JPH05140281A - Production of thermotropic liquid crystalline polyester - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] A uniform liquid crystalline polyester that can contain a large amount of structural units of hydroxyaromatic carboxylic acid typified by paraacetoxybenzoic acid, has excellent heat resistance and fluidity, and is simple And the method of manufacturing continuously is provided. [Structure] A reaction product obtained by reacting a hydroxyaromatic carboxylic acid ester of the formula [I] with a diol of the formula [II] in the presence of an organometallic compound catalyst is added to an aromatic dicarboxylic acid of the formula [III]. And a hydroxyaromatic carboxylic acid of the formula [IV] and an aliphatic carboxylic acid anhydride for acyloxylation, and then an alcohol of the formula [V] for polycondensation. Method for producing liquid crystalline polyester. (In the formula, Ar ¹ , Ar ² and Ar ³ are C _6-18 aromatic hydrocarbon groups, R ¹ , X ¹ and X ² are aliphatic hydrocarbon groups, etc.)

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a thermotropic liquid crystalline polyester (hereinafter referred to as a liquid crystalline polyester). The liquid crystalline polyester produced according to the present invention has excellent heat resistance and excellent fluidity and uniformity.

[0002]

2. Description of the Related Art In recent years, with the development of electric / electronic fields and automobile fields, demands for higher performance of plastics have increased, and many plastics have been developed and provided to the market. Among them, a group of polymer compounds that exhibit optical anisotropy when melted and whose molecular chains are arranged in parallel are called thermotropic liquid crystalline polymers, which are excellent in moldability and improve the mechanical properties of the molded body. It's getting a lot of attention.

A typical example of the liquid crystalline polyester is a copolyester having only an ester bond of a polyethylene terephthalate unit and a parahydroxybenzoic acid unit (WJ Jackson et al., Journal of Polymer Scien.
ce Polymer Chemical Edition Volume 14, Pages 2043 (1976
), U.S. Pat. No. 3,804,805, JP-A-51
-8395 gazette etc.).

In the above-mentioned Japanese Patent Laid-Open No. 51-8395, a polyethylene terephthalate unit and paraacetoxybenzoic acid (hereinafter referred to as p-ABA) are mixed to give 24
A method for producing a liquid crystalline polyester by polymerizing by heating at 0 to 300 ° C. is described. p-AB
It is known that increasing the content of the component A improves the heat resistance of the liquid crystalline polyester.
-When the ABA component is 75 mol% or more of the total aromatic groups in the polymer, the polymer considered to be produced by the block-polymerization of p-ABA is mixed as an insoluble and infusible foreign substance (Comparative Example 1), The resulting liquid crystalline polyester has a problem that the fluidity is deteriorated and the moldability is deteriorated.
This generation of foreign matter can be inferred from the fact that a large amount of insoluble substance is present when dissolved in a good solvent for this type of polymer and at the flow initiation temperature.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is p-
An object of the present invention is to provide a method for simply and continuously producing a uniform liquid crystalline polyester which can contain a large amount of structural units of hydroxyaromatic carboxylic acid represented by ABA, has excellent heat resistance and fluidity.

[0006]

According to the present invention, a hydroxyaromatic carboxylic acid ester represented by the following general formula [I] and a diol represented by the following general formula [II] are reacted in the presence of an organometallic compound catalyst. An aromatic dicarboxylic acid represented by the following general formula [III], a hydroxyaromatic carboxylic acid represented by the following general formula [IV], and an aliphatic carboxylic acid anhydride are added to the reaction product thus obtained. After acyloxylation, the following general formula [V]
The method for producing a thermotropic liquid crystalline polyester is characterized in that an alcohol represented by the formula (1) is added and polycondensed.

[0007]

[Chemical 2]

(In the formula, Ar ¹ , Ar ² and Ar ³ are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ¹
Is a saturated aliphatic hydrocarbon group having 1 to 15 carbon atoms, and X ¹
Is a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms or a phenyl group, and X ² is a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms or an arylene group.) Ar ¹ , Ar ² and Ar ³ are Each independently has 6 to 18 carbon atoms
An aromatic hydrocarbon group of, specifically, phenylene group, naphthylene group, biphenylene group, anthrylene group,
Terphenylene group and the like, these are alkyl groups,
It may have an alkoxyl group, a phenyl group, a halogen atom or the like as a substituent.

