KR101544211B1 - A wholly aromatic liquid-crystalline polyester resin having improved viscosity stability, a method for producing the same, and a resin compound containing the resin - Google Patents

Abstract

A wholly aromatic liquid-crystalline polyester resin, a method for producing the same, and a resin compound comprising the resin are disclosed. The disclosed wholly aromatic liquid-crystalline polyester resin contains an aromatic dicarboxylic acid per 1 mole of at least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic diol, a repeating unit derived from an aromatic diamine and a repeating unit derived from an aromatic hydroxyamine From 1.01 to 1.05 moles of the repeating unit derived from the compound Also disclosed is a process for preparing a wholly aromatic liquid-crystalline polyester comprising polymerizing a plurality of monomers, wherein the monomer is selected from the group consisting of aromatic dicarboxylic acids per 1 mole of at least one monomer selected from the group consisting of aromatic diols, aromatic diamines and aromatic hydroxyamines And 1.01 to 1.05 moles of the acid. Further, the disclosed compound of the wholly aromatic liquid-crystalline polyester resin includes the above-mentioned wholly aromatic liquid-crystalline polyester resin and the additive.

Description

The present invention relates to a wholly aromatic liquid crystalline polyester resin having improved viscosity stability, a method for producing the same, and a resin compound containing the resin,

A wholly aromatic liquid-crystalline polyester resin, a method for producing the same, and a resin compound comprising the resin are disclosed. More specifically, repeating units derived from an aromatic dicarboxylic acid per 1 mole of at least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic diol, a repeating unit derived from an aromatic diamine, and a repeating unit derived from an aromatic hydroxyamine A wholly aromatic liquid-crystalline polyester resin comprising 1.01 to 1.05 moles of a unit, a process for its production, and a resin compound comprising the resin are disclosed.

The wholly aromatic liquid-crystalline polyester resin is excellent in heat resistance and dimensional stability and has excellent fluidity in melting, and is widely used as a precision injection molding material mainly in the field of electronic parts. Particularly, since it is excellent in dimensional stability and electrical insulation, its use as a film for electronic materials and a substrate is expanding.

The wholly aromatic liquid-crystalline polyester resin is a type of thermoplastic polymer produced by condensation polymerization, and the condensation polymerization proceeds continuously at the time of high-temperature processing after the production to increase the molecular weight, thereby increasing the viscosity and deteriorating the processability .

One embodiment of the present invention relates to a method for producing an aromatic dicarboxylic acid, which comprises reacting an aromatic dicarboxylic acid with an aromatic dicarboxylic acid per 1 mole of at least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic diol, a repeating unit derived from an aromatic diamine and a repeating unit derived from an aromatic hydroxyamine The total aromatic liquid-crystalline polyester resin comprising 1.01 to 1.05 mol of the resulting repeating unit.

Another embodiment of the present invention provides a wholly aromatic liquid-crystalline polyester resin compound comprising the wholly aromatic liquid-crystalline polyester resin.

Another embodiment of the present invention is a process for producing a wholly aromatic liquid-crystalline polyester resin by polymerizing a plurality of monomers, wherein the monomer is selected from the group consisting of an aromatic diol, an aromatic diamine, and an aromatic hydroxyamine in an amount of 1 mole of at least one monomer selected from the group consisting of There is provided a method for producing a wholly aromatic liquid-crystalline polyester resin comprising 1.01 to 1.05 mol of an aromatic dicarboxylic acid.

According to an aspect of the present invention,

A repeating unit derived from an aromatic dicarboxylic acid per 1 mole of at least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic diol, a repeating unit derived from an aromatic diamine and a repeating unit derived from an aromatic hydroxyamine, Mol. ≪ / RTI >

The wholly aromatic liquid-crystalline polyester resin may further include at least one repeating unit derived from an aromatic hydroxycarboxylic acid and a repeating unit derived from an aromatic aminocarboxylic acid.

When measured using a capillary viscometer at a temperature of 380 ° C and a shear rate of 100 / s, the viscosity change of the wholly aromatic liquid-crystalline polyester resin with time may be less than 3.0 poise / sec.

Another aspect of the present invention provides a wholly aromatic liquid-crystalline polyester resin compound comprising the wholly aromatic liquid-crystalline polyester resin and the additive.

