KR101840065B1 - Method of preparing aromatic liquid crystalline polyester resin and method of aromatic liquid crystalline polyester resin compound using the aromatic liquid crystalline polyester resin prepared by the method - Google Patents

Abstract

A process for producing an aromatic liquid crystal polyester resin and a process for producing an aromatic liquid crystal polyester resin compound are disclosed. The process for producing an aromatic liquid-crystalline polyester resin according to the present invention comprises a step (acetylation step) of reacting a first monomer having at least one functional group of a hydroxyl group and an amino group with an acid anhydride to thereby acetylate the acetylated first monomer and the dicar LE by an acid condensation reaction and the esterification reaction includes the step of synthesizing the aromatic liquid-crystalline polyester prepolymer (polycondensation and esterification step), the condensation and esterification steps are first to an elevated temperature to a temperature T ₁ temperature increase step, and a second temperature raising step of raising the temperature to the temperature of the constant-temperature keeping step of keeping at a temperature T ₁ for a certain period of time (t ₁₎ and T _2, wherein T ₁ is 240 ~ 270 ℃, wherein T ₂ is 300 to 340 ° C. The aromatic liquid-crystalline polyester resin compound described above is produced by using the aromatic liquid-crystalline polyester resin produced by the above method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aromatic liquid crystalline polyester resin and an aromatic liquid crystalline polyester resin,

A process for producing an aromatic liquid crystal polyester resin and a process for producing an aromatic liquid crystal polyester resin compound are disclosed. More specifically, the present invention relates to a process for producing an aromatic liquid-crystalline polyester resin capable of reducing the amount of unreacted monomers and an outgassing amount, and a process for producing an aromatic liquid-crystalline polyester resin compound using the aromatic liquid- A manufacturing method is disclosed.

The aromatic liquid-crystalline polyester resin exhibits a rigid molecular structure and forms a liquid crystal state without entanglement between molecules even in a molten state, and exhibits a molecular chain oriented in the flow direction by a shearing force during molding.

Due to these properties, aromatic liquid-crystalline polyester 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 remarkable development of the industry in recent years, the use of aromatic liquid-crystalline polyester resins tends to become more sophisticated and specialized. In addition, the aromatic liquid-crystalline polyester resin is excellent in fluidity and can be injection-molded efficiently and economically. Such an aromatic liquid-crystalline polyester resin is excellent in heat resistance, resistance to hydrolysis and dimensional stability at high temperature, excellent in mechanical strength such as flexural strength, tensile strength and impact strength, and can be used as a coil bobbin coil bobbin), connectors for electric and electronic parts, relays, materials for various automobile parts, materials for containers, films and substrates.

Such an aromatic liquid-crystalline polyester resin can be produced by polycondensation reaction of at least two kinds of monomers. This polycondensation reaction proceeds at a high temperature, in which sublimation monomers and intermediate products sublimate among the monomers used as a reaction raw material. The sublimable monomer reacts with the non-solubilizing monomer before sublimation but does not react with the non-solubilizing monomer after sublimation. Therefore, the non-solubilizing monomer can not react with the sublimable monomer by the amount of sublimation, so that not only the sublimable monomer but also the non-solubilizing monomer remains as unreacted monomers. As a result, the monomer composition ratio of the final resin is different from the initial monomer addition ratio, and the sludge and unreacted monomers are the main causes of outgassing during processing of the resin.

An embodiment of the present invention provides a method of producing an aromatic liquid-crystalline polyester resin capable of reducing the amount of unreacted monomers and the amount of outgas generated.

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

According to an aspect of the present invention,

Reacting a first monomer having at least one functional group selected from a hydroxyl group and an amino group with an acid anhydride to acetylate (acetylation step); And

(Polycondensation and esterification) of an aromatic liquid-crystalline polyester prepolymer by subjecting the acetylated first monomer and a dicarboxylic acid to a polycondensation reaction and an esterification reaction,

The polycondensation and esterification step is the second temperature increase step of raising the temperature to the first temperature raising step of raising the temperature to a temperature of T _1, constant-temperature keeping step and the temperature T ₂ for holding for a predetermined time (t ₁₎ at a temperature T ₁ Including,

Wherein T ₁ is from 240 to 270 ° C, and T ₂ is from 300 to 340 ° C.

