or 1. Is used as a starting material and the general formula (I)

[0011]

[Chemical 5]

(Where p = 0, q = r = 3-60
0, when q = r = 0, p = 3 to 600, p + q + r = 3
~ 600, and m, n and X are as defined in the general formula (IV). In producing the aromatic polyester represented by the formula (1), a compound selected from the group of compounds represented by the general formulas (II), (III), and (IV) is reacted with an acid anhydride in the first-stage reaction tank. Then, an acetylation reaction is carried out to prepare a monomer, in which the by-produced acid is removed, and an oligomer is or is not formed from a part or all of the monomer, and then the reaction product of the first step is obtained. The reaction product is transferred to the second-stage reaction tank, where the monomers and / or oligomers are polycondensed in the second-stage reaction tank to form a prepolymer, and then the second-step reaction product is transferred to the third-stage reaction tank. The prepolymer is made to have a high molecular weight in the reaction tank at the stage.

As described above, in the method disclosed in JP-A-55-94930, an acid is produced as a by-product during the preparation of the monomer, but there is a problem that the acid produced as a by-product corrodes the production apparatus. Moreover, this method has a problem that the number of manufacturing steps is complicated.

Further, in JP-A-55-94930, for example, diphenyl terephthalate is mentioned as the compound represented by the formula (III), but such an example is not specifically described.

Further, Japanese Patent Application Laid-Open No. Sho 6 (1994) previously disclosed by the applicant of the present application.
JP-A-3-10624 contains a specific aromatic oxycarboxylic acid residue, an aromatic diol residue, a 4,4′-dihydroxydiphenyl ether residue and an aromatic dicarboxylic acid residue. Disclosed is a melt-moldable wholly aromatic polyester in which is contained in a specific ratio. This polyester was remarkably excellent in various properties such as heat resistance and mechanical strength such as bending strength.
However, it was found by the present inventors that when a wholly aromatic polyester is produced by the method described in the examples of this publication, acetic acid is by-produced and the acetic acid produced as a by-product corrodes the production equipment.

Therefore, as a result of intensive studies by the present inventors,
In a method for producing an aromatic polyester by a polycondensation reaction of a diaryl ester of an aromatic dicarboxylic acid and an aromatic dihydroxy compound, a specific tin compound is used as a catalyst, and more preferably a specific compound as the diaryl ester of the aromatic dicarboxylic acid. It has been proposed that an aromatic polyester having a high degree of polymerization, which is excellent in hue and the like, can be obtained by a simple process in a short time and has no side effects such as carboxylic acid by using Flat 2-606
84).

However, as a result of further diligent research, when a specific monomer component was used in combination with the specific aromatic dicarboxylic acid or its diaryl ester as described above, mechanical properties such as flexural modulus, heat resistance, and melting were obtained. It has been found that a wholly aromatic polyester having excellent moldability can be obtained, and the present invention has been completed.

[0018]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, in which by-products do not corrode the production apparatus, mechanical properties such as bending elastic modulus, and heat resistance. It is an object of the present invention to provide a method for producing a wholly aromatic polyester which is excellent in properties and can be melt-molded.

[0019]

SUMMARY OF THE INVENTION The method for producing a wholly aromatic polyester according to the present invention comprises the following compound (Y) and the following compound (Y) when an aromatic diol compound and an aromatic dicarboxylic acid are esterified to produce a wholly aromatic polyester: Using the compounds (A) and (B), or the following compound (Y)
Together with the following compounds (A) and (C), or together with the following compound (Y), the following compounds (A), (B) and (C)
It is characterized by using and. In the following formula ^{(Y) Ar 51 -OOC-Ar} 52 -COO-Ar 53 ··· (Y) ( wherein (Y), Ar ⁵¹ and Ar ⁵³ are each independently selected from among phenyl groups and hydrogen A group or atom, Ar ⁵² is a phenylene group, and Ar ⁵¹ , Ar ^53, and Ar ⁵² may have a substituent such as an alkyl group). The following formula (A) ROOC-Ar ¹¹ —OH (A) (In the formula (A), R is hydrogen or a phenyl group, and Ar
¹¹ is a divalent aromatic hydrocarbon group, and R or Ar ¹¹ may have a substituent such as an alkyl group). Formula (B) HO—Ar ²¹ —OH (B) (In the formula (B), Ar ²¹ is an aromatic group and may have a substituent such as an alkyl group). Aromatic diols. In the following formula ^{(C) HO-Ar 31 -O} -Ar 31 -OH ··· (C) ( formula (C), Ar ³¹ is a phenylene group, which may have a substituent such as an alkyl group ) 4,4'-dihydroxydiphenyl ether represented by

