WO2017091049A1 - Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared thereby - Google Patents

Abstract

The present invention relates to a method for preparing a wholly aromatic polyester resin, wherein, in the preparation process of a wholly aromatic polyester resin by a mass-production scale polycondensation reaction, a polycondensation reaction is carried out such that the molar ratio of initially fed raw monomers is maintained by minimizing the outflow of the monomers and the acetylated monomers, which does not participate in the polycondensation reaction, together with acetic acid gas at a high temperature, and thus, the physical properties of the finally prepared wholly aromatic polyester resin can be equalized. In addition, the wholly aromatic polyester resin prepared according to the present invention has desired physical properties, which are equally expressed for respective batches, and thus, can improve the reliability of automobile parts, electric and electronic parts, small-sized precision molded articles, and the like, which are manufactured by molding the wholly aromatic polyester resin.

Description

Manufacturing method of wholly aromatic polyester resin and the wholly aromatic polyester resin produced accordingly

The present invention relates to a method for producing a wholly aromatic polyester resin and to a wholly aromatic polyester resin prepared according to this, more specifically, to a batch-wise wholly aromatic in the process of producing a wholly aromatic polyester resin by mass production scale polycondensation reaction The present invention relates to a method for producing an wholly aromatic polyester resin capable of equally producing physical properties of a polyester resin, and a wholly aromatic polyester resin produced accordingly.

Since the wholly aromatic liquid crystal polyester resin is composed entirely of aromatic chains and has high heat resistance and strength, it is important as a raw material of a product requiring high strength and high heat resistance, and thus has great commercial applicability.

The wholly aromatic liquid crystal polyester resin is widely used as a material for automobile parts, electric and electronic parts, and small and precision molded articles because of its excellent flowability and heat resistance.

Polymerization of such wholly aromatic polyester is determined to apply to any polymerization reaction according to the final (if crystalline) T _g, the melting point of the polymer, heat stability and solubility.

Among the synthetic methods of the wholly aromatic polyester, the most widely used synthetic method is a polymerization method using a melt method without using a solvent, but using a transesterification reaction.

The synthesis method of the conventional wholly aromatic polyester is as follows.

Korean Patent No. 1111645 discloses a step of synthesizing a wholly aromatic liquid crystal polyester prepolymer by polycondensing a raw material monomer including aromatic hydroxy carboxylic acid, aromatic diol and aromatic dicarboxylic acid but not containing aromatic amino carboxylic acid. Wherein the aromatic diol does not include an aromatic compound in which two phenylenes are bonded to an element other than carbon, and the content of the aromatic dicarboxylic acid in the raw material monomer is 1.02 to 1.08 mole based on 1 mole part of the aromatic diol. The manufacturing method of the denier wholly aromatic liquid-crystalline polyester resin is published.

Korean Unexamined Patent Publication No. 2010-0102923 (a) polycondensing at least two raw material monomers using a metal acetate catalyst to synthesize a wholly aromatic liquid-crystalline polyester prepolymer; And (b) synthesizing the wholly aromatic liquid crystal polyester resin by solid-phase polycondensation of the prepolymer.

The polycondensation reaction for producing a conventional wholly aromatic polyester resin proceeds at a high temperature, and monomers and acetylated monomers that do not participate in the polycondensation reaction are sublimed and flowed out together with acetic acid gas, resulting in the molar ratio and polycondensation reaction of the monomer initially introduced. As the molar ratio of the participating monomers is different, there is a problem that a difference occurs in the physical properties of the wholly aromatic polyester resin for each batch.

[Preceding technical literature]

[Patent Documents]

Korean Patent Publication No. 2010-0102923

Korean Registered Patent No. 0927383

Japanese Laid-Open Patent Publication No. 10-158482

In order to solve the above-mentioned problems of the prior art, the inventors of the present invention, in the production process of the wholly aromatic polyester resin by the mass production scale polycondensation reaction, the monomer and acetylated monomer that does not participate in the polycondensation reaction having a sublimation high temperature In order to minimize the outflow with the acetic acid gas generated in the research has been repeated as a result of the present invention was completed.