T ₁ may be 0.5 to 2 hours.

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

The amount of the acid anhydride to be used may be 1.0 to 1.5 moles per 1 mole of the sum of the amino group and the hydroxyl group contained in the first monomer.

The first monomer may be selected from the group consisting of 4,4'-biphenol, 2,2'-biphenol, bisphenol A, hydroquinone, resorcinol, 1,2-benzene diol, 1,4-dihydroxynaphthalene, - dihydroxynaphthalene < / RTI > At least one aromatic diol; 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, At least one aliphatic diol selected from the group consisting of diols, 1,8-octanediol, ethylene glycol, etohexadiol, p-menthane-3,8-diol and 2-methyl- ; At least one compound selected from the group consisting of parahydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid and 4'- An aromatic hydroxycarboxylic acid; Glycolic acid, lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid and 2-hydroxyhexanoic acid. At least one aliphatic hydroxycarboxylic acid; Amino-2-naphthol, 1-amino-2-naphthol, 4-amino-1-naphthol, Amino-2-naphthol, 6-amino-2-naphthol, 6-amino-2-naphthol, At least one aromatic hydroxylamine selected from the group consisting of: At least one aliphatic hydroxylamine selected from the group consisting of 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol; 1,3-phenylenediamine, 1,2-phenylenediamine, naphthalene-1,2-diamine, naphthalene-1,4-diamine, naphthalene- At least one aromatic diamine selected from the group consisting of 5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene and naphthalene-2,6-diamine; At least one aliphatic diamine selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane; Aminobenzoic acid, 2-aminobenzoic acid, 2-amino-naphthalene-6-carboxylic acid, 4-amino-biphenyl-4-carboxylic acid, 5-amino-naphthalene- Amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-1-naphthoic acid and At least one aromatic aminocarboxylic acid selected from the group consisting of 3-amino-naphthalene-1-carboxylic acid; At least one aliphatic aminocarboxylic acid selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid; Or a combination thereof.

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

Wherein the dicarboxylic acid is selected from the group consisting of isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 7-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicar At least one compound selected from the group consisting of carboxylic acid, carboxylic acid, terephthalic acid, phthalic acid, 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid, and 1,5-pentanedicarboxylic acid .

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

According to another aspect of the present invention,

The present invention provides a process for producing an aromatic liquid-crystalline polyester resin compound using an aromatic liquid-crystalline polyester resin produced according to the above-described process for producing an aromatic liquid-crystalline polyester resin.

According to the process for producing an aromatic liquid-crystalline polyester resin according to an embodiment of the present invention, an aromatic liquid-crystalline polyester resin in which the amount of unreacted monomers is reduced after the production of the resin and the amount of outgas generated is reduced can be obtained.

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

The method for producing an aromatic liquid-crystalline polyester resin according to an embodiment of the present invention comprises a step (acetylation step) of reacting a first monomer having at least one functional group of a hydroxyl group and an amino group with an acid anhydride, And a step (polycondensation and esterification step) of synthesizing an aromatic liquid-crystalline polyester prepolymer by polycondensation reaction and esterification reaction of the first monomer and the dicarboxylic acid.

In the acetylation step, an acetyl group (-COCH ₃ ) is introduced into an amino group (-NH ₂ ) included in the first monomer to form an acetylamino group (-NHCOCH ₃ ) and / or an acetyl group an acetyl group (-COCH ₃₎ a hydroxyl group (-OH) is introduced to form an acetyl-oxy group (-OCOCH _3), and the acetic acid is produced as a by-product. Here, the by-product acetic acid can be removed from the product in a gaseous state.

In the acetylation step, the amount of the acid anhydride may be 0.5 to 2.0 moles (for example, 1.0 to 1.5 moles) based on 1 mole of the sum of the amino group and the hydroxyl group contained in the first monomer. When the amount of the acid anhydride used is within the above range (0.5 to 2.0 moles), the first monomer is sufficiently acetylated, so that browning does not occur in the synthesized resin and the amount of unreacted acid anhydride is small, Removal is facilitated.

