KR101834703B1 - 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 isomeric non-isomeric aromatic dicarboxylic acid, the content of the first monomer is 1.0 to 14.0 parts by mol based on 100 parts by mol of the second monomer, and the monomer ingredient is an aromatic hydroxycarboxylic acid having a kink structure And an aromatic hydroxycarboxylic acid having a linear structure.

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,

The first monomer and the second monomer are not isomeric and are aromatic dicarboxylic acids,

Wherein the content of the first monomer is 1.0 to 14.0 parts by mol based on 100 parts by mol of the second monomer,

Wherein the monomer raw material comprises an aromatic hydroxycarboxylic acid having a kink structure and an aromatic hydroxycarboxylic acid having a linear structure.

The first monomer may have a larger molecular weight than the second monomer.

The content of the aromatic hydroxycarboxylic acid in the kink structure may be 5 to 750 moles per mole of the linear hydroxycarboxylic acid.

The aromatic hydroxycarboxylic acid of the kink structure may contain at least one compound selected from the group consisting of 1-hydroxy-2-naphthoic acid and 6-hydroxy-2-naphthoic acid, and the aromatic hydroxycarboxylic acid The acid may comprise at least one compound of parahydroxybenzoic acid and 4- (4-hydroxyphenyl) benzoic acid.

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

The aromatic diol may be at least one selected from the group consisting of hydroquinone, resorcinol, 4,4'-biphenol, 2,2'-biphenol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 1, , 7-dihydroxynaphthalene, and bisphenol A, and the aromatic hydroxylamine may include at least one compound selected from the group consisting of 3-acetaminophenol, 2-acetaminophenol, 4-acetaminophenol, Acetaminino-2-hydroxynaphthalene, 1-acetamino-2-hydroxynaphthalene, 4-acetamino-1-hydroxynaphthalene, -Hydroxynaphthalene, 4-acetamino-2-hydroxynaphthalene, 6-acetamino-1-hydroxynaphthalene, 6- Acetamino-2-hydroxynaphthalene, 7-acetamino-2-hydroxynaphthalene, 7-acetamino-2-hydroxynaphthalene, Biphenol and 3-acetamino-4'-biphenol, and the aromatic diamine may include at least one compound selected from the group consisting of 1,2-phenylenediamine, 1,3-phenylenediamine, 2 , 2'-biphenyldiamine, 3,4'-biphenyldiamine, 1,4-phenylenediamine, naphthalene-1,2-diamine, naphthalene-1,4-diamine, naphthalene- Diamine, naphthalene-1,8-diamine, naphthalene-2,3-diamine, and naphthalene-2,6-diamine.

The content of the first monomer may be 0.25 to 3.0 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-methane-3,8-diol and 2-methyl- Aliphatic diols including; And at least one aliphatic aminocarboxylic acid selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid.

The first monomer may be selected from the group consisting of 1,5-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7- Aromatic dicarboxylic acid containing at least one compound selected from the group consisting of dicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid and isophthalic acid It can be acid.

The second monomer may be an aromatic dicarboxylic acid containing at least one compound of terephthalic acid and biphenyl-4,4'-dicarboxylic acid.

The method for producing the aromatic liquid-crystalline polyester resin comprises the steps of: contacting the monomer raw material containing at least one of a hydroxyl group and an amino group with an acid anhydride to acetylate at least a part of hydroxyl groups and amino groups in the monomer raw material to obtain an acetylated monomer , Synthesizing an aromatic liquid-crystalline polyester prepolymer by condensation reaction of the monomer material containing the acetylated monomer, 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 one embodiment of the present invention, the solidification rate of the reaction product is retarded during the condensation reaction at a high temperature, the polymerization reaction proceeds smoothly, and gaseous by- . 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. As a result, aromatic liquid-crystalline polyester resins having uniform physical properties as a whole, resin compounds having improved fluidity, mechanical strength (particularly, flexural characteristics) and heat resistance, and high mechanical strength and heat resistance, It is possible to obtain a molded article having little thermal deformation (that is, excellent in dimensional stability). 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 (i.e., two carboxyl groups) are arranged so as to minimize the electrostatic force and steric hindrance therebetween, Linear structure ".

The first monomer and the second monomer are not in an isomeric relationship.

The first monomer and the second monomer are aromatic dicarboxylic acids.

The first monomer serves to lower the solidification rate (viscosity increase 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 condensation reaction progresses 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.

(5) It is possible to provide a resin which can be used in the production of an ultra-thin molded article (for example, a long-pin connector) because of its excellent fluidity and low-temperature molding capability.

(6) It is possible to provide a molded article of a resin compound excellent in dimensional stability with less warpage due to thermal deformation even in a high-temperature reflow process at 280 캜 or more.

The first monomer may have a larger molecular weight than the second monomer.

