KR101817366B1 - Method of preparing aromatic liquid crystalline polyester resin and aromatic liquid crystalline polyester resin compound including the aromatic liquid crystalline polyester resin prepared by the method - Google Patents

Abstract

A process for producing an aromatic liquid crystalline polyester resin and an aromatic liquid crystalline polyester resin compound are disclosed. The process for producing an aromatic liquid-crystalline polyester resin includes the steps of: polymerizing a monomer raw material comprising a first monomer of a kink structure and a second monomer of a straight structure, The second monomer is an isomer of an aromatic dicarboxylic acid, an aromatic diol, an aromatic hydroxylamine, an aromatic diamine or an aromatic aminocarboxylic acid, and the content of the first monomer is 4 to 25 molar parts per 100 molar parts of the second monomer , And the monomer raw material includes a monomer containing at least one of a hydroxyl group and an amino group.

Description

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 crystalline polyester resin and an aromatic liquid crystalline polyester resin compound are disclosed. More particularly, the present invention relates to a process for producing an aromatic liquid-crystalline polyester resin comprising a step of polymerizing a monomer material comprising a first monomer of a kink structure and a second monomer of a linear structure, and an aromatic liquid- An aromatic liquid-crystalline polyester resin compound containing a resin is disclosed.

The conventional aromatic liquid-crystalline polyester resin has low fluidity when the heat resistance is high, and thus is difficult to be used in the production of thin film molded articles and has a problem in that warpage characteristics are deteriorated at high temperatures.

The resin applicable to the ultra-thin molded article includes repeating units derived from a naphthalene-based monomer as a main skeleton. In the liquid phase polymerization reaction, the viscosity of the reactor is rapidly increased at a temperature of 300 ° C or higher, A phenomenon occurs. Therefore, the polymerization reaction and the discharge of gaseous by-products from the reactor are not smooth, resulting in blisters in the final product (i.e., molded article). In addition, the extrusion processability of the resin compound is deteriorated due to the rapid solidification rate of the resin compound extrudate containing the resin. Therefore, the appearance of the pellets becomes poor, and the mechanical properties of the resin compound and the molded article also deteriorate.

One embodiment of the present invention provides a method for producing an aromatic liquid-crystalline polyester resin comprising the step of polymerizing a monomer raw material comprising a first monomer of a kink structure and a second monomer of a linear structure.

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

According to an aspect of the present invention,

Polymerizing a monomeric raw material comprising a first monomer of a kink structure and a second monomer of a straight structure,

Wherein the first monomer and the second monomer are isomers, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxylamines, aromatic diamines or aromatic aminocarboxylic acids,

The content of the first monomer is 4 to 25 molar parts relative to 100 molar parts of the second monomer,

Wherein the monomer raw material comprises a monomer containing at least one of a hydroxyl group and an amino group.

The monomer raw material may include at least one compound selected from the group consisting of an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic dicarboxylic acid, an aromatic hydroxylamine, an aromatic diamine, and an aromatic aminocarboxylic acid.

Wherein the aromatic hydroxycarboxylic acid comprises an aromatic hydroxycarboxylic acid having a kink structure and an aromatic hydroxycarboxylic acid having a linear structure, and the content of the aromatic hydroxycarboxylic acid in the kink structure is the aromatic hydroxycarboxylic acid It may be 5 to 750 parts by mole based on 1 part by mol of the carboxylic acid.

Wherein the aromatic hydroxycarboxylic acid of the kink structure comprises at least one compound selected from the group consisting of 1-hydroxy-2-naphthoic acid and 6-hydroxy-2-naphthoic acid, Hydroxybenzoic acid, and 4'-hydroxy-4-biphenylcarboxylic acid.

The content of the first monomer may be 1 to 5 moles per 100 moles of the total amount of the monomer raw material.