In the present invention, as the raw material, the compounds (A) and (B), the compounds (A) and (C), or the compounds (A) and (B) together with the carboxylic acid compound (Y) are used. Since (C) is used, a melt-moldable wholly aromatic polyester having excellent mechanical properties such as flexural modulus, tensile strength and impact strength, heat resistance and hydrolysis resistance is obtained. Tend.

Moreover, the compound produced as a by-product in the production process does not corrode the polyester production apparatus. Further, in a preferred embodiment of the present invention, when a wholly aromatic polyester is produced using the above raw materials, as a catalyst,
The following general formula [S]

[0022]

[Chemical 6]

(In the formula [S], R ^{1 to} R ⁴ represent an alkyl group or an aryl group, and X ¹ and X ² represent a hydroxy group, an alkoxy group or an aryloxy group, respectively). Is preferably used.

When such a tin compound is used, especially the initial reaction of the polymerization becomes a homogeneous reaction, the oligomerization and further the solid-state polymerization reaction easily proceed, and a polymer excellent in mechanical properties and the like tends to be obtained. There is.

[0025]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a wholly aromatic polyester according to the present invention will be specifically described below.

In the present invention, when the wholly aromatic polyester is produced by subjecting an aromatic diol compound and an aromatic dicarboxylic acid to an esterification reaction, the aromatic dicarboxylic acid is represented by the following formula (Y) Ar ⁵¹ —OOC-Ar. ⁵² —COO—Ar ⁵³ ... (Y) (In the formula (Y), Ar ⁵¹ and Ar ⁵³ are each independently a group or atom selected from a phenyl group and hydrogen, and Ar ⁵² is a phenylene group. And Ar ⁵¹ , Ar ⁵³ and Ar ⁵² may have a substituent such as an alkyl group)
A carboxylic acid compound represented by

Specific examples of the carboxylic acid compound (Y) include terephthalic acid, 4,4'-dicarboxydiphenyl ether, 3,4'-dicarboxydiphenyl ether, 4,4'-
Dicarboxydiphenyl, isophthalic acid, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene, diphenyl terephthalate, phenyl terephthalate, diphenyl isophthalate, diphenyl (4,4'-dicarboxydiphenyl), diphenyl (3,4 '-Dicarboxydiphenyl), diphenyl [bis (4-carboxyphenyl) ether], diphenyl [bis (4-carboxyphenyl)
Methane], diphenyl [2,2-bis (4-carboxyphenyl) propane], diphenyl [bis (4-carboxyphenyl) ketone], diphenyl [bis (4-carboxyphenyl) sulfone], diphenyl-1,4-naphthalene dicarboxylic Acid, diphenyl 1,5-naphthalene dicarboxylic acid, diphenyl 1,6-naphthalene dicarboxylic acid, diphenyl 1,7-naphthalene dicarboxylic acid, diphenyl 2,7-naphthalene dicarboxylic acid, and the like.

Among these carboxylic acid compounds, terephthalic acid, diphenyl terephthalate, diphenyl 1,
6-naphthalenedicarboxylic acid is preferably used. Such carboxylic acid compounds may be used alone or in combination of two or more. In the present invention, since such a carboxylic acid compound is used when the wholly aromatic polyester is produced, a compound such as acetic acid that corrodes the production apparatus is not by-produced. In particular, when terephthalic acid or diphenyl terephthalate is used as the carboxylic acid compound, it tends to be an aromatic polyester having excellent mechanical properties such as flexural modulus, excellent heat resistance, and good melt moldability.

