KR20170070866A - Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared by the method - Google Patents
Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared by the method Download PDFInfo
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- KR20170070866A KR20170070866A KR1020150166365A KR20150166365A KR20170070866A KR 20170070866 A KR20170070866 A KR 20170070866A KR 1020150166365 A KR1020150166365 A KR 1020150166365A KR 20150166365 A KR20150166365 A KR 20150166365A KR 20170070866 A KR20170070866 A KR 20170070866A
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- polyester resin
- aromatic polyester
- wholly aromatic
- acid
- reaction
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/133—Hydroxy compounds containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
Abstract
The present invention relates to a wholly aromatic polyester resin which is capable of minimizing the outgassing amount in a molded product to which a compound using a wholly aromatic polyester resin produced by a mass-production scale polycondensation reaction is applied, And a wholly aromatic polyester resin produced thereby.
The present invention relates to a process for producing a wholly aromatic polyester resin by controlling the amount of acetic anhydride used in an acetylation reaction and minimizing the amount of acetic acid generated as a by-product, It is possible to solve the corrosion problem of metal wiring by acetic acid.
Description
The present invention relates to a process for producing a wholly aromatic polyester resin and a wholly aromatic polyester produced thereby, and more particularly, to a process for producing a wholly aromatic polyester resin by using a wholly aromatic polyester resin produced by a mass- To a method for producing a wholly aromatic polyester resin in which blistering may not occur in a high temperature reflow process by minimizing the amount of gas generated and a wholly aromatic polyester resin produced thereby.
The wholly aromatic polyester resin has high heat resistance and strength because it is entirely composed of an aromatic chain and therefore is important as a raw material for a product requiring high strength and high heat resistance and has a large commercial application.
Since the wholly aromatic polyester resin is excellent in flowability and heat resistance, it is widely used as a material for automobile parts, electric / electronic parts, and small-size and precision molded articles.
The polymerization of such a wholly aromatic polyester determines which polymerization reaction is to be applied depending on the T g of the final polymer, melting point (in the case of crystalline), thermal stability, solubility and the like.
Among the synthesis methods of the wholly aromatic polyester, the synthesis method most widely used is to polymerize by a melt method without using a solvent, but employs an ester exchange reaction.
A conventional method for synthesizing a wholly aromatic polyester is as follows.
Korean Patent No. 1111645 discloses a process for synthesizing a wholly aromatic polyester prepolymer by polycondensation of raw monomers containing an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid but not containing an aromatic aminocarboxylic acid Wherein the aromatic diol does not contain an aromatic compound in which two phenylene is bonded to an element other than carbon, and the content of the aromatic dicarboxylic acid in the starting monomer is 1.02 to 1.08 moles relative to one mole of the aromatic diol A method for producing a wholly aromatic liquid-crystalline polyester resin is disclosed.
Korean Patent Laid-Open No. 2010-0102923 discloses a process for producing a wholly aromatic liquid-crystalline polyester prepolymer, comprising: (a) synthesizing a wholly aromatic liquid-crystalline polyester prepolymer by polycondensation of at least two raw monomers using a metal acetate catalyst; And (b) synthesizing the wholly aromatic liquid-crystalline polyester resin by solid-phase polycondensation of the prepolymer.
The process for producing a wholly aromatic polyester resin is divided into an acetylation reaction of an aromatic monomer having a hydroxy group and a polycondensation reaction of an acetylated monomer and an aromatic carboxylic acid monomer produced by the reaction.
In the acetylation reaction, anhydrous acetic acid is used as an acetylating agent, and excess amount of the hydroxy group equivalent to the hydroxy group is substituted for the acetyl group, and acetic acid is generated as a byproduct through the acetylation reaction and the polycondensation reaction.
At this time, if the acetic acid produced in the polycondensation reaction with the excess acetic anhydride is not completely removed, the wholly aromatic polyester resin remains, and when the molded product manufactured by using the resin is used in the electric and electronic products, acetic anhydride and acetic acid are generated The metal wiring is corroded.
Also, in the case of the aromatic hydroxycarboxylic acid monomer, it is difficult to participate in the polycondensation reaction when the hydroxyl group is not substituted with the acetyl group in the acetylation reaction, and phenol is produced as a by-product through the decarbonation reaction at a high temperature. If the aromatic diol monomer is not substituted with an acetyl group, it can not participate in the polycondensation reaction but remains in the polycondensation reaction tank and remains in the wholly aromatic polyester resin.