Wherein said monomeric raw material further comprises a third monomer and said third monomer is selected from the group consisting of glycolic acid, lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, and 2-hydroxyhexanoic acid At least one aliphatic hydroxycarboxylic acid; An aliphatic dicarboxylic acid comprising at least one compound selected from the group consisting of 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid and 1,5-pentanedicarboxylic acid; 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, At least one compound selected from the group consisting of diols, 1,8-octanediol, ethylene glycol, etohexadiol, p-menthane-3,8-diol and 2-methyl- Aliphatic diols including; At least one aliphatic hydroxylamine selected from the group consisting of 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol; At least one aliphatic diamine selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane; And at least one aliphatic aminocarboxylic acid selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid.

Wherein the first monomer is selected from the group consisting of isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, An aromatic dicarboxylic acid containing at least one compound selected from the group consisting of 2,6-naphthalene dicarboxylic acid and biphenyl-2,2'-dicarboxylic acid (diphenic acid); Resorcinol, 2,2'-biphenol, 3,3'-biphenol, pyrocatechol, 1,2-naphthalene diol, 1,3-naphthalene diol, 1,4-naphthalene diol, Aromatic compounds containing at least one compound selected from the group consisting of diols, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol and 2,7- Diol; Amino-1-naphthol, 3-amino-2-naphthol, 5-amino-2-naphthol and 8-amino-2-naphthol An aromatic hydroxylamine comprising at least one compound selected from the group consisting of: 1,3-phenylenediamine and 1,2-phenylenediamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8- An aromatic diamine comprising at least one compound selected from the group consisting of 3-diaminonaphthalene, 2,2'-biphenyldiamine and 3,4'-biphenyldiamine; Or an aromatic aminocarboxylic acid comprising at least one compound selected from the group consisting of 3-aminobenzoic acid, 2-aminobenzoic acid, 3-amino-2-naphthoic acid and 6-amino-2-naphthoic acid.

The second monomer is an aromatic dicarboxylic acid containing at least one compound of terephthalic acid and biphenyl-4,4'-dicarboxylic acid; An aromatic diol comprising at least one compound selected from the group consisting of 4,4'-biphenol and hydroquinone; Aromatic hydroxylamines comprising 4-aminophenol; An aromatic diamine comprising at least one compound selected from the group consisting of 1,4-phenylenediamine and 4,4'-diaminobiphenyl; Or an aromatic aminocarboxylic acid comprising 4-aminobenzoic acid.

The method for producing an aromatic liquid-crystalline polyester resin includes the steps of: contacting the monomer raw material with an acid anhydride to obtain an acetylated monomer by acetylating at least a part of the hydroxyl and amino groups in the monomer raw material; Synthesizing an aromatic liquid-crystalline polyester prepolymer by a polycondensation reaction of the monomer raw material, and synthesizing an aromatic liquid-crystalline polyester resin by solid-phase polycondensation reaction of the synthesized aromatic liquid-crystalline polyester prepolymer.

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 content 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 monomer raw material.

According to another aspect of the present invention,

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

According to the process for producing an aromatic liquid-crystalline polyester resin according to an embodiment of the present invention, the solidification rate of the reaction product is retarded during the polycondensation reaction at a high temperature, the polymerization reaction proceeds smoothly, and the by- Can be discharged. Thus, deterioration of the physical properties of the resin and the molded article which occurs when the by-product is contained in the resin and the molded article can be prevented. This makes it possible to obtain an aromatic liquid-crystalline polyester resin having overall uniform physical properties, a resin compound having improved flowability, mechanical strength and heat resistance, and a molded article improved in mechanical strength (in particular, bending property) and heat resistance. Particularly, even if the amount of by-products remaining in the resin as the final product is small and the heat treatment at a high temperature is carried out, a molded article free from deformation due to warping and blistering can be obtained.

