KR20130069045A - Method of preparing wholly aromatic liquid crystalline polyester resin and method of wholly aromatic liquid crystalline polyester resin compound using the wholly aromatic liquid crystalline polyester resin prepared by the method - Google Patents

Abstract

PURPOSE: A manufacturing method of a wholly aromatic liquid crystalline polyester resin is provided to obtain a wholly aromatic liquid crystalline polyester resin with high thermal stability and low gas generation. CONSTITUTION: A manufacturing method of a wholly aromatic liquid crystalline polyester resin comprises a step of acetylating a carboxylic anhydride by reaction of a carboxylic anhydride and aromatic monomer with one or more aromatic monomer; a step of synthesizing a wholly aromatic liquid crystal polyester prepolymer by reaction of an aromatic monomer and aromatic dicarboxylic acid; and a step of injecting the wholly aromatic liquid crystal polyester prepolymer into a solid phase polymerization reactor; and a step of increasing the temperature of the reactor with a rate of 2.5-3.5 °C/min, at 310-340 °C.

Description

Method of preparing wholly aromatic liquid crystalline polyester resin and method of wholly aromatic liquid crystalline polyester resin prepared by the wholly aromatic liquid crystalline polyester resin prepared by the method}

A method for producing a wholly aromatic liquid crystal polyester resin and a method for producing a wholly aromatic liquid crystal polyester resin compound are disclosed. In more detail, the wholly aromatic liquid-crystalline polyester prepolymer synthesized using one or more aromatic monomers is introduced into a solid phase polymerization reactor maintained at a first temperature, and then the temperature of the solid phase polymerization reactor is set to a second temperature at a predetermined temperature increase rate. Disclosed is a method for producing a wholly aromatic liquid crystal polyester resin comprising the step of heating to a solid phase polycondensation, and a method for producing a wholly aromatic liquid crystal polyester resin compound using the wholly aromatic liquid crystal polyester resin prepared by the above method.

The wholly aromatic liquid crystal polyester resin has excellent heat resistance and excellent fluidity upon melting, and thus has been widely used in the field of electronic components as a precision injection molding material. In particular, its dimensional stability and electrical insulation are excellent, and its use is expanding as a material for films and substrates for electronic materials.

The wholly aromatic liquid crystal polyester resin is a kind of thermoplastic polymer produced by a polycondensation reaction, and has to have a certain level of mechanical strength and thermal properties in order to be used as a material for electronic products.

In general, in order to prepare a wholly aromatic liquid crystal polyester resin having a high molecular weight, a wholly aromatic liquid crystal polyester prepolymer synthesized by liquid polymerization is further solid-phase polymerized to increase the degree of polymerization. In many cases, the resin having a wide molecular weight distribution has a problem of lowering thermal stability and generating a large amount of gas during injection molding.

In one embodiment of the present invention, the mono-aromatic liquid crystal polyester prepolymer synthesized using at least one aromatic monomer is introduced into a solid phase polymerization reactor maintained at a first temperature, and then the temperature of the solid phase polymerization reactor is controlled at a predetermined temperature raising rate. It provides a method for producing a wholly aromatic liquid-crystalline polyester resin comprising the step of raising the temperature to 2 temperatures, the polyphase condensation.

Another embodiment of the present invention provides a method for producing an wholly aromatic liquid crystal polyester resin compound using the wholly aromatic liquid crystal polyester resin prepared by the method for producing an wholly aromatic liquid crystal polyester resin.

According to an aspect of the present invention,

Acetylating (acetylation step) by reacting one or more aromatic monomers each having at least one of a hydroxyl group and an amino group with a carboxylic anhydride;

Polycondensation of the acetylated aromatic monomer and aromatic dicarboxylic acid to synthesize a wholly aromatic liquid-crystalline polyester prepolymer (prepolymer synthesis step);

Injecting the wholly aromatic liquid-crystalline polyester prepolymer into a solid phase polymerization reactor having an internal temperature of 180 to 230 ° C. (first temperature increase step); And

It provides a method for producing a wholly aromatic liquid-crystalline polyester resin comprising the step (second temperature increase step) of raising the temperature of the solid-phase polymerization reactor to 310 ~ 340 ℃ at a temperature increase rate of 2.5 ~ 3.5 ℃ / min.