Therefore, the sublimable phenol and aromatic diol monomer remain in the aromatic polyester resin and are generated as a gas during high-temperature molding and solidified in the mold to block the gas vent of the mold, And remains in the molded product, thereby causing the problem of generating blisters in a high-temperature reflow process.
[Prior Art Literature]
[Patent Literature]
Korea Patent Publication No. 2010-0102923
Korean Patent No. 0929383
Japanese Laid-Open Patent Publication No. 10-158482
In order to solve the problems of the prior art described above, the inventors of the present invention have found that, in the acetylation reaction in the production of a wholly aromatic polyester resin, acetic anhydride, aromatic hydroxy The hydroxyl group of the carboxylic acid monomer is not substituted with the acetyl group and the phenol produced as a byproduct and the aromatic diol monomer not participating in the polycondensation reaction remain in the wholly aromatic polyester resin, As a result, the present invention has been completed.
Accordingly, an object of the present invention is to reduce the amount of acetic acid, phenol and non-reactive aromatic diol remaining in the wholly aromatic polyester resin by controlling the amount of acetic anhydride used as an acetylating agent in comparison with the hydroxyl group equivalent of the aromatic monomer Aromatic polyester resin, and to provide a wholly aromatic polyester resin which can minimize the outgassing amount in a molded article to which a compound using a wholly aromatic polyester resin is applied, and a wholly aromatic polyester resin produced by the method.
Another object of the present invention is to provide a method for producing a wholly aromatic polyester resin compound having enhanced blister resistance and a wholly aromatic polyester resin compound prepared thereby.
In order to accomplish the above object, the present invention provides a method for producing a wholly aromatic polyester resin by carrying out an acetylation reaction and an esterification reaction of raw monomers to produce a prepolymer by polycondensation and solid-phase polycondensation of the prepolymer , And the use amount of acetic anhydride to be added during the acetylation reaction is controlled according to the following formula 1:
[Formula 1]
Hydroxy equivalents of aromatic monomers x 1.05 < acetic anhydride equivalents < hydroxy equivalents of aromatic monomers x 1.15
In one embodiment of the present invention, the unreacted acetic anhydride and acetic acid are removed in the polycondensation reaction of the raw monomers, and the unreacted acetic anhydride and acetic acid are removed at a temperature of 300 ° C or higher to 150-300 torr To maintain the pressure for 30 to 60 minutes.
In one embodiment of the present invention, the heated nitrogen may be introduced in the solid-phase polycondensation reaction of the prepolymer to remove acetic anhydride, acetic acid, phenol, and unreacted monomer.
In one embodiment of the present invention, it is preferable to use nitrogen heated to a temperature of 50 to 250 DEG C as the nitrogen.
The present invention also provides a wholly aromatic polyester resin produced by the above-described method for producing a wholly aromatic polyester resin.
The present invention also provides a method for producing a wholly aromatic polyester resin compound comprising the above-described method for producing a wholly aromatic polyester resin, and a wholly aromatic polyester resin compound produced thereby.
The present invention minimizes the amount of acetic acid generated as a by-product by controlling the amount of acetic anhydride used in the acetylation reaction in the production process of the wholly aromatic polyester resin, so that the molded article manufactured using the resin is used for electric and electronic products A method for producing a wholly aromatic polyester resin capable of solving corrosion problems of metal wiring by acetic acid and a wholly aromatic polyester resin produced thereby are provided.
The method for producing a wholly aromatic polyester resin according to the present invention is a method for producing a wholly aromatic polyester resin, which comprises reacting an acetic acid, an aromatic hydroxycarboxylic acid monomer The phenol produced as a byproduct and the aromatic diol monomer not participating in the polycondensation reaction remain in the wholly aromatic polyester resin because the hydroxy group can not be substituted with the acetyl group and the blister is generated in the high temperature reflow process of the molded product have.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings.
However, the present invention is not limited to the embodiments described below, but may be embodied in various other forms.
The present embodiments are provided so that the disclosure of the present invention is thoroughly disclosed and that those skilled in the art will fully understand the scope of the present invention.
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 specifically described to avoid an undesirable interpretation of the present invention.
In this specification, the singular forms include plural forms unless the context clearly dictates otherwise, and the constituents and acts referred to as " comprising (or having) " do not exclude the presence or addition of one or more other constituents and actions .
Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs.
Also, commonly used predefined terms are not ideally or excessively interpreted unless they are defined.
Hereinafter, a method for producing a wholly aromatic polyester resin according to the present invention will be described in detail.