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

A method of producing an aromatic liquid-crystalline polyester resin according to an embodiment of the present invention includes a step of polymerizing a monomer raw material comprising a first monomer of a kink structure and a second monomer of a straight structure . As used herein, the term " linear structure "means a structure in which two functional groups (e.g., functional groups selected from a hydroxyl group, a carboxyl group and an amino group) are arranged so as to minimize electrostatic force and steric hindrance therebetween, Refers to a structure in which functional groups are arranged and not a "linear structure ".

The first monomer and the second monomer are isomers. For example, the first monomer and the second monomer are structural isomers.

The first monomer and the second monomer are an aromatic dicarboxylic acid, an aromatic diol, an aromatic hydroxylamine, an aromatic diamine, or an aromatic aminocarboxylic acid.

The first monomer serves to lower the solidification rate of the reaction product in the resin synthesis process and the resin compound manufacturing process (particularly, the extrusion process). The lowering of the solidification rate of the reaction product in each of the above steps has the following advantages:

(1) Gaseous by-products such as acetic acid can be smoothly discharged from the reactor, and the amount of by-products remaining in the reaction products (i.e., prepolymer, resin and resin compound) decreases. As a result, the polycondensation reaction proceeds smoothly, the fluidity of the resin and the resin compound increases, and blisters do not occur in the molded article.

(2) The prepolymer synthesized after the prepolymer synthesis can be easily discharged from the reactor.

(3) The crushing operation of the prepolymer for the solid-state polycondensation can proceed easily.

(4) the extrusion of the extrudate of the resin compound formed in the extrusion process is reduced, and the subsequent pelletization process can proceed easily.

Wherein the first monomer is selected from the group consisting of isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, An aromatic dicarboxylic acid containing at least one compound selected from the group consisting of 2,6-naphthalene dicarboxylic acid and biphenyl-2,2'-dicarboxylic acid (diphenic acid); Resorcinol, 2,2'-biphenol, 3,3'-biphenol, pyrocatechol, 1,2-naphthalene diol, 1,3-naphthalene diol, 1,4-naphthalene diol, Aromatic compounds containing at least one compound selected from the group consisting of diols, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol and 2,7- Diol; Amino-1-naphthol, 3-amino-2-naphthol, 5-amino-2-naphthol and 8-amino-2-naphthol An aromatic hydroxylamine comprising at least one compound selected from the group consisting of: 1,3-phenylenediamine and 1,2-phenylenediamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8- An aromatic diamine comprising at least one compound selected from the group consisting of 3-diaminonaphthalene, 2,2'-biphenyldiamine and 3,4'-biphenyldiamine; Or an aromatic aminocarboxylic acid comprising at least one compound selected from the group consisting of 3-aminobenzoic acid, 2-aminobenzoic acid, 3-amino-2-naphthoic acid and 6-amino-2-naphthoic acid.

The second monomer is an aromatic dicarboxylic acid containing at least one compound of terephthalic acid and biphenyl-4,4'-dicarboxylic acid; An aromatic diol comprising at least one compound selected from the group consisting of 4,4'-biphenol and hydroquinone; Aromatic hydroxylamines comprising 4-aminophenol; An aromatic diamine comprising at least one compound selected from the group consisting of 1,4-phenylenediamine and 4,4'-diaminobiphenyl; Or an aromatic aminocarboxylic acid comprising 4-aminobenzoic acid.

The content of the first monomer is 4 to 25 molar parts relative to 100 molar parts of the second monomer. If the content of the first monomer is less than 4 molar parts with respect to 100 molar parts of the second monomer, the solidification rate of the reaction product is accelerated in the resin synthesis step and the resin compound manufacturing step to deteriorate the polymerizability and processability, The heat resistance and mechanical properties of the synthesized resin, resin compound and / or molded article are deteriorated.

The content of the first monomer may be 1 to 5 molar parts, for example, 1 to 3 molar parts, based on 100 molar parts of the total amount of the monomeric raw materials. If the content of the first monomer is within the above range (1 to 5 molar parts), the solidification rate of the reaction product in the step of synthesizing the resin and the step of producing the resin compound is slowed to improve the polymerizability and workability. The fluidity, heat resistance and mechanical properties of the compound and / or the molded article can be improved.