Specifically, 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.

When the capillary viscometer is used and the temperature is measured under conditions of a temperature of 380 ° C and a shear rate of 100 / s, the viscosity change of the wholly aromatic liquid-crystalline polyester resin compound with time may be less than 3.0 poise / sec.

According to another aspect of the present invention,

A method for producing a wholly aromatic liquid-crystalline polyester resin by polymerizing a plurality of monomers, wherein the monomer is an aromatic dicarboxylic acid having an aromatic dicarboxylic acid content of from 1.01 to 1.05 per 1 mole of at least one monomer selected from the group consisting of aromatic diols, aromatic diamines and aromatic hydroxyamines A method for producing a wholly aromatic liquid-crystalline polyester resin comprising molybdenum.

The monomer may further comprise at least one monomer selected from an aromatic hydroxycarboxylic acid and an aromatic aminocarboxylic acid.

According to one embodiment of the present invention, a wholly aromatic liquid-crystalline polyester resin in which the progress of the undesired condensation polymerization is suppressed at the time of high-temperature processing after the production to reduce the molecular weight and the viscosity increase and thus the processability is improved, and the resin compound containing the same Can be provided.

Hereinafter, the wholly aromatic liquid-crystalline polyester resin according to one embodiment of the present invention will be described in detail.

The wholly aromatic liquid-crystalline polyester resin according to this embodiment contains at least one repeating unit (A) selected from the group consisting of a repeating unit derived from an aromatic diol, a repeating unit derived from an aromatic diamine, and a repeating unit derived from an aromatic hydroxyamine, And 1.01 to 1.05 moles, for example, 1.02 to 1.04 moles, of the repeating unit (B) derived from an aromatic dicarboxylic acid per mole. If the content of the recurring unit (B) is less than 1.01 mol per mol of the recurring unit (A), the viscosity stability is poor (that is, the change in viscosity due to heat is not suppressed) . When the content of the recurring unit (B) is 1 mole per 1 mole of the recurring unit (A), the resulting resin has different functional groups at the end of the polymer chain, And the workability deteriorates. When the content of the repeating unit (B) is smaller or larger than 1 mole per 1 mole of the repeating unit (A), the produced resin has the same functional group at the end of the polymer chain. .

The wholly aromatic liquid-crystalline polyester resin can be produced by the following steps:

(a) synthesizing a wholly aromatic liquid-crystalline polyester prepolymer by condensation polymerization of at least two kinds of monomers; And

(b) synthesizing the wholly aromatic liquid-crystalline polyester resin by solid-phase polycondensing the prepolymer.

The monomers used in the step (a) include at least one compound selected from the group consisting of aromatic diols, aromatic diamines and aromatic hydroxyamines, and aromatic dicarboxylic acids. In addition, the monomer may further comprise an aromatic hydroxycarboxylic acid and / or an aromatic aminocarboxylic acid.

As the synthesis method of step (a), a solution condensation polymerization method or a bulk condensation polymerization method may be used. In order to accelerate the condensation reaction in the step (a), a monomer having increased reactivity (that is, an acylated monomer) pretreated with a chemical substance such as an acylating agent (particularly, an acetylating agent) may be used.

For the solid-phase polycondensation reaction in the step (b), suitable heat should be provided to the prepolymer. Examples of the heat providing method include a method using a hot plate, a method using hot air, and a method using a high temperature fluid. In order to remove the byproducts generated during the solid-phase condensation polymerization, it is possible to purge or remove by vacuum using an inert gas.

When the ratio of the number of moles of aromatic dicarboxylic acid to the total number of moles of aromatic diol, aromatic diamine and aromatic hydroxyamine in the monomer used in step (a) is controlled to 1: 1, the prepared wholly aromatic liquid- The resin is produced in a state in which the condensation polymerization reaction is not terminated and undesirable condensation polymerization proceeds continuously at a high temperature post-processing such as the production of a resin compound to be described later. Therefore, in this case, there arises a problem that the molecular weight and viscosity of the resin increase at the time of post-processing at a high temperature. However, when the ratio of the number of moles of aromatic dicarboxylic acid to the total number of moles of aromatic diol, aromatic diamine and aromatic hydroxyamine in the monomers used in step (a) is controlled to 1: 1.01 to 1.05, And the polycondensation reaction of the wholly aromatic liquid-crystalline polyester resin prepared in the step (b) is almost completed, so that the polycondensation reaction does not occur further at the high-temperature post-processing. As a result, the molecular weight of the resin and the viscosity Is suppressed.