The first monomer may be selected from the group consisting of 1,5-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7- Aromatic dicarboxylic acid containing at least one compound selected from the group consisting of dicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid and isophthalic acid It can be acid.

The second monomer serves to increase the mechanical properties and heat resistance of the synthesized resin and the resin compound. Such a second monomer may be an aromatic dicarboxylic acid comprising at least one compound of terephthalic acid and biphenyl-4,4'-dicarboxylic acid.

The content of the first monomer is 1.0 to 14.0 parts by mol based on 100 parts by mol of the second monomer. If the content of the first monomer is less than 1.0 part by mol based on 100 parts by mol of the second monomer, the solidification rate of the reaction product is accelerated in the resin synthesis step and the resin compound production step, The heat resistance and dimensional stability of the synthesized resin, resin compound and molded article are lowered.

The content of the first monomer may be 0.25 to 3.0 moles per 100 moles of the total amount of the monomer raw material. When the content of the first monomer is within the above range, the solidification rate of the reaction product in the resin synthesis step and the resin compound manufacturing step is slowed, so that the process failure does not occur and the polymerizability and workability are excellent. The fluidity, heat resistance, mechanical properties and dimensional stability of the resin, the resin compound and / or the molded article can be improved.

The total content of the first monomer and the second monomer (i.e., the total content of the aromatic dicarboxylic acid) may be 8 to 30 moles per 100 moles of the total amount of the monomer raw material. If the content of the total content of the first monomer and the second monomer 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 discharge of the prepolymer becomes smooth, And productivity can be improved.

The monomer raw material includes an aromatic hydroxycarboxylic acid of a kink structure and an aromatic hydroxycarboxylic acid of a linear structure.

The aromatic hydroxycarboxylic acid of the kink structure and the linear hydroxycarboxylic acid of the linear structure may form the main skeleton of the synthesized resin.

The content of the aromatic hydroxycarboxylic acid in the kink structure may be 5 to 750 moles per mole of the linear hydroxycarboxylic 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, mechanical properties and dimensional stability of the resin compound and / or the molded article can be improved.

The aromatic hydroxycarboxylic acid of the kink structure may contain at least one compound selected from the group consisting of 1-hydroxy-2-naphthoic acid and 6-hydroxy-2-naphthoic acid, and the aromatic hydroxycarboxylic acid The acid may comprise at least one compound of parahydroxybenzoic acid and 4- (4-hydroxyphenyl) benzoic acid.

The total content of the aromatic hydroxycarboxylic acid of the kink structure and the aromatic hydroxycarboxylic acid of the linear structure 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 monomer raw material may further include at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxylamine, and an aromatic diamine.

The aromatic diol may be at least one selected from the group consisting of hydroquinone, resorcinol, 4,4'-biphenol, 2,2'-biphenol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 1, , 7-dihydroxynaphthalene, and bisphenol A. In the present invention,

The aromatic hydroxylamine is selected from the group consisting of 3-acetaminophenol, 2-acetaminophenol, 4-acetaminophenol, 5-acetamino-1 -hydroxynaphthalene, 2-hydroxynaphthalene, 4-acetamino-2-hydroxynaphthalene, 4-acetamino-2-hydroxynaphthalene, Acetamino-2-hydroxynaphthalene, 3-acetamino-2-hydroxynaphthalene, 7-acetamino-1-hydroxynaphthalene, 7- 4'-biphenol, and 3-acetamino-4'-biphenol.

The aromatic diamine may be at least one selected from the group consisting of 1,2-phenylenediamine, 1,3-phenylenediamine, 2,2'-biphenyldiamine, 3,4'-biphenyldiamine, Diamine, naphthalene-2,7-diamine, naphthalene-1,5-diamine, naphthalene-1,8-diamine, naphthalene-2,3-diamine and naphthalene- A diamine, and a diamine.

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. If the content of the aromatic diol is within the above range, the physical properties of the prepolymer are improved, the mechanical properties of the resin compound are increased, the amount of the monomer to be sublimed and the amount of the acetylated monomer to be reduced The generation of process troubles can be suppressed and the physical properties of the prepolymer and the resin can be made uniform for each production unit.

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. When the content of the aromatic hydroxylamine is within the above range, 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.

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-methane-3,8-diol and 2-methyl- Aliphatic diols including; 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 monomeric raw material contains at least one of a hydroxyl group and an amino group, and does not contain an aromatic aminocarboxylic acid such as 3-aminobenzoic acid and an acetylated aromatic aminocarboxylic acid such as 3-acetaminobenzoic acid.