The monomer raw material may include at least one compound selected from the group consisting of an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic dicarboxylic acid, an aromatic hydroxylamine, an aromatic diamine, and an aromatic aminocarboxylic acid.

When the monomer raw material comprises an aromatic hydroxycarboxylic acid, the aromatic hydroxycarboxylic acid may form a main skeleton of the synthesized resin.

Wherein the aromatic hydroxycarboxylic acid comprises an aromatic hydroxycarboxylic acid having a kink structure and an aromatic hydroxycarboxylic acid having a linear structure, and the content of the aromatic hydroxycarboxylic acid in the kink structure is the aromatic hydroxycarboxylic acid It may be 5 to 750 parts by mole based on 1 part by mol of the carboxylic acid. When the content of the aromatic hydroxycarboxylic acid in the above kink structure is within the above range, the solidification rate of the reaction product in the process of synthesizing the resin and the process of producing the resin compound is lowered and the polymerizing property and processability are excellent. The fluidity, heat resistance and mechanical properties of the resin compound and / or the molded article can be improved.

Wherein the aromatic hydroxycarboxylic acid of the kink structure comprises at least one compound selected from the group consisting of 1-hydroxy-2-naphthoic acid and 6-hydroxy-2-naphthoic acid, Hydroxybenzoic acid, and 4'-hydroxy-4-biphenylcarboxylic acid.

The content of the aromatic hydroxycarboxylic acid may be 40 to 85 moles per 100 moles of the total amount of the monomer raw material. When the content of the aromatic hydroxycarboxylic acid is within the above range, monomers and acetylated monomers are reduced in the resin synthesis step, the physical properties of the resin become uniform, the mechanical properties and heat resistance of the resin compound may be increased, The occurrence of blisters in the molded article can be reduced, the flowability of the resin and the processability of the resin compound can be improved, and the tensile strength of the resin compound can be improved.

The aromatic diol, aromatic dicarboxylic acid, aromatic hydroxylamine, aromatic diamine and / or aromatic aminocarboxylic acid contained in the monomer raw material may be the same as or different from those described as examples of the first monomer and the second monomer have.

When the monomer raw material contains an aromatic dicarboxylic acid, the content of the aromatic dicarboxylic acid may be 8 to 30 moles per 100 moles of the total amount of the monomer raw material. When the content of the aromatic dicarboxylic acid is within the above range, physical properties of the prepolymer are improved and the solid state polymerization reaction can proceed smoothly. In addition, the dischargeability in the prepolymer synthesis step is improved, and the progress of the continuous reaction is facilitated, .

When the monomer raw material comprises an aromatic diol, the aromatic diol may be present in an amount of 8 to 30 mol based on 100 mol of the total amount of the monomer raw material. When the content of the aromatic diol is within the above range, the physical properties of the prepolymer are improved and the solid state polymerization reaction can proceed smoothly. In the prepolymer synthesis step, the dischargeability is improved, and the progress of the continuous reaction is facilitated and the productivity can be improved.

When the monomer raw material comprises an aromatic hydroxylamine, the aromatic hydroxylamine may be present in an amount of more than 0 to 1 mole based on 100 mole of the total amount of the monomer raw material. A molded article having excellent heat resistance can be obtained. The aromatic hydroxylamine may be acetylated to prevent the negative effects of oxidation of the amino group by acetylating the amino group easily oxidized by oxygen in the air.

When the monomer raw material comprises an aromatic diamine, the aromatic diamine may be present in an amount of more than 0 to 1.0 mole based on 100 mole of the total amount of the monomer raw material. When the content of the aromatic diamine is within the above range, a resin, a resin compound and a molded article excellent in heat resistance can be obtained, and a molded article free from blistering even at high temperature heat treatment can be obtained.