Accordingly, it is an object of the present invention to provide a method for producing a wholly aromatic polyester resin having equivalent physical properties for each batch and a wholly aromatic polyester resin prepared accordingly.

In order to achieve the above object, the present invention is to perform the acetylation reaction and esterification reaction of the raw material monomer and polycondensation to prepare a prepolymer, the solid phase polycondensation of the prepolymer in the method for producing a wholly aromatic polyester resin ,

The wholly aromatic polyester resin characterized in that the polycondensation of the raw material monomer to recover the sublimable unreacted monomer and acetylated monomer discharged together with acetic acid and acetic anhydride through the outflow pipe to the polycondensation reactor. It provides a method of manufacturing.

In one embodiment of the present invention, an outlet tube provided with a cooling jacket for discharging together with the acetic acid and acetic anhydride and allowing cooling water to be introduced to recover unreacted monomers and acetylated monomers into a polycondensation reactor is used. Can be.

In one embodiment of the present invention, the outlet pipe is provided with an outlet tube upper thermometer to adjust the amount of cooling water flowing into the cooling jacket so that the temperature of the top can be maintained in the 120 ~ 140 ℃ range.

In one embodiment of the present invention, when the upper temperature of the outlet pipe is less than 120 ℃ can be added to the cooling water.

In addition, the present invention provides a method for producing a wholly aromatic polyester resin compound, including a method for producing a wholly aromatic polyester resin, and a wholly aromatic polyester resin compound prepared accordingly.

In addition, the present invention is used in the liquid phase polycondensation reaction for producing an aromatic polyester resin, and as a polycondensation reaction tank, an outlet tube for discharging the resulting acetic acid and acetic anhydride; An outlet tube upper thermometer provided at an upper portion of the outlet tube; And it provides a polycondensation reaction tank including a cooling jacket for supplying cooling water to the outlet pipe.

The present invention is to minimize the outflow of monomers and acetylated monomers that did not participate in the polycondensation reaction with acetic acid gas at high temperature in the manufacturing process of the wholly aromatic polyester resin by the mass production scale polycondensation reaction By carrying out a polycondensation reaction by maintaining a molar ratio, the physical property of the wholly aromatic polyester resin finally manufactured can be made equal.

In addition, the wholly aromatic polyester resin prepared according to the present invention can improve the reliability of the automotive parts, electrical and electronic parts, small-size precision molded products, etc., produced by molding the desired physical properties are equally expressed by batch.

1 is a schematic diagram schematically showing the structure of a polycondensation reaction tank including an outlet tube with a cooling jacket used in the manufacturing process of the wholly aromatic polyester resin according to the present invention.

Advantages and features of the present invention, and methods for achieving them will be apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings.

However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms.

In this specification, the embodiments are provided so that the disclosure of the present invention may be completed and the scope of the present invention may be completely provided to those skilled in the art.

And the present invention is only defined by the scope of the claims.

Thus, in some embodiments, well known components, well known operations and well known techniques are not described in detail in order to avoid obscuring the present invention.

As used herein, the singular forms "a", "an" and "the" include plural unless the context clearly dictates otherwise, and the elements and acts referred to as 'comprises' or 'do' not exclude the presence or addition of one or more other components and acts. .

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used in a sense that can be commonly understood by those skilled in the art.

In addition, the terms defined in the commonly used dictionary are not ideally or excessively interpreted unless they are defined.

Hereinafter, the manufacturing method of the wholly aromatic polyester resin which concerns on this invention is demonstrated in detail.