The acetylation step may be conducted at a temperature ranging from 140 to 220 DEG C for 60 to 180 minutes. If the temperature and the time are within the above ranges, the amino group and the hydroxyl group of the first monomer can be sufficiently converted into the acetyl group, so that the subsequent polycondensation reaction and the esterification reaction can proceed at a low temperature, and the aromatic liquid- It does not deteriorate and the browning of the prepolymer does not occur.

The polycondensation and esterification step is the second temperature increase step of raising the temperature to the first temperature raising step of raising the temperature to a temperature of T _1, constant-temperature keeping step and the temperature T ₂ for holding for a predetermined time (t ₁₎ at a temperature T ₁ .

The initial temperature of the first heating step may be the end point temperature of the acetylation step (i.e., 140 to 220 ° C).

T ₁ is 240 to 270 ° C. When the T ₁ is less than 240 ° C, the amount of unreacted monomers and the amount of outgas are reduced (hereinafter simply referred to as "effect") because the amount of the reaction between the first monomer and the dicarboxylic acid is small, If T ₁ exceeds 270 ° C, the sublimation of the first monomer has already proceeded considerably and the effect becomes insignificant.

T ₁ may be 0.5 to 2 hours. If t ₁ is within the range (0.5 to 2 hours), the energy cost can be reduced and the total duration of the polycondensation and esterification steps can be shortened to increase the productivity.

The above T ₂ is 300 to 340 ° C. If T ₂ is less than 300 ° C, the polycondensation reaction and the removal of acetic acid are not sufficiently performed to increase the amount of unreacted monomers and outgas, and if the temperature exceeds 340 ° C, An aromatic liquid-crystalline polyester prepolymer having physical properties suitable for a solid-phase polycondensation reaction can not be obtained.

The first temperature raising step and the second raising temperature step may be performed at a temperature raising rate of 0.3 to 1.0 占 폚 / min, respectively. However, the present invention is not limited to this, and the first heating step and the second heating step may be performed at different heating rates.

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

The aromatic diol is selected from the group consisting of 4,4'-biphenol, 2,2'-biphenol, bisphenol A, hydroquinone, resorcinol, 1,2-benzene diol, 1,4-dihydroxynaphthalene, Dihydroxynaphthalene < / RTI > At least one kind of compound.

The aliphatic diol may be selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- At least one selected from the group consisting of 5-pentanediol, 1,8-octanediol, ethylene glycol, etohexadiol, p-menthane-3,8-diol and 2- Or < / RTI >

Wherein the aromatic hydroxycarboxylic acid is selected from the group consisting of parahydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid and 4'- At least one kind of compound.

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 is selected from the group consisting of 3-aminophenol, 4-aminophenol, 5-amino-1-naphthol, Amino-2-naphthol, 7-amino-1-naphthol, 7-amino-2-naphthol, 6-amino- 7-naphthol, and the like.

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

Wherein the aromatic diamine is selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine, 1,2-phenylenediamine, naphthalene-1,2-diamine, naphthalene- And at least one compound selected from the group consisting of diamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene and naphthalene-2,6-diamine.

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.

Wherein the aromatic aminocarboxylic acid is selected from the group consisting of 4-aminobenzoic acid, 3-aminobenzoic acid, 2-aminobenzoic acid, 2-amino-naphthalene- Naphthalene-1-carboxylic acid, 3-amino-2-naphthoic acid, -1-naphthoic acid, and 3-amino-naphthalene-1-carboxylic acid.

The aliphatic aminocarboxylic acid may include at least one compound selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid.

The polycondensation and esterification steps may be carried out by solution polycondensation or bulk condensation polymerization.

Wherein the dicarboxylic acid is selected from the group consisting of isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 7-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicar At least one compound selected from the group consisting of carboxylic acid, carboxylic acid, terephthalic acid, phthalic acid, 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid, and 1,5-pentanedicarboxylic acid .