R ¹ is a saturated aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, Nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, which may be linear or cyclic, or may have a branched chain.

X ¹ is a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms or a phenyl group, and examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. However, it may be linear or cyclic, and may have a branched chain. X ² has 1 carbon
-10 is a saturated aliphatic hydrocarbon group or arylene group, the saturated aliphatic hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Heptyl group, octyl group, nonyl group, decyl group,
It may be linear or cyclic, and may have a branched chain. Examples of the arylene group include a benzyl group and a β-phenylethyl group.

Raw material hydroxyaromatic carboxylic acid ester The hydroxyaromatic carboxylic acid ester represented by the general formula [I] is an alkyl ester or phenyl ester of the hydroxyaromatic carboxylic acid represented by the general formula [IV] described below. The position of the hydroxyl group may be any of ortho, meta and para, but is preferably the para position. As a specific example, methyl 4-hydroxybenzoate,
Ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, pentyl 4-hydroxybenzoate, hexyl 4-hydroxybenzoate, methyl 3-hydroxybenzoate, methyl 2-hydroxybenzoate, 2 -Methyl hydroxy-6-naphthoate, ethyl 2-hydroxy-6-naphthoate, propyl 2-hydroxy-6-naphthoate, 2-hydroxy-6
-Butyl naphthoate, pentyl 2-hydroxy-6-naphthoate, hexyl 2-hydroxy-6-naphthoate,
Methyl 1-hydroxy-4-naphthoate, methyl 1-hydroxy-5-naphthoate, methyl 1-hydroxy-6-naphthoate, methyl 2-hydroxy-7-naphthoate, 4-hydroxy-4′-biphenylcarboxylic acid Methyl, ethyl 4-hydroxy-4′-biphenylcarboxylate, propyl 4-hydroxy-4′-biphenylcarboxylate, butyl 4-hydroxy-4′-biphenylcarboxylate, pentyl 4-hydroxy-4′-biphenylcarboxylate, Hexyl 4-hydroxy-4'-biphenylcarboxylate, methyl 3-hydroxy-4'-biphenylcarboxylate, methyl 2-hydroxy-4'-biphenylcarboxylate, methyl 4-hydroxy-3'-biphenylcarboxylate, 4 -Methyl hydroxy-2'-biphenylcarboxylate and the like.

Specific examples of the diol represented by the general formula [II] include:
Ethylene glycol, 1,2-propanediol, 1,
3-propanediol, 1,2-butanediol, 1,
3-butanediol, 1,4-butanediol, 2,3
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,7-heptanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
Chain diols such as 10-decanediol and 1,4-
Examples thereof include alicyclic diols such as cyclohexanedimethanol and tricyclodecanedimethanol.

Aromatic Dicarboxylic Acid Specific examples of the aromatic dicarboxylic acid represented by the general formula [III] include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 1,8. -Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4 "-terphenylenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 1,5-
Examples thereof include anthracene dicarboxylic acid and 9,10-anthracene dicarboxylic acid.

Hydroxyaromatic Carboxylic Acid The position of the hydroxyl group of the hydroxyaromatic carboxylic acid represented by the general formula [IV] may be ortho, meta or para, but the para position is particularly preferred. Specific examples include 4-hydroxybenzoic acid and 2-hydroxy-
6-naphthoic acid, 4-hydroxy-4′-biphenylcarboxylic acid and the like can be mentioned. Aliphatic Carboxylic Anhydride Specific examples of the aliphatic carboxylic acid anhydride used as the esterifying agent include acetic anhydride, propionic anhydride, butyric anhydride and the like.

Alcohol Specific examples of the alcohol represented by the general formula [V] include:
Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, pentanol, hexanol, heptanol,
Octanol, nonanol, decanol, cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, benzyl alcohol and the like can be mentioned.

Production of Liquid Crystalline Polyester In the present invention, the reaction product obtained by reacting [1] a hydroxyaromatic carboxylic acid ester and a diol in the presence of an organometallic compound catalyst, [2] an aromatic dicarboxylic acid And a hydroxyaromatic carboxylic acid and an aliphatic carboxylic acid anhydride are added for acyloxylation, and then [3] alcohol is further added for polycondensation, thereby producing a thermotropic liquid crystalline polyester. is there.