When the wholly aromatic liquid-crystalline polyester resin produced by the above-mentioned condensation polymerization reaction is measured under the conditions of a temperature of 380 ° C and a shear rate of 100 / s using a capillary viscometer, the viscosity change with time is, for example, 3.0 poise / sec < / RTI >

In addition, the wholly aromatic liquid-crystalline polyester resin contains various repeating units in the chain, and may include, for example, the following repeating units:

(1) a repeating unit derived from an aromatic diol:

-O-Ar-O-

(2) a repeating unit derived from an aromatic diamine:

-HN-Ar-NH-

(3) repeating unit derived from aromatic hydroxyamine:

-HN-Ar-O-

(4) repeating unit derived from an aromatic dicarboxylic acid:

-OC-Ar-CO-

(5) repeating unit derived from an aromatic hydroxycarboxylic acid:

-O-Ar-CO-

(6) a repeating unit derived from an aromatic aminocarboxylic acid:

-HN-Ar-CO-

In the above formulas, Ar is an aromatic compound in which phenylene, biphenylene, naphthalene or two phenylene are bonded to carbon or a non-carbon element, or an aromatic compound in which phenylene, biphenylene, naphthalene, Or an aromatic compound in which one or more hydrogens among aromatic compounds bonded with non-carbon elements are replaced with other elements.

Another embodiment of the present invention provides a wholly aromatic liquid-crystalline polyester resin compound comprising the wholly aromatic liquid-crystalline polyester resin and the additive.

The wholly aromatic liquid-crystalline polyester resin compound can be produced by melt-kneading the wholly 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.

The wholly aromatic liquid-crystalline polyester resin compound produced by the above-mentioned melt-kneading, when measured under the conditions of a temperature of 380 ° C and a shear rate of 100 / s using a capillary viscometer, shows a viscosity change with time of 3.0 poise / sec < / RTI >

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

Production Example 1: Preparation of wholly aromatic liquid-crystalline polyester prepolymer

In a 100 liter batch reactor capable of temperature control, 180.0 mol of 4-hydroxybenzoic acid, 60.0 mol of 4,4-dihydroxydiphenyl, 53.5 mol of 1,4-benzenedicarboxylic acid, 9 mol of the carboxylic acid and 330 mol of ethanoic acid anhydride were charged and the reaction mixture was heated with stirring using a stirrer until the temperature of the reaction mixture reached 150 DEG C and maintained at the temperature for 2 hours And acetylating the alcohol functional groups of the monomers to prepare wholly aromatic liquid crystal polyester prepolymer. At the end of the acetylation reaction, the temperature of the reaction mixture was raised at a rate of 1 ° C per minute while the ethane generated as a byproduct was removed by condensation and the prepolymer was recovered when the temperature reached 310 ° C.

Example 1-1: Preparation of wholly aromatic liquid-crystalline polyester resin

The wholly aromatic liquid-crystalline polyester prepolymer as prepared in Preparation Example 1 was pulverized to an average particle size of 1 mm, and 20 kg was introduced into a 100-liter rotary kiln reactor. The temperature was raised from room temperature to 1 ° C per minute, Lt; 0 > C, the wholly aromatic liquid-crystalline polyester resin produced was recovered. During the course of the reaction, the rotary kiln reactor was purged with heated nitrogen gas at a flow rate of 20 liters per minute to remove byproducts generated during the reaction.

Example 1-2: Preparation of wholly aromatic liquid-crystalline polyester resin

Aromatic liquid crystal polyester resin was prepared in the same manner as in Example 1-1, except that the amount of 1,4-benzenedicarboxylic acid was changed to 52.5 mol.

Comparative Example 1-1: Preparation of wholly aromatic liquid-crystalline polyester resin

Aromatic liquid crystal polyester resin was prepared in the same manner as in Example 1-1 except that the amount of 1,4-benzenedicarboxylic acid was changed to 51.0 mol.