Further, in the polycondensation and esterification steps, acetic acid metal may be further used as a catalyst for accelerating 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 0.10 parts by weight or less based on 100 parts by weight of the total amount of the first monomers.

The method for producing an aromatic liquid-crystalline polyester resin may further include a step of synthesizing an aromatic liquid-crystalline polyester resin by solid-phase polycondensation of the aromatic liquid-crystalline polyester prepolymer. For the solid-phase polycondensation reaction, appropriate heat should be provided to the aromatic liquid-crystalline polyester prepolymer. Examples of the method for providing the heat include a heating plate, hot air, or a high-temperature fluid. Further, in order to remove by-products 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 a process for producing an aromatic liquid-crystalline polyester resin compound using the aromatic liquid-crystalline polyester resin produced by the process for producing an aromatic liquid-crystalline polyester resin.

The method for producing an aromatic liquid-crystalline polyester resin compound includes the steps of synthesizing an aromatic liquid-crystalline polyester resin according to the above-described method for producing an aromatic liquid-crystalline polyester resin, and 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.

The organic additive may include carbon fibers.

The first monomer and the dicarboxylic acid may each be an aromatic compound. In this case, in each of the above-mentioned steps, a wholly aromatic liquid crystalline polyester prepolymer, a wholly aromatic liquid a crystalline polyester resin, a wholly aromatic liquid crystalline polyester 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  1 to 3 and Comparative Example  1 to 2: Wholly aromatic  The liquid crystal polyester resin and the resin Compound  Produce

(Acetylation step)

60 parts by mol of parahydroxybenzoic acid (HBA), 20 parts by mol of 4,4'-biphenol (BP), 15 parts by mol of terephthalic acid (TPA) and 10 parts by mol of 4,4'-biphenol (BP) were placed in a 10 L reactor equipped with a stirrer, a nitrogen gas inlet, a thermometer and a reflux condenser. And 5 molar parts of isophthalic acid (IPA) were charged, and nitrogen gas was injected to render the internal space of the reactor inactive. Here, the sum of the molar fraction of the HBA, the molar fraction of BP, the molar fraction of TPA and the molar fraction of IPA is 100 molar parts. Thereafter, the reactor was subjected to an acetylation reaction together with 1.1 molar parts of acetic anhydride (Ac ₂ O) (i.e., molar amount of [Ac ₂ O to 1 molar part of [mol of HBA + 2 * (mol of BP)]) 0.007 parts by weight of calcium acetate (that is, parts by weight of calcium acetate based on 100 parts by weight of [HBA + BP + TPA + IPA]) was further added to smoothly proceed the sum reaction and the esterification reaction. Thereafter, the reactor temperature was raised to 145 캜 over 30 minutes, and refluxed for 2 hours while maintaining the temperature.

(Polycondensation and esterification steps)

Then, by-products of the then with the removal of acetic acid heated to a temperature of T ₁ the temperature of the reactor contents at a heating rate of 0.4 ℃ / min, maintained for a time t ₁ at the temperature of the T ₁ and then (this "Isothermal Maintaining step "), and the temperature was raised to 330 ° C at a rate of 0.4 ° C / min to proceed the polycondensation reaction and the esterification reaction of the monomers, thereby preparing a wholly aromatic liquid-crystalline polyester prepolymer. T ₁ and t ₁ set in the respective Examples and Comparative Examples are shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 T ₁ (° C) 250 270 260 235 280 t ₁ (hr) One One One One One

(Synthesis step of resin and preparation of resin compound)

The prepolymer prepared in the above polycondensation and esterification step was recovered from the reactor, cooled to room temperature (25 캜), and then filtered using a Feather Mill (FM-1S, manufactured by Hosokawa Co., Ltd.) with a screen having a mesh size of 1.5 mm And crushed into a uniform particle size.