[1] Transesterification reaction This reaction is carried out by charging a starting material hydroxyaromatic carboxylic acid ester and a diol, further adding an organometallic compound catalyst, and heating. The molar ratio of the hydroxy aromatic carboxylic acid ester and the diol is /=0.1 to 2.0, preferably 0.5 to 2.
It is 0. As the organometallic compound catalyst, an organotitanium compound having an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or an aryl group as an organic group, an organoaluminum compound,
Examples thereof include organic tin compounds, organic magnesium compounds, organic lead compounds, and aluminates.

As an example of the organic titanium compound, tetra-
Examples thereof include n-butyl titanate, tetraisopropoxide titanate, titanium butoxide, tetra-2-ethylhexyl titanate and the like. Examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, diethylaluminum chloride and the like. Examples of the organic tin compound include di-n-butyltin oxide, di-n-butyltin dilaurate, di-n-butyltin diacetate and the like.

Examples of the organic magnesium compound include methyl magnesium chloride, ethyl magnesium chloride, propyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide,
Propyl magnesium bromide etc. are mentioned. Examples of organic lead compounds include tetraethyl lead, tetrapropyl lead, tetrabutyl lead and the like. Examples of the aluminate include calcium aluminate, barium aluminate, beryllium aluminate, strontium aluminate and the like. The catalyst amount is 0.001 with respect to the raw materials (the total of hydroxyaromatic carboxylic acid ester and diol).
10 to 10% by weight, preferably 0.05 to 1% by weight.
Among these, organic titanium compounds and organic tin compounds are preferable in terms of reaction activity.

The reaction temperature is 150 to 275 ° C, preferably 200 to 250 ° C. Reaction pressure is 0.01mmH
It is in the range of g to 10 atm. Although the reaction time varies depending on the reaction temperature and the like, for example, the reaction temperature is 200 to 250 ° C.
In the case of, it is about 5 to 12 hours. Incidentally, this reaction is preferably carried out under an inert gas stream. Nitrogen, argon or the like can be used as the inert gas, and it is preferable to continuously introduce it into the system.

As the transesterification reaction proceeds, an alcohol represented by the following general formula [VI] is produced as a by-product. X ¹ —OH [VI] The theoretical amount of this by-produced alcohol and the excess amount of diol must be distilled out of the system when the reaction is carried out in excess of diol, and in terms of reaction time and the like. However, in the latter half of the reaction, it is preferable to carry out the reaction under reduced pressure. Specifically, in the latter half of the reaction, the reaction is performed at a vacuum degree of 1 mmHg or less for about 1 to 6 hours. The transesterification reaction is completed by distilling off by-produced alcohol and excess diol to the outside of the theoretical amount system.

[2] Acyloxylation Reaction Following the above transesterification reaction, an aromatic dicarboxylic acid, a hydroxyaromatic carboxylic acid, and an aliphatic carboxylic acid anhydride are added to the reaction product and heated to reflux. Acylate the hydroxy end of the reaction product and hydroxyaromatic carboxylic acid.

The amount of the aromatic dicarboxylic acid compound used is
The molar ratio to the hydroxyaromatic carboxylic acid ester is /=0.9 to 1.1, preferably 0.9.
It is in the range of 5 to 1.05. The amount of hydroxyaromatic carboxylic acid used is in the range of 0.05 to 10 mol times that of the hydroxyaromatic carboxylic acid ester.

The amount of the aliphatic carboxylic acid anhydride used is 1.0 to 2. with respect to the total hydroxyl groups of the aromatic carboxylic acid ester and the hydroxyaromatic carboxylic acid.
It is 0 equivalent, preferably 1.0 to 1.5 equivalent. The reaction temperature for acyloxylation is in the range of 150 to 220 ° C, preferably 170 to 200 ° C. The reaction time is about 1 to 4 hours, depending on the reaction temperature.

[3] Polycondensation Following the above acyloxylation reaction, an alcohol is further added to cause polycondensation, whereby a liquid crystalline polyester can be obtained. The amount of the alcohol used is substantially equivalent to the excess amount of the aliphatic carboxylic acid anhydride with respect to the total hydroxyl groups of the hydroxyaromatic carboxylic acid ester and the hydroxyaromatic carboxylic acid anhydride.

In the polycondensation reaction, the reaction product of the acyloxylation reaction and the alcohol are charged, and first, the mixture is heated under reflux for about 30 minutes to 1 hour to esterify the excess aliphatic carboxylic acid anhydride with the alcohol. The degree of esterification can be confirmed by measuring a hydroxyl value or the like. Subsequently, the reaction temperature is 200 to 350 ° C., preferably 250 to
The temperature is set to 325 ° C. to cause polycondensation.