When the monomer raw material comprises an aromatic aminocarboxylic acid, the content of the aromatic aminocarboxylic acid may be more than 0 and not more than 2.0 moles based on 100 moles of the total amount of the monomer raw material. When the content of the aromatic aminocarboxylic acid is within the above range, the solidification rate of the reaction product in the resin synthesis step and the resin compound production step is slowed, so that the process trouble does not occur and the polymerizability and workability are excellent. The fluidity, heat resistance and mechanical properties of the resin compound and / or the molded article can be improved.

The monomer raw material includes a monomer containing at least one of a hydroxyl group and an amino group.

The monomer raw material may further comprise a third monomer. These third monomers are selected from the group consisting of glycolic acid, lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid and 2-hydroxyhexanoic acid At least one aliphatic hydroxycarboxylic acid; An aliphatic dicarboxylic acid comprising at least one compound selected from the group consisting of 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid and 1,5-pentanedicarboxylic acid; 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, At least one compound selected from the group consisting of diols, 1,8-octanediol, ethylene glycol, etohexadiol, p-menthane-3,8-diol and 2-methyl- Aliphatic diols including; At least one aliphatic hydroxylamine selected from the group consisting of 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol; At least one aliphatic diamine selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane; And at least one aliphatic aminocarboxylic acid selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid.

The content of the third monomer may be more than 0 and less than 1 part by mole based on 100 parts by mole of the total amount of the monomer raw material. When the content of the third monomer is within the above range, the solidification time of the resin synthesized in the resin synthesis step is shortened, so that troubles are not generated in the pulverization step, and a molded article having excellent heat resistance can be obtained.

The method for producing an aromatic liquid-crystalline polyester resin comprises the steps of (acetylating) a step of obtaining an acetylated monomer by contacting the monomer raw material with an acid anhydride to acetylate at least a part of the hydroxyl and amino groups in the monomer raw material, (Polycondensation step) of synthesizing an aromatic liquid-crystalline polyester prepolymer by a polycondensation reaction of a monomer raw material containing a monomer which has been subjected to a solid-phase polycondensation reaction, and synthesizing an aromatic liquid-crystalline polyester resin by subjecting the synthesized aromatic liquid- Step (solid state polycondensation step).

The acetylation step, the acetyl group (-COCH ₃₎ to at least one of a hydroxyl group (-OH) and amino (-NH ₂₎ contained in the monomer raw material is introduced acetyl oxy group (-OCOCH ₃₎ and the acetylamino group (- NHCOCH ₃ ) and acetic acid gas is produced as a by-product. Here, the by-product acetic acid gas can be easily removed from the product.

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 total amount of the acid anhydride (that is, the total amount of the acid anhydride used in the acetylation step) may be 0.5 to 2.0 mols based on one molar part of the sum of the amino group and the hydroxyl group contained in the monomer raw material. When the total amount of the acid anhydride is within the above range, the amino group and the hydroxyl group contained in the monomer raw material are sufficiently acetylated. Thus, browning does not occur in the synthesized resin and the unreacted amount of the used acid anhydride is small Removal is facilitated.

The acetylation step may be carried out at 140 to 220 ° C for 60 to 100 minutes. If the acetylation reaction temperature and time are respectively within the above ranges, all or almost all of the hydroxyl groups and amino groups contained in the monomer raw material may be converted to acetyl groups and the subsequent polycondensation reaction may proceed at a low temperature, The polyester prepolymer is not deteriorated and the browning of the prepolymer does not occur.

The step of synthesizing an aromatic liquid-crystalline polyester prepolymer by a polycondensation reaction of the monomer material containing the acetylated monomer may be carried out by solution polycondensation or bulk condensation polymerization.

In the synthesis of the aromatic liquid-crystalline polyester prepolymer, 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, for example, 0.10 parts by weight or less based on 100 parts by weight of the total amount of the monomer raw materials.