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, (Condensation step) of synthesizing an aromatic liquid-crystalline polyester prepolymer by a condensation reaction of a monomer raw material containing a monomer to be produced, and synthesizing an aromatic liquid-crystalline polyester resin by solid-phase polycondensation reaction of the synthesized aromatic liquid-crystalline polyester prepolymer Solid phase 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 150 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 can be converted to acetyl groups and the subsequent condensation reaction can proceed at a low temperature. The ester prepolymer does not deteriorate and the browning of the prepolymer does not occur.

The step of condensing a monomer raw material containing the acetylated monomer to synthesize an aromatic liquid-crystalline polyester prepolymer may be carried out by solution condensation polymerization 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 the solid-phase polycondensation reaction is obtained without causing a discharge process failure after the condensation 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

Examples 1 to 3 and Comparative Examples 1 to 3: Manufacture of a wholly aromatic liquid-crystalline polyester resin and the resin

(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. , Terephthalic acid (TPA) and 2,6-naphthalene dicarboxylic acid (NDA) were charged in the ratios listed in the following Table 1, nitrogen gas was injected to make the inner space of the reactor inactive, and acetic anhydride (Ac ₂ O), calcium acetate and magnesium acetate were added in an amount as shown in Table 1 below to facilitate the acetylation reaction and the subsequent condensation reaction. 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 elevating the temperature to 330 ° C over 5 hours while removing the by-product acetic acid to proceed the condensation 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 elevated to 310 DEG C 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 TPA NDA Ac ₂ O Calcium acetate Magnesium acetate Example 1 48 2 25 24.75 0.25 1.1 0.01 0.02 Example 2 48 2 25 24.0 One 1.1 0.01 0.02 Example 3 48 2 25 22.0 3 1.1 0.01 0.02 Comparative Example 1 48 2 25 21.0 4 1.1 0.01 0.02 Comparative Example 2 48 2 25 25.0 0 1.1 0.01 0.02

* 1: [molar fraction of HNA + molar fraction of HBA + molar fraction of BP + molar fraction of TPA + molar fraction of NDA] = 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 or magnesium acetate to 100 parts by weight of [HNA + HBA + BP + TPA + NDA]

Evaluation example

Melt viscosity, melting temperature and crystallization temperature of each of the wholly aromatic liquid-crystalline polyester resins prepared in Examples 1 to 3 and Comparative Examples 1 to 3; The melt viscosity of each of the wholly aromatic liquid-crystalline polyester resin compounds prepared in Examples 1 to 3 and Comparative Examples 1 to 3; And flexural strength, flexural elastic modulus, flexural elongation, impact strength, heat resistance temperature and dimensional stability of the injection molded article were measured or evaluated by the following methods, and the results are shown in Table 2 below. In addition, whether or not a solidification phenomenon occurred in the production of each of the wholly aromatic liquid-crystalline polyester resins was evaluated, and the results are shown in Table 2 below.

 (1) Method of measuring melt viscosity

The melt viscosity was measured using a melt viscosity measuring apparatus (Rosand, RH2000) under a temperature of 1.0 mm x 32 mm capillary (melting temperature + 10 deg. C) and a shear rate of 1000 / s. Here, the lower the melt viscosity, the higher the fluidity.

(2) 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.

 (3) Evaluation method of resin yield and solidification phenomenon occurrence

The calculated value was defined as the yield by dividing the actual production amount of resin by the theoretical production amount of resin. When the yield of the wholly aromatic liquid-crystalline polyester prepolymer produced in each of the Examples and Comparative Examples was 90% or more, it was evaluated that no solidification phenomenon occurred. When the yield was less than 90%, the solidification phenomenon was evaluated to have occurred.

(4) Method of measuring flexural strength, flexural modulus, flexural elongation 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, Tensile strength (ASTM D638), tensile elongation (ASTM D638), flexural strength (ASTM D790), flexural modulus (ASTM D790), flexural elongation (ASTM D790) and heat resistance temperature (ASTM D648) of the specimens were measured.

(5) Method of evaluating dimensional stability

Specimens of each of the above-prepared all-aromatic liquid crystal polyester resin compounds were prepared using an injection molding machine (FANUC Co., Ltd., S-2000i 50B). Using the reflow apparatus (Samsung Techwin, RF30102) A 0.3 mm thick polyester resin compound specimen was subjected to a reflow process (i.e., a soldering process) for 5 minutes after setting the test temperature at 280 캜, and then the warpage of each of the specimens before the reflow process and after the reflow process Were observed with a microscope and the results are shown in Table 2 below. The degree of bending of each of the specimens was measured after cooling the specimens to room temperature (25 DEG C). Here, the smaller the degree of warpage after the reflow process, the greater the dimensional stability.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Whether a solidification phenomenon occurs during the manufacture of resin No No No No Yes Yield of resin (%) 97.1 97.8 98.3 98.5 79.4 Of resin
Properties Melting point
(@ 360 ℃, Poise) 424 408 362 337 450 Melting temperature (캜) 348 345 343 340 349 Crystallization temperature (캜) 327 320 315 312 329 Properties of resin compounds Melting point
(@ 360 ℃, Poise) 516 462 402 388 585 Properties of Injection Molded Parts Flexural Strength (MPa) 175 180 178 175 163 Flexural modulus
(GPa) 11.8 11.5 10.4 10.0 10.2 Flexural Elongation (%) 2.63 2.71 3.17 3.48 2.50 Impact strength (J / m) 234 251 289 319 195 Heat temperature (℃) 313 306 302 291 301 Before reflow
Degree of bending (mm) 0.35 0.34 0.29 0.28 0.38 After reflow
Degree of bending (mm) 1.09 0.89 0.98 1.12 1.38