The second temperature increase step may be performed after 10 to 30 minutes from the time when the wholly aromatic liquid crystal polyester prepolymer is introduced into the solid state polymerization reactor in the first temperature increase step.

After the second temperature increase step, the temperature of the solid phase polymerization reactor can be maintained for 1 to 3 hours at the temperature raised by the second temperature increase step.

The method for producing the wholly aromatic liquid crystal polyester resin further includes the step of obtaining prepolymer particles having a particle size of 0.1 mm to 3.0 mm by grinding the wholly aromatic liquid crystal polyester prepolymer after the prepolymer synthesis step and before the first temperature raising step. It can be included as.

Another aspect of the invention,

Provided is a method for producing an wholly aromatic liquid crystalline polyester resin compound using an wholly aromatic liquid crystalline polyester resin prepared according to the above-described method.

According to the manufacturing method of the wholly aromatic liquid crystal polyester resin according to an embodiment of the present invention, the phenomenon that the prepolymer particles are fused to the inner wall of the reactor during the solid phase polycondensation is reduced, the molecular weight distribution is narrow, the thermal stability is high, during extrusion and injection molding The wholly aromatic liquid-crystalline polyester resin with little gas generation can be obtained.

In addition, the wholly aromatic liquid crystal polyester resin compound prepared using the wholly aromatic liquid crystal polyester resin may have high mechanical properties and heat resistance.

Hereinafter will be described in detail a method for producing a wholly aromatic liquid crystal polyester resin and a method for producing a wholly aromatic liquid crystal polyester resin compound using the wholly aromatic liquid crystal polyester resin prepared by the method according to an embodiment of the present invention. .

Method for producing a wholly aromatic liquid crystal polyester resin according to an embodiment of the present invention comprises the steps of acetylating by reacting at least one aromatic monomer each having at least one of a hydroxyl group and an amino group with a carboxylic anhydride (acetylation step), Polycondensation of the acetylated aromatic monomer and aromatic dicarboxylic acid to synthesize a wholly aromatic liquid crystal polyester prepolymer (prepolymer synthesis step), the wholly aromatic liquid crystal polyester prepolymer having an internal temperature of 180 ~ 230 ℃ Including a step (increase in the first temperature rise step), and the temperature of the solid-phase polymerization reactor to the temperature rise rate of 310 ~ 340 ℃ at a temperature increase rate of 2.5 ~ 3.5 ℃ / min (second temperature increase step).

As used herein, “solid phase polymerization reactor” means a reactor in which the raw material (ie, the wholly aromatic liquid crystal polyester prepolymer) is polymerized in the solid state.

In the acetylation step of the aromatic monomer, an acetyl group (-COCH ₃ ) is introduced into a hydroxyl group (-OH) and / or an amino group (-NH ₂ ) included in the aromatic monomer, thereby acetyloxy group (-OCOCH ₃ ) and / or Acetylamino group (-NHCOCH ₃ ) is formed and acetic acid is produced as a by-product. Here, the byproduct acetic acid can be removed from the product in a gaseous state.

In the acetylation of the aromatic monomer, the amount of the carboxylic acid anhydride may be 0.5 to 2.0 mole parts with respect to 1 mole part of the hydroxyl group and the amino group included in the aromatic monomer. When the amount of the carboxylic acid anhydride is within the above range, the acetylation of the aromatic monomer is sufficient, so that browning does not occur in the synthesized resin product, and the amount of unreacted in the carboxylic acid anhydride used is less, so that the removal It becomes easy.

Acetylation of the aromatic monomer may be performed for 1 to 3 hours in the temperature range of 140 ~ 160 ℃. When the temperature and time are respectively within the above ranges, the hydroxyl group and / or amino group of the aromatic monomer can be sufficiently converted to the acetyl group so that the subsequent polycondensation reaction can proceed at low temperature, and thus the synthesized wholly aromatic liquid crystal polyester prepolymer is not degraded. Therefore, browning of the prepolymer does not occur.