Next, 3,000 g of wholly aromatic liquid-crystalline polyester prepolymer having a uniform particle size was charged into a 10-liter capacity rotary kiln reactor, nitrogen was continuously supplied at a flow rate of 1 Nm 3 / hr, , The temperature was maintained at 200 캜 for 2 hours, the temperature was further raised to 300 캜 over 8 hours, and the temperature was maintained for 1 hour to prepare a wholly aromatic liquid-crystalline polyester resin. Subsequently, the reactor was cooled to room temperature (25 ° C) over 1 hour, and the wholly aromatic liquid-crystalline polyester resin was recovered from the reactor.

Then, the above-prepared wholly aromatic liquid crystal polyester resin and glass fibers (10 mu m in diameter and pulverized glass fiber having an average length of 150 mu m) were mixed at a ratio of 70:30 by weight, and the mixture was extruded by a twin-screw extruder / D: 40, diameter: 20 mm) to prepare a compound of wholly aromatic liquid-crystalline polyester resin. During the preparation of the resin compound, a vacuum was applied to the biaxial extruder to remove by-products.

Comparative Example  3: Wholly aromatic  The liquid crystal polyester resin and the resin Compound  Produce

In the polycondensation and esterification steps, the temperature of the reactor contents obtained after completion of the acetylation step was immediately heated to 330 ° C at a rate of 0.4 ° C / min without the isothermal holding step, And Comparative Examples 1 and 2, a compound of the wholly aromatic liquid-crystalline polyester resin and the resin was prepared.

Evaluation example

The melting temperature and melt viscosity of each of the wholly aromatic liquid-crystalline polyester resins prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 2 below. In addition, the amount of generated sublimate was measured in each of the Examples and Comparative Examples, and the results are shown in Table 2 below. The outgassing amounts of the respective resin compounds were measured, and the results are shown in Table 2 below.

(1) Method of measuring melting temperature

The melting temperature was measured using a differential scanning calorimeter (TA Instruments, DSC 2910). When the resin sample is heated at a temperature elevation condition of 40 ° C to 20 ° C / min, the temperature indicated by the observed endothermic peak is referred to as a _first melting temperature (Tm ₁ ) and maintained at a temperature 30 ° C higher than Tm ₁ for 10 minutes After cooling to 40 캜 under a temperature condition of 10 캜 / min and then heating at a temperature rising rate of 20 캜 / min, the temperature indicated by the observed endothermic peak was recorded up to the melting temperature.

(2) Method of measuring melt viscosity

Using a melt viscosity measuring apparatus (Rosand, RH2000), the viscosity was measured at a temperature of 1.0 mm × 32 mm capillary (melting temperature + 10 ° C.) and a shear rate of 100 / s, and the melt viscosity was recorded.

(3) Method of measuring the amount of generated sublimate

In each of the above Examples and Comparative Examples, after the completion of the polycondensation and esterification steps, the material remaining on the reactor wall was collected and the content thereof was measured. The measured value was compared with the content of the sublimate (i.e., Content). Then, the value obtained by dividing the content of the sublimate by the total content of HBA and BP fed into the reactor was recorded as the amount (wt%) of the sublimate.

(4) Method of measuring outgassing amount

Gas was produced from each of the prepared wholly aromatic liquid-crystalline polyester resin compounds at 290 ° C by using a gas chromatograph (Agilent 7890A) and a TDS (Gerstel, TDS2) equipped with a mass detector (Agilent 5975) The composition and content of outgas were measured. Thereafter, the total content of the measured outgas components was expressed as a ratio (wtppm) to the content of each of the wholly aromatic liquid crystal polyester resin compounds, and was recorded as an outgassing amount.

Example Comparative Example One 2 3 One 2 3 Properties of resin Melting temperature (캜) 343 344 343 344 344 342 Melting point (@ 350 ℃, poise,) 860 758 829 825 831 786 Generated amount of sublimate (wt%) 0.27 0.28 0.25 0.36 0.39 0.34 Outgas generation (wtppm) of resin compound 216 235 229 339 362 350

With reference to Table 2, the amount of the sublimated product produced in the production process of each of the wholly aromatic liquid-crystalline polyester resins of Examples 1 to 3 was such that the amount of the sublimated product produced during the manufacturing process of each of the wholly aromatic liquid- Respectively. Each of the wholly aromatic liquid-crystalline polyester resin compounds prepared in Examples 1 to 3 was found to have a smaller amount of outgas than the respective wholly aromatic liquid-crystalline polyester resin compounds prepared in Comparative Examples 1 to 3.

