KR101819752B1 - Method of preparing aromatic liquid crystalline polyester amide resin and aromatic liquid crystalline polyester amide resin compound including the aromatic liquid crystalline polyester amide resin prepared by the method - Google Patents

Abstract

A process for producing an aromatic liquid crystalline polyester amide resin and an aromatic liquid crystalline polyester amide resin compound are disclosed. The process for preparing an aromatic liquid-crystalline polyester amide resin comprises reacting a first monomer having a hydroxyl group and a second monomer having an amino group with an acid anhydride at a first temperature to at least partially acetylate the first monomer and the second monomer, respectively, Reacting at least one of the monomers with an acid anhydride at a second temperature higher than the first temperature to further acetylate the monomers; and polycondensing the acetylated monomers with a dicarboxylic acid to form an aromatic liquid-crystalline polyester amide prepolymer . The disclosed aromatic liquid-crystalline polyester amide resin compound includes the aromatic liquid-crystalline polyester amide resin produced by the above-described method.

Description

Method of preparing aromatic liquid crystalline polyester amide resin and aromatic liquid crystalline polyester amide resin compound [0001] The present invention relates to a method for preparing aromatic liquid crystalline polyester amide resin,

A process for producing an aromatic liquid crystalline polyester amide resin and an aromatic liquid crystalline polyester amide resin compound are disclosed. More specifically, at least partially acetylating each of a first monomer having a hydroxyl group and a second monomer having an amino group with an acid anhydride at a first temperature, at least one of the first monomer and the second monomer, Reacting with an acid anhydride at a second temperature higher than the first temperature to further acetylate and synthesizing an aromatic liquid-crystalline polyester amide prepolymer by polycondensation reaction of the acetylated monomers with a dicarboxylic acid A process for producing an aromatic liquid-crystalline polyester amide resin and an aromatic liquid-crystalline polyester amide resin compound comprising the aromatic liquid-crystalline polyester amide resin produced by the above-described process are disclosed.

The aromatic liquid crystalline polyester amide resin exhibits a liquid crystal state in which molecules are rigid and free from entanglement between molecules even in a molten state and exhibits a molecular chain oriented in the flow direction by shearing force at the time of molding.

Due to these properties, aromatic liquid-crystalline polyester amide resins are widely used as materials for automobile parts, electric / electronic parts, and small-sized and precision molded articles because of their excellent flow properties and heat resistance.

With the recent development of the industry, the use of aromatic liquid-crystalline polyester amide resins tends to become more sophisticated and specialized. In addition, the aromatic liquid-crystalline polyester amide resin is excellent in fluidity and can be injection-molded efficiently and economically. Such an aromatic liquid-crystalline polyester amide resin is excellent in heat resistance, resistance to hydrolysis and dimensional stability at high temperatures, excellent in mechanical strength such as bending strength, tensile strength and impact resistance, (coil bobbin), connectors for electric and electronic parts, relays, materials for various automotive parts, materials for containers, films and substrates.

Such an aromatic liquid-crystalline polyester amide resin can be produced by subjecting at least two kinds of monomers to polycondensation reaction. The polycondensation reaction proceeds at a high temperature, and when the produced by-product of the gaseous phase is not effectively removed, foam is formed on the surface of the product to swell the surface. If the surface of the product swells up to the upper end of the reactor, the column for removing gaseous by-products is closed and the by-product is no longer removed. In this case, the physical properties of the aromatic liquid-crystalline polyester amide prepolymer and the aromatic liquid-crystalline polyester amide resin are lowered, resulting in a process failure requiring disassembly and cleaning of the reactor.

Further, even if the generation of bubbles due to gaseous by-products does not advance to the upper end of the reactor, if the by-product can not be removed from the product during the polymerization reaction, the synthesized aromatic polyester amide resin does not have uniform physical properties as a whole do. In this case, the aromatic polyester amide resin compound and the molded product thereof do not have uniform physical properties as a whole, so that the physical properties of the resin compound such as mechanical strength are deteriorated, and when the molded article is left in a high temperature air or liquid for a long time, ) Is generated.