In the present invention, when forming a wholly aromatic polyester, together with the carboxylic acid compound (Y),
At least the following compounds (A) and (B), the following compounds (A) and (C) or the following compounds (A), (B) and (C) are used.

That is, the following formula (A) ROOC-Ar ¹¹ --OH (A) (In the formula (A), R is hydrogen or a phenyl group, and Ar
¹¹ is a divalent aromatic hydrocarbon group, R or Ar ¹¹ may have a substituent such as an alkyl group), and an aromatic oxycarboxylic acid represented by

Examples of the aromatic oxycarboxylic acid represented by the above formula (A) include p-oxybenzoic acid, m-oxybenzoic acid, 6-oxy-2-naphthoic acid and the like. In the present invention, such an ester derived from an aromatic oxycarboxylic acid can also be used. Examples of such a compound include an ester having an ester bond formed in the oxy group of these aromatic oxycarboxylic acids, for example, a lower alkanoyl ester having 2 to 6 carbon atoms, a benzoyl ester, or a carboxyl group of these aromatic oxycarboxylic acids. In the above, an ester bond-forming ester, for example, a lower alkyl ester having 2 to 6 carbon atoms, phenyl ester, benzoyl ester and the like can be mentioned. Among such compounds, para-hydroxybenzoic acid, 6-oxy-2-naphthoic acid and the like are preferably used.

In the above formula (A), phenyl parahydroxybenzoate in which R and A ¹¹ are phenyl groups can be obtained, for example, by reacting parahydroxybenzoic acid with diphenyl carbonate. Formula (B) HO-Ar ²¹ -OH (B) (In the formula (B), Ar ²¹ is an aromatic group, preferably a divalent group such as p-phenylene group or 4,4′-diphenylene group. , Which may have a substituent such as an alkyl group), and an aromatic diol represented by

Examples of the aromatic diol represented by the above (B) include hydroquinone and 4,4'-dihydroxydiphenyl. A compound derived from an aromatic diol, for example, a lower alkanoyl ester having 2 to 6 carbon atoms or a benzoyl ester can also be used.

Examples of diols other than the above include, for example, resorcin, 3,4'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 3,4'-dihydroxydiphenyl ether, phenylhydroquinone, chlorohydroquinone, methylhydroquinone, 2,2. An aromatic diol having 6 to 15 carbon atoms such as -bis (4-hydroxyphenyl) propane can be mentioned as a preferable compound.

Examples of derivatives of these diols include lower alkanoyl esters or benzoyl esters having 1 to 6 carbon atoms. Among these compounds, hydroquinone and 4,4′-dihydroxydiphenyl are preferably used.

Further, the following formula (C) HO—Ar ³¹ —O—Ar ³¹ —OH (C) (In the formula (C), Ar ³¹ is a phenylene group and has a substituent such as an alkyl group. 4,4'-dihydroxydiphenyl ether represented by the formula (4) may be used.

A compound derived from 4,4'-dihydroxydiphenyl ether can also be used, and such a compound is represented by, for example, the above formula (C).
Examples thereof include lower alkanoyl ester having 2 to 6 carbon atoms or benzoyl ester derived from 4,4′-dihydroxydiphenyl ether. Among such compounds, 4,4'-dihydroxydiphenyl ether is preferably used.

In the present invention, the wholly aromatic polyester is produced by using the above-mentioned raw materials. When the wholly aromatic polyester is produced in this manner, a catalyst represented by the following general formula [S] may be used as a catalyst if necessary.

[0039]

[Chemical 7]

A tin compound represented by the following, or a hydroxide of an alkali or alkaline earth metal such as potassium hydroxide, lithium hydroxide or sodium hydroxide can be used.

However, in the formula [S], R _{1 to} R ₄ each independently represent an alkyl group or an aryl group, and X ₁ and X
_2's each independently represent a hydroxy group, an alkoxy group or an aryloxy group.

Specific examples of the tin compound represented by the above formula [S] include the following compounds.

[0043]

[Chemical 8]

[0044]

[Chemical 9]

Etc. These catalysts can be used alone or in combination of two or more. Among these catalysts, it is desirable to use a tin compound.