The method for producing a wholly aromatic polyester resin according to the present invention comprises a step (acetylation step) of reacting an aromatic monomer having a hydroxy group with an acid anhydride to effect acetylation, an esterification reaction of the acetylated aromatic monomer with an aromatic dicarboxylic acid, A step of synthesizing a wholly aromatic polyester prepolymer by liquid phase polycondensation (an esterification reaction and a liquid polycondensation step), and a step of solid-phase polycondensation of the wholly aromatic polyester prepolymer to synthesize a wholly aromatic polyester resin (solid phase polycondensation step) do.
The present invention is characterized in that the content of acetic anhydride used as an acetylating agent in the acetylation step in the process of preparing the wholly aromatic polyester resin is controlled according to the following formula 1:
[Formula 1]
Hydroxy equivalents of aromatic monomers x 1.05 < acetic anhydride equivalents < hydroxy equivalents of aromatic monomers x 1.15
In the process of preparing the wholly aromatic polyester resin according to the present invention, when the anhydrous acetic acid is used at a hydroxy equivalent of the aromatic monomer of less than 1.05, the monomer in which the hydroxyl group of the aromatic monomer is not substituted by the acetyl group, Resulting in a difference in the molar ratio of the product, so that the physical properties of the wholly aromatic polyester resin may be varied depending on the arrangement. Also, when acetic anhydride is used in excess of the hydroxy equivalent of the aromatic monomer x 1.15, it is difficult to completely remove the acetic anhydride having a boiling point higher than acetic acid in the reaction system, thereby increasing the outgass content and increasing the color of the prepolymer It causes.
The present invention relates to a process for producing a wholly aromatic polyester resin which is produced by minimizing the by-product phenol and unreacted dihydroxy monomer generated by hydroxycarboxylic acid by raising the conversion ratio of the hydroxy group of the aromatic monomer to the acetyl group in the acetylation step Thereby minimizing the content of the outgassing gas.
The aromatic hydroxycarboxylic acid as the raw material monomer may include at least one compound selected from the group consisting of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and the aromatic diol may be at least one of biphenol and hydroquinone 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 the wholly aromatic polyester resin And may further contain known raw material monomers that can be used.
In one embodiment of the present invention, the acetylation step may be conducted at a temperature ranging from 140 to 160 ° C for 1 to 3 hours. If the temperature and time are within the above ranges, the hydroxy group of the aromatic monomer can be sufficiently converted to the acetyl group, and then the esterification reaction and the liquid polycondensation can proceed at a low temperature. Thus, the synthesized wholly aromatic polyester prepolymer is not deteriorated The propylene polymer is not browned.
The acetylation of the aromatic monomer may be performed by solution condensation polymerization or bulk condensation polymerization.
In the above acetylation step, 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 esterification reaction and the liquid polycondensation may be carried out 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, the esterification reaction and the discharge process failure after the liquid polycondensation do not occur, and then the wholly aromatic polyester prepolymer having physical properties suitable for the solid phase polycondensation reaction can be obtained.
The present invention is further characterized in that the step of removing acetic acid and unreacted acetic anhydride generated as a by-product after the acetylation reaction in the liquid polycondensation step is further performed.
In one embodiment of the present invention, the step of removing acetic acid and unreacted acetic anhydride generated as a by-product in the liquid polycondensation step is performed at a temperature of 300 ° C. or higher and a stepwise reduced pressure in the range of 150 to 300 torr and maintained for 30 to 60 minutes .
When the pressure is reduced to less than 150 torr at the high temperature liquid polycondensation stage, the generated acetic acid and unreacted acetic anhydride can be rapidly removed from the reactor and the polycondensation reaction can proceed rapidly. In this case, the molecular weight of the wholly aromatic polyester prepolymer to be produced is also rapidly increased, so that a prepolymer having a melting point higher than the external temperature is generated and solidified in the reactor, resulting in a problem in the process. Therefore, it is preferable that the pressure is reduced to 150 to 300 torr in a stepwise manner to remove the acetic acid gas generated in the reactor and the acetic anhydride not participating in the reaction while minimizing the liquid polycondensation reaction.
In order to perform the solid phase polycondensation step, the wholly aromatic polyester prepolymer should be provided with appropriate heat. Examples of the method for providing the heat include a heating plate, hot air, and a high temperature fluid.
In the present invention, the step of removing the acetic anhydride, acetic acid, phenol and unreacted monomer is further performed in the solid-phase polycondensation step.