One embodiment of the present invention is a process for the preparation of a polymer comprising reacting a first monomer having a hydroxyl group and a second monomer having an amino group with an acid anhydride at a first temperature to at least partially acetylate the first monomer and the second monomer, Reacting the acid anhydride with an acid anhydride at a second temperature higher than the first temperature to further acetylate the acetylated monomers and synthesizing an aromatic liquid-crystalline polyester amide prepolymer by polycondensation reaction of the acetylated monomers with a dicarboxylic acid The present invention also provides a process for producing an aromatic liquid-crystalline polyester amide resin.

Another embodiment of the present invention provides an aromatic liquid-crystalline polyester amide resin compound comprising the aromatic liquid-crystalline polyester amide resin produced by the process for producing the aromatic liquid-crystalline polyester amide resin.

According to an aspect of the present invention,

Reacting a first monomer having a hydroxyl group and a second monomer having an amino group with an acid anhydride at a first temperature to at least partially acetylate each of them;

Reacting at least one of the first and second monomers with an acid anhydride at a second temperature above the first temperature to further acetylate; And

And polycondensing the acetylated monomers with a dicarboxylic acid to synthesize an aromatic liquid-crystalline polyester amide prepolymer. The present invention also provides a method for producing an aromatic liquid-crystalline polyester amide resin.

The first monomer may include at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxycarboxylic acid, an aliphatic hydroxycarboxylic acid, an aromatic hydroxylamine, and an aliphatic hydroxylamine.

The second monomer may include at least one compound selected from the group consisting of aromatic hydroxylamine, aliphatic hydroxylamine, aromatic diamine, aliphatic diamine, aromatic aminocarboxylic acid and aliphatic aminocarboxylic acid.

Wherein the acid anhydride comprises at least one compound selected from the group consisting of acetic anhydride, anhydrous propionic acid, isobutyric anhydride, anhydrous valeric acid, anhydrous pivalic acid, anhydrous butyric acid, diphenyl carbonate and benzyl acetate, The used amount may be 0.5 to 2.0 moles per 1 mole of the sum of the amino group and the hydroxyl group contained in the first monomer and the second monomer.

The first monomer and the second monomer may have a hydroxyl group and an amino group together.

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

The first temperature may be 140 to 170 ° C, and the second temperature may be 190 to 220 ° C.

The step of synthesizing the aromatic liquid-crystalline polyester amide prepolymer may be carried out at a temperature ranging from 310 to 340 ° C.

The first monomer, the second monomer and the dicarboxylic acid may each be an aromatic compound.

The method for producing an aromatic liquid-crystalline polyester amide resin may further include a step of synthesizing an aromatic liquid-crystalline polyester amide resin by solid-phase polycondensation of the synthesized aromatic liquid-crystalline polyester amide prepolymer.

According to another aspect of the present invention,

There is provided an aromatic liquid-crystalline polyester amide resin compound comprising an aromatic liquid-crystalline polyester amide resin produced according to the above-mentioned production method.

According to the process for producing an aromatic liquid-crystalline polyester amide resin according to an embodiment of the present invention, the amount of generated by-products during the polycondensation reaction at a high temperature and the amount of bubbles generated on the surface of the product due to the by- Can be reduced. Accordingly, in the polycondensation reaction, the closure of the by-product removal column in the gaseous phase and the deterioration of the physical properties of the resin and the molded article, which are caused when the by-product is contained in the product, can be prevented. This makes it possible to produce aromatic liquid-crystalline polyester amide resins having overall uniform physical properties and resin compounds and injection molded articles having improved mechanical strength (particularly, flexural characteristics) and heat resistance. In addition, an injection molded article which does not cause blistering can be produced even if the heat treatment is carried out at a high temperature.

Hereinafter, a method for producing an aromatic liquid-crystalline polyester amide resin according to an embodiment of the present invention and a method for producing an aromatic liquid-crystalline polyester amide resin compound using the aromatic liquid-crystalline polyester amide resin produced by the method will be described in detail .