The reaction time of the polycondensation reaction after the reaction between the excess aliphatic carboxylic acid anhydride and the alcohol varies depending on the reaction temperature. For example, the reaction temperature is 200 to 3
It takes about 5 to 10 hours to gradually raise the temperature to 25 ° C. The polymerization reaction is preferably carried out under an inert gas stream. Nitrogen, argon, etc. can be used as the inert gas, and it is preferable to continuously introduce them into the system.

As the polycondensation reaction proceeds, an aliphatic carboxylic acid is produced as a by-product. In the latter stage of the polycondensation reaction, it is necessary to efficiently remove the by-produced aliphatic carboxylic acid, excess aliphatic carboxylic acid ester and ester consisting of alcohol, and also in terms of reaction time, etc. It is preferable to carry out the reaction under reduced pressure. Specifically, at the end of the reaction, a vacuum degree of 1 mmHg or less is applied for about 1 to 6 hours, and more preferably, a vacuum degree of 0.1 mmHg or less is 0.1.
The reaction is performed for about 5 to 1 hour.

The reaction is terminated by distilling off the by-produced aliphatic carboxylic acid and the ester composed of the aliphatic carboxylic acid ester and the alcohol out of the stoichiometric amount system. The liquid crystalline polyester produced according to the present invention has a molar ratio of the structural unit of hydroxybenzoic acid (corresponding to Ar ¹ + Ar ³ ) to the total number of moles of aromatic groups (corresponding to Ar ¹ + Ar ² + Ar ³ ) of 68 to 96. %, Preferably 70 to 95%.

The liquid crystalline polyester produced according to the present invention should have a sufficiently high molecular weight. This liquid crystalline polymer has a logarithmic viscosity of 0.4 or more, preferably 0.
It is 6 or more. The flow starting temperature is 160 ° C or higher, preferably 180 ° C or higher.

Use of Liquid Crystalline Polyester The liquid crystalline polyester of the present invention is used for injection molding, extrusion molding,
It can be subjected to ordinary melt molding such as compression molding and blow molding, and can be processed into three-dimensional molded products, films, fibers, containers and the like. Further, a polymer alloy can also be obtained by mixing with another thermoplastic resin. At the time of molding, the liquid crystalline polyester of the present invention is added with additives such as a reinforcing agent such as glass fiber and carbon fiber, a filler, an antioxidant, a stabilizer, a plasticizer, and a release agent to obtain a molded product. Can be provided with desired characteristics.

[0032]

According to the present invention, a liquid crystalline polyester which can contain a large amount of structural units of hydroxyaromatic carboxylic acid, is highly uniform, has excellent fluidity, and has excellent heat resistance can be easily prepared. And it can be manufactured continuously.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The logarithmic viscosity, the thermogravimetric reduction start temperature (TGA), the flow start temperature and the liquid crystallinity of the liquid crystalline polyester were determined as follows.

(1) Logarithmic viscosity It was measured in a pentafluorophenol solvent at 50 ° C. using an Ubbelohde viscometer. However, those that did not dissolve under these conditions are shown by the horizontal line in Table 1. (2) Thermogravimetric reduction start temperature (TGA) Using TG / DTA20 manufactured by SEIDO I & E, measurement was performed in nitrogen at a heating rate of 10 ° C / min. (3) Flow start temperature and liquid crystallinity It was visually confirmed using a polarizing microscope with a hot stage.

<Example 1> (Transesterification reaction) In a 300 ml separable flask equipped with a stirring blade, a thermometer, a distilling tube, and a nitrogen introducing tube, 60.8604 g (0.4mo) of methyl hydroxybenzoate was added.
l), 37.242 g of ethylene glycol (0.6 mo
1) and 0.1 g of tetra-n-butyl titanate (0.1% by weight based on the total weight of raw materials) were charged. After replacing the inside of the reaction system with argon three times, the mantle heater was heated to 200 ° C. and heated for 30 minutes to melt the contents. Start agitation and turn on the mantle heater at 225 ° C for 30 minutes, then 25
When the reaction was carried out at 0 ° C. for 3.5 hours, the theoretical amount of methanol and about 70% of the theoretical amount of excess ethylene glycol were distilled. Next, the pressure was reduced to 1 mmHg or less at 250 ° C., and a theoretical amount of ethylene glycol was distilled off under reduced pressure for 6 hours.