The method for producing an wholly aromatic polyester resin according to the present invention comprises the steps of acetylating an aromatic monomer having a hydroxy group with an acid anhydride (acetylation step), esterifying the acetylated aromatic monomer with an aromatic dicarboxylic acid and Liquid polycondensation to synthesize the wholly aromatic polyester prepolymer (esterification reaction and liquid polycondensation step) and solid phase polycondensation of the wholly aromatic polyester prepolymer to synthesize the wholly aromatic polyester resin (solid phase polycondensation step). do.

In the acetylation reaction of an aromatic monomer having a hydroxy group in the raw material monomer, acetic anhydride or the like is used as an acetylating agent to sufficiently replace the hydroxyl group of the aromatic monomer with an acetyl group, and acetic acid is produced as a by-product. By-product acetic acid can be removed from the product in a gaseous state.

In one embodiment of the present invention, the acetylation step may be performed for 1 to 3 hours in the temperature range of 140 ~ 160 ℃. When the temperature and time are respectively within the above range, the hydroxyl group of the aromatic monomer is sufficiently converted to the acetyl group, so that the esterification reaction and the liquid polycondensation may proceed at low temperature, and thus the synthesized wholly aromatic polyester prepolymer is not degraded. Browning of the copolymer does not occur.

As the raw material monomer, the aromatic hydroxy carboxylic acid may include at least one compound of para hydroxy benzoic acid and 2-hydroxy-6-naphthoic acid, and the aromatic diol is at least one of biphenol and hydroquinone. It may include a compound of the species, the aromatic dicarboxylic acid may include at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid, in the production of wholly aromatic polyester resin It may further comprise known raw monomers that can be used.

In one embodiment of the present invention, the acetylation step may be performed for 1 to 3 hours in the temperature range of 140 ~ 160 ℃. When the temperature and time are respectively within the above range, the hydroxyl group of the aromatic monomer is sufficiently converted to the acetyl group, and then the esterification reaction and the liquid polycondensation may proceed at low temperature, and thus the synthesized wholly aromatic polyester prepolymer is not degraded. Browning of the copolymer does not occur.

Acetylation of the aromatic monomer may be performed by solution condensation polymerization or bulk condensation polymerization.

In the acetylation step, metal acetate may be additionally used as a catalyst for promoting the reaction. The metal acetate catalyst may include at least one selected from the group consisting of magnesium acetate, potassium acetate, calcium acetate, zinc acetate, manganese acetate, lead acetate, antimony acetate and cobalt acetate.

The esterification reaction and the liquid phase polycondensation step may be performed for 5-8 hours in the temperature range of 310 ~ 340 ℃. When the temperature and time are each within the above range, no discharge process failure occurs after the esterification reaction and the liquid polycondensation, and thus a wholly aromatic polyester prepolymer having physical properties suitable for the solid phase polycondensation reaction may be obtained.

In the present invention, the step of removing the acetic acid and unreacted acetic anhydride produced as a by-product after the acetylation reaction in the liquid phase polycondensation step, the monomer and acetylated monomer that did not participate in the polycondensation reaction in the process It is characterized in that the physical properties of each of the batch by equally by producing a wholly aromatic polyester while maintaining the molar ratio of the raw material monomer initially introduced by preventing the outflow with acetic acid gas at a high temperature.

In the present invention, the polycondensation reaction tank 1 shown in FIG. 1 is used in the liquid phase polycondensation reaction.

The polycondensation reaction tank 1 includes an outlet pipe 10 for discharging the generated acetic acid and acetic anhydride; Outflow pipe upper thermometer (5) provided on the top of the outlet pipe; And a cooling jacket 4 for supplying cooling water to the outlet pipe.

In the present invention, while removing the acetic acid and unreacted acetic anhydride produced in the acetylation and polycondensation reaction through the outlet pipe 10, the polycondensation reactor temperature is raised to a temperature range of 310 ~ 340 ℃ wherein the reaction temperature is When the temperature is higher than 260 ° C., the amount of the sublimed monomer and the acetylated monomer increases rapidly.