The method for producing an aromatic liquid-crystalline polyester amide resin according to an embodiment of the present invention comprises reacting a first monomer having a hydroxyl group and a second monomer having an amino group at a first temperature with an acid anhydride to at least partially acetylate Reacting at least one of the first monomer and the second monomer with an acid anhydride at a second temperature higher than the first temperature to further acetylate (a second acetylation step), and reacting the acetyl And synthesizing an aromatic liquid-crystalline polyester amide prepolymer by polycondensation reaction of the monomers with dicarboxylic acid.

The first monomer and the second monomer may have a hydroxyl group and an amino group together.

The first acetylation step in the first monomer and optionally acetylated in a hydroxyl group (-OH) contained in the second monomer group (-COCH ₃₎ is introduced acetyl oxy group (-OCOCH ₃₎ the formation and by-product (-COCH ₃ ) is introduced into the amino group (-NH ₂ ) contained in the second monomer and optionally the first monomer to form an acetylamino group (-NHCOCH ₃ ), and the acetyl group Acetic acid gas is produced as a product. Here, the by-product acetic acid gas can be easily removed from the product. By using the second monomer having an amino group, an aromatic liquid-crystalline polyester amide resin, a resin compound thereof and a molded product excellent in mechanical strength (particularly, bending property) can be produced.

In the first acetylation step, at least a part of each of the hydroxyl and amino groups contained in the first monomer and the second monomer may be acetylated, and in the second acetylation step, the first monomer and the second monomer The remainder of at least one of the included hydroxyl and amino groups may be acetylated. Specifically, in the first acetylation step, a portion of the hydroxyl groups contained in the first monomer and the second monomer and all of the amino groups may be acetylated, and in the second acetylation step, the first monomer and, optionally, The remainder of the hydroxyl groups contained in the second monomer may be acetylated. As described above, the acetylation of the first monomer and the second monomer may be performed in two steps, thereby satisfying the acetylation of each of the hydroxyl and amino groups contained in the first and second monomers. Therefore, the amount of bubbles generated on the surface of the product during the subsequent polycondensation reaction can be reduced to prevent the by-product removal column from being closed, and the amount of gaseous by-products contained in the product can be reduced. As a result, an aromatic liquid-crystalline polyester amide resin, a resin compound thereof, and a molded product having overall uniformity and excellent physical properties can be produced.

The first acetylation step is for controlling the overall polycondensation reaction rate by first acetylating the highly reactive amino groups contained in the second monomer and optionally the first monomer at a low temperature (i.e., a first temperature). Since the amino group is more reactive than the hydroxyl group, acetylation is possible even at low temperatures. In addition, the amino group may react with the by-product acetic acid before the acetylation in the acetylation step to form an ammonium ion. Since the ammonium ion acts as a surfactant, bubbles are generated on the product surface when the concentration of the ammonium ion is increased. If the first acetylation step is carried out at a high temperature (for example, a second temperature) as in the second acetylation step, the amount of acetic acid is rapidly increased, so that the second monomer and optionally the first monomer Is used in the reaction with acetic acid rather than in the acetylation reaction to increase the amount of ammonium ion. As a result, a large amount of bubbles are generated on the surface of the product during the subsequent polycondensation reaction. Therefore, the amino group contained in the second monomer and optionally the first monomer is sufficiently converted to an acetyl group at a low temperature (for example, a first temperature) condition that minimizes the generation of bubbles, so that the amino group can participate in the polycondensation reaction And the acetylation step of the second monomer is carried out by raising the temperature of the first monomer and optionally the hydroxyl group contained in the second monomer after the acetylation step of the first monomer so that the hydroxyl group contained in the first monomer and optionally the hydroxyl group contained in the second monomer is additionally sufficiently acetylated.

The total amount of the acid anhydrides (i.e., the total content of the acid anhydrides used in the first acetylation step and the second acetylation step) is preferably such that the sum of the amino groups and the hydroxyl groups contained in the first monomer and the second monomer 0.5 to 2.0 mols based on one molar portion. When the total amount of the acid anhydride is within the above range, the first monomer and the second monomer are sufficiently acetylated, so that browning does not occur in the synthesized resin and the unreacted amount of the used acid anhydride is small Removal is facilitated.