Acetylation of the aromatic monomer may be performed by solution condensation polymerization or bulk condensation polymerization.

The aromatic monomer may include at least one compound selected from the group consisting of aromatic diols, aromatic hydroxy carboxylic acids, aromatic hydroxylamines, aromatic diamines and aromatic amino carboxylic acids.

The aromatic diol is selected from the group consisting of 4,4'-biphenol, hydroquinone, 1,4-dihydroxy naphthalene and 2,6-dihydroxy naphthalene At least one kind of compound.

The aromatic hydroxy carboxylic acid may comprise at least one compound of para hydroxy benzoic acid and 6-hydroxy-2-naphthoic acid.

The aromatic hydroxylamine may include at least one compound selected from the group consisting of 3-aminophenol, 4-aminophenol and 2-amino-6-naphthol.

The aromatic diamine may include at least one compound selected from the group consisting of 1,4-phenylene diamine, 1,3-phenylene diamine, and 2,6-naphthalene diamine.

The aromatic amino carboxylic acid may include at least one compound selected from the group consisting of 4-aminobenzoic acid, 2-amino-naphthalene-6-carboxylic acid and 4-amino-biphenyl-4-carboxylic acid. .

The carboxylic anhydride may comprise at least one compound selected from the group consisting of acetic anhydride, diphenyl carbonate and benzyl acetate.

The aromatic dicarboxylic acid isophthalic acid, 2,6-naphthalene dicarboxylic acid, terephthalic acid, 1,3-propanearomatic dicarboxylic acid, 1,4-butanearomatic dicarboxylic acid and 1,5-pentanearomatic dicarboxylic acid It may include at least one compound selected from the group consisting of leric acid.

In the synthesis of the wholly aromatic liquid crystal polyester prepolymer, metal acetate may be additionally used as a catalyst for promoting the reaction. The metal acetate catalyst may include at least one selected from the group consisting of magnesium acetate, potassium acetate, calcium acetate, zinc acetate, manganese acetate, lead acetate, antimony acetate, and cobalt acetate. The amount of the metal acetate catalyst used may be, for example, 0.10 parts by weight or less based on 100 parts by weight of the total amount of the aromatic monomer.

Synthesis of the wholly aromatic liquid crystal polyester prepolymer may be performed for 5 to 8 hours in the temperature range of 310 ~ 340 ℃. When the temperature and time are within the above ranges, the discharge process failure does not occur after the polycondensation reaction, and a wholly aromatic liquid crystal polyester prepolymer having physical properties suitable for the solid phase polycondensation reaction can be obtained.

Synthesis of the wholly aromatic liquid crystal polyester prepolymer may be carried out by a solution polycondensation method or a bulk polycondensation method.

When the temperature of the solid phase polymerization reactor in the first temperature rising step is less than 180 ℃ reaction rate is slow and the reaction time is long, the productivity is lowered, if it exceeds 230 ℃ to the wholly aromatic liquid crystal polyester prepolymer introduced into the solid phase polymerization reactor The heat transfer of does not occur sufficiently and evenly, so that the molecular weight distribution is widened, and thus a wholly aromatic liquid crystal polyester resin having low physical properties can be obtained.

The method for producing the wholly aromatic liquid crystal polyester resin further includes the step of obtaining prepolymer particles having a particle size of 0.1 mm to 3.0 mm by grinding the wholly aromatic liquid crystal polyester prepolymer after the prepolymer synthesis step and before the first temperature raising step. It can be included as. Prepolymer particles having a particle size of less than 0.1mm adhere to the inner wall of the reactor by static electricity during the solid state polycondensation, and then heat is fused to the inner wall of the reactor to block heat transferred from the external heater into the reactor. In contrast, prepolymer particles having a particle size of greater than 3.0 mm are not fused to the reactor inner wall but prevent the smooth removal of the acetic acid gas produced during solid phase condensation. The grinding of the wholly aromatic liquid crystal polyester prepolymer may be performed using a grinder (eg, a feather mill) having a screen having a mesh size of 1.5 mm to 3.0 mm.