[0046]

[Chemical 10]

When the tin compound represented by the formula (3) is used, especially the initial reaction becomes a homogeneous reaction, and the oligomerization, and further the solid-phase polymerization reaction easily proceeds, so that a copolymer having excellent mechanical properties tends to be obtained.

In the present invention, such a raw material and, if necessary, the above catalyst, particularly {(C ₄ H ₉ ) ₂ -Sn-O-
A wholly aromatic polyester can be produced, for example, in two steps using a tin compound represented by (phenylene)} ₂ O.

That is, in the first step, the above-mentioned raw material, that is, the carboxylic acid compound (Y) and, if necessary, the above-mentioned compounds (A) to (C) are usually added in the range of 180 to 300.
C., preferably at a temperature of 200 to 250.degree. C., and reacted for 3 to 20 hours, preferably 5 to 10 hours, and further the reaction contents are 200 to 400.degree. C., preferably 250 to 350.
0.1-10 hours at a temperature of ℃, if necessary under reduced pressure,
The reaction is preferably carried out for 0.5 to 5 hours to give an intrinsic viscosity [η] (measured in pentafluorophenol at 60 ° C) of 4.0 dl / g or less, preferably 0.2 to 3.0 dl /.
g, more preferably 0.3 to 2.0 dl / g,
Melting temperature Tm ₁ (first endothermic peak of temperature rise) is 200-4
An oligomer is formed which is at 50 ° C, preferably 250-400 ° C.

When carrying out the above reaction, for example, the carboxylic acid compound (Y) is used in an amount of 10 to 35 mol%, preferably 15 to 30 mol% in 100 mol% of the raw material monomer, and the aromatic compound is used. Oxycarboxylic acid (A) 30-80
The amount of the aromatic diol (B) is 1 to 20 mol%, preferably 3 to 16 mol%, and the amount of 4,4′-dihydroxydiphenyl ether (C) is 1 mol%. It is desirable to use in an amount of ˜32 mol%, preferably 3 to 25 mol%.

When the above raw materials are used in the amounts as described above,
In particular, a melt-moldable wholly aromatic polyester having excellent mechanical properties such as flexural modulus, tensile strength and impact resistance, heat resistance and hydrolysis resistance tends to be obtained.

In the present invention, the amount of the catalyst used is not particularly limited, but usually 0.001 to 5 parts by weight, preferably 0.01 to 0.
Used in an amount of 5 parts by weight. When the catalyst is used in such an amount, especially the initial reaction becomes a homogeneous reaction, and it tends to be easy to increase the molecular weight of the produced oligomer and copolymer.

Then, in the second step, the oligomer obtained in the first step is taken out of the reactor and transferred to a polymerization vessel such as an oven for solid-state polymerization to be co-condensed by a polymerization reaction, preferably a solid-state polymerization reaction. Preferably. The solid phase polymerization reaction is usually performed at a temperature of about 30 to 100 ° C. lower than the melting point of the wholly aromatic polyester (copolymer) obtained, preferably about 40 to 60 ° C. and 100 to 250-Nl.
/ MinN ₂ under a flow of 0.5 to 40 hours, preferably 1 to 15 hours. In this way, when the solid phase polymerization reaction is carried out, the intrinsic viscosity [η] (measured in pentafluorophenol at 60 ° C) is 7.0 dl / g or less, preferably 3.0 to 6.0 dl / g, and more preferably Is from 2.5
It is 5.0 dl / g and the melting temperature Tm ₁ (endothermic peak of the first temperature rise) is 200 to 450 ° C., preferably 250 to 4
A wholly aromatic polyester such as in the range of 00 ° C. is obtained.

In 100 mol% of the wholly aromatic polyester thus obtained, a component unit derived from the carboxylic acid compound (Y), for example, a terephthalic acid component component unit is 10 to 35 mol%, preferably 15 The amount of the aromatic diol (B) is 30 to 80 mol%, preferably 30 to 80 mol%, more preferably 50 to 70 mol% of the component unit derived from the aromatic oxycarboxylic acid (A). The amount of the constituent unit derived from 4,4'-dihydroxydiphenyl ether (C) is 1 to 20 mol%, preferably 3 to 16 mol%.
It is desirable that it is contained in an amount of 2 mol%, preferably 3 to 25 mol%.