The first acetylation step may proceed for a first time at the first temperature. The first temperature may be 140-170 ° C, and the first time may be 60-100 minutes. If the first temperature and the first time are within the respective ranges, a part of the hydroxyl groups included in the first monomer and the second monomer and most of the amino groups are converted to acetyl groups, and the subsequent polycondensation reaction can proceed at a low temperature , So that the synthesized aromatic liquid-crystalline polyester amide prepolymer is not deteriorated and the browning of the prepolymer does not occur.

The first monomer may include at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxycarboxylic acid, an aliphatic hydroxycarboxylic acid, an aromatic hydroxylamine, and an aliphatic hydroxylamine.

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

The aromatic hydroxycarboxylic acid may include at least one compound of parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.

Wherein the aliphatic hydroxycarboxylic acid is selected from the group consisting of glycolic acid, lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid and 2-hydroxyhexanoic acid. At least one kind of compound.

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 aliphatic hydroxylamine may include at least one compound selected from the group consisting of 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol.

The second acetylation step may proceed for a second time at the second temperature. The second temperature may be 190 to 220 ° C, and the second time may be 60 to 100 minutes. If the second temperature and the second time are within the respective ranges, the remainder of the hydroxyl groups contained in the first monomer and the second monomer and the remainder (if any) of the amino group are sufficiently converted into an acetyl group, It can proceed at a low temperature, and thus the aromatic liquid-crystalline polyester amide prepolymer synthesized does not deteriorate and the browning of the prepolymer does not occur.

The second monomer may include at least one compound selected from the group consisting of aromatic hydroxylamine, aliphatic hydroxylamine, aromatic diamine, aliphatic diamine, aromatic aminocarboxylic acid and aliphatic aminocarboxylic acid.

The aromatic hydroxylamine and the aliphatic hydroxylamine may be respectively as described above.

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

The aliphatic diamine may include at least one compound selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane.

The aromatic aminocarboxylic 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 aliphatic aminocarboxylic acid may be at least one selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid. ≪ / RTI > compounds.

The acid anhydride may include at least one compound selected from the group consisting of acetic anhydride, anhydrous propionic acid, anhydrous isobutyric acid, anhydrous valeric acid, anhydrous pivalic acid, anhydrous butyric acid, diphenyl carbonate and benzyl acetate.

The step of synthesizing the aromatic liquid-crystalline polyester amide prepolymer by the polycondensation reaction of the acetylated first monomer, the acetylated second monomer and the dicarboxylic acid is carried out by solution polycondensation or bulk condensation polymerization .

Wherein the dicarboxylic acid is selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid, terephthalic acid, 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid, and 1,5-pentanedicarboxylic acid At least one kind of compound.

In addition, in the synthesis step of the aromatic liquid-crystalline polyester amide prepolymer, acetic acid metal may be further used as a catalyst for promoting the reaction. The nitric acid metal catalyst may include at least one member selected from the group consisting of magnesium acetate, potassium acetate, calcium acetate, zinc acetate, manganese acetate, acetic acid, antimony acetate and cobalt acetate. The amount of the metal acetate catalyst to be used may be, for example, 0.10 parts by weight or less based on 100 parts by weight of the total amount of the first and second monomers.

The step of synthesizing the aromatic liquid-crystalline polyester amide prepolymer may be carried out at a temperature ranging from 310 to 340 ° C. for 5 to 8 hours. When the temperature and time are within the above ranges, the aromatic liquid-crystalline polyester prepolymer having physical properties suitable for the solid-phase polycondensation reaction can be obtained without causing a discharge process failure after the polycondensation reaction.