In one embodiment of the present invention, the step of removing acetic anhydride, acetic acid, phenol and unreacted monomer in the solid phase polymerization step is carried out by introducing nitrogen heated to 50 to 250 ° C.
Adding nitrogen at a low temperature in the solid-phase polycondensation step lowers the internal temperature of the reactor. In the case of the solid-state polycondensation reaction proceeding at a high temperature, the internal temperature of the reactor is lowered by the low temperature nitrogen, and if the temperature of the external heater is increased to compensate for the low temperature, fusion may occur inside the reactor. Therefore, it is preferable to add nitrogen by heating at a temperature range in which the solid-phase polycondensation reaction proceeds, for example, at 50 to 250 ° C. In addition, nitrogen acts to remove the monomer that sublimates in the solid-phase polycondensation reaction from the inside of the reactor. When the temperature is lower than 50 ° C., the monomer is made into a solid and mixed with the wholly aromatic polyester resin in the reactor. It is caused by gas.
In the synthesis step of the wholly aromatic 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 synthesis of the wholly aromatic polyester prepolymer may be carried out 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, a wholly aromatic polyester prepolymer having physical properties suitable for the solid-phase polycondensation reaction can be obtained without causing a discharge process failure after the polycondensation reaction.
In one embodiment of the present invention, the method for producing the wholly aromatic polyester resin further comprises a step of pulverizing the wholly aromatic polyester prepolymer before the esterification reaction and the liquid phase polycondensation step, and subsequent to the solid phase polymerization step .
The size of the particles of the pulverized wholly aromatic polyester prepolymer may be, for example, 0.5 mm to 2.5 mm.
The milling of the wholly aromatic polyester prepolymer can be carried out using a mill equipped with a screen having a mesh size of 0.5 mm to 2.5 mm (for example, Feather Mill).
In one embodiment of the present invention, the method for producing a wholly aromatic polyester resin is characterized in that the wholly aromatic polyester prepolymer is added between the liquid-phase polycondensation step in which the esterification reaction proceeds in the liquid phase and the wholly aromatic polyester prepolymer milling step Cooling step may be further included. In the cooling step of the wholly aromatic polyester prepolymer, the wholly aromatic polyester prepolymer may be cooled to a temperature of 20 to 70 ° C. Accordingly, the pulverization of the wholly aromatic polyester prepolymer may be carried out 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 a wholly aromatic polyester resin compound using the wholly aromatic polyester resin produced by the method for producing the wholly aromatic polyester resin and an additive.
The method for producing the wholly aromatic polyester resin compound includes the steps of synthesizing a wholly aromatic polyester resin according to the above-described method for producing wholly aromatic polyester resin, and melt-kneading the synthesized wholly aromatic 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 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 fibers. 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.
For the 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 wholly aromatic polyester resin compound according to one embodiment of the present invention having the above-described structure has excellent heat resistance (load deformation temperature of 250 ° C or higher) and high fluidity property of the resin contained in the wholly aromatic polyester resin compound, ≪ / RTI >
The wholly aromatic polyester resin compound produced according to the present invention has an out gas content of 100 ppm or less at the time of molding (see Table 1 below)
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these embodiments.
Example
Example 1
In a polycondensation reactor equipped with a stirrer, a reflux condenser and a vacuum regulator, 888 kg of para-hydroxybenzoic acid, 399 kg of biphenol, 267 kg of terephthalic acid, 89 kg of isophthalic acid and 1,203 kg of acetic anhydride were introduced. In a nitrogen atmosphere, 0.13 kg of potassium acetate, (4 hydrate) was added to the reaction mixture and the mixture was stirred for 30 minutes. The reactor was cycled and the temperature of the reactor was raised to 150 ° C for 1 hour and refluxed for 2 hours to conduct the acetylation reaction. The reactor temperature was raised to 300 ° C for 5 hours while the acetic acid generated through the acetylation reaction and the polycondensation reaction was removed. Thereafter, the polycondensation reaction was carried out while the temperature of the reactor was raised to 320 ° C, and acetic acid and anhydrous acetic acid were removed under the condition that the internal pressure of the reactor was reduced in three steps of 500 torr, 300 torr and 150 torr. After completion of the polycondensation reaction, the prepolymer was cooled while being discharged from the reactor, and then pulverized to have an average particle size of 0.5 to 1.5 mm through a pulverizer. The pulverized prepolymer having a uniform size was charged into a rotary solid-state reactor, and the temperature was raised to 280 deg. C over 8 hours while nitrogen exceeding 200 deg. C was added. The polycondensation reaction was completed at this temperature for 3 hours, and after cooling to 100 ° C or less for 1 hour, the wholly aromatic polyester resin was recovered.