The method for producing the wholly aromatic liquid crystal polyester resin may further include cooling the wholly aromatic liquid crystal polyester prepolymer between the wholly aromatic liquid crystal polyester prepolymer synthesis step and the wholly aromatic liquid crystal polyester prepolymer crushing step. In the wholly aromatic liquid crystal polyester prepolymer cooling step, the wholly aromatic liquid crystal polyester prepolymer may be cooled to a temperature of 50 ~ 70 ℃. Accordingly, the pulverization step of the wholly aromatic liquid crystal polyester prepolymer (this is referred to as a pulverization step) may be performed while maintaining the wholly aromatic liquid crystal polyester prepolymer at a temperature of 50 to 70 ° C.

Immediately before the cooling of the wholly aromatic liquid crystal polyester prepolymer, the wholly aromatic liquid crystal polyester prepolymer may be coarse ground to a particle size of 1 cm to 3 cm.

The second temperature increase step may be performed after 10 to 30 minutes from the time when the wholly aromatic liquid crystal polyester prepolymer is introduced into the solid state polymerization reactor in the first temperature increase step. When the elapsed time is within the above range, heat transfer to the wholly aromatic liquid crystal polyester prepolymer introduced into the solid phase polymerization reactor may sufficiently occur.

When the temperature increase rate is less than 2.5 ℃ / min in the secondary temperature increase step, the reaction rate is slowed down and the reaction time is long, the productivity is lowered, and when the temperature exceeds 3.5 ℃ / min, the wholly aromatic liquid crystal polyester prepolymer introduced into the solid phase polymerization reactor Is fused to the inside of the reactor, which causes heat transfer to the inside of the reactor not to be made sufficiently evenly to obtain a wholly aromatic liquid crystal polyester resin having a wide molecular weight distribution and low physical properties.

If the temperature of the solid phase polymerization reactor in the second temperature rising step is less than 310 ℃ polymerization reaction is not sufficiently achieved to obtain the desired physical properties of the prepolymer, in order to obtain the desired physical properties it is necessary to proceed the reaction for a long time at low temperature, productivity is lowered When the temperature exceeds 340 ° C, the resin obtained by the polymerization reaction is thermally decomposed immediately after the polymerization to cause browning and a decrease in the viscosity of the resin.

After the second temperature increase step, the temperature of the solid phase polymerization reactor can be maintained for 1 to 3 hours at the temperature raised by the second temperature increase step. When the said temperature holding time is in the said range, reaction fully advances and the highly aromatic liquid crystalline polyester resin with high molecular weight can be obtained.

In order to remove the by-products generated during the solid state polycondensation reaction, purging with an inert gas or vacuum removal may be performed.

Another embodiment of the present invention provides a method for producing an wholly aromatic liquid crystal polyester resin compound using the wholly aromatic liquid crystal polyester resin prepared by the method for producing an wholly aromatic liquid crystal polyester resin.

The method for producing the wholly aromatic liquid crystal polyester resin compound comprises the steps of synthesizing the wholly aromatic liquid crystal polyester resin according to the method for producing the wholly aromatic liquid crystal polyester resin, and melting the synthesized wholly aromatic liquid crystal polyester resin and the additive. And kneading. For such melt kneading, a batch type kneader, a twin screw extruder or a mixing roll may be used. Further, for the purpose of smooth melt-kneading, an activator may be used for melt-kneading.

The additive may include at least one of an inorganic additive and an organic additive.

The inorganic additive may include glass fiber, talc, calcium carbonate, mica or a mixture of two or more thereof, and carbon fiber may be used as the organic additive.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these embodiments.