Meanwhile, the method for producing the aromatic liquid-crystalline polyester amide resin may further include the step of synthesizing the aromatic liquid-crystalline polyester amide resin by solid-phase polycondensation of the aromatic liquid-crystalline polyester amide prepolymer. In order to perform the solid-phase polycondensation reaction, the aromatic liquid-crystalline polyester amide prepolymer should be provided with suitable heat. Examples of the method for providing the heat include a heating plate, hot air, and a high-temperature fluid. In order to remove the byproducts generated during the solid-phase polycondensation reaction, it is possible to purge or remove by vacuum using an inert gas.

Another embodiment of the present invention provides an aromatic liquid-crystalline polyester amide resin compound comprising the aromatic liquid-crystalline polyester amide resin produced by the process for producing the aromatic liquid-crystalline polyester amide resin.

The aromatic liquid-crystalline polyester amide resin compound is obtained by synthesizing an aromatic liquid-crystalline polyester amide resin according to the above-described method for producing an aromatic liquid-crystalline polyester amide resin, and then melt-kneading the synthesized aromatic liquid- . 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 the organic additive may include carbon fibers.

The first monomer, the second monomer, and the dicarboxylic acid may be an aromatic compound. In this case, in the respective steps described above, the wholly aromatic liquid-crystalline polyester amide prepolymer, the wholly aromatic liquid-crystalline polyester amide resin, the wholly aromatic liquid- A resin compound and a molded article thereof, respectively.

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  One: Wholly aromatic  The liquid crystal polyester amide resin (1) and the resin Compound (1) Manufacturing

(Acetylation reaction)

(18 moles) of parahydroxybenzoic acid, 282 g (1.5 moles) of 6-hydroxy-2-naphthoic acid, and 4,4'-dicyclohexylcarbodiimide were placed in a 10 liter reactor equipped with a stirrer, a nitrogen gas inlet, a thermometer and a reflux condenser. (5.3 moles) of biphenol, 872 g (5.3 moles) of terephthalic acid and 164 g (1.5 moles) of 4-aminophenol were charged and nitrogen gas was injected to make the internal space of the reactor inactive. Then, acetic anhydride 3,025 3 g of calcium acetate was added to facilitate the acetylation reaction and the subsequent polycondensation reaction with g (29.6 mol). Thereafter, the temperature of the reactor was raised to 150 캜 over 15 minutes, and the temperature was maintained for 1 hour. Thereafter, the temperature of the reactor was raised again to 200 ° C over 10 minutes, and then refluxed for 1 hour while maintaining the temperature.

(Synthesis reaction of prepolymer and resin, production of resin compound)

Next, the wholly aromatic liquid-crystalline polyester amide prepolymer was prepared by raising the temperature to 330 ° C. over 5 hours while removing acetic acid as a by-product to proceed the polycondensation reaction of the monomers. Next, the prepolymer was recovered from the reactor, cooled to room temperature (25 캜), and pulverized into a uniform particle size using a Feather Mill (FM-1S) equipped with a screen having a mesh size of 1.5 mm Respectively. Next, 3,000 g of wholly aromatic liquid-crystalline polyester amide prepolymer having a uniform particle size was charged into a 100-liter capacity rotary kiln reactor, nitrogen was continuously flowed at a flow rate of 1 Nm 3 / hr, and 1 The temperature was raised over a period of time, and the temperature was further raised to 290 ° C over 5 hours and maintained for 2 hours to obtain a wholly aromatic liquid-crystalline polyester amide resin (1). Then, the reactor was cooled to room temperature (25 DEG C) over 1 hour, and the wholly aromatic liquid-crystalline polyester amide resin (1) was recovered from the reactor.

Then, the above-prepared wholly aromatic liquid-crystalline polyester amide resin (1), glass fiber (10 μm diameter, pulverized glass fiber having an average length of 150 μm) and talc (2-15 μm diameter) : 10, and melt-kneaded using a twin-screw extruder (L / D: 40, diameter: 20 mm, manufactured by Collin Co.) to prepare a compound (1) of the wholly aromatic liquid-crystalline polyester amide resin. During the production of the resin compound (1), a vacuum was applied to the biaxial extruder to remove by-products.