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

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, the aromatic liquid-crystalline polyester 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 resin compound comprising an aromatic liquid-crystalline polyester resin produced by the above-described process for producing an aromatic liquid-crystalline polyester resin.

The aromatic liquid-crystalline polyester resin compound can be produced by synthesizing an aromatic liquid-crystalline polyester resin according to the above-described method for producing an aromatic liquid-crystalline polyester resin, and then melt-kneading the synthesized aromatic liquid-crystalline polyester resin and the additive. 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.

In this case, the wholly aromatic liquid-crystalline polyester prepolymer, the wholly aromatic liquid-crystalline polyester resin, the wholly aromatic liquid-crystalline polyester resin compound, and the molded article thereof are each produced in each of the above-described steps.

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 reaction)

Hydroxy-2-naphthoic acid (HNA), parahydroxybenzoic acid (HBA), 4,4'-biphenol (BP) and the like were added to a 10-liter reactor equipped with a stirrer, a nitrogen gas inlet, a thermometer and a reflux condenser. , Isophthalic acid (IPA), and terephthalic acid (TPA) were charged in the ratios listed in Table 1 below, nitrogen gas was injected to make the internal space of the reactor inactive, and acetic acid anhydride (Ac ₂ O) To accelerate the acetylation reaction and the subsequent polycondensation reaction together, potassium acetate was added in an amount as shown in Table 1 below. Thereafter, the temperature of the reactor was raised to 150 캜 over 30 minutes, and refluxed for 2 hours while maintaining the temperature.

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

Next, the wholly aromatic liquid-crystal polyester 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 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 310 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, glass fiber (10 mu m in diameter, pulverized glass fiber having an average length of 150 mu m) and mica (diameter 2-25 mu m) were mixed in a ratio of 65:10:25 , And melt-kneaded using a twin-screw extruder (L / D: 40, diameter: 20 mm, manufactured by Collin Co.) to produce 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.

division Amount used (molar ^{* 1} ) usage
(Mover ^{* 2} ) usage
(Parts by weight ^{* 3} ) HNA HBA BP IPA TPA Ac ₂ O Potassium acetate Example 1 48 2 25 One 24 1.1 0.007 Example 2 48 2 25 2 23 1.1 0.007 Example 3 48 2 25 5 20 1.1 0.007 Comparative Example 1 48 2 25 0 25 1.1 0.007 Comparative Example 2 48 2 25 6 19 1.1 0.007

* 1: [molar fraction of HNA + molar fraction of HBA + molar fraction of BP + molar fraction of IPA + molar fraction of TPA] = 100 molar fraction

* 2: molar ratio of Ac ₂ O to 1 molar amount of [mol of HNA + mol of HBA + 2 * (mol of BP)]

* 3: Weight ratio of calcium acetate to 100 parts by weight of [HNA + HBA + BP + IPA + TPA]

Evaluation example

The melting temperature (Tm), the crystallization temperature (Tc), the temperature difference (Tm-Tc), and the melt viscosity of each of the wholly aromatic liquid-crystalline polyester resins prepared in Examples 1 to 3 and Comparative Examples 1 and 2; The temperature difference (Tm-Tc) of each of the wholly aromatic liquid-crystalline polyester resin compounds prepared in Examples 1 to 3 and Comparative Examples 1 and 2; And the tensile strength, tensile elongation, flexural strength, flexural modulus, flexural elongation, impact strength, heat resistance temperature and occurrence of blisters of injection molded articles were measured or evaluated by the following methods, and the results are shown in Table 2 below.

(1) Method of measuring crystallization temperature and melting temperature

The melting temperature was measured using a differential scanning calorimeter (TA Instruments, Q20). The temperature represented by the observed endothermic peak when the resin or the resin compound sample is heated from 40 ° C to 360 ° C at an elevation temperature of 20 ° C / min is referred to as a primary melting temperature (Tm ₁ ), and a temperature 20 ° C higher than Tm ₁ For 5 minutes, and the temperature at which the observed exothermic peak appeared when cooled to 40 DEG C at a temperature of 10 DEG C / min was recorded as the crystallization temperature. Thereafter, 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. Here, the lower the melting temperature, the easier the low-temperature molding.