Accordingly, in the present invention, a polycondensation reactor having an outlet tube 10 provided with a cooling jacket 4 capable of introducing cooling water to recover the unreacted monomer and the acetylated monomer into the polycondensation reactor 1 1), the outlet pipe 10 is installed in the outlet tube thermometer (5) when the upper temperature is out of the range 120 ~ 140 ℃ range of cooling water to the cooling jacket (4) automatically proceeds to stop It is characterized by.

That is, in the present invention, the upper temperature of the outlet tube 10 is lower than the sublimation temperature of the unreacted monomer and the acetylated monomer so that the unreacted monomer and the acetylated monomer are not discharged together with the acetic acid and the acetic anhydride through the outlet tube 10. And it adjusts to 120-140 degreeC temperature range more than the boiling point of acetic acid and acetic anhydride.

More specifically, in the present invention, when the temperature of the upper portion of the outlet pipe 10 is measured to be higher than 120 to 140 ° C., which is the boiling point of acetic acid and acetic anhydride, cooling water is introduced into the cooling jacket 4, and the outlet pipe (10) By controlling the process so that the cooling water is stopped when the temperature of the upper portion is less than 120 ℃, through this the outlet pipe 10 to recover only acetic acid and acetic anhydride with low boiling point by-product recovery drum (3) and high temperature The monomer and acetylated monomer having sublimation of are again recovered into the polycondensation reactor 1 to participate in the reaction.

Accordingly, since the polycondensation reaction of the wholly aromatic polyester in the present invention is a batch reaction, the polycondensation reaction according to the ratio of the monomers added to each batch proceeds, so that the physical properties of the produced wholly aromatic polyester resin are equal.

In order to perform the solid phase polycondensation step, appropriate heat must be provided to the wholly aromatic polyester prepolymer, and the heat providing method includes a method using a heating plate, a method using a hot air, a method using a high temperature fluid, and the like.

In the synthesis of the wholly aromatic polyester prepolymer, metal acetate may be additionally used as a catalyst for promoting the reaction. The metal acetate catalyst may include at least one selected from the group consisting of magnesium acetate, potassium acetate, calcium acetate, zinc acetate, manganese acetate, lead acetate, antimony acetate, and cobalt acetate.

Synthesis of the wholly aromatic polyester prepolymer may be performed for 5 to 8 hours in the temperature range of 310 ~ 340 ℃. When the temperature and time are respectively within the above range, no impairment of the discharge process after the polycondensation reaction occurs, it is possible to obtain a wholly aromatic polyester prepolymer of physical properties suitable for the solid-phase polycondensation reaction.

In one embodiment of the present invention, the method for producing the wholly aromatic polyester resin further comprises the step of pulverizing the wholly aromatic polyester prepolymer before the solid phase polymerization step described later after the esterification reaction and liquid phase polycondensation step Can be.

The particle size of the ground wholly aromatic polyester prepolymer may be, for example, 0.5mm to 2.5mm.

The grinding of the wholly aromatic polyester prepolymer may be performed using a grinder (eg, a feather mill) having a screen having a mesh size of 0.5 mm to 2.5 mm.

In one embodiment of the present invention, the method for producing the wholly aromatic polyester resin comprises the wholly aromatic polyester prepolymer between the liquid phase polycondensation step of the esterification reaction in the liquid phase and the grinding of the wholly aromatic polyester prepolymer It may further comprise the step of cooling. In the cooling step of the wholly aromatic polyester prepolymer, the wholly aromatic polyester prepolymer may be cooled to a temperature of 20 ~ 70 ℃. Accordingly, the grinding of the wholly aromatic polyester prepolymer may be performed while maintaining the wholly aromatic polyester prepolymer at a temperature of 20 to 70 ° C.

Another embodiment of the present invention provides a method for producing an wholly aromatic polyester resin compound using an wholly aromatic polyester resin and additives prepared by the method for producing an wholly aromatic polyester resin.