Comparative Example  One: Wholly aromatic  The liquid crystal polyester amide resin (2) and the resin Compound (2) Manufacturing

In the above acetylation reaction, except that the reactor temperature was raised to 160 DEG C over 1 hour and refluxed for 2 hours while maintaining the temperature (i.e., the acetylation reaction was not carried out in two stages but in 1 stage , The wholly aromatic liquid-crystalline polyester amide resin (2) and the resin (2) were prepared in the same manner as in Example 1.

Evaluation example

The melting point and melting temperature of each of the wholly aromatic liquid-crystalline polyester amide resins prepared in Example 1 and Comparative Example 1; Melt viscosity of each of the wholly aromatic liquid-crystalline polyester amide resin compounds prepared in Example 1 and Comparative Example 1; And the tensile strength, bending strength, impact strength, heat resistance temperature and blister generation of the injection molded article were measured or evaluated by the following methods. The results are shown in Table 1 below. In addition, whether or not a process failure such as a phenomenon in which foam of product reaches to the upper end of the reactor during the production of each of the wholly aromatic liquid-crystalline polyester amide resins is observed is shown in Table 1 below.

(1) Method of measuring melt viscosity

Using a melt viscosity measuring apparatus (Rosand, RH2000), the viscosity was measured under a temperature of 1.0 mm × 32 mm capillary (melting temperature + 10 ° C.) and a shear rate of 1000 / s, and the melt viscosity was recorded.

(2) Method of measuring melting temperature

The melting temperature was measured using a differential scanning calorimeter (TA Instruments, Q20). When the resin sample is heated from 40 ° C to 360 ° C under a temperature elevation condition of 20 ° C / min, the temperature indicated by the observed endothermic peak is referred to as a _first melting temperature (Tm ₁ ), and the temperature is elevated 20 ° C above Tm ₁ for 5 minutes And then cooled to 40 ° C at a temperature of 10 ° C / min. Then, when the temperature was again raised at a rate of 20 ° C / min, the temperature indicated by the observed endothermic peak was recorded as the melting temperature.

(3) Method of measuring tensile strength, bending strength, impact strength and heat resistance temperature

Each specimen of each of the above-prepared all-aromatic liquid-crystalline polyester amide resin compounds was prepared using an injection molding machine (FANUC Co., Ltd., S-2000i 50B). The specimens were cooled to room temperature and allowed to stand for 5 hours, The tensile strength (ASTM D638), flexural strength (ASTM D790), impact strength (ASTM D256) and heat resistance temperature (ASTM D648) of each specimen were measured.

(4) Evaluation method of blister occurrence

Flexible specimens of each of the prepared wholly aromatic liquid-crystalline polyester amide resin compounds were prepared using an injection molding machine (FANUC Co., Ltd., S-2000i 50B). The specimens were thermally treated at 280 ° C for 5 minutes, (Samsung Techwin, RF30102) was used to evaluate whether blisters were formed on the surface of each of the heat-treated specimens.

division
fair
obstacle Properties of resin Melting point of resin compound
(poise) Properties of Injection Molded Parts Melting
Viscosity
(poise) Melting
Temperature
(° C) Seal
burglar
(MPa) curve
burglar
(MPa) Shock
burglar
(J / m) Heat resistance
Temperature
(° C) Blister
Occurrence
(Occurrence: O, not occurring: X) Example 1 No 370 333 330 116 150 857 267 × Comparative Example 1 Yes 220 326 180 105 126 618 258 ○

Referring to Table 1, the injection molded articles of the wholly aromatic liquid-crystalline polyester amide resin compound prepared in Example 1 had excellent physical properties as compared with the injection molded articles of the wholly aromatic liquid-crystalline polyester amide resin compound prepared in Comparative Example 1 appear. In addition, in the production of the wholly aromatic liquid-crystalline polyester amide resin, the above-described process disorder did not occur in Example 1, but the process disorder occurred in Comparative Example 1. On the other hand, the wholly aromatic liquid-crystalline polyester amide resin prepared in Comparative Example 1 showed lower melting point and melting temperature than the wholly aromatic liquid-crystalline polyester amide resin prepared in Example 1, Since the reaction did not proceed sufficiently during the production of the ester amide resin, the wholly aromatic liquid-crystalline polyester amide resin having a low degree of polymerization was obtained. The melt viscosity of the wholly aromatic liquid-crystalline polyester amide resin compound prepared in Comparative Example 1 was also lower than that of the wholly aromatic liquid-crystalline polyester amide resin compound prepared in Example 1, This is because the polymerization degree of the wholly aromatic liquid-crystalline polyester amide resin produced was low.