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 exemplary 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 (9)

Reacting a first monomer having at least one functional group selected from a hydroxyl group and an amino group with an acid anhydride to acetylate (acetylation step); And
(Polycondensation and esterification) of an aromatic liquid-crystalline polyester prepolymer by subjecting the acetylated first monomer and a dicarboxylic acid to a polycondensation reaction and an esterification reaction,
The polycondensation and esterification step is the second temperature increase step of raising the temperature to the first temperature raising step of raising the temperature to a temperature of T _1, constant-temperature keeping step and the temperature T ₂ for holding for a predetermined time (t ₁₎ at a temperature T ₁ Including,
Wherein T ₁ is 240 to 270 ° C, T ₂ is 300 to 340 ° C,
Wherein an outgassing amount is less than 230 wtppm. The method according to claim 1,
Wherein t ₁ is 0.5 to 2 hours. The method according to claim 1,
Further comprising the step of synthesizing the aromatic liquid-crystalline polyester resin by solid-state polycondensation of the synthesized aromatic liquid-crystalline polyester prepolymer. The method according to claim 1,
Wherein the amount of the acid anhydride to be used is 1.0 to 1.5 mol per one molar portion of the sum of the amino group and the hydroxyl group contained in the first monomer. The method according to claim 1,
The first monomer may be selected from the group consisting of 4,4'-biphenol, 2,2'-biphenol, bisphenol A, hydroquinone, resorcinol, 1,2-benzene diol, 1,4-dihydroxynaphthalene, - dihydroxynaphthalene < / RTI > At least one aromatic diol; 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, At least one aliphatic diol selected from the group consisting of diols, 1,8-octanediol, ethylene glycol, etohexadiol, p-menthane-3,8-diol and 2-methyl- ; At least one compound selected from the group consisting of parahydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid and 4'- An aromatic hydroxycarboxylic acid; Glycolic acid, lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid and 2-hydroxyhexanoic acid. At least one aliphatic hydroxycarboxylic acid; Amino-2-naphthol, 1-amino-2-naphthol, 4-amino-1-naphthol, Amino-2-naphthol, 6-amino-2-naphthol, 6-amino-2-naphthol, At least one aromatic hydroxylamine selected from the group consisting of: At least one aliphatic hydroxylamine selected from the group consisting of 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol; 1,3-phenylenediamine, 1,2-phenylenediamine, naphthalene-1,2-diamine, naphthalene-1,4-diamine, naphthalene- At least one aromatic diamine selected from the group consisting of 5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene and naphthalene-2,6-diamine; At least one aliphatic diamine selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane; Aminobenzoic acid, 2-aminobenzoic acid, 2-amino-naphthalene-6-carboxylic acid, 4-amino-biphenyl-4-carboxylic acid, 5-amino-naphthalene- Amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-1-naphthoic acid and At least one aromatic aminocarboxylic acid selected from the group consisting of 3-amino-naphthalene-1-carboxylic acid; At least one aliphatic aminocarboxylic acid selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid; Or a combination thereof. ≪ / RTI > The method according to claim 1,
Wherein the acid anhydride comprises at least one compound selected from the group consisting of acetic anhydride, propionic anhydride, isobutyric anhydride, anhydrous diacetic acid, anhydrous pivalic acid and anhydrous butyric acid. The method according to claim 1,
Wherein the dicarboxylic acid is selected from the group consisting of isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, Naphthalene dicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, terephthalic acid, phthalic acid, 1, Propanedicarboxylic acid, 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid, and 1,5-pentanedicarboxylic acid. The method according to claim 1,
Wherein the first monomer and the dicarboxylic acid are aromatic compounds, respectively. A process for producing an aromatic liquid-crystalline polyester resin compound using an aromatic liquid-crystalline polyester resin produced by the method according to any one of claims 1 to 8.