The wholly aromatic polyester obtained by the method of the present invention preferably has a melt viscosity of usually 10 when measured at a temperature 30 ° C. higher than the melting point of the wholly aromatic polyester and a shear rate of 100 sec ^{−1. 2} to 10 ⁷ poise, preferably 2 × 10 ² to 10 ⁵ poise, preferably 5
× 10 ² to 10 ⁵ poise is shown.

When it is difficult to measure the melting point of this wholly aromatic polyester, the same melting viscosity range as above can be defined by using the softening point as an index instead of the above melting point.

The wholly aromatic polyester obtained by the method of the present invention is preferably substantially linear.
Further, at the end of this polymer, for example, the above residue (A) to
Either (C) or (Y) may be located. Also,
The obtained polymer has its terminal carboxyl group esterified with a monovalent lower alcohol such as methanol, ethanol or isopropanol or a monovalent aromatic hydroxy compound such as phenol or cresol by a conventional method. Also, the terminal hydroxyl group may be one such as acetic acid, propionic acid, benzoic acid.
It may be esterified with a divalent carboxylic acid.

The glass transition temperature (Tg) of the wholly aromatic polyester obtained by the present invention is usually not detected by a differential scanning calorimeter (DSC), and the melting point (Tm) measured by DSC is usually 200 to 450 ° C. Preferably 250
It is in the range of to 400 ° C.

The wholly aromatic polyester obtained by the present invention has excellent heat resistance and mechanical strength such as flexural modulus, tensile strength and impact strength, excellent heat resistance and high temperature hydrolysis resistance, and further has melt moldability. Therefore, various molded products or fibers can be manufactured by utilizing such characteristics.

[0060]

INDUSTRIAL APPLICABILITY In the present invention, when the wholly aromatic polyester is produced by subjecting an aromatic diol compound and an aromatic dicarboxylic acid to an esterification reaction to produce a wholly aromatic polyester, a carboxylic acid such as acetic acid is used. No acid is by-produced and the production equipment is not corroded.

In particular, if the wholly aromatic polyester is produced by the two-step process as described above, the wholly aromatic polyester can be obtained by a simple process. The wholly aromatic polyester obtained is excellent in mechanical properties such as bending elasticity, heat resistance, and the like, and can be melt-molded.

Hereinafter, the method for producing the wholly aromatic polyester according to the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

[0063]

EXAMPLES The performance evaluation of the aromatic copolyester was carried out according to the following method. Tg, Tm: Differential scanning calorimeter (D
SC type II), a sample amount of about 10 mg of aromatic polyester is heated from 50 ° C. to 450 ° C. at a rate of 20 ° C./min, then lowered to 50 ° C. at 20 ° C./min, and again 450 ° C. The temperature was raised up to 20 ° C./min and the endothermic thermogram was measured. The melting point Tm (° C.) was determined from the endothermic peak values at the first and second temperature increases, and the glass transition point Tg (° C.) was determined from the value at the second temperature increase (first inflection point).

Melt viscosity: Measured at a shear rate of 100 sec ^-1 using a capillary type rheometer manufactured by Shimadzu Corporation. However, the measurement was performed at a temperature 30 ° C. higher than the melting point (Tm) of the second temperature increase. <Conditions for measuring physical properties of LCP>・Preparation and installation of sample : Plunger type small injection molding machine (TU-05) manufactured by Toyo Kikai Kinzoku Co., Ltd. Screw diameter: 20mm Clamping force: 5.0ton Injection amount: ~ 3.0cm ³ Barrel temperature: MAX.450 ℃ Mold temperature: MAX.250 ℃ ・ Shape: Rectangular test piece (L = 100, W = 5.0, T = 1.0mm) ・ Molding temperature: 320 to 400 ℃ ・Bending test・ ASTM Complies with D790-84a However, span distance: 32.0mm Deformation temperature: t / 2mm / min (t =
Sample thickness) ・ Device: Instron universal testing machine ・ Test material: Injection test piece (100 * 5 * 1mm) ・T-HDT test (Tensile Heat Distortion Temperat)
ure)・ Compliant with ASTM D1637 However, load: 3.45Kg / cm ² Temperature rising rate: 2.0 ℃ / min Chuck distance: 70mm 2.0% Elongation temperature is T-HDT.