While the 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 (11)

Reacting a first monomer having a hydroxyl group and a second monomer having an amino group with an acid anhydride at a first temperature to at least partially acetylate each of them and then removing the gas;
Reacting at least one of the first and second monomers with an acid anhydride at a second temperature above the first temperature to further acetylate and then remove the gas; And
And polycondensing the acetylated monomers with a dicarboxylic acid to synthesize an aromatic liquid-crystalline polyester amide prepolymer
Wherein the first temperature is from 140 to 170 ° C, and the second temperature is from 190 to 220 ° C. The method according to claim 1,
Wherein the acid anhydride comprises at least one compound selected from the group consisting of acetic anhydride, anhydrous propionic acid, isobutyric anhydride, anhydrous valeric acid, anhydrous pivalic acid, anhydrous butyric acid, diphenyl carbonate and benzyl acetate, Wherein the amount of the monomer to be used is 0.5 to 2.0 moles relative to 1 mole of the sum of the amino group and the hydroxyl group contained in the first monomer and the second monomer. The method according to claim 1,
Wherein the first monomer is selected from the group consisting of 4,4'-biphenol, hydroquinone, 1,4-dihydroxynaphthalene and 2,6-dihydroxynaphthalene At least one aromatic diol; At least one aromatic hydroxycarboxylic acid in parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; Glycolic acid, lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid and 2-hydroxyhexanoic acid. At least one aliphatic hydroxycarboxylic acid; At least one aromatic hydroxylamine selected from the group consisting of 3-aminophenol, 4-aminophenol and 2-amino-6-naphthol; And at least one aliphatic hydroxylamine selected from the group consisting of 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol; and a method for producing an aromatic liquid-crystalline polyester amide resin . The method according to claim 1,
Wherein the second monomer is at least one aromatic hydroxylamine selected from the group consisting of 3-aminophenol, 4-aminophenol, and 2-amino-6-naphthol; At least one aliphatic hydroxylamine selected from the group consisting of 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol; At least one aromatic diamine selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine and 2,6-naphthalenediamine; At least one aliphatic diamine selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane; At least one aromatic aminocarboxylic acid selected from the group consisting of 4-aminobenzoic acid, 2-amino-naphthalene-6-carboxylic acid and 4-amino-biphenyl-4-carboxylic acid; And at least one aliphatic aminocarboxylic acid selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid, and an aromatic liquid-crystalline polyester amide A method for producing a resin. The method according to claim 1,
Wherein the first monomer and the second monomer together have a hydroxyl group and an amino group. The method according to claim 1,
Wherein the dicarboxylic acid is selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid, terephthalic acid, 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid, and 1,5-pentanedicarboxylic acid A method for producing an aromatic liquid-crystalline polyester amide resin comprising at least one compound. delete The method according to claim 1,
Wherein the step of synthesizing the aromatic liquid-crystalline polyester amide prepolymer proceeds in a temperature range of 310 to 340 ° C. The method according to claim 1,
Wherein the first monomer, the second monomer, and the dicarboxylic acid are each an aromatic compound. The method according to claim 1,
And synthesizing the aromatic liquid-crystalline polyester amide prepolymer by solid-phase polycondensation of the synthesized aromatic liquid-crystalline polyester amide prepolymer. An aromatic liquid-crystalline polyester amide resin compound comprising an aromatic liquid-crystalline polyester amide resin produced according to the method of any one of claims 1 to 6 or 8 to 10.