Example 2-1: Preparation of a compound of a wholly aromatic liquid-crystalline polyester resin

The wholly aromatic liquid crystal polyester resin and glass fibers (crushed glass fibers having a diameter of 10 mu m and an average length of 150 mu m) such as those prepared in Example 1-1 were mixed at a ratio of 6: 4 on the basis of weight, And then melt-kneaded using an extruder 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.

Example 2-2: Compound production of wholly aromatic liquid-crystalline polyester resin

A compound of wholly aromatic liquid-crystalline polyester resin was prepared in the same manner as in Example 2-1, except that the wholly aromatic liquid-crystalline polyester resin as prepared in Example 1-2 was used.

Comparative Example 2-1: Manufacture of a compound of a wholly aromatic liquid-crystalline polyester resin

A compound of the wholly aromatic liquid-crystalline polyester resin was prepared in the same manner as in Example 2-1, except that the wholly aromatic liquid-crystalline polyester resin prepared in Comparative Example 1-1 was used.

Evaluation example

(Viscosity measurement)

The wholly aromatic liquid-crystalline polyester resin prepared in Examples 1-1 and 1-2 and Comparative Example 1-1 and the wholly aromatic liquid-crystalline polyester resin compound prepared in Examples 2-1 and 2-2 and Comparative Example 2-1 The viscosity change was measured over time for 30 minutes under the conditions of 380 ° C and 100 / s using a capillary viscometer for each resin and resin compound, and then the viscosity change curve with time Are calculated and shown in Table 1 below. ≪ tb > < TABLE >

[Table 1]

division The slope of the viscosity change (poise / sec) Example 1-1 1.2 Examples 1-2 2.5 Comparative Example 1-1 7.1 Example 2-1 1.1 Example 2-2 2.3 Comparative Example 2-1 5.7

Referring to Table 1, in the case of the wholly aromatic liquid-crystalline polyester resin, the resin prepared in Examples 1-1 and 1-2 had a viscosity change of 3 to 6 times as much as the resin prepared in Comparative Example 1-1 In the case of the wholly aromatic liquid-crystalline polyester resin compound, the resin compound prepared in Examples 2-1 and 2-2 had a slope of viscosity change of 2.5 to 5 times as compared with the resin compound prepared in Comparative Example 2-1 Times. Therefore, the wholly aromatic liquid-crystalline polyester resin and the resin compound according to one embodiment of the present invention are advantageous because the change in physical properties is not large even when the resin is recycled a plurality of times.

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 (9)

A repeating unit derived from an aromatic dicarboxylic acid per 1 mole of at least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic diol, a repeating unit derived from an aromatic diamine and a repeating unit derived from an aromatic hydroxyamine, Moles, A wholly aromatic liquid-crystalline polyester resin having a viscosity change of less than 3.0 poise / sec when measured at a temperature of 380 ° C and a shear rate of 100 / s using a capillary viscometer. The method according to claim 1, A wholly aromatic liquid-crystalline polyester resin further comprising at least one repeating unit derived from an aromatic hydroxycarboxylic acid and a repeating unit derived from an aromatic aminocarboxylic acid. delete A wholly aromatic liquid-crystalline polyester resin compound comprising a wholly aromatic liquid-crystalline polyester resin according to any one of claims 1 to 2 and an additive. 5. The method of claim 4, Wherein the additive comprises at least one of an inorganic additive and an organic additive. 6. The method of claim 5, Wherein the inorganic additive comprises glass fiber, talc, calcium carbonate, mica or a mixture of at least two of the foregoing, wherein the organic additive is carbon fiber-containing wholly aromatic liquid-crystalline polyester resin compound. delete A method for producing a wholly aromatic liquid-crystalline polyester resin by polymerizing a plurality of monomers, Wherein the monomer comprises from 1.01 to 1.05 moles of aromatic dicarboxylic acid per mole of at least one monomer selected from the group consisting of aromatic diols, aromatic diamines and aromatic hydroxyamines, A method for producing a wholly aromatic liquid crystalline polyester resin having a viscosity change of less than 3.0 poise / sec when measured under a condition of a capillary viscometer at a temperature of 380 ° C and a shear rate of 100 / s. 9. The method of claim 8, Wherein the monomer further comprises at least one monomer selected from the group consisting of an aromatic hydroxycarboxylic acid and an aromatic aminocarboxylic acid.