-Device: Testing machine manufactured by our company-Test material: Injection test piece (100 * 5 * 1mm)

[0066]

Example 1 In a reactor having a capacity of 2 liter equipped with a stirrer, a nitrogen inlet, a distillation outlet and a bottom oligomer outlet, para-hydroxybenzoic acid 338.1 g (2.45 mol) and biphenol 32.6 g (0 175 mol), 4,
70.7 g of 4'-dihydroxydiphenyl ether (0.
35 mol), diphenyl terephthalate 167.0 g
(0.525 mol), diphenyl carbonate 576.
7 g (2.695 mol) and as catalyst

[0067]

[Chemical 11]

The compound represented by the formula: 0.654 g (0.9
(8 × 10 ⁻³ mol) was charged and the content was heated to 190 ° C. and stirred at 190 ° C. for 1 hour. Subsequently, the temperature was raised to 225 ° C and the reaction was carried out at 225 ° C for 8 hours. During this period, carbon dioxide and phenol were distilled off with the formation of phenyl parahydroxybenzoate, and the content became a transparent homogeneous solution.
After that, it takes 2 hours to raise the temperature to 300 ° C and increase to 300 ° C.
Held for 3 hours.

Further, the pressure in the reaction system was reduced to 1 mmHg over 30 minutes, and the pressure was 1 mmHg at a temperature of 300 ° C. under stirring.
The reaction was carried out for 0.5 hours. The reaction content (oligomer) was extracted at 300 ° C. in the form of flakes from the bottom outlet in about 10 minutes.

The intrinsic viscosity [η] of the oligomer is 1.06.
(Dl / g) [value measured at 60 ° C. in pentafluorophenol]. The oligomer was put into an oven for atmospheric pressure solid-state polymerization in the form of particles of 30 mesh or less with a Willey crusher, heated to 270 ° C. in a nitrogen stream at 200 Nl / min (standard state equivalent amount) for 5 hours. Solid phase polymerization reaction was carried out at that temperature for 3 hours to obtain a copolyester.

Although the copolyester had a lacgan shape, it could be easily loosened into particles before solid phase polymerization without being firmly fused. Intrinsic viscosity of the copolyester [η]
Was 3.38 (dl / g), and Tm ₁ measured by DSC was 322 ° C.

The flexural modulus of the copolyester by injection molding was 153 × 10 ³ Kg / cm ² , and the flexural strength was 1.
790 Kg / cm ² , and T-HDT was 258 ° C.

[0073]

Comparative Example 1 An oligomer was synthesized in the same manner as in Example 1 except that the Sn catalyst was not used.

At the final stage of oligomerization, the content was a homogeneous melt, and the intrinsic viscosity [η] of the oligomer was 0.65.
(Dl / g). Further, the oligomer was subjected to solid phase polymerization according to Example 1 to obtain a copolymer, but there was a substance insoluble in pentafluorophenol, and its intrinsic viscosity [η] could not be measured.

[0075]

Example 2 In Example 1, as the amount of monomer and the catalyst shown in Table 1,

[0076]

[Chemical formula 12]

0.80 g of the compound represented by
10 ⁻³ mol) was charged. Same as Example 1 except that the final conditions for oligomerization and final conditions for polymerization were changed as shown in Table 2. The apparent properties of the oligomer and copolymer were the same as in Example 1.

[0078]

Example 3 The catalyst, the catalyst amount and the monomer amount shown in Table 1 in Example 1 were charged and the content was heated to 190 ° C. and stirred at 190 ° C. for 1 hour. Subsequently, the temperature was raised to 225 ° C and the reaction was carried out at 225 ° C for 8 hours. During this period, carbon dioxide and phenol were distilled off with the formation of phenyl parahydroxybenzoate, and the content became a transparent homogeneous solution.
Then, the temperature was raised to 310 ° C. over 2 hours, and the reaction was carried out at a temperature of 310 ° C. for 4 hours with stirring under normal pressure.