The method for producing the wholly aromatic polyester resin compound may include the steps of synthesizing the wholly aromatic polyester resin according to the above-described method for producing the wholly aromatic polyester resin and melt kneading the synthesized wholly aromatic polyester resin and the additive. It may include. A batch kneader, a twin screw extruder or a mixing roll may be used for such melt kneading. In addition, a lubricant may be used during melt kneading for smooth melt kneading.

The additive may comprise an inorganic filler and / or an organic filler. The inorganic filler may include glass fiber, talc, calcium carbonate, mica, clay or a mixture of two or more thereof, and the organic filler may include carbon fiber. The inorganic filler and the organic filler serve to improve the mechanical strength of the injection molded article during the injection molding of the wholly aromatic polyester resin compound.

A batch kneader, a twin screw extruder or a mixing roll may be used for the melt kneading. In addition, a lubricant may be used during melt kneading for smooth melt kneading.

The wholly aromatic polyester resin compound according to one embodiment of the present invention having the above configuration is an engineering plastic suitable for electric and electronic parts due to the high heat resistance (load deformation temperature of 250 ° C. or higher) and high flowability characteristics of the resin contained therein. It is suitable to prepare.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example

Examples 1-5

A polycondensation reactor equipped with a stirrer, a reflux device and a vacuum control device was charged with 888 kg of para-hydroxy benzoic acid, 399 kg of biphenol, 267 kg of terephthalic acid, 89 kg of isophthalic acid, and 1,203 kg of acetic anhydride, and 0.13 kg of potassium acetate and magnesium acetate in a nitrogen atmosphere. 0.495 kg (quadhydrate) was added as a catalyst, followed by stirring for 30 minutes. After circulating the fruit, the reactor temperature was raised to 150 ° C. for 1 hour, followed by acetylation while refluxing for 2 hours. The reactor temperature was raised to 320 ° C. for 6 hours while removing acetic acid produced through the acetylation and polycondensation reactions. At this time, the outflow pipe to recover the acetic acid generated in the polycondensation reaction tank was carried out the polycondensation reaction while maintaining a constant temperature of 140 ℃ at the top to prepare a prepolymer. The contents of unreacted and acetylated monomers in the recovered by-products were measured. The prepolymer having completed the polycondensation reaction was cooled while being discharged from the reactor, and then pulverized to an average particle size of 0.5 to 1.5 mm through a grinder. The prepolymer pulverized into a uniform size was introduced into a rotary solid-state reactor and heated to 280 ° C over 8 hours while introducing nitrogen at 250 ° C. The polycondensation reaction was completed while maintaining at this temperature for 3 hours, and after cooling to 100 ° C. or less for 1 hour, the wholly aromatic polyester resin was recovered to check physical properties. In the same polycondensation reaction conditions, five batches were carried out continuously (Examples 1 to 5 for each batch), and then the physical properties of the wholly aromatic polyester resin were confirmed and shown in Table 1 below.

Comparative Examples 1 to 5

As described in Table 1, except that the process that does not cool the outflow tube during the liquid phase condensation reaction was applied in the same batch as in the five (batch) batch (Comparative Examples 1 to Comparative Examples by batch) 5) After proceeding to confirm the physical properties of the wholly aromatic polyester resin is shown in Table 1 below.