The pellets were melt-kneaded using a twin-screw extruder so as to contain the glass fiber (diameter 10 m, length 3 mm) of the wholly aromatic polyester resin subjected to the polycondensation reaction, and the out gas content thereof was confirmed.
Example 2
The wholly aromatic polyester resin pellets were prepared in the same manner as in Example 1 except that the content of acetic anhydride added during the condensation reaction in the liquid phase and the degree of vacuum according to the reduced pressure were changed as shown in Table 1, And the results are shown in Table 1.
Example 3
The procedure of Example 1 was repeated to prepare a wholly aromatic polyester resin pellet except that the vacuum holding time was changed according to the reduced pressure during the condensation reaction in liquid phase as shown in Table 1, Respectively.
Example 4
The wholly aromatic polyester resin pellets were prepared in the same manner as in Example 1 except that the nitrogen temperature was changed during the solid-phase condensation reaction as shown in Table 1, and the outgass content was confirmed and shown in Table 1 .
Comparative Example 1
The wholly aromatic polyester resin pellets were prepared in the same manner as in Example 1, except that the pressure reduction step was not applied during the condensation reaction in liquid phase as shown in Table 1, and the outgass content was confirmed and shown in Table 1 .
Comparative Example 2
The wholly aromatic polyester resin pellets were prepared in the same manner as in Example 1, except that nitrogen at room temperature was added during the solid-state condensation reaction and the polymerization reaction proceeded as shown in Table 1, and the outgass content was confirmed Are shown in Table 1.
Comparative Example 3
The procedure of Example 1 was repeated except that the content of anhydrous acetic acid added during the condensation reaction in the liquid phase was changed as shown in Table 1 to prepare a wholly aromatic polyester resin pellet. Respectively.
Acetic anhydride equivalent ratio
(torr)
(min)
(° C)
(Nm 3 / hr)
Acetic acid
Monomer
Referring to Table 1, the amounts of unreacted monomers, which did not participate in the polycondensation reaction with acetic acid and phenol, generated as by-products in outgas of the wholly aromatic polyester resin pellets of Examples 1 to 4 prepared according to the present invention Is significantly smaller than those of Examples 1 to 3.
The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.
Claims (13)
Wherein the amount of acetic anhydride to be added during the acetylation reaction is adjusted according to the following formula 1. < EMI ID = 1.0 >
[Formula 1]
Hydroxy equivalents of aromatic monomers x 1.05 < acetic anhydride equivalents < hydroxy equivalents of aromatic monomers x 1.15
Wherein the raw material monomer is an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic dicarboxylic acid, and an anhydrous acetic acid.
Wherein the aromatic hydroxycarboxylic acid comprises at least one compound selected from the group consisting of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.
Wherein the aromatic diol comprises at least one compound selected from the group consisting of biphenol and hydroquinone.
Wherein the aromatic dicarboxylic acid comprises at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid.
Wherein the unreacted acetic anhydride and acetic acid are removed in the polycondensation reaction of the starting monomer.
The process for removing unreacted acetic anhydride and acetic acid in the polycondensation reaction of the raw monomers is carried out at a temperature of 300 ° C. or higher to a pressure in the range of 150 to 300 torr while being maintained at a reduced pressure for 30 to 60 minutes. A method for producing a resin.
Wherein the heated nitrogen is introduced in the solid-phase polycondensation reaction of the prepolymer to remove anhydrous acetic acid, acetic acid, phenol, and unreacted monomer.
Wherein the nitrogen is nitrogen heated to a temperature of 50 to 250 占 폚.
Wherein the content of the out gas at the time of molding is 100 ppm or less.
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| KR1020150166365A KR20170070866A (en) | 2015-11-26 | 2015-11-26 | Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared by the method |
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| KR1020150166365A KR20170070866A (en) | 2015-11-26 | 2015-11-26 | Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared by the method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023199854A1 (en) * | 2022-04-11 | 2023-10-19 | 東レ株式会社 | Liquid crystal polyester resin, liquid crystal polyester resin composition, and molded product comprising same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023199854A1 (en) * | 2022-04-11 | 2023-10-19 | 東レ株式会社 | Liquid crystal polyester resin, liquid crystal polyester resin composition, and molded product comprising same |
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