Example

Example  1 to 6 and Comparative example  1-6: Wholly aromatic  The liquid crystal polyester resin and the resin Compound  Produce

In a 10 liter batch reactor equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser capable of measuring torque, 1850 g (13.4 moles) of 4-hydroxybenzoic acid, 740 g (6.7 moles) of hydroquinone, 450 g (2.7 moles) of terephthalic acid Mole), 865 g (4.0 mole) of 2,6-naphthalene dicarboxylic acid, 3010 g (29.5 mole) of acetic anhydride, and 0.685 g of potassium acetate (70 wtppm of potassium ions relative to the total amount of monomers) were added as a catalyst. Nitrogen gas was injected to make the internal space of the reactor inert, and then the reactor temperature was raised to 150 ° C. over 30 minutes while stirring the reaction mixture with a stirrer and maintained at the temperature for 2 hours to maintain the hydroxyl groups of the monomers. Acetylated . Subsequently, the acetic acid produced as a byproduct in the acetylation reaction was removed by condensation and the reactor temperature was raised to 250 ° C. at a rate of 1 ° C./min, and then maintained at 250 ° C. for 2 hours. Subsequently, the reactor temperature was again raised at a rate of 1 ° C./min to discharge the product (ie, wholly aromatic liquid crystal polyester prepolymer) out of the reactor when the torque value of the stirrer reached 6 N · m. Next, the product was recovered from the reactor and then coarsely ground to a particle particle size of 1 cm to 3 cm using a coarse grinder (self-made). Thereafter, the product was ground using a Feather Mill (Hosegawa Co., Ltd., FM-1S) having a screen having a mesh size of 2.0 mm.

Thereafter, the crude milled product was cooled to 55 ° C., and then 3,000 g of the product was introduced into a 10 liter rotary kiln reactor having an internal temperature maintained at a first temperature, while rotating the rotary kiln reactor. At the same time, while continuously flowing nitrogen into the rotary kiln reactor at a flow rate of 1Nm 3 / hr, the temperature was heated to the second temperature at the first heating rate and maintained at the second temperature for 2 hours. At this time, the operation of heating to the second temperature at the first temperature increase rate was started after the rotary kiln reactor rotation and nitrogen input for 20 minutes. As a result, the wholly aromatic liquid-crystalline polyester resin was obtained. Thereafter, the reactor was cooled to room temperature over 1 hour, and then the wholly aromatic liquid crystal polyester resin was recovered from the reactor. The first temperature, the first temperature increase rate and the second temperature applied in each Example and Comparative Example are shown in Table 1 below.

Subsequently, the prepared wholly aromatic liquid crystal polyester resin, glass fiber (diameter 10 탆, pulverized glass fiber having an average length of 150 탆) and talc (diameter 2-15 탆) were mixed in a ratio of 60:30:10 by weight. The compound of the wholly aromatic liquid-crystalline polyester resin was manufactured by melt-kneading using the twin screw extruder (L / D: 40, diameter: 25 mm). In the preparation of the resin compound, a vacuum was applied to the twin screw extruder to remove the byproducts.

First temperature (℃) First temperature increase rate (℃ / min) 2nd temperature (degreeC) Total reaction time (min) Example 1 210 3.0 310 173 Example 2 210 3.0 340 183 Example 3 210 2.5 325 186 Example 4 210 3.5 325 173 Example 5 180 3.0 325 188 Example 6 230 3.0 325 172 Comparative Example 1 210 3.0 300 170 Comparative Example 2 210 3.0 350 187 Comparative Example 3 210 2.0 325 198 Comparative Example 4 210 4.0 325 169 Comparative Example 5 170 3.0 325 192 Comparative Example 6 240 3.0 325 168

Referring to Table 1, in Comparative Examples 3 and 5, the production time of the wholly aromatic liquid crystal polyester resin was found to be too long compared to Examples 1 to 6 and Comparative Examples 1 and 2, Comparative Examples 4 and 6. .