	Outlet Pipe Upper Temperature (℃)	Concentration in by-products (ppm)		Fully aromatic polyester properties
		Unreacted Monomer	Acetylated monomer	Tf (℃)	Tm (℃)	Mv (Poise)
Example 1	140	3	12	330	351	647
Example 2	140	5	18	330	350	639
Example 3	140	4	15	329	350	641
Example 4	140	2	15	331	351	652
Example 5	140	3	14	330	350	640
Comparative Example 1	178	58	129	334	356	893
Comparative Example 2	181	73	184	329	350	588
Comparative Example 3	180	65	179	331	352	672
Comparative Example 4	179	85	166	335	355	1007
Comparative Example 5	184	107	204	338	357	1356

Referring to Table 1, the temperature of the outlet pipe for discharging acetic acid and acetic anhydride generated in the polycondensation reaction tank is maintained at 140 ℃, and the unreacted monomer and acetylated monomer are recovered in the polycondensation reaction tank to complete the polycondensation reaction. For example, the concentration of by-products was significantly lower than that of Comparative Examples 1 to 5, which prepared the wholly aromatic polyester without cooling the outflow tube during the polycondensation reaction, and thus the wholly aromatic poly prepared in Examples 1 to 5. The physical properties of the esters appeared similar.

On the other hand, the viscosity of the wholly aromatic polyester prepared in Comparative Examples 1 to 5 in which the wholly aromatic polyester was prepared without cooling the outflow tube during the polycondensation reaction was not constant for each batch, and the difference was large.

The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and changes without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (14)

1. In the method for producing a prepolymer by carrying out the acetylation reaction and esterification reaction of the raw material monomer and polycondensation, and solid-phase polycondensation of the prepolymer,

   The wholly aromatic polyester resin characterized in that the polycondensation of the raw material monomer to recover the sublimable unreacted monomer and the acetylated monomer discharged together with acetic acid and acetic anhydride through the outflow pipe to the polycondensation reactor. Manufacturing method.
2. The method according to claim 1,

   A wholly aromatic polyester, characterized by using an outlet tube equipped with a cooling jacket for discharging together with the acetic acid and acetic anhydride and at the same time to recover the unreacted monomers and acetylated monomers to the polycondensation tank. Method for producing a resin.
3. The method according to claim 1,

   The outflow pipe is installed in the outlet tube upper thermometer is the manufacturing method of the wholly aromatic polyester resin, characterized in that the cooling water is introduced into the cooling jacket when the temperature of the upper reaches 120 ~ 140 ℃.
4. The method according to claim 3,

   Method of producing a wholly aromatic polyester resin, characterized in that the cooling water is stopped when the upper temperature of the outlet pipe is less than 120 ℃.
5. The method according to claim 1,

   The raw material monomer is an aromatic hydroxy carboxylic acid, aromatic diol, aromatic dicarboxylic acid and acetic anhydride, the production method of the wholly aromatic polyester resin.
6. The method according to claim 5,

   And said aromatic hydroxy carboxylic acid comprises at least one compound of para hydroxy benzoic acid and 2-hydroxy-6-naphthoic acid.
7. The method according to claim 5,

   The aromatic diol is a method for producing a wholly aromatic polyester resin, characterized in that it comprises at least one compound of biphenol and hydroquinone.
8. The method according to claim 5,

   The aromatic dicarboxylic acid comprises at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid.
9. The manufacturing method of the wholly aromatic polyester resin compound containing the manufacturing method of the wholly aromatic polyester resin of any one of Claims 1-8.
10. A wholly aromatic polyester resin compound prepared according to claim 9.
11. The wholly aromatic polyester resin prepared according to any one of claims 1 to 8.
12. As a polycondensation reaction tank used in the liquid phase polycondensation reaction to prepare an aromatic polyester resin,

    An outlet pipe for discharging the produced acetic acid and acetic anhydride;

    An outlet tube upper thermometer provided at an upper portion of the outlet tube; And

    A cooling jacket supplying cooling water to the outlet pipe;

    Polycondensation reaction tank comprising a.
13. The method according to claim 12,

    When the temperature of the upper portion of the outlet pipe reaches 120 ~ 140 ℃ polycondensation reactor, characterized in that the cooling water is introduced into the cooling jacket.
14. The method according to claim 12,

    When the upper temperature of the outlet pipe is less than 120 ℃ polycondensation reactor, characterized in that the input of the cooling water is stopped.

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