The intrinsic viscosity [η] of the oligomer is 0.23.
(Dl / g) [value measured at 60 ° C. in pentafluorophenol]. The oligomer was put into a normal pressure solid-state polymerization oven in the form of particles of 30 mesh or less with a Willey crusher and heated to 260 ° C. under a nitrogen stream of 200 Nl / min (standard state conversion amount) for 5 hours. A solid-state polymerization reaction was carried out at that temperature for 16 hours to obtain a copolyester.

The copolyester had a lacgan shape, but could be easily loosened into particles before solid phase polymerization without being firmly fused. Intrinsic viscosity of the copolyester [η]
Is 3.65 (dl / g) and Tm by DSC measurement
₁ was 321 ° C.

The physical properties of the oligomer and polymer are
Shown in the table.

[0082]

Example 4 The catalyst amount of the catalyst in Example 1 and the amount of monomers shown in Table 1 were charged, the content was heated to 190 ° C. and stirred at 190 ° C. for 1 hour. Subsequently, the temperature was raised to 225 ° C and the reaction was carried out at 225 ° C for 8 hours. During this period, carbon dioxide and phenol were distilled off with the formation of phenyl parahydroxybenzoate, and the content became a transparent homogeneous solution.
Then, the temperature was raised to 350 ° C. over 2 hours, and the reaction was carried out at 350 ° C. for 1.0 hour under normal pressure with stirring.

The intrinsic viscosity [η] of the oligomer was 0.66.
(Dl / g) [value measured at 60 ° C. in pentafluorophenol]. Same as Example 1 except that the final polymerization conditions were changed as shown in Table 2.

Table 2 shows the physical properties of the oligomers and copolymers.

[0085]

Example 5 In a reactor having a capacity of 2 liter equipped with a stirrer, a nitrogen inlet, a distillation outlet and a bottom oligomer outlet, para-hydroxybenzoic acid 338.1 g (2.45 mol) and biphenol 32.6 g (0. 175 mol), 4,
70.7 g of 4'-dihydroxydiphenyl ether (0.
35 mol), terephthalic acid 87.2 g (0.525 mol), diphenyl carbonate 913.8 g (4.27)
Mol) and as a catalyst

[0086]

[Chemical 13]

The compound represented by the formula: 0.654 g (0.9
(8 × 10 ⁻³ mol) was charged and the content was heated to 190 ° C. and stirred at 190 ° C. for 1 hour. Then, the temperature was raised to 225 ° C. and the reaction was carried out at 225 ° C. for 10 hours. During this period, carbon dioxide and phenol were distilled off with the formation of phenyl parahydroxybenzoate, and the content became a transparent homogeneous solution. After that, it took 2 hours to raise the temperature to 300 ° C and
Hold at 0 ° C. for 3 hours.

The pressure in the reaction system was further reduced to 1 mmHg in 30 minutes, and the pressure was 1 mmHg at 300 ° C. under stirring.
Then, the reaction was performed for 0.5 hours. The reaction content (oligomer) was about 10 in the form of flakes from the bottom outlet at 300 ° C.
I took it out in minutes.

The intrinsic viscosity [η] of the oligomer was 0.48.
(Dl / g) [value measured at 60 ° C. in pentafluorophenol]. The oligomer was subjected to solid phase polymerization reaction at 270 ° C. for 3 hours according to Example 1 to obtain a copolyester.

The physical properties of the copolymer are shown in Table 2.

[0091]

Comparative Example 2 An oligomer was synthesized in the same manner as in Example 5 except that the Sn catalyst was not used.

At the final stage of oligomerization, the content was a homogeneous melt, and the intrinsic viscosity [η] of the oligomer was 0.47.
(Dl / g). Further, the oligomer was subjected to solid-phase polymerization according to Example 1 to obtain a copolymer, but there was a substance insoluble in pentafluorophenol, and the intrinsic viscosity [η] of the copolymer could not be measured.