Referring to Table 2, the injection molded articles of the wholly aromatic liquid-crystalline polyester resin compound prepared in Comparative Example 1 had heat-resistant temperature and dimensional stability compared to injection molded articles of the wholly aromatic liquid-crystalline polyester resin compound prepared in Examples 1 to 3 Respectively. In addition, the wholly aromatic liquid-crystalline polyester resin and the resin compound prepared in Comparative Example 2 showed lower fluidity than the wholly aromatic liquid-crystalline polyester resin and the resin compound prepared in Examples 1 to 3. In addition, solidification phenomenon occurred when the wholly aromatic liquid-crystalline polyester resin (specifically, wholly aromatic liquid-crystalline polyester prepolymer) of Comparative Example 2 was produced.

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 (12)

Polymerizing a monomeric raw material comprising a first monomer of a kink structure and a second monomer of a straight structure,
The first monomer and the second monomer are not isomeric and are aromatic dicarboxylic acids,
Wherein the amount of the first monomer is 1 to 12 moles relative to 100 moles of the first monomer and the second monomer,
Wherein the monomer raw material further comprises an aromatic hydroxycarboxylic acid of a kink structure, an aromatic hydroxycarboxylic acid of a linear structure, and an aromatic diol. The method according to claim 1,
Wherein the first monomer has a larger molecular weight than the second monomer. The method according to claim 1,
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. 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- (4-hydroxyphenyl) benzoic acid, wherein the aromatic liquid-crystalline polyester resin comprises at least one compound selected from the group consisting of hydroxybenzoic acid and 4- (4-hydroxyphenyl) benzoic acid. The method according to claim 1,
Wherein the monomer raw material further comprises at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxylamine, and an aromatic diamine. 6. The method of claim 5,
The aromatic diol may be at least one selected from the group consisting of hydroquinone, resorcinol, 4,4'-biphenol, 2,2'-biphenol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 1, , 7-dihydroxynaphthalene and bisphenol A, wherein the aromatic hydroxylamine is at least one compound selected from the group consisting of 3-acetaminophenol, 2-acetaminophenol, 4-acetaminophenol, 5- Acetono-2-hydroxynaphthalene, 1-acetamino-2-hydroxynaphthalene, 4-acetamino-1-hyd 4-acetamino-2-hydroxynaphthalene, 6-acetamino-1-hydroxynaphthalene, 6-aceta Hydroxynaphthalene, 7-acetamino-2-hydroxynaphthalene, 4-acetamino-4'-bis Phenol and 3-acetamino-4'-biphenol, wherein the aromatic diamine is at least one compound selected from the group consisting of 1,2-phenylenediamine, 1,3-phenylenediamine, 2,2 ' -Biphenyldiamine, 3,4'-biphenyldiamine, 1,4-phenylenediamine, naphthalene-1,2-diamine, naphthalene-1,4-diamine, naphthalene- Diamine, naphthalene-1,8-diamine, naphthalene-2,3-diamine, and naphthalene-2,6-diamine. 6. The method of claim 5,
Wherein the content of the first monomer is 0.25 to 3.0 moles per 100 moles of the total content of the monomer raw materials. 6. The method of claim 5,
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-methane-3,8-diol and 2-methyl- Aliphatic diols including; 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,
The first monomer may be selected from the group consisting of 1,5-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7- Aromatic dicarboxylic acid containing at least one compound selected from the group consisting of dicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid and isophthalic acid Wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin. The method according to claim 1,
Wherein the second monomer is an aromatic dicarboxylic acid containing at least one compound of terephthalic acid and biphenyl-4,4'-dicarboxylic acid. The method according to claim 1,
Wherein the monomer raw material comprises at least one of a hydroxyl group and an amino group, and the acetylated monomer is obtained by contacting the monomer raw material with an acid anhydride to acetylate at least a part of the hydroxyl group and the amino group in the monomer raw material;
Synthesizing an aromatic liquid-crystalline polyester prepolymer by condensation 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. 12. The method of claim 11,
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.