Evaluation example

Evaluation example  1: on the inner wall of the solid phase reactor Prepolymer Welding  Status and gas generation evaluation

In Examples 1 to 6 and Comparative Examples 1 to 6, the total aromatic liquid crystal polyester prepolymer was fused to the inner wall of the rotary kiln reactor (ie, the solid phase reactor) and the amount of gas generated was visually observed. It is shown in Table 2 below.

division Rotary kiln on inner wall of reactor
Prepolymer Fusion Gas generation amount Example 1 X Little Example 2 X Little Example 3 X Little Example 4 X Little Example 5 X Little Example 6 X Little Comparative Example 1 X 多 Comparative Example 2 X 多 Comparative Example 3 X Little Comparative Example 4 O 多 Comparative Example 5 X Little Comparative Example 6 O 多

Referring to Table 2, in Examples 1 to 6, Comparative Examples 3 and 5, no fusion occurred and the gas generation amount was small in the solid phase polycondensation, but in Comparative Examples 4 and 6, fusion occurred and the gas generation amount also. Many. In Comparative Example 1, fusion did not occur, but the amount of gas generation was high and polymerization was not sufficiently progressed. In Comparative Example 2, fusion did not occur, but thermal decomposition of the resin occurred immediately after polymerization, resulting in a large amount of gas generation.

Evaluation example  2: Wholly aromatic  Liquid crystal polyester resin and said resin Compound  Evaluation of Properties of Injection Molded Products

Melt viscosity, melting temperature and time-dependent change time of each wholly aromatic liquid crystal polyester resin prepared in Examples 1 to 6 and Comparative Examples 1 to 6; And the tensile strength, flexural strength, impact strength and heat resistance temperature of the injection molded articles of each of the wholly aromatic liquid crystal polyester resin compounds prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were measured by the following methods, and the results were obtained. It is shown in Table 3 below.

(1) Method of measuring melt viscosity and change over time

By using a melt viscosity measuring device (Rosand, RH2000), the viscosity change with time was measured at a temperature of (melting temperature + 10 ° C.) and a shear rate of 100 / s using a 1.0 mm x 32 mm capillary tube. The constant viscosity value was referred to as melt viscosity, and the time taken until the viscosity increased or decreased rapidly after measurement was called change over time. The longer the change over time means that the thermal stability of the wholly aromatic liquid-crystalline polyester resin is excellent.

(2) Measuring method of melting temperature

Melting temperature was measured using a differential scanning calorimeter (TA Instruments, Q20). When the resin sample was heated from 40 ° C to 360 ° C in a temperature rising condition of 20 ° C / min, the temperature indicated by the observed endothermic peak was referred to as the primary melting temperature (Tm ₁ ) and 5 minutes at a temperature 20 ° C higher than Tm _1. After holding, after cooling to 40 ° C. under a temperature lowering condition of 10 ° C./min, and then heating to a temperature rising condition of 20 ° C./min, the temperature indicated by the observed endothermic peak was referred to as melting temperature.

(3) Measuring method of tensile strength, flexural strength, impact strength and heat resistance temperature

Using an injection machine (FANUC Co. Ltd, S-2000i 50B) to prepare a specimen of each of the prepared full aromatic liquid crystal polyester resin compound, and after cooling the specimen to room temperature for 5 hours, Tensile strength (ASTM D638), flexural strength (ASTM D790), impact strength (ASTM D256) and heat resistance temperature (ASTM D648) of the specimens were measured.

division Resin properties Properties of Injection Molded Parts Melting
Viscosity
(poise) Time change
(second) Seal
burglar
(MPa) curve
burglar
(MPa) Heat resistance
Temperature
(℃) Example 1 558 1800 137 165 290 Example 2 630 1868 143 168 293 Example 3 580 1810 140 167 292 Example 4 560 1780 138 165 290 Example 5 575 1850 140 166 292 Example 6 560 1770 139 164 289 Comparative Example 1 512 1540 128 142 276 Comparative Example 2 710 1860 150 174 295 Comparative Example 3 583 1840 142 168 292 Comparative Example 4 430 1510 117 130 265 Comparative Example 5 573 1850 140 165 292 Comparative Example 6 545 1580 130 148 278