(Acyloxylation reaction) 33.228 g of terephthalic acid was placed in the same separable flask without isolation and purification of the reaction product obtained by the above reaction.
(0.2 mol), p-acetoxybenzoic acid 72.06
4 g (0.4 mol), acetic anhydride 83.18 ml (0.
88 mol, 1.1 equivalents) was added and the mixture was refluxed at 200 ° C. for 2 hours to acetylate the hydroxyl terminal.

After completion of (polycondensation) acetylation, 1-
Pentanol (8.70 ml, 0.08 mol) was added, and the mixture was refluxed at 200 ° C for 30 minutes to esterify excess acetic anhydride (0.08 mol, 0.1 eq). Then at 200 ° C for 1 hour, then at 250 ° C for 1 hour,
By reacting at 275 ° C. for 2 hours, 300 ° C. for 2 hours, and 325 ° C. for 1 hour, acetic acid and ester were distilled out at about 90% of the theoretical amount. Furthermore, the pressure was reduced to 1 mmHg or less at 325 ° C. and the pressure was reduced for 30 minutes to distill the theoretical amount of acetic acid and ester. After completion of the polycondensation, the contents were taken out from the separable flask while it was hot. Melting anisotropy of this polymer was confirmed by a polarization microscope with a hot stage. Table 1 shows the physical properties of this liquid crystalline polyester.

Comparative Example 1 A reactor similar to that used in Example 1 was charged with 63.99 g (0.3%) of polyethylene terephthalate.
33 mol) and p-acetoxybenzoic acid 120.11 g
(0.667 mol) was charged. After purging with argon three times, the metal bath was heated to 200 ° C. and heated for 30 minutes to melt the contents. Then, stirring was started, and when a metal bath was heated at 250 ° C. for 2 hours and then at 275 ° C. for about 1 hour, a white solid was precipitated. I tried to measure the intrinsic viscosity of this white solid, but it did not dissolve in a mixed solvent of phenol / 1,1,2,2-terolachloroethane = 1/1 (weight ratio), p-chlorophenol, and pentafluorophenol. The intrinsic viscosity could not be measured. In addition, an insoluble substance was observed at the flow starting temperature, and a uniform liquid crystal phase could not be obtained.

Comparative Example 2 73.41 g (0.3%) of polybutylene terephthalate was added to the same reactor as in Example 1.
33 mol) and p-acetoxybenzoic acid 120.11 g
(0.667 mol) was charged. After purging with argon three times, the metal bath was heated to 200 ° C. and heated for 30 minutes to melt the contents. Then, stirring was started, and when a metal bath was heated at 250 ° C. for 2 hours and then at 275 ° C. for about 1 hour, a white solid was precipitated. I tried to measure the intrinsic viscosity of this white solid, but it did not dissolve in a mixed solvent of phenol / 1,1,2,2-terolachloroethane = 1/1 (weight ratio), p-chlorophenol, and pentafluorophenol. The intrinsic viscosity could not be measured. In addition, an insoluble substance was observed at the flow starting temperature, and a uniform liquid crystal phase could not be obtained.

<Example 2> In Example 1, the amount of acetic anhydride was set to 1.5 equivalents based on the number of moles of the hydroxy terminal, and the amount of 1-pentanol was 0.5 to the number of moles of the hydroxy terminal. The reaction was carried out in the same manner as in Example 1 except that the equivalent amount was used. The results are shown in Table 1. <Example 3> The reaction was performed in the same manner as in Example 1 except that the final temperature of the transesterification reaction was changed to 275 ° C. The results are shown in Table 1.

Example 4 The reaction was performed in the same manner as in Example 1 except that the amount of 1-pentanol was 3 equivalents with respect to the excess acetic anhydride. The results are shown in Table 1. <Examples 5 and 6> Example 1 except that the final temperature of the polymerization reaction was changed to 300 ° C and 350 ° C, respectively.
The reaction was performed in the same manner as in. The results are shown in Table 1.

Example 7 As Example 1, except that 0.1 g of n-dibutyltin oxide (0.1% by weight based on the total weight of the raw materials) was used as a catalyst for the transesterification reaction. The reaction was performed similarly. The results are shown in Table 1. <Examples 8 and 9> The reaction was performed in the same manner as in Example 1 except that butanediol and cyclohexanedimethanol were used instead of ethylene glycol. The results are shown in Table 1.