(2) 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. Here, the lower the melt viscosity, the higher the fluidity.

(3) Method of measuring tensile strength, tensile elongation, flexural strength, flexural modulus, flexural elongation, impact strength and heat resistance temperature

A specimen of each of the above prepared all-aromatic liquid crystal polyester 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, (ASTM D638), flexural strength (ASTM D790), flexural modulus (ASTM D790), flexural elongation (ASTM D790), impact strength (ASTM D256) and heat resistance temperature (ASTM D648) Were measured.

(4) Evaluation method of blister occurrence

Flexible specimens of each of the prepared wholly aromatic liquid-crystalline polyester 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 and then subjected to a reflow tester Samsung Techwin, RF30102) was used to set the test temperature to 280 ° C, and then heat treatment was performed to evaluate whether blisters were formed on the surface of each test piece.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Properties of resin Tm (占 폚) 349 348 346 349 340 Tc (占 폚) 324 314 306 330 298 Tm-Tc (占 폚) 25 34 40 19 42 Melting point
(@ 360 ℃, Poise) 482 526 455 450 324 Properties of resin compounds Tm-Tc (占 폚) 23 29 36 19 42 Properties of Injection Molded Parts The tensile strength
(MPa) 127 135 132 112 120 Tensile elongation
(%) 1.54 1.80 1.82 1.49 1.98 Flexural strength
(MPa) 172 189 188 163 161 Flexural modulus
(GPa) 10.8 12.9 13.2 10.2 9.2 Flexion elongation
(%) 2.59 2.74 2.72 2.50 2.86 Impact strength
(J / m) 232 306 341 195 225 Heat resistance temperature
(° C) 308 310 307 309 301 Blister
Occurrence
(Occurrence: O, not occurring: X) × × × ○ ○

Referring to the above Table 2, the injection molded articles of the wholly aromatic liquid-crystalline polyester resin compound prepared in Examples 1 to 3 were superior in all properties to the injection molded articles of the wholly aromatic liquid-crystalline polyester resin compound prepared in Comparative Example 1 . In addition, the injection molded articles of the wholly aromatic liquid-crystalline polyester resin compounds prepared in Examples 1 to 3 were superior in heat resistance to the injection molded articles of the wholly aromatic liquid-crystalline polyester resin compound prepared in Comparative Example 2. On the other hand, the wholly aromatic liquid-crystalline polyester resin prepared in Examples 1 to 3 showed a larger difference (Tm-Tc) between the melting temperature and the crystallization temperature than the wholly aromatic liquid-crystalline polyester resin prepared in Comparative Example 1, From this, it was confirmed that the solidification rate of the prepolymer and the resin was controlled. Similarly, the wholly aromatic liquid-crystalline polyester resin compound prepared in Examples 1 to 3 had a larger difference (Tm-Tc) between the melting temperature and the crystallization temperature than the wholly aromatic liquid-crystalline polyester resin compound prepared in Comparative Example 1 And it was confirmed that the rapid solidification phenomenon of the resin compound after the extrusion was prevented, thereby improving the processability of the resin compound.

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)