Referring to Table 3, the physical properties of each of the wholly aromatic liquid crystal polyester resins prepared in Examples 1 to 6 and the physical properties of the injection molded articles of the respective resin compounds were prepared in Comparative Examples 1, 4 and 6, respectively. It was shown that the physical properties of the wholly aromatic liquid crystal polyester resin and the properties of the injection molded articles of the respective resin compounds were excellent. In the case of Comparative Example 3 and Comparative Example 5, the physical properties are similar to those of Example 3, but the polymerization takes a long time (see Table 1), there is a disadvantage that the productivity is lowered, in the case of Comparative Example 2 overall physical properties Higher than the case of Examples 1-6, but the reaction time is long (see Table 1), the thermal decomposition of the resin occurs simultaneously with the polymerization, there is a lot of gas generation and the viscosity of the resin is too high injection processing is difficult.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (6)

Acetylating (acetylation step) by reacting one or more aromatic monomers each having at least one of a hydroxyl group and an amino group with a carboxylic anhydride;
Polycondensation of the acetylated aromatic monomer and aromatic dicarboxylic acid to synthesize a wholly aromatic liquid-crystalline polyester prepolymer (prepolymer synthesis step);
Injecting the wholly aromatic liquid-crystalline polyester prepolymer into a solid phase polymerization reactor having an internal temperature of 180 to 230 ° C. (first temperature increase step); And
Method of producing a wholly aromatic liquid crystal polyester resin comprising the step of raising the temperature of the solid-state polymerization reactor to 310 ~ 340 ℃ at a temperature increase rate of 2.5 ~ 3.5 ℃ / min (second temperature increase step). The method of claim 1,
The second temperature rising step is a method for producing a wholly aromatic liquid crystal polyester resin is carried out 10 to 30 minutes after the point of time when the fully aromatic liquid crystal polyester prepolymer in the solid phase polymerization reactor in the first temperature rising step. The method of claim 1,
Method for producing a wholly aromatic liquid-crystalline polyester resin for maintaining the temperature of the solid-phase polymerization reactor after the secondary temperature rising step for 1 to 3 hours at the temperature elevated by the secondary temperature rising step. The method of claim 1,
Preparation of the wholly aromatic liquid crystal polyester resin further comprising the step of pulverizing the wholly aromatic liquid crystal polyester prepolymer after the prepolymer synthesis step before the first temperature rising step to obtain prepolymer particles having a particle size of 0.1 mm to 3.0 mm. Way. The method of claim 1,
The aromatic monomer is selected from the group consisting of 4,4'-biphenol, hydroquinone, 1,4-dihydroxy naphthalene and 2,6-dihydroxy naphthalene At least one aromatic diol; At least one aromatic hydroxy carboxylic acid of para hydroxy benzoic acid and 6-hydroxy-2-naphthoic acid; At least one aromatic hydroxylamine selected from the group consisting of 3-aminophenol, 4-aminophenol and 2-amino-6-naphthol; At least one aromatic diamine selected from the group consisting of 1,4-phenylene diamine, 1,3-phenylene diamine and 2,6-naphthalene diamine; At least one aromatic amino carboxylic acid selected from the group consisting of 4-aminobenzoic acid, 2-amino-naphthalene-6-carboxylic acid and 4-amino-biphenyl-4-carboxylic acid; Containing one compound,
The carboxylic anhydride comprises at least one compound selected from the group consisting of acetic anhydride, diphenyl carbonate and benzyl acetate,
The aromatic dicarboxylic acid isophthalic acid, 2,6-naphthalene dicarboxylic acid, terephthalic acid, 1,3-propanearomatic dicarboxylic acid, 1,4-butanearomatic dicarboxylic acid and 1,5-pentanearomatic dicarboxylic acid The manufacturing method of the wholly aromatic liquid-crystalline polyester resin containing at least 1 sort (s) of compound which was selected from the group which consists of leric acid. The manufacturing method of the wholly aromatic liquid-crystalline polyester resin compound using the wholly aromatic liquid-crystalline polyester resin manufactured by the method of any one of Claims 1-5.