<Examples 10 and 11> In Example 1,
The reaction was performed in the same manner as in Example 1 except that 4,4′-biphenyldicarboxylic acid and 2,6-naphthalenedicarboxylic acid were used instead of terephthalic acid. The results are shown in Table 1. <Example 12> The reaction was performed in the same manner as in Example 1 except that the amount of p-hydroxybenzoic acid was changed to 110.4096 g (0.8 mol). The results are shown in Table 1.

<Example 13> 10.042 g of 1-hexanol instead of 1-pentanol in Example 1
The reaction was performed in the same manner as in Example 1 except that (0.08 mol) was used. The results are shown in Table 1.

[0045]

[Table 1]

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[Procedure amendment]

[Submission date] December 9, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

<Example 1> (Transesterification reaction) Stirring blade, thermometer, distilling tube, Argo
In a 300 ml separable flask equipped with a gas inlet tube, 60.8604 g of methyl hydroxybenzoate (0.
4 mol) and 37.242 g of ethylene glycol (0.
6 mol) and 0.1 g of tetra-n-butyl titanate (0.1% by weight based on the total weight of raw materials) were charged. After replacing the inside of the reaction system with argon three times, turn on the mantle heater 20.
The contents were melted by heating to 0 ° C. for 30 minutes. When stirring was started and the mantle heater was reacted at 225 ° C. for 30 minutes and then at 250 ° C. for 3.5 hours, a theoretical amount of methanol and about 70% of the theoretical amount of excess ethylene glycol were distilled. Next, the pressure was reduced to 1 mmHg or less at 250 ° C., and a theoretical amount of ethylene glycol was distilled off under reduced pressure for 6 hours.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Comparative Example 1 A reactor similar to that used in Example 1 was charged with 63.99 g (0.3%) of polyethylene terephthalate.
33 mol) and p-acetoxybenzoic acid 120.11 g
(0.667 mol) was charged. After purging with argon three times, the metal bath was heated to 200 ° C. and heated for 30 minutes to melt the contents. Then, stirring was started, and when a metal bath was heated at 250 ° C. for 2 hours and then at 275 ° C. for about 1 hour, a white solid was precipitated. Tried to measure the intrinsic viscosity of the white solid, a mixed solvent of phenol / 1,1,2,2-Te DOO la tetrachloroethane = 1/1 (weight ratio), p-chlorophenol, soluble in pentafluorophenol No, the intrinsic viscosity could not be measured. Further, at the flow starting temperature, an insoluble substance was observed and a uniform liquid crystal phase could not be obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

Comparative Example 2 73.41 g (0.3%) of polybutylene terephthalate was added to the same reactor as in Example 1.
33 mol) and p-acetoxybenzoic acid 120.11 g
(0.667 mol) was charged. After purging with argon three times, the metal bath was heated to 200 ° C. and heated for 30 minutes to melt the contents. Then, stirring was started, and when a metal bath was heated at 250 ° C. for 2 hours and then at 275 ° C. for about 1 hour, a white solid was precipitated. Tried to measure the intrinsic viscosity of the white solid, a mixed solvent of phenol / 1,1,2,2-Te DOO la tetrachloroethane = 1/1 (weight ratio), p-chlorophenol, soluble in pentafluorophenol No, the intrinsic viscosity could not be measured. In addition, an insoluble substance was observed at the flow starting temperature, and a uniform liquid crystal phase could not be obtained.

Claims (1)

[Claims] 1. A reaction product obtained by reacting a hydroxyaromatic carboxylic acid ester represented by the following general formula [I] with a diol represented by the following general formula [II] in the presence of an organometallic compound catalyst. After adding an aromatic dicarboxylic acid represented by the following general formula [III], a hydroxyaromatic carboxylic acid represented by the following general formula [IV], and an aliphatic carboxylic acid anhydride to acyloxylate, further: A method for producing a thermotropic liquid crystalline polyester, which comprises adding an alcohol represented by the general formula [V] to polycondensation. [Chemical 1] (In the formula, Ar ¹ , Ar ² and Ar ³ are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ¹ is 1 to ¹ carbon atoms.
15 is a saturated aliphatic hydrocarbon group, and X ¹ has 1 to ¹ carbon atoms.
A saturated aliphatic hydrocarbon group of 6 or a phenyl group, and X
² is a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms or an arylene group)