Polymerizing a monomeric raw material comprising a first monomer of a kink structure and a second monomer of a straight structure, an aromatic hydroxycarboxylic acid of a kink structure, and a linear structure of an aromatic hydroxycarboxylic acid ≪ / RTI >
Wherein the first monomer and the second monomer are isomers, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxylamines, aromatic diamines or aromatic aminocarboxylic acids,
The content of the first monomer relative to 100 moles of the first monomer and the second monomer is 4 to 20 moles,
Wherein the monomer raw material comprises a monomer containing at least one of a hydroxyl group and an amino group,
Wherein the content of the aromatic hydroxycarboxylic acid in the kink structure is 5 to 750 moles relative to 1 moles of the aromatic hydroxycarboxylic acid in the linear structure. delete delete The method according to claim 1,
Wherein the aromatic hydroxycarboxylic acid of the kink structure comprises at least one compound selected from the group consisting of 1-hydroxy-2-naphthoic acid and 6-hydroxy-2-naphthoic acid, Hydroxybenzoic acid, and 4'-hydroxy-4-biphenylcarboxylic acid. The method according to claim 1,
Wherein the content of the first monomer is 1 to 5 moles per 100 moles of the total content of the monomer raw materials. The method according to claim 1,
Wherein said monomeric raw material further comprises a third monomer and said third monomer is selected from the group consisting of glycolic acid, lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, and 2-hydroxyhexanoic acid At least one aliphatic hydroxycarboxylic acid; An aliphatic dicarboxylic acid comprising at least one compound selected from the group consisting of 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid and 1,5-pentanedicarboxylic acid; 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, At least one compound selected from the group consisting of diols, 1,8-octanediol, ethylene glycol, etohexadiol, p-menthane-3,8-diol and 2-methyl- Aliphatic diols including; At least one aliphatic hydroxylamine selected from the group consisting of 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol; At least one aliphatic diamine selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane; 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 resin ≪ / RTI > The method according to claim 1,
Wherein the first monomer is selected from the group consisting of isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, An aromatic dicarboxylic acid containing at least one compound selected from the group consisting of 2,6-naphthalene dicarboxylic acid and biphenyl-2,2'-dicarboxylic acid (diphenic acid); Resorcinol, 2,2'-biphenol, 3,3'-biphenol, pyrocatechol, 1,2-naphthalene diol, 1,3-naphthalene diol, 1,4-naphthalene diol, Aromatic compounds containing at least one compound selected from the group consisting of diols, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol and 2,7- Diol; Amino-1-naphthol, 3-amino-2-naphthol, 5-amino-2-naphthol and 8-amino-2-naphthol An aromatic hydroxylamine comprising at least one compound selected from the group consisting of: 1,3-phenylenediamine and 1,2-phenylenediamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8- An aromatic diamine comprising at least one compound selected from the group consisting of 3-diaminonaphthalene, 2,2'-biphenyldiamine and 3,4'-biphenyldiamine; Or an aromatic aminocarboxylic acid comprising at least one compound selected from the group consisting of 3-aminobenzoic acid, 2-aminobenzoic acid, 3-amino-2-naphthoic acid and 6-amino- A method for producing a resin. The method according to claim 1,
The second monomer is an aromatic dicarboxylic acid containing at least one compound of terephthalic acid and biphenyl-4,4'-dicarboxylic acid; An aromatic diol comprising at least one compound selected from the group consisting of 4,4'-biphenol and hydroquinone; Aromatic hydroxylamines comprising 4-aminophenol; An aromatic diamine comprising at least one compound selected from the group consisting of 1,4-phenylenediamine and 4,4'-diaminobiphenyl; Or an aromatic aminocarboxylic acid comprising 4-aminobenzoic acid. The method according to claim 1,
Contacting the monomeric raw material with an acid anhydride to acetylate at least a portion of the hydroxyl and amino groups in the monomeric raw material to obtain an acetylated monomer;
Synthesizing an aromatic liquid-crystalline polyester prepolymer by a polycondensation reaction of the monomer material containing the acetylated monomer; And
And subjecting the synthesized aromatic liquid-crystalline polyester prepolymer to a solid-phase polycondensation reaction to synthesize an aromatic liquid-crystalline polyester resin. 10. The method of claim 9,
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 content is 0.5 to 2.0 moles relative to one molar part of the sum of the amino group and the hydroxyl group contained in the monomer raw material. An aromatic liquid-crystalline polyester resin compound comprising an aromatic liquid-crystalline polyester resin produced according to the method of any one of claims 1 and 4 to 10.