[0093]

Example 6 87.2 g (0.525 mol) of terephthalic acid and 337.1 g (1.575 of diphenyl carbonate) were placed in a 2 liter reactor equipped with a stirrer, a nitrogen inlet, a distillation outlet and a bottom oligomer outlet. Mol) and as a catalyst

[0094]

[Chemical 14]

The compound represented by the formula: 0.654 g (0.9
(8 × 10 ⁻³ mol) was charged and the content was heated to 200 ° C. and stirred at 200 ° C. for 1 hour. Subsequently, the temperature was raised to 300 ° C. over 1 hour, and the reaction was carried out at 300 ° C. for 2 hours. During this period, carbon dioxide and phenol were distilled off with the formation of diphenyl terephthalate, and the content became a transparent homogeneous solution. After cooling the contents, p-hydroxybenzoic acid 338.1 g (2.45 mol) and biphenol 3 were added to the reactor.
2.6 g (0.175 mol), 4,4'-dihydroxydiphenyl ether 70.7 g (0.35 mol) and diphenyl carbonate 576.7 g (2.695 mol) were charged, and the content was heated to 190 ° C. And stirred at 190 ° C. for 1 hour. Subsequently, the temperature was raised to 225 ° C and the reaction was carried out at 225 ° C for 8 hours. During this period, carbon dioxide and phenol were distilled off with the formation of phenyl parahydroxybenzoate, and the content became a transparent homogeneous solution. Then, the temperature was raised to 300 ° C. over 2 hours, and the temperature was maintained at 300 ° C. for 3 hours.

The pressure in the reaction system was further reduced to 1 mmHg in 30 minutes, and the pressure was 1 mmHg at 300 ° C. under stirring.
Then, the reaction was performed for 0.5 hours. The reaction content (oligomer) was about 10 in the form of flakes from the bottom outlet at 300 ° C.
I took it out in minutes.

The intrinsic viscosity [η] of the oligomer was 0.68.
(Dl / g) [value measured at 60 ° C. in pentafluorophenol]. The oligomer was subjected to solid phase polymerization reaction at 270 ° C. for 5 hours according to Example 1 to obtain a copolymer.

Physical properties of the copolymer are shown in Table 2. In the table, POB is para-hydroxybenzoic acid, BP is biphenol, HQ is hydroquinone, and DHPE is 4,4'-.
Dihydroxyphenyl ether, TA is terephthalic acid,
DPT represents diphenyl terephthalate, and DPC represents diphenyl carbonate.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

[Table 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Kazu Takimoto, No. 6, 1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (1)

Claims: 1. When a wholly aromatic polyester is produced by subjecting an aromatic diol compound and an aromatic dicarboxylic acid to an esterification reaction to produce a wholly aromatic polyester, the following compound (A) and ( B), the following compounds (A) and (C) or the following compounds (A), (B) and (C) are used: A process for producing a wholly aromatic polyester. In the following formula ^{(Y) Ar 51 -OOC-Ar} 52 -COO-Ar 53 ··· (Y) ( wherein (Y), Ar ⁵¹ and Ar ⁵³ are each independently selected from among phenyl groups and hydrogen A group or atom, Ar ⁵² is a phenylene group, and Ar ⁵¹ , Ar ^53, and Ar ⁵² may have a substituent such as an alkyl group). The following formula (A) ROOC-Ar ¹¹ —OH (A) (In the formula (A), R is hydrogen or a phenyl group, and Ar
¹¹ is a divalent aromatic hydrocarbon group, and R or Ar ¹¹ may have a substituent such as an alkyl group). Formula (B) HO—Ar ²¹ —OH (B) (In the formula (B), Ar ²¹ is an aromatic group and may have a substituent such as an alkyl group). Aromatic diols. In the following formula ^{(C) HO-Ar 31 -O} -Ar 31 -OH ··· (C) ( formula (C), Ar ³¹ is a phenylene group, which may have a substituent such as an alkyl group ) 4,4'-dihydroxydiphenyl ether represented by 2. When a wholly aromatic polyester is produced, a catalyst represented by the following general formula [S] (In the formula [S], R ^{1 to} R ⁴ are an alkyl group or an aryl group, and X ¹ and X ² are a hydroxy group, an alkoxy group, or an aryloxy group, respectively). The method for producing a wholly aromatic polyester according to claim 1.